1st INTERNATIONALSYMPOSIUM
HYDROGENOMICS
combined with

14th INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
The 1st International Symposium “HYDROGENOMICS” combined with the 14th International
Symposium “Hydrogen & Energy” follows the 13th one that took place on January 20th - 25th, 2019, in
GYEONG WON JAE AMBASSADOR, Incheon, South Korea with more than 60 participants. It serves as
an information platform of the fundamental science and technology and the frontiers of research onhydrogen and energy.
The symposium consists top level keynote, invited, and contributed talks studying “HYDROGENOMICS”
and the key properties of the hydrogen cycle, i.e. the hydrogen production, hydrogen storage, hydrogen
combustion, and fuel cells. Furthermore, contributions on the batteries, synthetic fuels, and related
functional materials are very welcome. Early stage and experienced researchers present their newest
results also on posters.
The symposium will take place in The Hotel Monterey Edelhof Sapporo, Hokkaido, Japan; The numberof participants is limited to 80.

5(Sun.) – 10(Fri.) January, 2020
The Hotel Monterey Edelhof Sapporo
Nishi 1-1, Kita 2 Jyo, Chuo-ku, Sapporo,
Hokkaido, 060-0002, Japan
PHONE: +81-11-242-7111
URL: https://www.hotelmonterey.co.jp/en/edelhof/

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 20202

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ACKNOWLEDGEMENTMEXT Grant-in-Aid for Scientific Research on Innovative “Hydrogenomics”

WPI Advanced Institute for Materials Research (WPI-AIMR)

3

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 20204

combined with

1st INT’L SYMPOSIUM

and Advanced Measurement/Simulation, to fully utilize thediverse functionalities of hydrogen in materials• Hydrogenomics*• Hydrogen Production • Fuel Cells• Hydrogen Storage• Batteries• Hydrogen Combustion • Synthetic Fuels• Theory and Modeling • Functional Mater.
*Hydrogen Densification, Localization, Migration, Activation,

SUBJECTS

https://www.hydrogenomics.jp/
Contact: secretary@hydrogenomics.jp

January 5th -10th, 2020
Hotel Monterey Edelhof Sapporo,
SAPPORO, JAPANHYDROGEN & ENERGY

14th INT’L SYMPOSIUM

Dec.. 9, 2019

LOCATION

Keynote/Invited/Contributed

Abstract: October 11, 2019

TIMELINE
Registration: August 31 2019
(Limited 80 Persons)¥50,000; incl., Welcome Reception, Lunch,
Dinner, Conference Dinner, Coffee Breaks,
Social Event

CONFERENCE FEE

InvitedRyotaro ARITA, Marcello BARICCO, Craig BUCKLEY,
Martin DORNHEIM, Jianping GUO, Ikutaro HAMADA,
Bjørn HAUBACK, Michael HIRSCHER, Craig JENSEN,
Genki KOBAYASHI, Michel LATROCHE, Katsutoshi
NAGAOKA, Chikashi NISHIMURA, Minoru OSADA,
Astrid PUNDT, Hiroyuki SAITOH, Katsuya SHIMIZU, Hotel Monterey Edelhof Sapporo
Nishi 1-1, Kita 2 Jyo, Chuo-ku,
Petra SZILÁGYI, Min ZHU (in alphabet order)
Sapporo, Hokkaido, 060-0002, JapanPROGRAM+81-11-242-7111
https://www.hotelmonterey.co.jp/en/edelhof/

KeynoteAndreas ZÜTTEL, EPFL, Switzerland
Hans-Joachim FREUND, MPl-Berlin, Germany
Anibal Javier (Timmy) RAMIREZ-CUESTA
Oak Ridge National Laboratory, USA
Masaru TSUKADA, Univ. Tokyo, JapanKEYNOTE and INVITED SPEAKERS

Shin-ichi ORIMO, Tohoku University
Taro HITOSUGI, Tokyo Institute of Technology
Katsuyuki FUKUTANI, University of Tokyo
Andreas ZÜTTEL, EPFL, Switzerland

ORGANIZERS

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 20206

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

Contents
Timetable

17

Abstracts

19

SundayThe Hotel Monterey Edelhof Sapporo

05.01.2020
15:00

Registration

17:00

Welcome Reception at The Hotel Monterey Edelhof Sapporo

19:00

End

MondayThe Hotel Monterey Edelhof Sapporo

06.01.2020
09:00

Opening: Shin-ichi ORIMOHYDROGENOMICS: CREATION OF INNOVATIVE MATERIALS, DEVICES, AND
REACTION PROCESSES USING HIGHER-ORDER HYDROGEN FUNCTIONS

21

Coffee Break
10:30

Chair: Shin-ichi ORIMO
K01: Andreas ZÜTTEL
200 YEARS AFTER INDUSTRIALISATION THE TRANSITION TO RENEWABLE
ENERGY

22

11:10

I01: Michael HIRSCHERHYDROGEN STORAGE IN NANOPOROUS MATERIALS: STATUS AND FUTURE
CONCEPTS

23

13:30

Chair: Michael HIRSCHER
I02: Min ZHUMG BASED AMORPHOUS FOR HYDROGEN AND ELECTRIC STORAGE

24

14:00

C01: Kenichi OYAIZUREVERSIBLE HYDROGEN STORAGE WITH ORGANIC POLYMERS

25

14:20

C02: Joseph TEPROVICHENHANCED ELECTROCHEMICAL PROPERTIES OF HYDROGEN STORAGE
MATERIALS

26

14:40

C03: Toyoto SATOHYDROGEN STORAGE PROPERTIES AND CRYSTAL STRUCTURALINVESTIGATIONS ON MG CONTAINING ALLOYS

27

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Sapporo, Hokkaido, Japan, 2020

Coffee Break
15:20

Chair: Min ZHU
I03: Craig BUCKLEY
Thermal Battery Development for Concentrated Solar Power Systems

28

15:50

I04: Chikashi NISHIMURANEW DEVICE FOR HYDROGEN SEPARATION FROM DECOMPOSED GAS OF
ENERGY CARRIERS, NH3 AND MCH, USING FLAT VANADIUM ALLOYSMEMBRANES

29

18:00

Poster Session
Chair: Chikashi NISHIMURA
P01: Hiroshi AKIBASTRUCTURAL AND DYNAMICAL STUDY ON PdPt HYDRIDE NANOPARTICLES30

P02: Elvis ARGUELLES
H2 Nuclear Spin Conversion on Metal Surfaces: Physisorption vs.
Molecular Chemisorption

31

P03: Ho-Chol CHANG
PHOTOCHEMICAL HYDROGEN EVOLUTION FROM MOLECULAR IRONCOMPLEXES WITH PHENYLENEDIAMINES

32

P04: Ken-Ichi FUJITADEVELOPMENT OF EFFICIENT SYSTEMS FOR HYDROGEN PRODUCTION
BASED ON CATALYTIC ACTIVITY OF IRIDIUM COMPLEXES IN
DEHYDROGENATIVE REACTIONS

33

P05: Jun HARUYAMAFIRST PRINCIPLES STUDY OF HYDRIDE ION CONDUCTOR

34

P06: Yoshiki HIGUCHINEW ASSAY METHOD FOR THE ENZYMES REACTING WITH GASEOUS
SUBSTRATES BY RAMAN SPECTROSCOPY

35

P07: Taro HITOSUGIEpitaxial growth of Ca2NH thin films using reactive magnetron sputtering

36

P08: Soshi IIMURA
H− ION CONDUCTION AND ANHARMONIC VIBRATION IN OXYGEN-DOPEDLANTHANUM HYDRIDE

37

P09: Munehiro INUKAIGLASS-PHASE
COORDINATIONPOLYMER DISPLAYINGCONDUCTIVITY AND GUEST-ACCESSIBLE POROSITY

38
PROTON

P10: Takayoshi ISHIMOTO
THEORETICAL STUDY OF H/D ISTOPE EFFECT WITH METAL BY USINGCOMBINED PLANE WAVE AND LOCALIZED BASIS SET APPROACH

39

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20:00

Sapporo, Hokkaido, Japan, 2020

P11: Yuki KANAZAWA
DEVELOPMENT OF POWDER NEUTRON HOLOGRAPHY FOR INVESTIGATIONOF HYDRIDES

40

P12: Hiroyuki KATO
ATTEMPT TO CONTROL H+ TRANSFER IN MOLECULAR BILAYERS FOR A
FUTURE HYDROGENOMIC DEVICE41

P13: Kazuaki KISU
ALL SOLID-STATE BATTERIES USING LIBH4-BASED SOLID ELECTROLYTE AND
LITHIUM METAL ELECTRODE

42

P14: Masaaki KITANOLANTHANUM OXYHYDRIDES SUPPORTED RUTHENIUM CATALYST FOR
AMMONIA SYNTHESIS

43

P15: Youngdon KO
EFFETS OF Ni-CONTAING POROUS CARBON SHEETS (Ni-PCS) ON THE
DEHYDROGENATION PROPERTIES OF Mg(AlH4)244

P16: Takahiro KONDOCARBON DOPING OF HYDROGEN BORIDE SHEET REDUCES H2 RELEASETEMPERATURE

45

P17: Akihiko MACHIDALOCAL STRUCTURE STUDY OF METAL–HYDROGEN SYSEMS BY X-RAY TOTALSCATTERING

46

P18: Mitsuhiko MAESATOLOW TEMPERATURE HYDROGEN ION BEAM IRRADIATION FOR EXPLORINGEXOTIC PHYSICAL PROPERTIES

47

P19: Hiroki MIYAOKAANALYSIS OF AMMONIA ABSORPTION STATE OF METAL BOROHYDRIDE

48

P20: Naoya MIYAUCHILOCAL DIFFUSION COEFFICIENT OF DEUTERIUM PERMEATING THROUGH
STAINLESS STEEL MEMBRANE

49

P21: Hatsumi MORIANHYDROUS PROTON CONDUCTIVITY OF IMIDAZOLIUM HYDROGENDICARBOXYLATES

50

P22: Masakazu MORIMOTOADVANCED MOLECULAR MATERIALS BASED ON PHOTOCHROMIC
DIARYLETHENES BEARING HYDROGEN-FUNCTIONAL UNITS

51

P23: Shin MURAKAMI
HIGH-PRESSURE AND HIGH-TEMPERATURE SYNTHESIS OF NOVEL AL-TM(TM=ZR, HF) HYDRIDES

52

End

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Tuesday

Sapporo, Hokkaido, Japan, 2020

The Hotel Monterey Edelhof Sapporo

07.01.2020
09:00

09:40

Chair: Miho YAMAUCHI
K02: Hans-Joachim FREUNDHYDROGEN ON AND IN CERIA AND HYDROGENATION OF UNSATURATEDHYDROCARBONS

53

I05: Katsutoshi NAGAOKACATALYST DESIGN FOR PRODUCTION AND DECOMPOSITION OFAMMONIA AS A HYDROGEN CARRIER

54

Coffee Break
10:30

Chair: Katsutoshi NAGAOKA
I06: Jianping GUO
THE ROLE OF HYDRIDES IN N2 REDUCTION AND NH3 FORMATION

55

11:00

C04: Jun YOSHINOBUHYDROGENATION OF FORMATE ON THE Pd-Cu SINGLE ATOM ALLOY
MODEL CATALYSTS

56

11:20

C05: Takanori SHIMADINITROGEN ACTIVATION BY MOLECULAR MULTIMETALLIC TITANIUM
POLYHYDRIDES

57

13:30

Chair: Jianping GUO
I07: Craig M. JENSEN
DETERMINATION OF BCX HYDROGEN BINDING ENERGIES BY HIGHPRESSURE, VARIABLE TEMPERATURE 1H NMR SPECTROSCOPY

58

14:00

C06: Ken-ichi FUKUINOVEL SPECTROSCOPY USING FAR UV LIGHT APPLIED FOR ELECTRONICSTATES ANALYSES OF INTERFACIAL ELECTROLYTE AND HYDROGENSTORING MATERIALS

59

14:20

C07: Jinqiu ZHANG
ELECTRODEPOSITED COPPER CATALYST FOR CO2 REDUCTION REACTION

60

14:40

C08: Motoyuki SHIGA
NUCLEAR QUANTUM EFFECTS OF HYDROGEN IN MATERIALS

61

Coffee Break
15:20

15:50

Chair: Craig M. JENSEN
I08: Marcello BARICCOMISCIBILITY IN LIBH462

I09: Minoru OSADAHYDROGEN FUNCTIONS IN 2D NANOSHEETS AND RELATED COMPOUNDS

63

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18:00

Sapporo, Hokkaido, Japan, 2020

Poster Session
Chair: Minoru OSADA
P24: Akinobu NAKADALIGHT-DRIVEN C-H CARBOXYLATION BY CARBON DIOXIDE

64

P25: Yuki NAKAGAWAENHANCEMENT OF LITHIUM ION CONDUCTIVITY OF COMPLEX HYDRIDESBY BORON NITRIDE ADDITIVES

65

P26: Masashi NAKAMURAEFFECTOF
HYDROPHBIC
CATIONSONTHE
HYDROGENOXIDATION/EVOLUTION REACTIONS ON SINGLE-CRYSTAL PT ELECTRODES

66

P27: Takashi NAKAMURA
SOFT X-RAY ABSORPTION SPECTROSCOPIC STUDIES ON HYDROGENATED
TITANIUM DIOXIDE

67

P28: Masayuki OCHIEFFECTIVE COULOMB INTERACTION IN STRONTIUM VANADIUMOXYHYDRIDES EVALUATED BY THE CONSTRAINED RANDOM-PHASE
APPROXIMATION

68

P29: Kenji OHOYAMACHALLENGE OF DETERMINATION OF HYDROGEN POSITIONS IN HYDRIDES
BY WHITE NEUTRON HOLOGRAPHY

69

P30: Kouki OKA
Poly(dihydroxybenzoquinone): Its High-density and Robust Charge Storage
Capability in Rechargeable Acidic Polymer-air Batteries

70

P31: Toyoto SATOHYDROGEN STORAGE PROPERTIES AND CRYSTAL STRUCTURALINVESTIGATIONS ON MG CONTAINING ALLOYS
P32: Ryuhei SATO
CRYSTAL STRUCTURE PREDICTION OF LI(CB9H10) BY XRD-ASSISTED
MOLECULAR DYNAMIC SIMULATION

27

P33: Yasuteru SHIGETA
THEORETICAL ANALYSIS ON STRUCTURES OF RESTING OXIDIZED STATES OF[NIFE] HYDROGENASE

72

P34: Keita SHINZATOHYDROGENATION PROPERTIESMODIFICATION BY CARBON

73
OF

TITANIUM

WITH

71

SURFACE

P35: Masanori TACHIKAWA
DEVELOPMENT OF MULTICOMPONENT QUANTUM CHEMISTRY METHODSFOR ACCURATE PREDICTION AND ELUCIDATION OF HYDROGENFUNCTIONAL MECHANISM

74

P36: Hidekazu TANAKACONTROL OF ELECTRICAL PROPERTIES ON TRANSITION METAL OXIDES VIAPROTONIC-ELECTRONIC COUPLING

75

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

20:00

Sapporo, Hokkaido, Japan, 2020

P37: Bo THOMSENCALCULATING THE pKW OF SUBCRITICAL AND SUPERCRITICAL H2O AND D2O

76

P38: Hayato TSURUGIHYDROSILYLATION OF BENZOPHENONE DERIVATIVES CATALYZED BY RAREEARTH METAL COMPLEXES: IMPORTANCE OF AGOSTIC INTERACTION
BETWEEN RARE-EARTH METALS AND HYDROSILANE

77

P39: Noritaka USAMI
ROLE OF HYDROGENS AROUND HETEROINTERFACES IN IMPROVINGPASSIVATION PERFORMACE OF SOLAR CELLS

78

P40: Teppei YAMADAAPPLICATION OF PROTON-COUPLED ELECTRON TRANSFER REACTIONTOWARD THERMOCELL WITH HIGH SEEBECK COEFFICIENT

79

P41: Takayoshi YAMAMOTOSTUDY OF HYDROGEN POSITION IN HYDRIDES USING WHITE NEUTRONHOLOGRAPHY

80

P42: Yoshiyuki YAMAMOTOFIRST-PRINCIPLES CALCULATIONSNONADIABATIC CARRIER CAPTURE

81
OF

HYDROGENDIFFUSION

VIA

P43: Osamu YAMAMURO
FAST AND SLOW DYNAMICS OF HYDROGEN CLUSTER MATERIAL Li6NbH11

82

P44: Miho YAMAUCHICATALYTIC ENHANCEMENT ON RUTHENIUM-IRON NANOALLOY CATALYSTS
FOR AMMONIA SYNTHESIS

83

P45: Heena YANGMAGNESIUM HYDRIDE ON NITROGEN DOPED GRAPHENE FOR HYDROGEN
STORAGE

84

End

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

Wednesday The Hotel Monterey Edelhof Sapporo
08.01.2020
09:00

Chair: Katsuyuki FUKUTANI
K03: Masaru TSUKADAQUANTUM TRANSITION OF HYDROGEN/ELECTRONS IN SOLID AND
SURFACES -Some theoretical aspects-

85

I10: Katsuya SHIMIZUSYSTHESIS OF SUPERHYDRIDES UNDER HIGH PRESSURE

86

10:30

I11: Ryotaro ARITAQUANTUM CRYSTAL STRUCTURE IN THE 250 K SUPERCONDUCTINGLANTHANUM HYDRIDE

87

11:00

Network Meeting

09:40
Coffee BreakSocial Event
Attendant: Miki HINO and Yasuko ITO
12:00

Bus leaves for Social Event
Lunch in the bus

13:00

Otaru Canal Day Cruise and sightseeing in Otaru

16:30

Departure from Otaru

18:00

Dinner at The Sapporo Beer Garden

20:00

Bus return to The Hotel Monterey Edelhof Sapporo

Thursday

The Hotel Monterey Edelhof Sapporo

09.01.2020
09:00

09:40

Chair: Taro HITOSUGI
K04: A. J. Timmy RAMIREZ-CUESTAVIOLATION OF THE SWITENDICK CRITERION IN METAL HYDRIDESEVIDENCED BY INELASTIC NEUTRON SCATTERING

88

I12: Petra SZILÁGYI
METAL-ORGANIC FRAMEWORKS FOR THE HYDROGEN ECONOMY

89

Coffee Break
10:30

Chair: Petra SZILÁGYI
I13: Astrid PUNDT
Phase transitions and ultra-high mechanical stress in Nb-H thin films

90

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

11:00

C09: Saya AJITO
A NEW TECHNIQUE FOR VISUALIZATION OF HYDROGEN PERMEATED
THROUGH PURE IRON USING AN IRIDIUM COMPLEX

91

11:20

C10: Loris LOMBARDOCOMPLEX HYDRIDES FOR CO2 CAPTURE AND TRANSFORMATION

92

13:30

Chair: Astrid PUNDT
I14: Bjørn C. HAUBACKMULTIFUNCTIONAL METAL HYDRIDES

93

14:00

C11: Toshiya OTOMOSTRUCTURAL STUDY OF HYDRIDES BY A HIGH INTENSITY TOTALSCATTERING INSTRUMENT, NOVA

94

14:20

C12: Yoshinori OHMASASTRUCTURE AND DYNAMICS OF HYDROGEN CLUSTER MATERIAL Li6NbH11

95

14:40

C13: Terry HUMPHRIESRECENT DEVELOPMENTS IN HIGH TEMPERATURE METAL HYDRIDES FOR
THERMAL BATTERY APPLICATIONS

96

Coffee Break
15:20

Chair: Bjørn C. HAUBACK
I15: Martin DORNHEIMNOVEL METAL HYDRIDES DISCOVERY AND APPLICATION

97

15:50

I16: Michel LATROCHEHYDRIDE-BASED SOLID STATE LI-ION BATTERIES FOR ENERGY STORAGE

98

18:00

Conference Dinner at The Hotel Monterey Edelhof Sapporo
Chair: Andreas ZÜTTEL and Yasuko ITO

20:00

End

FridayThe Hotel Monterey Edelhof Sapporo

10.01.2020
09:00

09:30

Chair: Osamu YAMAMURO
I17: Hiroyuki SAITO
HIGH-PRESSURE SYNGHESIS OF NOVEL ALUMINUM-BASED HYDRIDESUSING SYNCHROTRON RADIATION X-RAYS

99

I18: Genki KOBAYASHIMATERIAL DEVELOPMENT OF H– CONDUCTIVE OXYHYDRIDES

100

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1st Int. Symposium "Hydrogenomics" combined with
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Sapporo, Hokkaido, Japan, 2020

10:00

I19: Ikutaro HAMADAHETEROGENEOUS CATALYTIC REACTIONS FROM VAN DER WAALS DENSITYFUNCTIONAL

10:30

Closing: Shin-ichi ORIMO

101

Science of Hydrogen & Energy Award

103

List of Participants

115

Information

123

Notes

135

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Sapporo, Hokkaido, Japan, 2020

16

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Time/Day

Welcome Reception
Light Meal

Registration

01/05/20
SundayOpening: Shin-ichi ORIMO

01/06/20
MondayChair: Minoru OSADA
24: Akinobu NAKADA
25: Yuki NAKAGAWA
26: Masashi NAKAMURA
27: Takashi NAKAMURA
28: Masayuki OCHI
29: Kenji OHOYAMA
30: Kouki OKA
31: Toyoto SATO
32: Ryuhei SATO
33: Yasuteru SHIGETA
34: Keita SHINZATO
35: Masanori TACHIKAWA
36: Hidekazu TANAKA
37: Bo THOMSEN
38: Hayato TSURUGI
39: Noritaka USAMI
40: Teppei YAMADA
41: Takayoshi YAMAMOTO
42: Yoshiyuki YAMAMOTO
43: Osamu YAMAMURO
44: Miho YAMAUCHI
45: Heena YANG

DinnerDinnerChair: Chikashi NISHIMURA
1: Hiroshi AKIBA
2: Elvis ARGUELLES
3: Ho-chol CHANG
4: Ken-ichi FUJITA
5: Jun HARUYAMA
6: Yoshiki HIGUCHI
7: Taro HITOSUGI
8: Soshi IIMURA
9: Munehiro INUKAI
10: Takayoshi ISHIMOTO
11: Yuki KANAZAWA
12: Hiroyuki KATO
13: Kazuaki KISU
14: Masaaki KITANO
15: Youngdon KO
16: Takahiro KONDO
17: Akihiko MACHIDA
18: Mitsuhiko MAESATO
19: Hiroki MIYAOKA
20: Naoya MIYAUCHI
21: Hatsumi MORI
22: Masakazu MORIMOTO
23: Shin MURAKAMI

9: Minoru OSADA

6: Ken-ichi FUKUI
7: Jinqiu ZHANG
8: Motoyuki SHIGA
Coffee Break
Chair: Craig M. JENSEN
8: Marcello BARICCO

1: Kenichi OYAIZU
2: Joseph TEPROVICH
3: Toyoto SATO
Coffee Break
Chair: Min ZHU
3: Craig BUCKLEY

4: Chikashi NISHIMURA

Chair: Jianping GUO
7: Craig M. JENSEN

Lunch

Chair: Michael HIRSCHER
2: Min ZHULunch

1: Michael HIRSCHER

Coffee Break
Chair: Katsutoshi NAGAOKA
6: Jianping GUO

5: Katsutoshi NAGAOKA

2: Hans-Joachim FREUND

01/07/20
Tuesday
Chair: Miho YAMAUCHI

4: Jun YOSHINOBU
5: Takanori SHIMA

1: Andreas ZÜTTEL

Coffee Break
Chair: Shin-ichi ORIMOTIMETABLE

Social Event
Incl. Lunch & Dinner

Attendant: Miki HINO and Yasuko ITO

Network Meeting

11: Ryotaro ARITA

Coffee Break

10: Katsuya SHIMIZU

3: Masaru TSUKADA

01/08/20
Wednesday
Chair: Katsuyuki FUKUTANI

Conference Dinner

Chair: Andreas ZÜTTEL and Yasuko ITO

16: Michel LATROCHE

11: Toshiya OTOMO
12: Yoshinori OHMASA
13: Terry HUMPHRIES
Coffee Break
Chair: Bjørn C. HAUBACK
15: Martin DORNHEIM

Chair: Astrid PUNDT
14: Bjørn C. HAUBACKLunch

9: Saya AJITO
10: Loris LOMBARDO

Coffee Break
Chair: Petra SZILÁGYI
13: Astrid PUNDT

12: Petra SZILÁGYI

01/09/20
Thursday
Chair: Taro HITOSUGI
4: A. J. Timmy
RAMIREZ-CUESTA

KeynoteInvitedContributed
Poster

Departure

Closing: Shin-ichi ORIMO

19: Ikutaro HAMADA

18: Genki KOBAYASHI

01/10/20
FridayChair: Osamu YAMAMURO
17: Hiroyuki SAITO

4 Persons
19 Persons
13 Persons
45 Persons

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"
Sapporo, Hokkaido, Japan, 202017

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 202018

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ABSTRACTS

19

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 202020

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROGENOMICS:
CREATION OF INNOVATIVE MATERIALS, DEVICES, AND REACTION PROCESSESUSING HIGHER-ORDER HYDROGEN FUNCTIONS
Shin-ichi ORIMO1
1 WPI-AIMR / Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan

Hydrogen in materials exhibits a wide range of concentration, high mobility, quantum nature, and superiorchemical reactivity. All these features of hydrogen originate from its bonding and size flexibilities. The purposeof an MEXT (Ministry of Education, Culture, Sports, Science and Technology, Japan) project is to develop a
new materials science of hydrogen / hydrides (hereafter referred to as “HYDROGENOMIC”, i.e., hydrogenomics) as a guideline to “fully utilize” the diverse functionalities of hydrogen in materials.
The MEXT 5-years large-scale project will focus on
the four most important functionalities of hydrogen
originated from its bonding and size flexibilities(hereafter, referred to as “hydrogen functions”); i.e.,“high densification ability (#1)”, “interfacial
localizability (#2)”, “fast migration ability (#3)” and“high activation ability (#4)”.

Then the project will merge them to induce
unprecedented “higher-order hydrogen functions(synergistic effect between its individual hydrogen
functions)” with the support of “advanced analysis
and simulation techniques (#5)”, which will also be
developed within this project to capture the hydrogen
functions more accurately (Fig. 1).

Synergetic Effects betw. Individual Functions
Promotion#2 Localization#3 Migration#4 Activation

NH3#5 Advanced
Measurement/Simulation#1 Densification

Innovative Materials, …

Factorization

e–

e–

N

H+
H– H

hv

Research
Strategy

Hydrogen-related properties
・Important・Complicated・UnclearFig. 1 Basic concept of MEXT, Grant‐in‐Aid for Scientific Research on Innovative Areas,“HYDROGENOMICS: Creation of innovative materials, devices, and reaction processes
using higher-order hydrogen functions”

Shin-ichi ORIMO received his Ph.D. in 1995. He was a JSPS research fellow, a research associate
in Hiroshima University, and a guest researcher in Max-Planck Institute for Metal Research awarded
by Alexander von Humboldt Fellowship and MEXT Fellowship. He worked as the Special Advisor to
the University President, and is currently Director of WPI-AIMR, and Head of Section of Institute ofMaterials Research (IMR), Tohoku University. The related research was recently awarded by“Metals Meritorious Award (Japanese Institute of Metals, 2011), “The Commendation for Scienceand Technology (The Minister of MEXT, 2012)”, “Hydrogen & Energy Award (2015)”, and so on.
http://www.hydrogen.imr.tohoku.ac.jp/
Shin-ichi ORIMO
Corresponding author: Shin-ichi ORIMO, Email: orimo@imr.tohoku.ac.jp, Tel. (+81)22-215-2093.

21

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

200 YEARS AFTER INDUSTRIALISATIONRENEWABLE ENERGY

THE

TRANSITIONTO

Andreas ZÜTTEL*1,2, Heena YANG1,2, Loris LOMBARDO1,2, Youngdon KO1,2
1Laboratory of Materials for Renewable Energy (LMER), ISIC, Basic Science Faculty, École polytechnique fédérale deLausanne (EPFL) Valais/Wallis, Rue de l’Industrie
2Empa Materials Science & technology, Dübendorf, Switzerland17,

CH-1950

Sion,

Switzerland

Switzerland

The peak power of installed renewable energy is growing exponentially since 20 years and will cover the world energy
demand before the year 2030 if large scale energy storage is technically realized. The main energy demand from fossil
fuels in Switzerland is for heating, mobility and air transport. Storage of renewable energy with hydrogen and hydrocarbons
are the economically feasible and resource compatible options. However, storing hydrogen in a small volume with a highgravimetric density is a materials challenge while hydrocarbons require the capture of CO 2 from the atmosphere and thecontrol of the reduction reaction to a specific synthetic fuel.

Introduction
The intermittence of renewable energy as well as themobile applications require massive storage. The
gravimetric and volumetric energy density determine therange in mobile applications and the quantity of material
needed in general. Beside the size of the storage the cost
and the scarcity of the storage material are crucial
parameters for the global distribution of energy storage.

Analysis
The end use and primary energy demand was analysed indetail on the example of Switzerland with the goal todetermine the requirements of renewable energy
converters and energy storage. The technical challenges
are complemented with an economic analysis and thefeasibility is discussed.

representative example because the energy demand andthe wealth are directly connected. The major investment isfor the energy storage (seasonal and mobility) rather thanfor the energy conversion. However, the success of themineral water business in Switzerland demonstrates theenormous value of storage. Even water is available inlarge quantities to everybody everywhere, in most cases
drinking water quality, it is a business to sell water inplastic bottles for up to 15 CHF/litre. This is not peculiar for
Switzerland e.g. French and Italian companies are sellingbottled water in Japan. Therefore, energy storage is not
only a cost or required investment but a great business
opportunity.

Results and Discussion
The comparison of the energy intensity for renewableenergy conversion and population density is a direct
measurement of the potential to use renewable energy.
The energy storage depends very much on the technology
and therefore on the achievements in capturing CO2 andthe control of the CO2 reduction reaction for the storage ofhydrogen in synthetic hydrocarbons.
The Swiss energy demand is only 0.03 TW as comparedto the world energy demand of 18 TW. However, theexample shows the feasibility and the market opportunities
for the future. Even Switzerland is a wealthy country it is a

AndreasZÜTTEL

References[1] Zuttel, A; Remhof, A; Borgschulte, A; Friedrichs, O,'Hydrogen: the future energy carrier', PhilosophicalTransactions of the Royal Society A-Mathematical
Physical and Engineering Sciences 368:1923 (2010),
pp. 3329 - 3342.
[2] Andreas ZÜTTEL, Noris GALLANDAT, "The technicaland economic challenges for the energy transition to
renewables", to be submitted to NATURE (2019).

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf, Switzerland.
1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr. rer. nat. fromthe science faculty UniFR. 1994 Post Doc with AT&T Bell Labs in Murray Hill, New Jersey, USA. 1997
Lecturer at the Physics Department UniFR. 2003 External professor at the Vrije Universiteit
Amsterdam, Netherlands. 2004 Habilitation in experimental physics at the science faculty UniFR.
President of the Swiss Hydrogen Association „HYDROPOLE“. 2006 Head of the section “Hydrogen &Energy” at EMPA and Prof. tit. in the Physics department UniFR. 2009 Guest Professor at IMR,
Tohoku University in Sendai, Japan. 2012 Visiting Professor at Delft Technical University, The
Netherlands, 2014 Full Professor for Physical Chemsitry, Institut des Sciences et Ingénierie
Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland

Corresponding author: Andreas ZÜTTEL, e: andreas.zuettel@epfl.ch, m: +41 79 484 2553

22

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROGEN STORAGE IN NANOPOROUS MATERIALS: STATUS AND
FUTURE CONCEPTS
Michael Hirscher
Max Planck Institute for Intelligent Systems, Stuttgart, Germany
Hydrogen storage in nanoporous materials has been attracting a great deal of attention in recent years, as high gravimetricH2 capacities can be achieved at 77 K using materials with particularly high surface areas. Cryogenic storage byphsisorption of hydrogen molecules will safely operate at low pressures, is fully reversible and possesses fast kinetics.

Introduction
The change from a fossil fuel-based energy economy to
one based on renewable energy sources requires an easy
and reliable method of storing energy, since renewables
have daily and seasonal fluctuations. Chemical storage
seems to be the best solution, and here hydrogen has
gained major importance as an energy carrier. A largescale Power-to-Hydrogen infrastructure can suppliedhydrogen to the transport sector or back by Hydrogen-toPower. Besides, large, long-term storage in geologicalcavities, stores of medium size are needed, which are safe,
reversible, consuming low energy, and possessing quick
response times. Here, cryo-adsorption of hydrogen inporous materials could be an attractive option.

Results and Discussion
The development of metal-organic frameworks (MOFs)
with extremely high specific surface areas has pushed thisfield resulting in very high gravimetric storage densities at
cryogenic temperatures [1]. Recently, an empirical relation
between the volumetric and gravimetric hydrogen density
has been obtained by predicting theoretically the hydrogen
uptake of 4000 MOFs [2]. Experimental data of thegravimetric and volumetric hydrogen uptake have been
analysed for many MOFs and correlated to the framework
structures [3]. The gravimetric absolute uptake shows alinear correlation with the specific surface area (Chahine’srule) [1,3]. A linear relation is found for the volumetricabsolute hydrogen uptake as a function of the volumetricsurface area, yielding the same hydrogen surface density
as in Chahine’s rule [4]. The specific total volume occupied
by a porous material, i.e. the inverse of its packing or
single crystal density, as a function of its specific surface
area yields a linear relationship, which is in good
agreement with results on compacted MOF-177 [5]. A

M. Hirscher

phenomenological model is developed for the volumetricabsolute uptake as a function of the gravimetric absolute
uptake [4]. Many MOFs follow this relation, butinterpenetrated frameworks show a deviation andgenerally higher volumetric hydrogen uptakes [6].
Additionally, for technical applications the key parameteris the usable capacity, which is the amount of hydrogenthat can be delivered between the maximum tank pressure
and the back pressure required by the end-user [7]. Finally,
this presentation will give a short overview on future
concepts for improving hydrogen storage in nanoporous
materials [8].

References[1] M. Hirscher, Angew. Chem. Int. Ed. 50, 581 (2011)[2] J. Goldsmith, A.G. Wong-Foy, M.J. Cafarella, D.J.
Siegel, Chem. Mater. 25, 3373 (2013)[3] M. Schlichtenmayer, M. Hirscher, J. Mater. Chem. 22,10134 (2012)[4] R. Balderas-Xicohténcatl, M. Schlichtenmayer, M.
Hirscher, Energy Technol. 6, 578 (2018)[5] R. Zacharia, D. Cossement, L. Lafi, R. Chahine, J.
Mater. Chem. 20, 2145 (2010[6] R. Balderas-Xicohténcatl, P. Schmieder, D.
Denysenko, D. Volkmer, M. Hirscher, Energy Technol. 6,510 (2018)[7] M. Schlichtenmayer, M. Hirscher, Appl Phys A 122,
379 (2016)[8] D.P. Broom, C.J. Webb, G.S. Fanourgakis, G.E.
Froudakis, P.N. Trikalitis, M. Hirscher, Int. J. Hydrogen
Energy 44, 7768 (2019)

Michael Hirscher is leading the “Hydrogen Storage Group” at the Max Planck Institute for Intelligent
Systems, Stuttgart, Germany. He studied physics at University of Stuttgart, Germany and at Oregon
State University, Corvallis, USA, receiving his Dr. rer. nat. in Stuttgart. In 1988 he was awarded with
the Otto-Hahn-Medal of the Max-Planck-Society. At the International Symposium on Hydrogen &Energy in Switzerland he received the “Hydrogen & Energy Award 2015”. From 2013 to 2018 he has
been Operating Agent of Task 32 “Hydrogen-based Energy Storage” of the International Energy
Agency (IEA) Hydrogen TCP and now is leading Task 40 “Energy storage and conversion based onhydrogen” since 2019. He has been vice chair and chair of the Gordon Research Conference on
Hydrogen-Metal Systems in 2017 and 2019, respectively.

Corresponding author: Michael Hirscher, hirscher@is.mpg.de, Tel. +49-711-689-1808

23

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

MG BASED AMORPHOUS FOR HYDROGEN AND ELECTRIC STORAGE
J.L.Huang1, H.J.Lin2, L.J. Huang1, M.Zhu1
1 School of Mater. Sci. Eng. South China Univ of Tech & Key Lab for Adv Energy Storage Mater of Guangdong Province,
2 Inst of Adv Wear & Corrosion Resistant and Functional Mater,Jinan Univ, Guangzhou, China
Abstract The amorphous Mg based alloys are investigated to improve their hydrogen storage and electric storage
performance. It has been found the amorphous phase can absorb large quantity of H with appropriate composition and aphase separation may occurs which influences hydrogen absorption kinetics. The electrochemical capacity of milled MgNi is determined by the hydrogen desorb from its amorphous phase and the crystallization of amorphous is also a key
reason for the electrochemical capacity decay.

Introduction
Mg based alloys have high hydrogen storage capacity
but suffer from high working temperature which is related
to the strong bonding of Mg-H. Amorphous phase has
disordered atom structure and may lead to Mg-H
interaction different to that in crystal MgH2. Thus, Mg
based amorphous alloys have been developed for H
storage with the aiming of tuning the Mg-H interaction[1,2]. In addition, ball milled Mg-Ni based alloy exhibit
very high electrochemical capacity as anode for Ni-MH
battery. However, it suffers from poor cyclic stability
which was attributed to corrosion of Mg in alkali
electrolyte but not substantially overcome by improving
their corrosion resistance. Thus, the dependence ofelectrochemical performance on structure has been
examined for Mg-Ni based amorphous, and the
crystallization of amorphous phase has been found playa key role for that [3,4].

the hydrogen absorption results in phase separation atcertain composition range. This phase separation
accelerates the hydrogen absorption kinetics. However,
the hydrogen desorption temperature is still high and theamorphous crystallizes to multi-phase during desorption
process. By adding the element, such as Cu, to reduce
the affinity to H,*hydrogen desorption temperature can be
modified as also shown in Fig.1.
With respect to electrochemical performance of Mg-Ni
amorphous, it has been found that the amorphous phasecrystallized gradually in the charge/discharge cycling andthe capacity is proportional to the amount of amorphousand the fully crystallized sample could not delivercapacity. By adding Ti, the stability amorphous increased
and the capacity decay improved.****

Experimental
The Mg-Ni-RE-TM(RE: rare earth, TM: transition metal)
alloys were prepared by induction melting and melt
spinning under Ar atmosphere with commercial Mg, Ce,
Ni and Cu ingots (99.9% purity) as raw materials. The
Mg-Ni based amorphous was prepared by mechanicalalloying Mg2Ni with Ni powder by planetary milling. XRD,
TEM, TGA and DSC were used to characterize themicrostructure. Hydrogen storage properties andelectrochemical properties were measured by PC
isothermal, TG-MS and a tri-electrode cell.

Results and Discussion
Based on affinity to H, atomic size and glass forming
ability, a series Mg-RE-Ni-TM alloys are designed and ahydrogen absorption capacity of more than 5wt% is
obtained as shown in Fig.1, which is a little bit higher
than the crystalline alloy of the same composition, and

Min ZhuFig. 1 a) Hydrogenation kinetics of Mg80Ce10Ni10 MG, b)
TG curves of Mg-Ce-Ni-X (X= Ti, Co, Cu, Zn, Ag) MGs.
inserts show the HAADF-STEM image of amorphousalloys and hydrides, and the mixing enthalpy of X-H pairs.

References[1] H J Lin, et al, Acta Mater 120, 68 (2016)[2] J L Huang et al Electrochimica Acta 305, 145 (2019)[3] J L Huang, et al J Power Sources 438,226984 (2019)[4] L J Huang, et al J Alloys & Compounds 792 835 (2019)

Short CV: Received his Ph.D from Dalian University of Technology in 1988 and was a Humboldt
Research Fellow in Technical University of Berlin. He is now professor and vice president of South
China University of Technology. He has been dedicated to the research and development ofadvanced hydrogen storage materials and battery materials, with emphasis on high-performance
metallic energy storage materials based on the multi-phase multi-scale structure, to boost themassive utilization of renewable energy source. Also, he invented a unique plasma milling techniquefor efficient powder materials preparation. He has authored and co-authored over 300 academic
papers and published over 30 patents.

Corresponding author: Min Zhu, memzhu@scut.edu.cn, Tel. +86-20-87113924

24

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

REVERSIBLE HYDROGEN STORAGE WITH ORGANIC POLYMERSKenichi Oyaizu
Department of Applied Chemistry, Waseda University, Tokyo 169-8555, Japan
Abstract
Organic compounds capable of reversibly reacting with H2 to yield hydrogenated products have been studied as hydrogen
carriers. However, these compounds often suffer from safety issues and are usually hydrogenated only at high H 2 pressure
and/or temperature. We have found that the hydrogenation/dehydrogenation cycle is accomplished at moderate conditions
with ketone/alcohol-containing polymers that can even be molded into a plastic sheet. All of the ketone groups in thepolymer were hydrogenated by simply placing the sheet at room temperature under 1 atm of H2 in the presence of aniridium catalyst, which then underwent H2 release upon warming above 60 oC. The easy handling and moldable nature of
the polymers indicate the feasibility of applying the materials as pocketable hydrogen carriers.

Introduction
Redox-active polymers with electrochemical reversibility
and rapid reaction rates are employed to develop organic
electrode-active materials, based on their self-exchange
reactions in polymer layers [1]. Negative charging of theelectroneutral redox polymers result in a significant
increase in basicity to allow hydrogenation of each redoxactive site in the polymer. Since most of the hydrogenatedproducts are no longer redox-active, aprotic battery
electrolytes are employed to avoid the hydrogenation.
Organic compounds that undergo hydrogenation, such as
toluene to yield methylcyclohexane, have been studied ashydrogen storage materials. However, the hydrogenation
with H2 usually proceed via a highly energy consuming
process. We anticipated that electrolytic hydrogenation of
the redox-active molecules would provide a much simpler
process, and found that ketone-containing polymers
stored H2 via the electrolytic process in H2O at room
temperature. The resulting alcohol polymer evolved H2 bywarming under mild conditions with an iridium catalyst [2].
Here we report that some of the relevant polymers
represent an intriguing aspect of a non-electrolytic process,allowing the hydrogenation by simply reacting with H2 gas.

storage, according to the temperature. A high massdensity of ca. 5 wt% was accomplished with the compact
unit structure of the methylpyrazine-containing polymer. A
temperature to dominate the equilibrium, R + (n/2)H2 ⇄ RHn,
is given by ΔrHo/ΔrSo, where ΔrHo and ΔrSo are theenthalpy and entropy changes for the hydrogenation.
These functional groups are characterized by small ΔrHo(for example, ca. -50 kJ/mol for fluorenone) compared totoluene (ca. -200 kJ/mol), resulting in the moderate criticaltemperature. Preliminary calculation supported that thefluorenone polymer was hydrogenated with H2 at room
temperature, but the reverse reaction proceeded above 60
oC to release H
2.
The results also gave insight into the nature of thereversible storage of H2 where the bistablity of thehydrogenated and dehydrogenated states seemed to be
responsible, which was reminiscent of the electrochemical
bistability required for the storage of charge in organic
electrode-active materials.
n

n
O

O

O

-1.2 V vs. Ag/AgCl
0.96 wt%

Experimental
Polymers in Fig. 1 were prepared by radical polymerizationof corresponding monomers, or by crosslinking of bis(diethylamino)fluorenone and tri(bromomethyl)benzene.

n

n

n

O
N+

N
N+
n

-1.2
0.28

N

N

N
N

-0.8
2.6

N

-0.35
1.3

N
N

-0.3
4.5

-0.25
2.2

Fig. 1 Polymers for H2 storage, shown in the order of theapproximate reduction potentials in V vs. Ag/AgCl, alongwith the mass storage density in wt%.

Results and Discussion

References

Polymers functionalized with fluorenone, quinoxalines andmethylpyrazine (Fig. 1) demonstrated the reversible H2[1] T. Kawai, et al., Bull. Chem. Soc. Jpn. 91, 721 (2018).
[2] R. Kato, et al., Nature Commun. 7, 13032 (2016).

1995 Ph.D. Department of Applied Chemistry, Waseda University. 1995-96 Research Assistant,
Department of Applied Chemistry, Waseda University. 1997-2003 Lecturer, Advanced ResearchInstitute for Science and Engineering, Waseda University. 2003-06 Associate Professor, Institute for
Colloid and Interface Science, Tokyo University of Science. 2007-12 Associate Professor, Department
of Applied Chemistry, Waseda University. 2012-present Professor. 2001 Award for Encouragementof Research in Polymer Science in The Society of Polymer Science, Japan. 2002 Chemical Societyof Japan Award for Young Chemists. 2013 Prizes for Science and Technology, The Commendationfor Science and Technology by the Minister of Education, Culture, Sports, Science and Technology.
Kenichi Oyaizu
Corresponding author: Kenichi Oyaizu, oyaizu@waseda.jp, +81-3-5286-3214

25

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

ENHANCED ELECTROCHEMICALSTORAGE MATERIALS

Sapporo, Hokkaido, Japan, 2020

PROPERTIESOF

HYDROGEN

Joseph A. Teprovich Jr1*, Matthew Green1, Miguel Orozco1, Paulo Simon1, Jovy Santos1, Christopher
Babasi1, Patrick A. Ward2, Ragaiy Zidan2, Puru Jena3
1

California State University Northridge, 18111 Nordhoff St, Northridge, CA 91330, USA 2 Savannah River National Laboratory, Aiken, SC
29803, USA 3 Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284, USA
This talk will focus on: (1) the utilization of hydrogenated fullerenes (i.e. C60Hx) as high capacity lithium intercalation anodes and (2) boron based clusters as
solid-state electrolytes for lithium ion batteries. We have recently demonstrated that the quantity of chemisorbed hydrogen on C60 can be utilized to modulate
the electrochemical properties of C60. The attachment of chemisorbed hydrogen on C60 enables the reversible lithiation of the material for 2,000 cycles andan electrochemical capacity higher than that of the commonly utilized graphite electrode (588 mAh/g vs. 372 mAh/g). We have also investigated the use of
LiBH4 and Li2B12H12 based electrolytes. The destabilization of the LiBH4 salt by the addition of C60 and partial dehydrogenation of the material enables thenanocomposite to be utilized as a solid-state electrolyte well below the orthorhombic to hexagonal phase transition temperature of LiBH4 (~115°C). We havealso shown that the ionic conductivity of Li2B12H12 can be enhanced by high-energy milling with 1 mS/cm ionic conductivity achieved at ~55°C. Current work
is focused on evaluating the ionic conductivity of Li2B12H12 based composite materials to simultaneously achieve high ionic conductivity at or below room
temperature and reducing the thickness of solid-state electrolyte.

Introduction
There is a need to develop higher gravimetric and volumetricenergy density batteries to power the next generation of
consumer electronics and automobiles of the future. To achieve
this goal there needs to be major advancements in the anode andthe electrolyte used in batteries. Metal hydride based materials
can potentially fill this void and advance to utilization incommercially available electrochemical systems.

Experimental / Computational
C60Hx was prepared by direct hydrogenation for 6-72 hours at 100
bar H2 and 350°C for different hydrogenation times.
Electrochemical cycling was performed with LiPF6 in EC/DMC.
Li2B12H12 was synthesized by an all-solid state route. The
electrolyte was infused into the matrix via appropriate solvent.
Cycling was performed at the indicated rates and temperatures.

Fig. 1 Cycle stability and effect of current density on the C60Hx
anode.1

Results and Discussion
A systematic experimental and theoretical analysis of a series of
C60Hx materials determined that they have the potential to be
utilized as high capacity anodes for lithium ion batteries. It wasdetermined that C60, with an average of 2.5 wt.% hydrogen is
optimal for this application. A reversible capacity of 588 mAh/g
was achieved for this anode (Fig 1).
On-going work with Li2B12H12 has shown it to be an effective andstable solid-state electrolyte for batteries.2 We have recently
found that it is possible to incorporate this electrolyte into a matrix
that enables it to utilized at room temperature at high cycling rates(up to 10C) with good capacity retention (Fig. 2). Additional,
cycling tests showed that this electrolyte can also operate below
room temperature and is compatible with LTO anodes and TiS2
cathodes.

Fig. 2 Cycling of Li2B12H12 infused matrix at various current
densities with LTO anode. Inset shows voltage profile for the
LTO anode at 20°C and 0°C.

References[1] Teprovich, J.A. et.al. ACS Applied Energy Materials.
Accepted (2019), DOI: 10.1021/acsaem.9b01040[2] Teprovich, J.A. et.al. J. Mater. Chem. A. 2015, 3, 22853-22859

Joseph A.
Teprovich Jr

Joseph received his Ph.D in Chemistry from Lehigh University in 2008. He worked at Savannah River National
Laboratory as a post-doctoral research scientist from 2009-2011 and was a staff scientist from 2011-2017. In
2017, he became a professor at California State University Northridge in the Department of Chemistry &Biochemistry. He has numerous publications and patents regarding the use of metal hydrides in a variety of energy
storage applications and presented this research at a variety of national and international conferences. This
research includes the synthesis of alane (AlH3) for portable power systems, boron based hydrides for solid ionic
conductors, alanate for use as high capacity anode materials, metal intercalated carbon nanocomposites forhydrogen storage, and metal hydride based thermal energy storage systems for concentrating solar power.

Corresponding author: Joseph Teprovich, joseph.teprovich@csun.edu, +1 570-578-7842.

26

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROGEN STORAGE PROPERTIES AND CRYSTAL STRUCTURALINVESTIGATIONS ON MG CONTAINING ALLOYS
Toyoto Sato1, Tomohiro Mochizuki1, Kazutaka Ikeda2, Toshiya Otomo2, Heena Yang3,
Wen Luo3, Andreas Züttel3, Shigeyuki Takagi1, Tatsuoki Kono1, Shin-ichi Orimo1, 4
1Institutefor Materials Research, Tohoku University, Japan, 2Institute of Materials Structure Science, High Energy
Accelerator Research Organization, KEK, Japan, 3Swiss Federal Institute of Technology in Lausanne, Switzerland, 4WPIAdvanced Institute for Materials Research (AIMR), Tohoku University, Japan
Mg containing alloys, Y(2–x)MgxNi4, with an FCC crystal structure were synthesized by heat-treatment at ≤ 1123 K of powder
mixtures of (2–x)YNi2 + xMgNi2 (x: 0.6, 0.8, 1.0 and 1.2). Their hydrogen storage properties were investigated at 323 K,
and reversible hydrogen absorption and desorption reactions were observed. Crystal structure of hydrogen absorbed
phase of YMgNi4 (x = 1.0) was studied by neutron diffraction, of which pattern was reproduced by an orthorhombic crystal
structure with a = 5.0280(3) Å, b = 5.3827(4) Å and c = 7.2718(31) Å.

Introduction
Magnesium (Mg) is an abundant and light element andhas a good reactivity with hydrogen. Therefore, Mg or Mg
containing alloys are expected to be a promising material
for hydrogen storage. In particular, REMgNi4 (RE: rareearth metals) with a similar crystal structure with the C15
Laves phase alloy exhibits reversible hydrogen absorption
and desorption reactions at room temperature [1–3]. Even
though Y is the lightest element in the RE, hydrogen massdensity of YMgNi4 is almost the same with the other
REMgNi4. To improve the hydrogen capacity of YMgNi4,
we have attempted to synthesize
Y(2–x)MgxNi4 withsystematically changed molar ratios of Y and Mg andinvestigate their hydrogen storage properties. In addition,
we have clarified crystal structures of YMgNi 4, which is abasis of this study, in the hydrogen absorption reaction by
neutron diffraction.

Experimental / Computational
The samples were synthesized from heat-treatment at ≤1123 K of powder mixtures of YNi2 and MgNi2 with 2–x : x
in molar rations (x: 0.6, 0.8, 1.0 and 1.2). The hydrogenstorage properties on the samples were studied bypressure–composition–temperature measurements (socalled the PCT measurement) at 323 K. Crystal structureof hydrogen absorbed YMgNi4 (x = 1.0) were determinedfrom neutron diffraction under 5 MPa of deuterium gas
pressure studied by NOVA at MLF, J–PARC.

reported by Aono et al. and Shtender et al. This indicatedthat YMgNi4 was synthesized from YNi2 and MgNi2.
Furthermore, the unit cell parameters (Table 1) wereincreasing with decreasing amount of Mg. This suggested
that excess Mg atoms (x > 1.0) are located in Y atomic
sites and excess Y atoms (x < 1.0) are located in Mg
atomic sites. From the PCT measurements, reversiblehydrogen absorption and desorption reactions at 323 K
were observed.
Intheneutrondiffraction Table 1 Unit cellofexperiments on YMgNi4 under 5 parameters
MPa of D2 pressure, crystal (2–x)YNi2 + xMgNi2
structure of hydrogen (deuterium)
absorbed phase of YMgNi4 wasan orthorhombic crystal structure(a = 5.0280(3) Å, b = 5.3827(4) Åand c = 7.2718(31) Å.). Details of
the hydrogen storage properties
and the crystal structure arepresented in the symposium.
This work was supported by JSPS KAKENHI(JP18H05513 and JP18H05518) and JST SICORP(JPMJSC 1802). The neutron diffraction experiment was
performed by NOVA, J–PARC (2019A0068).

References[1] K. Aono, S. Orimo, H. Fujii, J. Alloys Compd. 309,
L1–L4, (2000).

Results and Discussion[2] K. Sakaki, N, Terashita, S. Tsunokake, Y. Nakamura,
E. Akiba, J. Phys. Chem. C 116, 19156–19163, (2012).

After the syntheses, all samples were characterized by
X–ray diffraction, in which major Bragg peaks wereindexed by an FCC unit cell. In the x = 1.0, the unit cellparameter was close to previous results of YMgNi4[3] V. V. Shtender, R. V. Denys, V. Paul-Boncour,A. B. Riabov, I. Yu. Zavaliy J. Alloys Compd. 603, 7–13,(2014).

2006:
2006 – 2007:
2007 – 2009:2009 – 2012:

Ph.D, Stockholm University, Sweden
Research Scientist, Arizona State University, USA
Research Scientist, Institute for Materials Research, Tohoku University, Japan
Assistant Professor, WPI-Advanced Institute for Materials Research,
Tohoku University, Japan
2012 – Present: Assistant Professor, Institute for Materials Research, Tohoku University, Japan
Toyoto Sato
Corresponding author: Toyoto Sato, toyoto@imr.tohoku.ac.jp, +81-22-215-2094

27

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

Thermal Battery Development for Concentrated Solar Power Systems
C.E. Buckley, M. Paskevicius, T.D. Humphries, M.V. Sofianos, K. Moller, L. Poupin
Department of Physics and Astronomy, Fuels and Energy Technology Institute, Curtin University, GPO Box U1987, Perth
6845, WA, Australia

Solar energy is the most abundant renewable energy resource and therefore logically represents the most important
renewable energy resource for the future. The International Energy Agency (IEA) roadmap for solar energy set a target of 22% of global electricity production from solar energy by 2050, with 50% being produced from concentrating solar thermal(CST) power systems. Achieving this target will be possible only if the costs of producing electricity from solar energy are
significantly reduced and cost effective energy storage technologies can be developed.
A major challenge is to achieve continuous, low-variability power generation from renewable energy sources, for standalone applications or for integration with domestic power grids. Solar mirror collection fields can collect thermal energy
during the day and run a heat engine to convert it into electricity, but cannot provide power at night. However, if some ofthe heat is used to remove hydrogen from a metal hydride, the reverse reaction where hydrogen absorbs back into themetal hydride can then occur at night, releasing heat for power generation. This allows solar energy to provide 24 hour
power generation. By combining a high temperature metal hydride with a low temperature metal hydride, a coupled pair
reversible metal hydride thermochemical solar energy storage system is created [1]. Concentrated solar thermal coupled
to a high and low temperature metal hydride has the potential to provide a continuous supply of electricity to remote areasin Australia and around the World. I will discuss the use of CST worldwide and will present some results on the propertiesof materials that are suitable for CST applications, focussing on high temperature hydrides [2 – 8].

References[1] D.N. Harries, M. Paskevicius, D.A. Sheppard, T.E.C. Price, C.E. Buckley. Proc. of the IEEE, 100 (2012) 539-549.
[2] M. Fellet, Feature Editors: C.E. Buckley, M. Paskevicius, D.A. Sheppard. MRS Bulletin 38 (2013) 1012-1013.
[3] D.A. Sheppard, T.D. Humphries, C.E. Buckley. Materials Today 18 (2015) 414-415.
[4] M. Paskevicius, D.A. Sheppard, K. Williamson, C.E. Buckley. Energy, 88 (2015) 469-477.
[5] Q. Lai, M. Paskevicius, D.A. Sheppard, C.E. Buckley, K.F Aguey-Zinsou et al. ChemSusChem, 8 (2015) 2789-2825.
[6] P. Javadian, D.A. Sheppard, T.R. Jensen, C.E. Buckley. RSC Advances 6, (2016) 94927-94933.
[7] T.D. Humphries, D.A. Sheppard, M.R. Rowles, M.V. Sofianos, C.E. Buckley. J Materials Chemistry A, 4 (2016) 1217012178.
[8] K.T. Møller, D.A. Sheppard, D.B. Ravnsbæk, C.E. Buckley, E. Akiba, Hai-Wen Li, T.R. Jensen. Energies, 10 (2017)1645 1-30.
[9] D. Dong, T.D. Humphries, D.A. Sheppard, M. Paskevicius, M.V. Sofianos, A.L. Chaudhary, M. Dornheim, C.E. Buckley.
Sustainable Energy and Fuels, 1, (2017) 1820-1829.
[10] T. Nguyen, D.A. Sheppard, C.E. Buckley. Journal of Alloys and Compounds, 716 (2017) 291-298.
[11] M.S. Tortoza, T.D. Humphries, D.A. Sheppard, M. Paskevicius, M. R. Rowles, M. V. Sofianos, K.F. Aguey-Zinsou, C.
E. Buckley. Physical Chemistry Chemical Physics 20 (2018) 2274-2283.
[12] D. Dong, T.D. Humphries, D.A. Sheppard, M. Paskevicius, M.V. Sofianos, A.L. Chaudhary, M. Dornheim, C.E. Buckley.
Sustainable Energy and Fuels, 1, (2017) 1820-1829.
[13] T.D. Humphries, K.T. Møller, W.D.A. Rickard, M.V. Sofianos, S.Liu, C.E. Buckley, M. Paskevicius. Journal of Materials
Chemistry A, 7 (2019) 1206-1215.
[14] L. Poupin, T.D. Humphries, M. Paskevicius, C.E. Buckley. Sustainable Energy & Fuels, 3 (2019) 985-995.
[15] D.A. Sheppard, C.E. Buckley. International Journal of Hydrogen Energy, 44 (2019) 9143 - 9163.
[16] D.A. Sheppard, M. Paskevicius, P. Javadian, I. Davies, C.E. Buckley. Journal of Alloys and Compounds, 787 (2019)1225-1237.
[17] K. Manickam, P. Mistry, G. Walker, D. Grant, C.E. Buckley, T.D. Humphries, M. Paskevicius, T. Jensen, R. Albert, K.
Peinecke, M. Felderhoff. International Journal of Hydrogen Energy, 44 (2019) 7738–7745.

Professor Craig Buckley is the Head of the Hydrogen Storage Research Groupand Deputy Director of the Fuels & Energy Technology Institute at Curtin
University, Australia. Since being awarded his Ph.D. in 1994 from Griffith
University he has held various research positions in the U.K, USA and Australia
prior to being awarded tenure at Curtin University. His research is focussed onhydrogen storage materials and the investigation of the structural properties ofa wide range of materials. Craig has published 163 scientific papers in peer
reviewed journals.
Professor Craig Buckley
Corresponding author: Professor Craig Buckley, c.buckley@curtin.edu.au, +61401103602

28

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

NEW DEVICE FOR HYDROGEN SEPARATION FROM DECOMPOSED GAS
OF ENERGY CARRIERS, NH3 AND MCH, USING FLAT VANADIUM
ALLOYS MEMBRANES
Name(s) Chikashi NISHIMURA1
Affiliation 1 National Institute for Materials Science, Tsukuba, JAPAN
Abstract: Hydrogen permeation performance of our device using flat vanadium membranes to separate highly
pure hydrogen from a gas mixture of hydrogen and nitrogen will be presented. We heve achieved the hydrogen

permeation flow rate over 9 L/min at 623 K, using a newly designed multi-membrane device. Effects ofhydrogen on mechanical properties of vanadium alloy will be also shown.

Introduction
Recently, there is a growing interest to develop newhydrogen permeable membranes which can substitutecurrent palladium alloy membranes to reduce the cost.
Group 5 elements, having BCC crystal structure, are goodcandidates for new membrane materials. Especiallyamong them, vanadium has been recognized as promisingelement because of its high diffusivity and fair solubility ofhydrogen. In this work, a new device using vanadium-ironalloy membranes were developed and hydrogen
permeation performance was tested.

our device is promising to extract pure hydrogen gas fromdecomposed gas of energy carriers, ammonia and also
methyl cyclohexane.
Effects of hydrogen on mechanical properties of V-10Fe
and also, effects of trace amounts of ammonia andmethylecyclohexane (MCH) on hydrogen permeation
performance will also be shown.
Most part of this work has been supported by JST-CREST,
grant number JPMJCR1443.

Experimental
Round-shaped sheets of V-10Fe alloy with about 100mm
diameter and 0.1mm thick were cut from cold-rolled sheet
and annealed, and then 100nm thick catalytic layers of Pd25Ag alloy were deposited on both sides of the V-10Fe
sheets, which gave hydrogen separation membranes.
Hydrogen permeation tests were performed from a gas
mixture of 75% H2 + 25% N2, at 623 K.

Results and Discussion
Four membranes of V-10Fe were equipped to give ahydrogen separation device [1]. Figure 1 shows an
appearance of the device. When we applied 0.53 MPa of
the gas mixture, 75% H2 + 25% N2, at 623 K, the hydrogenflow rate of 9.3 L/min. (=540 L/hr.) was achieved at a
separation efficiency of 80%. The hydrogen flow rate, 540
L/hr. overpasses the flow rate necessary for operation of
the ENE-FARM for home usage, 500 L/Hr. We believe that*****************************************************************
Fig. 1 Hydrogen Separation Device equipped with four
membranes of V-10Fe alloy with 98mm diameter for
permeation. ******************************************

References[1] C. Nishimura, Impact (Web Journal, 2019)https://www.ingentaconnect.com/content/sil/impact/2019/
00002019/00000005/art00011*

1984.3: Master’s degree, Waseda University, 1984.4: Researcher, National Research Institute for
Metals (NRIM), 1990.9: Visiting Researcher at Metals & Ceramics Division, Oak Ridge National
Laboratory (ORNL), Tennessee, USA for 1 year. 1996.2: Ph. D. (Engineering) from Waseda
University, Associate Director, Eco-materials Center, National Institute for Materials Science (NIMS),
2006.4 – 2011.3: Managing Director, Fuel Cell Materials Center, NIMS, 2011.4 – 2016.3: Unit Director,
Hydrogen Materials Center, NIMS, 2104.11- present: Project Leader, JST-CREST “Development of
Innovative Hydrogen Production Technology from Energy Carriers Based on Vanadium Alloy
Membranes”, 2016.4 – present: Director, Corporate Planning Division, NIMS
C. NISHIMURA
Corresponding author: Chikashi NISHIMURA, NISHIMURA.Chikashi@nims.go.jp, +81-298-59-2652

29

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

STRUCTURAL AND
NANOPARTICLESDYNAMICAL

Sapporo, Hokkaido, Japan, 2020

STUDY

ON

PdPt

HYDRIDE

Hiroshi Akiba1, Hirokazu Kobayashi2, Hiroshi Kitagawa2, Kazutaka Ikeda3, Toshiya Otomo3,
Nicolas De Souza4, Richard Mole4, Osamu Yamamuro1
1ISSP, University of Tokyo, 2Graduate School of Science, Kyoto University, 3IMSS, KEK, 4ACNS, ANSTO

The nanometer-sized metals attract much attention since their physical and chemical properties are substantially different
from those of bulk metals. The phase-separated nanoparticles of Pd-core and Pt-shell are mixed to be solid solution alloy
by repeating hydrogen absorption/desorption processes at 373 K. To investigate the positions and diffusion dynamics ofhydrogen atoms in PdPt nanoparticles, we measured the neutron powder diffraction (NPD) and quasielastic neutron
scattering (QENS), respectively. Our QENS study suggested that the insertion of Pt atoms to Pd fcc lattice may deformthe potential energy surfaces of the hydrogen sites and enhance the diffusion of hydrogen atoms.

Introduction
The nanometer-sized metals attract much attention since
their physical and chemical properties are substantiallydifferent from those of bulk metals. Kobayashi et al. foundthat the phase-separated nanoparticles of Pd-core and Ptshell are mixed to be solid solution alloy by repeatinghydrogen absorption/desorption processes at 373 K [1]. In
this study, we have investigated the positions and diffusion
dynamics of hydrogen atoms in solid solution PdPt
nanoparticles by means of neutron powder diffraction(NPD) and quasielastic neutron scattering (QENS),
respectively.

previous QENS experiments [3]. The slow and fast
relaxation processes correspond to the hydrogen motionsin the interior and subsurface regions of nanoparticle,
respectively. The  and the activation energy of
Pd0.8Pt0.2H0.47 nanoparticles are smaller than those for
PdH0.47 nanoparticles. It should be noted that the fast
relaxation time is almost temperature independent below
250 K, suggesting tunneling processes. Thus, thesubstitution of Pt atoms may deform the potential energy
surfaces and enhance the diffusion of hydrogen atoms.

Experimental
The mean diameter of nanoparticles was determined to be
5.0 nm from TEM images. The NPD patterns of
Pd0.8Pt0.2D0.36 nanoparticles were measured on NOVA at
J-PARC. The QENS experiments of Pd0.8Pt0.2H0.47
nanoparticles were performed on Pelican and Emu at
ACNS, ANSTO. Neutron scattering is a powerful tool to
explore the position and dynamics of hydrogen atoms in
an atomic scale owing to the large coherent andincoherent scattering cross sections of hydrogen atoms.

Results and Discussion* The Rietveld and atomic pair distribution function (PDF)
analyses for the NPD patterns [2] revealed that D atoms
are located at the interstitial octahedral (O) and tetrahedral(T) sites of an fcc lattice, as schematically shown in theinset of Fig. 1. Interestingly, 47% of D atoms occupy the Tsites even at 300 K, which is larger than that for PdD 0.36
nanoparticles (31%). Figure 1 shows the Arrhenius plot of
the relaxation times () for Pd0.8Pt0.2H0.47 nanoparticles
together with  for PdH0.47 nanoparticles obtained in our

Fig. 1: Arrhenius plot of the relaxation times for
Pd0.8Pt0.2H0.47 and PdH0.47 nanoparticles.

References[1] H. Kobayashi et al., JACS 132, 5576 (2010).
[2] H. Akiba et al., JACS 138, 10238 (2016).
[3] M. Kofu et al., PRB 94, 064303 (2016

Hiroshi Akiba studied physics at the Toho University and received his Ph. D. in 2012 with studies on
the organic metals with a magnetic anion. He became a JST-CREST project researcher at the
University of Tokyo in 2012. Currently, he is a research associate at the University of Tokyo. Hispresent research interests are in the physical properties of metal hydrides and their nanoparticles.
These are investigated by means of adiabatic calorimetry and neutron scattering.
Hiroshi Akiba
Corresponding author: Hiroshi Akiba, E-mail: h-akiba@issp.u-tokyo.ac.jp, Tel: +81-4-7136-3298

30

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

H2 Nuclear Spin Conversion on Metal Surfaces: Physisorption vs.
Molecular Chemisorption
Elvis F. Arguelles1, Koji Shimizu1, Wilson Agerico Diño2, Hiroshi Nakanishi3, Hideaki Kasai3
1 Department of Materials Engineering, The University of Tokyo, 2 Department of Applied Physics, Osaka University, 3
National Institute of Technology, Akashi College
We investigate theoretically the ortho para conversion of H2 in two adsorption states on metal surfaces: physisorption andmolecular chemisorption. These two distinct states are prototypically represented by H2/Ag(111) and H2/Pd(210) for
physisorbed and MC, respectively, and revisited by means of first principles calculations based on density functional theory(DFT). The ortho-para (o-p) conversion probability is evaluated by means of 2nd order perturbation theory. We found thatthe o-p conversion time on Ag(111) is longer than on Pd(210), reflecting a strong dependence on the adsorption state.

Introduction
It has been known that physisorbed hydrogen undergoes
ortho-para (o-p) conversion in the order of minutes on nonmagnetic metal surfaces such as Ag(111)[1]. This has
been described by the virtual surface-molecule electrontransfer and the hyperfine Fermi contact interaction within
second order perturbation theory. Recent experiments
have shown that on relatively open surfaces such as
Cu(510)[2] and Pd(210)[3], H2 is in the so-calledmolecularly chemisorbed state and behaves as a 2dimensional quantum rotor, while the o-p conversion rateis 1 order magnitude faster than on flat surfaces. In thiswork we compare the adsorption state dependence of thehydrogen o-p conversion rate by means of model and firstprinciples calculations.

Computational
The adsorption states on two representative metal
surfaces are investigated by constructing an adsorption
potential energy surface (PES). DFT calculations are
performed using PBE-GGA, with a 500 eV plane wave
cutoff energy, and 9x9x1 kpoints for Brillouin zone
integration. PES is constructed by performing total energy
calculations at different surface-molecule distances andorientations. From DFT, we obtain the equilibrium
adsorption distance, bond length and electronic properties
of surface and molecule complex which are used asparameters in the model calculations. To calculate the o-p
conversion time, we considered a two-step process[1] inwhich perturbation is composed of Coulomb and Hyperfine
Fermi-contact Hamiltonians, describing the virtual surfacemolecule electron transfer and electron and nuclear spin
interactions. The o-p conversion probability is calculated
by Fermi’s golden rule and the conversion time is obtained
subsequently.

Results and Discussion
Figure 1 shows the adsorption potential energy profiles for
H2/Ag(111) and H2/Pd(210) systems. On Ag(111), H2 isweakly physisorbed with an adsorption energy of around 6
meV. This is in contrast with case on Pd(210) in which themolecule adsorption is characterised by shorter adsorption
height and stronger binding energy of around 300 meV.

This difference in adsorption states can be ascribed to theposition of the d-band centres of metal surfaces withrespect to the Fermi level. Pd(210) d bands are narrowerand shifted closer to EF than Ag(111), indicating higher
reactivity. Our derived expression of the nuclear spintransition probability depends on several parameters thatcan be directly obtained from the above first principles
calculations. We found that the transition rate depends on
the Fermi level-density of states and work functions of theisolated substrates, the adsorption height, bond length,surface wave function decay parameter and the antibonding level of adsorbed H2. Furthermore, since theelectron hopping parameter strongly depends on theadsorption height, the matrix element of the electron
contribution in the transition probability of H2/Pd(210) is
larger than that of H2/Ag(111). Using these parameters wefound that o-p conversion on Pd(210) is faster than on
Ag(111). Our results show that the conversion rate can bedirectly correlated to the chemical nature of adsorption on
metal surfaces.

Fig. 1 Adsorption potential energy profile of H2
on Ag(111) and Pd(210).
References[1] E. Ilisca, Phys. Rev. Lett. 66, 5 667 (1991).
[2] K. Svensson and S. Andersson, Phys. Rev. Lett. 98,
096105 (2007).
[3] S. Ohno, D. Ivanov, S. Ogura, M. Wilde, E. F.
Arguelles, W. A. Dino, H. Kasai, and K. Fukutani, Phys.
Rev. B 97, 085436 (2018).

Short CV
2014-2017 Doctor of Philosophy, Graduate School of Engineering, Osaka University, Osaka, Japan
2012-2014 Master of Science, Graduate School of Engineering, Osaka University, Osaka, Japan

Elvis F. Arguelles
Corresponding author: Elvis F. Arguelles, elvisarguelles@cello.t.u-tokyo.ac.jp,03-5841-1286
31

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

PHOTOCHEMICAL HYDROGEN EVOLUTION FROM MOLECULAR IRONCOMPLEXES WITH PHENYLENEDIAMINES
Ho-Chol Chang1
1Faculty of Science and Engineering, Chuo University, Japan

This paper report systematic studies on the iron complexes bearing o-phenylenediamines (opdas) and obenzoquiondiimines (bqdis) resulted by the stepwise two-electrons and two-protons transfer processes. Based on the factthat FeII(opda)3](ClO4)2 ([6R][ClO4]2) demonstrates photochemical hydrogen evolution (HER), a suggestive mechanism for
the HER will be discussed.

Introduction

Results and Discussion

Dihydrogen represents an attractive prospective energy
carrier with minimal environmental impact. Due to thedifficulties associated with the storage and transportationof dihydrogen gas, the development of safe andconvenient hydrogen-storage materials is essential.

The partially reduced and protonated complexes[2R][PF6]2 and [4R][PF6]2 were synthesized and fully
characterized both in the solid state and in solution asintermediates of the proton-coupled multi-electron-transfer
processes between [6R] and [6O]. Our findings offer
important molecular insight into the injection of multiple
proton-coupled electrons into the fully oxidized form, [6O],
to afford the reduced complexes [2R], [4R], and [6R],
which display photochemical HER activity, for the designof photo-driven molecular hydrogen-storage/-evolution
systems.

In 2013, we have reported a high-spin (hs) FeII complex
containing o-phenylenediamine (opda) ligands, hs[FeII(opda)3](ClO4)2([6R][ClO4]2),
whichexhibitedphotochemical HER (PHER) activity in THF underirradiation with UV light at room temperature.2 Furthermore,[6R][ClO4]2 is able to accept six electrons and six protons
to afford low-spin (ls) [FeII(bqdi)3][ClO4]2 (bqdi: obenzoquinodiimine) ([6O][ClO4]2) upon aerobic oxidation.
In the PHER, the opda ligand acts as an electron/proton
pool for the photochemical generation of hydrogen, andthe amount of evolved hydrogen is enhanced remarkably
by the coexistence of an electron and proton donor suchas hydroquinone, which is indicative of a catalytic
photochemical generation of hydrogen.
Here we report the stepwise chemical reduction of[6O][PF6]2 and the isolation of the corresponding series of
PLMV
complexes,
i.e.,ls-[FeII(bqdi)2(opda)][PF6]2([2R][PF6]2) and ls-[FeII(bqdi)(opda)2][PF6]2 ([4R][PF6]2)(Scheme 1). The detailed structural and spectroscopic
characterization both in the solid state and in solution
revealed the properties of the PLMV complexes, together
with those of [6R][ClO4]2 and [6O][PF6]2. These combined
results suggested characteristic electron systems, wherein
- and d-electrons are strongly correlated.

Ho-Chol
Chang

Scheme. 1 Six-electron- and six-proton-transfer processes
in ls-[FeII(bqdi)3]2+ [6O]/hs-[FeII(opda)3]2+ [6R].

References[1] Eberle, U.; Felderhoff, M.; Schüth, F. Angew. Chem.
Int. Ed. 48, 6608 (2009)[2] Matsumoto, T.; Chang, H.-C.; Wakizaka, M.; Ueno, S.;
Kobayashi, A.; Nakayama, A.; Taketsugu, T; Kato, M. J.
Am. Chem. Soc. 135, 8646 (2013)

Ho-Chol Chang was born in Kyoto, Japan in 1973. He studied chemistry and received his B.S. from
Korea University in Tokyo, Japan (1995). He then received his M.S. from Tokyo Metropolitan
University (1998) and earned his Ph.D. under the supervision of Professor S. Kitagawa of Kyoto
University (2001). He became an assistant professor in the Department of Synthetic Chemistry andBiological Chemistry at Kyoto University in 2001, working in the research group of Professor S.
Kitagawa. He was also a research member of the PRESTO project of the Japan Science andTechnology Agency (JST) in 2002–2006. He becomes an associate professor of chemistry at
Hokkaido University in 2008. From 2013, he is a full professor at Chuo University, Japan, where hisgroup’s interests are centered on rational construction and dynamic control of electronically labile
molecular assemblies in solid, liquid (solution), and liquid-crystalline phases.

Corresponding author: Ho-Chol Chang, chang@kc.chuo-u.ac.jp, +81-3-3817-1897.

32

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

DEVELOPMENTOFEFFICIENTSYSTEMSFOR
HYDROGENPRODUCTION BASED ON CATALYTIC ACTIVITY OF IRIDIUMCOMPLEXES IN DEHYDROGENATIVE REACTIONS
Ken-ichi Fujita
Graduate School of Human and Environmental Studies, Kyoto University, Japan
Abstract
An efficient catalytic system for the production of hydrogen from a methanol-water solution has been developed using a
new anionic iridium complex bearing a functional bipyridonate ligand as a catalyst. Additionally, we have also developed
an efficient system for the synthesis of acetic acid via dehydrogenation of an ethanol-water solution using a new iridium
catalyst bearing a functional bipyridonate ligand with N,N-dimethylamino substituents.

Introduction
Hydrogen is attracting considerable attention as analternative energy source to fossil fuels. To work towarda “hydrogen economy” it is highly important to develop an
efficient and practical method for the production ofhydrogen from renewable and easy-to-handle resources.
Therefore, the development of an efficient, safe, andsustainable hydrogen production method is required.
During the course of our studies on the catalytic activityof iridium complexes, we have previously reported thedehydrogenative oxidation of alcohols catalyzed byiridium complexes 1 and 2 bearing functional bipyridine
and bipyridonate ligands, respectively. 1-4 On the basis ofthese investigations, we have succeeded in developing
efficient systems for hydrogen production.

Furthermore, closely recently, we have also developed
an efficient system for the synthesis of acetic acid withconcomitant production of hydrogen from ethanol-water
solution using a new iridium catalyst 4 [Equation (2)].6 It
should be noted that the present system achieved
selective production of acetic acid from sustainable
resources (ethanol and water) without the use of any
oxidant.

References

Results and Discussion
First, we have succeeded in developing effectivehydrogen production from aqueous methanol under mild
conditions (under reflux at 88 °C in dilute basic solution)
and without an additional organic solvent by theemployment of the water-soluble anionic iridium catalyst
3 bearing a bipyridonate-type functional ligand [Equation(1)].5

Ken-ichi Fujita[1] R. Kawahara, K. Fujita, R. Yamaguchi, J. Am. Chem.
Soc. 134, 3643 (2012).
[2] K. Fujita, W. Ito, R. Yamaguchi, ChemCatChem 6,
109 (2014).
[3] R. Kawahara, K. Fujita, R. Yamaguchi, Angew. Chem.
Int. Ed. 51, 12790 (2012).
[4] K. Fujita, Bull. Chem. Soc. Jpn. 92, 344 (2019).
[5] K. Fujita, R. Kawahara, T. Aikawa, R. Yamaguchi,
Angew. Chem. Int. Ed. 54, 9057 (2015).
[6] M. Kuwahara, M. Nishioka, M. Yoshida, K. Fujita,
ChemCatChem 10, 3636 (2018).

Ken-ichi Fujita received Ph.D. degree in 1997 from Kyoto University under the direction of Professor
Take-aki Mitsudo. In 1997, he was appointed as an assistant professor at Faculty of Integrated
Human Studies, Kyoto University. In 2006, he worked as a postdoctoral fellow with Professor John
F. Hartwig at Yale University. He was promoted to an associate professor in 2006 and a full
professor in 2015 at Graduate School of Human and Environmental Studies, Kyoto University. He
received the Incentive Award in Synthetic Organic Chemistry, Japan in 2006, Nagase Foundation
Award in 2017, and The Chemical Society of Japan Award for Creative Work in 2018. His current
field of research is organometallic chemistry, synthetic organic chemistry, and homogeneous
catalytic chemistry.

Corresponding author: Ken-ichi Fujita, fujita.kenichi.6a@kyoto-u.ac.jp, +81-75-753-6827.

33

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

FIRST PRINCIPLES STUDY OF HYDRIDE ION CONDUCTOR
Jun Haruyama, Osamu Sugino
Institute for Solid State Physics, The University of Tokyo
Hydride (H−) ions have attracted attention because of their potential to enable high-performance electrochemical storage
device based on hydrogen. In this study, we focus on semiconductor- and metal-type H− ion conductors, i.e. LaLiHO3 andBaTiO3-xHx. The first-principles calculations were conducted to reveal the H− ion conduction mechanism. For example, theBader-charge analysis indicated that the H placed at oxygen sites in LaLiHO 3 and BaTiO3-xHx has negative charge c.a. 0.6. We also calculated that the activation energy of H− ion conduction path in LaLiHO3 is 0.48 eV, and the negative charge
H− state was retained. We will further investigate charge state of several type of H defect in the near future.

Introduction
Hydride H− conduction has been recently confirmed in theLa2-x-ySrx+yLiH1-x+yO3-y type oxyhydride material. [1]However, little is known about the H− diffusion mechanismin this oxyhydride material. The H− ion conductors of
La2LiHO3 [1] and BaTiO3-xHx [2,3] are expected to show
different H− conduction mechanism because theirelectronic conductivity is different from each other:
LaLiHO3 and BaTiO3-xHx have the semiconductor- andmetal-type band structure, respectively.

Computational
Density functional theory (DFT) calculations were
performed within pseudopotential framework implemented
in the Quantum Espresso package. [4] Defect-formationenergies are defined as the change in total energy due tothe intercalation of a defect into a supercell. [5]Fig. 1 Energy profile for H− conduction path in La2LiHO3.

Results and Discussion[2] Y. Kobayashi et al., Nat. Mater. 11, 507 (2012).

We performed the Bader-charge analysis firstly. The
results indicated that the H placed at oxygen sites in both
LaLiHO3 and BaTiO3-xHx crystal has negative charge c.a.
-0.6. We also conducted the nudged elastic band (NEB)
calculation to estimate the activation energy of H− ion
conduction path. Consequently, the activation energy of
H− diffusion in LaLiHO3 was obtained as 0.48 eV, which
value is consistent with previous studies. [6, 7] In the ion
conduction path, the negative charge H− state was always
retained. We will further investigate charge state of several
type of H defect in the near future.

[3] F. Takeiri, K. Aidzu, T. Yajima, T. Matsui, T.
Yamamoto, Y. Kobayashi, J. Hester, and H. Kageyama,
Inorg. Chem. 56, 13035 (2017).

References[1] G. Kobayashi, Y. Hinuma, S. Matsuoka, A. Watanabe,
M. Iqbal, M. Hirayama, M. Yonemura, T. Kamiyama, I.
Tanaka, and R. Kanno, Science 351, 1314 (2016).

[4] P. Giannozzi et al., J. Phys.: Condens. Matter. 21,395502 (2009).
[5] Y. Iwazaki, T. Suzuki, and S. Tsuneyuki, J. Appl.
Phys. 108, 083705 (2010).
[6] Ø. S. Fjellvåg, J. Armstrong, P. Vajeeston, and A. O.
Sjåstad, J. Phys. Chem. Lett. 9, 353–358 (2018).
[7] Q. Bai, X. He, Y. Zhu, and Y. Mo, ACS Appl. Energy
Mater. 1, 1626–1634 (2018).

Research Associate at Institute for Solid State Physics (ISSP),The University of Tokyo, Japan. The main concerns are theapplication of density-functional theory combined with implicit
solvation theory calculation to electrochemical interfaces, with aparticular emphasis on fuel cells and Li-ion batteries.

Corresponding author: Jun Haruyama, Email: haruyama@issp.u-tokyo.ac.jp, Tel: 04-7136-3291.

34

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

NEW ASSAY METHOD FOR THE ENZYMES REACTING WITH GASEOUS
SUBSTRATES BY RAMAN SPECTROSCOPY
Koji Nishikawa1, Yuka Kawahara1, Shota Inoue1, Takfumi Chuji1, Satoshi Nakashima2,
Yasuteru Shigeta3, Katsuyuki Fukutani4 and Yoshiki Higuchi1
1University of Hyogo, 2Nara Institute of Science and Technology, 3Tsukuba University, 4The University of Tokyo

We have developed a new assay system for measuring the enzymatic reactions involving gaseous substrates by Raman
spectroscopy. This system permits continuous monitoring of the gas composition in the reaction cuvette in a non-invasive
manner over a prolonged time period. We have applied this system to the H/D exchange reaction of the [NiFe] hydrogenase.
Based on a kinetic model, the ratio of the rate constants of the H/D exchange reaction at the active site and product release
rate were successfully estimated.

Introduction
Dihydrogen is spot-lighted as one of the clean energy
carriers. At present, dihydrogen is mainly produced bystream reforming of natural gas. It has been well known
that the enzyme, hydrogenases, catalyze the production
and decomposition of dihydrogen from biomass. We havestudied the structures of [NiFe]-hydrogenases by x-ray
crystallography in conjunction with various spectroscopic
methods to elucidate the essential structural unit for thecatalytic reaction. Since rapid and precise screening of thepotential enzymes are prerequisite for developing thenext-generation hydrogen bio-fuel cells, simple andreliable assay method for hydrogenases will provide a
valuable tool for the discovery of new excellent
hydrogenases, which are more active, resistant against O2or thermostable.
Hydrogenases also catalyze non-physiological two
reactions, H/D exchange reaction between H3O+(D3O+)
and D2(H2), and the nuclear spin isomer conversion
reaction between para-H2 and ortho-H2. The H/D
exchange reaction is conventionally measured by gas
chromatography, mass spectrometry, or a combination
thereof (GC/MS). Although these methods are wellestablished, they require the sampling of the gas from thecuvette at regular intervals, resulting in the changes thepressure of the gas phase after each operation.
Alternatively, the gas composition can be measured in situ
using Raman spectroscopy without sampling. This meansthat Raman method enables us to trace the time course of
the reaction without any data corrections. Raman

spectroscopy has the additional advantage of permitting
the continuous and simultaneous measurement.

Results and Discussion
The time course of the Raman peak intensities of
H/D/exchange reaction by [NiFe]-hydrogenase in theD2/H2O system was successfully monitored. The Raman
peak intensities of D2 and H2 exhibited a simple decay andrise, respectively. The calculated initial production rate of
HD (0.0018±0.0002 min−1) was almost equal to that of H2(0.0022±0.0003 min−1). These results indicate that not only
the single exchange reactions (D2 + H+ → HD + D+) but
also the double exchange reaction (D2 + 2H+ → H2 + 2D+)
occurred macroscopically in the reaction cuvette.
To analyze the time course of the H/D exchange reactionin the D2/H2O system quantitatively, we adopted thereaction model proposed by Leroux et al.[1] In this model,
k is the rate constant of the H/D exchange reaction at theactive site and kin and kout are the rate constants for thetrapping and release of the substrates, respectively. To
obtain the ratios of k to kout, the time courses of D2, HD andH2 at several enzyme concentrations were fitted against
the analytical solutions derived from the model equations.
The calculated values of k/kout (1.8–2.1) wereapproximately constant for enzyme concentrations in therange of 2–20 µM. Recent new results will be alsopresented in the poster.

References[1] F. Leroux et al., Proc. Natl. Acad. Sci. 105,11188–
11193 (2008)

Yoshiki Higuchi is a full professor in the Graduate School of Life Science, University of Hyogo. He
obtained his Ph.D. from Osaka University (1984). After a postdoctoral position at Osaka University,
he was appointed as an assistant professor at the Himeji Institute of Technology (1985). He moved
to Kyoto University in 1995 as an associate professor of the Graduate School of Science. In 2002,
he moved to the Himeji Institute of Technology (presently University of Hyogo) to become a full
professor in the Graduate School of Science (presently Graduate School of Life Science). He
received the award of The Crystallographic Society of Japan in 1999, 38th Iue Culture Award for
Science and Technology in 2014, and Hyogo Science Award in 2017.
Yoshiki Higuchi
Corresponding author: Yoshiki Higuchi, hig@sci.u-hyogo.ac.jp, +81-791-58-0179.

35

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

Epitaxial growth of Ca2NH thin films
using reactive magnetron sputtering
Seoungmin Chon1, Shigeru Kobayashi1, Kazunori Nishio1, Ryota Shimizu1,2, and Taro
Hitosugi1
1 School of Materials and Chemical Technology, Tokyo Institute of Technology

2 JST-PRESTO

Abstract
We here present the epitaxial growth of Ca2NH films on MgO(110) substrates. The study opens up the way to quantitively
investigate the catalytic activities on the surfaces of Ca2NH.

Introduction
CaNxHy is a promising catalyst for the production ofammonia, which is an important industrial chemical suchas fertilizers [1,2]. Among the compounds, Ca2NH attracts
much attention due to its high catalytic activity [2]. To
precisely understand the mechanism of such catalytic
reaction, preparation of well-defined surfaces with asmooth and highly-oriented structure is required. For thispurpose, epitaxial thin films can provide an ideal platform.
However, due to its chemical instability, neither thin film
nor single crystal has not been reported to date. In thisstudy, we introduce our approach to fabricate Ca2NH
epitaxial thin films using reactive magnetron sputtering.

51.4º. However, it is difficult to distinguish its chemicalcomposition with the data due to the structural similarity
between CaNxHy phases such as Ca2NH 440 (2θ = 51.0º),
CaNH 220 (2θ = 50.3º) and Ca(NH2)2 204 (2θ = 50.1º).
Therefore, reciprocal space mapping was performed. The
results indicate the fabrication of a single-phase Ca2NH.
Additionally, the epitaxial relationship between thesubstrate and thin film was verified through pole figure
measurements.

Experimental / Computational
Ca2NH thin films were deposited on MgO(110) substrates
using reactive magnetron sputtering. A Ca metal plate (1inch.) was used as a target material. The substratetemperature was set to 500ºC, and RF power of 30 W was
supplied. During the deposition, Ar, N2, and H2 gases wereintroduced to the growth chamber with flow rates of 10
sccm, 5 sccm, and 0.5 sccm, respectively. The totalpressure was set to 1.0 Pa. The deposition time and typicalfilm thickness was 1 hour, and 160 nm, respectively. Notethat the thicknesses were measured in the air using astylus profiler. The structural properties of thin films werecharacterized by X-ray diffraction (XRD) using a custombuilt vacuum cell to avoid atmospheric air.

Fig 1. X-ray diffraction pattern of the obtained thin film.

References[1]: J. Thomas et al., “Principles and practice ofheterogeneous catalysis, 2nd Ed.” (John Wiley &Sons) (2014).
[2]: M. Kitano et al., Chem. Sci. 7, 4036 (2016).

Results and Discussion
Figure 1 shows an out-of-plane XRD pattern of an
obtained CaNxHy film. A single peak has appeared at 2θ =Education: 1999 Ph.D.

Graduate School of Engineering, The University of Tokyo

Professional Career:2015 - present
Professor, Tokyo Institute of Technology
2007 - 2015
Associate Professor, Tohoku University
2003 - 2007
Assistant Professor, The University of Tokyo
Taro Hitosugi

Research Interests: solid-state chemistry, solid-state physics, solid-state electrochemistry, solid-state
ionics, surface/interface, thin films, herointerfaces, oxides, hydrides, scanning probe microscopy,
materials informatics, artificial intelligence (AI), Bayes optimization, robot

Corresponding author: Taro Hitosugi, hitosugi.t.aa@m.titech.ac.jp36

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

H− ION CONDUCTION AND ANHARMONIC VIBRATION IN OXYGENDOPED LANTHANUM HYDRIDE
Soshi Iimura1,2, Keiga Fukui1, Tomofumi Tada1, Satoru Fujitsu1, Masato Sasase1, Hiromu
Tamatsukuri3, Takashi Honda3, Kazutaka Ikeda3, Toshiya Otomo3, Hideo Hosono1
1 Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama 226-8503, Japan,
2 PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi 332-0012, Japan,
3 Institute of Materials Structure Science, KEK, Tsukuba 305-0801, Japan
Fast ionic conductors have considerable potential to enable novel technological development for energy storage andconversion. Hydride (H−) ions are a unique species because of their natural abundance, light mass, and large polarizability.
Herein, we investigate characteristic H− conduction, i.e., fast ionic conduction controlled by a pre-exponential factor.
Oxygen-doped LaH3 (LaH3−2xOx) has an optimum ionic conductivity of 2.6 × 10−2 S cm−1—the highest conductivity reported
to date among H− conductors at intermediate temperatures. With increasing oxygen content, the relatively high activationenergy remains unchanged, whereas the pre-exponential factor decreases dramatically. In this presentation, we discuss
the origin of the large pre-exponential factor in terms of anharmonic vibrations of hydride ion.

Introduction
Hydride ion (H−) which has a high standard redox
potential (−2.3 V) has recently attracted much interest as
not only an energy storage with high energy density, butalso an active species for chemical processes. H−
conduction in solids has recently been reported [1, 2],
however, a high H− conduction is only achieved atrelatively high temperature. In order to utilize theadvantage of H− for the applications, H− electrolyte with ahigh conductivity at lower temperature is highly required.

This indicates that the pre-factor determines the high σi
and its dependence on oxygen content. In thispresentation, we discuss the origin of the large preexponential factor in terms of anharmonic vibrations of
hydride ion.

Experimental / Computational
Here we study the electric properties of lanthanum
oxyhydride (LaH3−2xOx). By utilizing a high pressure
synthesis technique, we successfully synthesized the newphase of LaH3−2xOx with a fcc structure over a wide
composition range (0 ≤ x ≤ 1). For structure analyses weused XRD and NPD. The electronic and ionic conductivity
were measured by DC polarization and AC impedancetechniques, respectively.

Fig. 1 Arrhenius plots for ionic conductivity of
LaH3−2xOx[3]Results and Discussion
Fig.1 is Arrhenius plots of the ionic conductivity (σi)
measured by impedance spectroscopy. At 340°C a high σiover 10−2 S cm−1 was obtained at x = 0.25. The transportnumber of the ionic conductivity was estimated to be morethan 99%, indicating that the conduction is purely ionic.
Upon increasing x, the activation energy of ~1.2 eVremains almost unchanged, whereas the pre-exponential
factor decreases dramatically from the extraordinarily
large value of 1012 S cm−1 K at x = 0.24 to 108 at x = 0.99.

SOSHI IIMURA

References[1] M. C. Verbraeken et al., Nat. Mater., 14, 95-100 (2015).
[2] G. Kobayashi et al., Science, 351, 1314-1317 (2016).
[3] K. Fukui, S. Iimura, T. Tada et al., Nat. Commun. 10,2578-1-8 (2019).

I received the Ph.D. degree in materials science from Tokyo Institute of Technology, Tokyo, Japan, in
2017. I’m currently working as an Assistant Professor in Materials Research Center for Element
Strategy at Tokyo Tech. My research interests are to discover new materials such as superconductors,
semiconductors, and ionic conductors based on new design principles. It was around early 2011 that
I first recognized the usefulness of hydrogen in materials science. At that time I used hydride ion aselectron dopant for iron-based superconductors in order to suppress the magnetism and induce
superconductivity. Nowadays, I’m interested in exploring materials functionality derived from intrinsic
properties of hydrogen, such as high ionic conductivity, low thermal conductivity.

Corresponding author: Soshi Iimura, s_iimura@mces.titech.ac.jp, 045-924-5197

37

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

GLASS-PHASE COORDINATION POLYMER DISPLAYINGCONDUCTIVITY AND GUEST-ACCESSIBLE POROSITY

PROTON

Munehiro Inukai,1 Yusuke Nishiyama,2,3 Susumu Kitagawa,4 Satoshi Horike4
1 Graduate School of Technology, Industrial and Social Sciences, Tokushima University, 2 JEOL Resonance Inc., 3
RIKEN-JEOL Collaboration Center, 4 iCeMS, Kyoto University
Abstract
We describe the preparation of the crystalline and glassy state of a coordination polymer displaying proton conduction andguest-accessible porosity. EXAFS and solid-state NMR analyses indicated that pyrophosphate and phosphate ions are
the main proton transporters in the glass and that homogeneously distributed 5-chloro-1H-benzimidazole in the glass
provide the porosity.

Introduction
Metal-organic frameworks (MOFs) and coordination
polymers (CPs) have recently emerged as interestingclasses of proton-conductive solids because of theirdiverse crystal structures, and reasonably high thermaland chemical stability. Although some MOFs and CPs withhigh proton conductivity (above c.a. 10−2 S cm−1) havebeen reported, their use as, for example, electrolytes infuel cells has been limited.5 In fact, improvements withrespect to their conductivity, thermal durability, andforming ability are still required for these species to be
used in the devices. Herein, we report the preparation of aporous CP in crystalline and glassy states.[1]measured the proton conductivity of 1g at 298 K underhumid conditions. The conductivity under 98% relative
humidity condition was 1.2 × 10−4 S cm−1. The high proton
conductivity would be originated from effective protontransport in the adsorbed water molecules in the porosity.
The guest-accessible porosity is useful to enhance theconductivity of the glass CP. To investigate themechanism of proton conduction and the structures of 1aand 1g, we conducted EXAFS and solid-state NMR. The
results will be shown in poster presentation.

Results and Discussion
Crystalline powder sample of CP (hereafter referred to as1) was synthesized from ZnO, 5-chloro-1H-benzimidazole(Clbim), and an H3PO4 solution (85%) via the liquidassisted mechanochemical method using methanol (Fig.
1). To obtain the activated 1 (1a), 1 was heated at 120 °C
under vacuum. The glass-phase derivative of 1 (1g) was
prepared, in turn, by melt-quenching 1a. The powder X-ray
diffraction (PXRD) pattern of 1a displays slight differenceswith respect to that of 1, suggesting that only smallchanges occur in the crystalline structure. The PXRD
pattern of 1g was broadened with respect to that of 1,
suggesting that the structure of the former is amorphous.
The DSC profile of 1g shows a baseline shift at 72 °C,
supporting that 1g is in glassy state.
The maximum uptake values of water and methanol were118.0 and 61.5 mL g-1 (4.3 and 2.3 molecules per unit
formula) in the case of 1g. In AC impedance experiments,
1g displayed proton conductivity at 130 °C was 1.2 × 10−6
S cm−1, and the activation energy was 1.5 eV. We also

Fig. 1 Crystal structure of 1 viewed along the aaxis at 223 K and (c) DSC curve of glass-form
1 (1g).
References[1] M. Inukai, Y. Nishiyama, K. Honjo, C. Das, S.
Kitagawa and S. Horike, Chem. Commun., 2019, 55,
8528-8531

M. Inukai studied solid-state NMR and received his Ph.D. (science) from Osaka University in 2009.
After a postdoctoral fellow in the solid-state NMR group of K. Takegoshi (2009-2011) and materialscience group of S. Kitagawa (2011-2014) in Kyoto University, he has been associate professor ofchemical physics in Tokushima University. His research interests focus on solid-state NMR,
coordination polymers/metal-organic frameworks, and ion conductors.

Munehiro Inukai
Corresponding author: Munehiro Inukai, E-mail: inukai.munehiro@tokushima-u.ac.jp, Tel: +81-88-656-7550

38

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

THEORETICAL STUDY OF H/D ISTOPE EFFECT WITH METAL BY USINGCOMBINED PLANE WAVE AND LOCALIZED BASIS SET APPROACH
Takayoshi Ishimoto1
1 Graduate School of Nanobioscience, Yokohama City University
Abstract
H/D isotope effect has attracted attention in various fields, such as adsorption of atoms/molecules on metal surface andhydrogen absorption in metal. Electronic structure calculation is an effective tool to analyse the details of H/D isotope effect.
However, it is difficult to take into account the quantum effect of proton/deuteron with metal electronic structure of surface
or bulk in the conventional method. To tackle this problem, we developed combined approach of plane wave and localized
orbital treatment, named “combined plane wave and localized basis sets (CPLB)” method. By using this method, weanalysed the H/D isotope effect with metal surface and bulk metal.

Introduction
The behavior of hydrogen (H) in the material has
extensively attracted attention in the proton conduction,hydrogen absorption, and so on. In particular, theinteraction between hydrogen and transition metals is
dominant factors to control the absorption and diffusion
properties of H in the metal. In these analyses, thedeuterium (D) substitution from H are used to obtain thedetailed information of the difference of H/D behavior. The
H/D isotope effects are extensively studied by bothexperimental and theoretical approaches to understandthe quantum mechanical principles. Generally, H/Disotope effects are induced by the difference of quantum
nature of proton and deuteron. The quantum effects areclarified, such as zero-point energy, nuclear tunneling,vibrational excitation, and so on. The H/D isotope effects
are observed in the various fields in chemistry,
biochemistry, physics, and other related fields.
To consider the geometrical difference by H/D isotope
effect in the theoretical calculation, the both treatments ofnuclear quantum effect and surface or bulk structure ofmetal are necessary. Recently, we proposed the
combined plane wave and localized basis set (CPLB)
method [1]. This method is possible to perform highaccurate calculation including nuclear quantum effect by
localized (LO) basis sets with the large scale electronic
structure calculation for metal part by plane wave (PW). In
this study, we analyzed the H/D isotope effect in metal
surface and bulk by using the our developed CPLB method.

was used for the exchange and correlation functional. The
cutoff energy was set to be 400 eV. For the LO based
electronic structure calculation, we used multi-component
density functional theory (MC_DFT) approach to treat
nuclear quantum effect directly as well as electrons [3].
Implemented Gaussian 16 program package was used for
MC_DFT. The B3LYP with LanL2DZ electronic basis sets
was used for all calculation. The single s-type Gaussiantype function was set for proton and deuteron. The
optimized geometry and absorption energy were obtainedin the framework of CPLB approach.

Results and Discussion
Figure 1 shows an example of H/D absorption in Pd metal.
As a Pd bulk, we prepared the 108 atomic system. H or D
atom was placed in the both O and T sites. We clearly
demonstrated that the difference of quantum effect ofproton and deuteron affected to the geometrical structureof surrounding Pd atoms. Detailed analysis for H/D isotope
effect will be discussed in the presentation.

(a) Octahedral site(b) Tetrahedral site

Fig. 1 H/D absorption sites in Pd108.

Computational Details
For the PW based electronic structure calculation, weused the Vienna ab initio simulation package (VASP) withthe projector-augmented wave method. The PBE
approximation with a generalized gradient approximation

Takayoshi
Ishimoto

References[1] T. Ishimoto, H. Kai, Int. J. Quant. Chem. 118, e25452(2018)He received his Ph.D. at Rikkyo University in 2004. After Grid Research Center and Research Instituteof Computer Science in National Institute of Advanced Industrial Science and Technology, he moved
to Kyushu University as Assistant Professor of INAMORI Frontier Research Center in 2009. Since
2016, he has been an Associate Professor at Graduate School of Engineering, Hiroshima University.
Now, he is an Associate Professor at Graduate School of Nanobioscience, Yokohama City University.
Recent his research interest is H/D isotope effect of metal related materials.

Corresponding author: Takayoshi Ishimoto, tishimo@yokohama-cu.ac.jp, 045-787-2165

39

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

DEVELOPMENT OF POWDERINVESTIGATION OF HYDRIDES

Sapporo, Hokkaido, Japan, 2020

NEUTRON

HOLOGRAPHY

FOR

Yuki Kanazawa1, Kenji Ohoyama1, Masahide Harada2, Kenichi Oikawa2, Kouichi Hayashi3
1 Ibaraki University, 2 J-PARC Center, 3 Nagoya Institute of Technology
Abstract
Hydrogeneration of materials provide various and exotic properties. To understand these properties, we propose a novel
method that can visualize the local structures of/around hydrogen, powder neutron holography. In this study, we simulated
the signal of powder neutron holography in Cu and YH2. We discuss the difference of the two materials.

Introduction

Results and Discussion

Hydrogeneration of materials provides many exotic
properties such as hydrogen induced ferromagnetism orchange of transparency. In the view of structural physics,
hydrogen position or atomic structure around hydrogen(local structure) is important for understanding theseproperties. Though information on local structures are
obtained by X-ray absorption fine structure (XAFS) or Pair
Distribution Function (PDF) methods, these methods haveno sensitivity of hydrogen or element selectivity. To
overcome this, Neutron Holography (NH) was firstly
proposed by Cser in 2001 [1]. We succeeded in enhancing
the accuracy drastically by using white neutrons [2].
However, preparation of single crystals of hydrides, whichis indispensable for NH, is difficult because of hydrogen
embrittlement. Therefore, we propose world-first powder
neutron holography (PNH). Holography of powder
samples using X-ray already demonstrated by Nishino in2001 [3].

Fig.1 (a) and (b) are simulated χ(k) of Cu and YH2,
respectively. The amplitude of the oscillation is about 10-310-4. Sharp peaks are contained in Fig. 1. Note that thepeak positions can be explained by Bragg condition with2θ = π , indicating that these peaks are caused byinterference of incident neutron and the Bragg scattering.
Moreover, in Fig. 1(a), sharp peaks are positive, while, for
YH2, some of sharp peaks are negative. This is due to thedifference of sign of 𝑏 of Cu and H. These calculations
suggest that PNH is feasible in principle though highneutron flux measurement and development of accurate
data-correction are required. If PNH will be realized, it will
be an important prove of materials science, in particular,
Hydrogenomics.

In PNH, neutron wavenumber (𝑘 = , λ: wavelength)
dependence of γ-ray intensity, χ(k), is measured, which
includes information of Radial Distribution Function(RDF). χ(k) is calculated by the following formula (1).
χ(k) = 2Im

𝑏
𝑒
𝑘𝑟

(1)

, where 𝑏 and 𝑟 are neutron scattering length of i-th
atom and distance between selected atom and the i-th
atoms, respectively. In this study, we simulated χ(k) of
Cu and YH2 powder in the range of k = 1~11 Å . The
cluster size are 100 Å.

Cu

(b)

YH2

Simulated intensity

Computational(a)Fig. 1 Simulated 𝛘(𝐤) of γ-ray intensity in Cu and YH2References[1] L. Cser et al., Europhys. Lett. 54, 747 (2001).
[2] K. Hayashi et al., Sci. Adv. 3, e1700294 (2017).
[3] Y. Nishino et al., Phys. Rev. B, 64.201101 (2001).

Yuki Kanazawa was born in Iwate, Japan in 1996. He obtained his B. Eng. in Ibaraki univ. (2017). He
belong to institute of Quantum Beam Science, Ibaraki University graduate school of Sc. and Eng.. His
main research field is investigation of materials science by novel methods, neutron holography.

Yuki Kanazawa
Corresponding author: Yuki Kanazawa, 18nm914r@vc.ibaraki.ac.jp, 029-352-3240.

40

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ATTEMPT TO CONTROL H+ TRANSFER IN MOLECULAR BILAYERS FOR
A FUTURE HYDROGENOMIC DEVICE
H.S. Kato1, I. Matsuda2, A. Ueda2, S. Yoshimoto2, S. Yamamoto2, Y. Kanematsu3,
M. Tachikawa4, J. Yoshinobu2, and H. Mori2
1 Osaka Univ., 2 ISSP, Univ. Tokyo, 3 Hiroshima City Univ., 4 Yokohama City Univ.
Hydrogen-bonding heterogeneous bilayers on substrates have been studied as a basis for new functions of molecular
adlayers, by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), infrared reflection
absorption spectroscopy (IRAS), and density functional theory (DFT) calculations. Here, we report the formation of thecatechol-fused tetrathiafulvalene (Cat-TTF) derivative adlayer hydrogen-bonding to an imidazole-terminated alkanethiolate
self-assembled monolayer (Im-SAM) on Au(111), in which the former and latter layers should work as proton (H+)-donor
and acceptor layers, respectively. The potential of H+ transfer between the two layers is theoretically discussed as afunction of applied electric field.

Introduction
H+-electronThe
correlated properties of pure organic
molecular crystals have recently been materialized by Moriand coworkers synthesizing Cat-TTF derivatives [1,2], andprovide great interests in material science. In this study, it
has been tried to construct the H+-electron correlated
system in the two-dimensional molecular layer on solid
substrates. We have challenged to form Cat-TTF adlayer
bonding to the Im-SAM-covered Au substrate (Fig.1) in themanner of self-assembly, and characterized the bilayerusing several spectroscopic and microscopic methods
with theoretical calculations [3,4].

first, the cleaned Au substrate was immersed in the
deoxygenated ethanol solution containing 1 mM 1-(11mercaptoundecyl)-imidazole (Im-(CH2)11-SH) for morethan 20 h, and second, the Im-SAM-covered substrates
were immersed in deoxygenated chloroform solution
containing 1 mM synthesized Cat-TTF derivatives for morethan 20 h [3]. The bilayer morphology, amount of themolecules, and their adsorption states were examinedusing AFM, XPS, and IRAS, respectively. The DFT
calculations were also performed for estimation of H+
transfer potential curves depending on applied electricfield.

Results and Discussion

Fig. 1 Schematic view of the self-assembled bilayer: Cat-TTF
adlayer hydrogen-bonding to the Im-SAM-covered Au substrate.

The bilayer is designed with the connection via hydrogenbonds between the hydroxyl group (H+ donor) of Cat-TTF
derivative and the imino N site (H+ acceptor) of imidazole
group in Im-SAM (Fig. 1). The H+ transfer between the twolayers should be assisted by well-arranged bilayer
configuration and strong hydrogen bonds. Actually, we
confirmed the nearly ideal bilayer structure, molecularamounts, and especially strong hydrogen bonds in the
prepared bilayers. Then, we theoretically evaluated thepotential for H+ transfer between the H+ donor andacceptor sites. As a result, we found that, in the preparedbilayer, H+ can transfer between the two sites under asufficient electric field.

Experimental / Computational

References

Heterogeneous bilayers on the Au(111) surfaces werecreated by sequential two-step immersions of thesubstrates into individual solutions at room temperature:[1] T. Isono, et al, Nat. Commun. 4, 1344 (2013)[2] A. Ueda, et al, J. Am. Chem. Soc. 136, 12184 (2014)[3] H.S. Kato, et al, Langmuir 34, 2189 (2018)[4] S. Yamamoto, et al. e-JSSN 17, 49 (2019)

H. S. Kato

HSK and coworkers have investigated properties and functionalities of molecules adsorbed on welldefined surfaces, using several methods in the fundamental surface science: such as several
photoelectron spectroscopies (UPS / XPS / TR-2PPES), vibrational spectroscopy (IRAS), andscanning probe microscopies (AFM / STM). In the studies, recently, we focus on the nano-structural
self-assembled molecules on surfaces. Here, most of cases, hydrogen works as a key player in the
self-assembling reactions at room temperature. Now, we try to use the hydrogen reaction forcontrolling of molecular property in the self-assembled bilayer. Through these studies, hopefully, we
will build up a guiding principal for new types of molecular devices, i.e., the “hydrogenomic” moleculardevices.

Corresponding author: Hiroyuki S. Kato, hirokato@chem.sci.osaka-u.ac.jp, +81-6-6850-6570

41

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ALL
SOLID-STATEBATTERIESUSING
LIBH4-BASEDELECTROLYTE AND LITHIUM METAL ELECTRODE

SOLID

Kazuaki Kisu1, Sangryun Kim2, Shin-ichi Orimo1,2
1 WPI-Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, 2 Institute for Materials Research (IMR),
Tohoku University
The LiBH4-based complex hydrides have been collecting attention as a new class of solid electrolytes for all-solid-statelithium batteries. The notable features of LiBH4-based complex hydrides are their strong reducing ability. The ability is
expected to ensure high compatibility with lithium metal, a material that itself has a reducing ability. In the presentation, acomprehensive understanding of the phenomena at the interface between a lithium metal anode and two types of LiBH 4based solid electrolytes (LiBH4 and Li4(BH4)3I) are to be explained. Also, the performances of all-solid-state battery
fabricated using a Li metal anode and Li4(BH4)3I electrolyte will be presented.

Introduction
Lithium metal is one of the most promising anode materials
for next-generation energy storage systems owing to its
high energy density derived from its low redox potential (3.045 V vs. SHE) and high theoretical capacity (3,860 mAhg-1) [1]. Although LiBH4-based solid electrolytes are known
as a promising candidate with high compatibility withlithium metal due to its high reducing ability anddeformability[2], the capability of LiBH4-based complex
hydrides for the formation of a stable interface against
lithium metal has not been verified yet. In this study, we
aim to achieve a comprehensive understanding of thephenomena at the interface between a lithium metal
anode and two types of LiBH4-based solid electrolytes(LiBH4 and Li4(BH4)3I [3]) to verify the high compatibility of
LiBH4-based solid electrolytes with a lithium metal anode.

stability was also confirmed using Nyquist plots obtained
before and after the lithium plating/stripping test (Fig. 1right). The intersection of the portions of semi-circles in theplots corresponding to the bulk resistance did not change
after the test. Moreover, no additional semicircles
attributed to interface and/or grain boundary resistancewere observed [4]. In our presentation, the performancesof all-solid-state battery fabricated using a Li4(BH4)3I
electrolyte, Li metal anode, and S-C composite cathodewill also be presented.

Experimental
Li4(BH4)3I solid electrolyte was prepared via themechanical milling method [3]. The stability against lithium
electrode of the electrolyte was investigated by monitoring
the voltage evolution in a symmetric cell at a constantcurrent density of 0.2 mA cm-2 for 30 min. Sulfur-carbon(S-C) composites were also prepared using themechanical milling method. A battery cell consisting of SC composite and Li4(BH4)3I were assembled using a
stainless electrochemical cell holder.

Fig. 1 Voltage transients during Li plating/stripping with
Nyquist plots before and after Li plating and stripping
process for Li4(BH4)3I at 90˚C.

References[1] Goodenough et al., J. Am. Chem. Soc., 135, 1167
(2013)

Results and Discussion[2] M. Matsuo et al., Appl. Phys. Lett., 91, 224103 (2007).

To investigate the electrochemical stability of the interface
during lithium plating/stripping, charge and discharge
measurements over 100 cycles were implemented for alithium metal /solid electrolyte/ lithium metal symmetric cell.
For Li4(BH4)3I, there was no change in the voltage
transient during the test (Fig. 1 left). The electrochemical[3] H. Maekawa et al., J. Am. Chem. Soc., 131, 894(2009).
[4] K. Kisu et al., J. Power Sources, 436, 226821 (2019).

Kazuaki Kisu received his Ph.D. in engineering in 2015 from Tokyo University of Agriculture andTechnology. He worked as a project assistant professor (2015–2018) in Tokyo University ofAgriculture and Technology, and is currently an assistant professor in the Orimo group at theAdvanced Institute for Materials Research (AIMR), Tohoku University. His research interests are theelectrochemistry and solid-state ionics for electrochemical energy storage devices.
Kazuaki Kisu
Corresponding author: Kazuaki Kisu, Email: k-kisu@imr.tohoku.ac.jp, Tel. (+81)22-215-2094

42

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020LANTHANUM OXYHYDRIDES SUPPORTED RUTHENIUM CATALYST FOR
AMMONIA SYNTHESIS
Masaaki Kitano1,2, Kayato Ooya1, Keiga Fukui1, Shoshi Iimura1, Hideo Hosono1
1 Materials Research Center for Elemental Strategy, Tokyo Institute of Technology, 2 Precursory Research for Embryonic
Science and Technology (PRESTO), Japan Science and Technology Agency (JST),
Lanthanum oxyhydrides (LaH3-2xOx, x = 0.125~1.0) with high hydride ion conductivity have been synthesized byhydrogenation treatment of the mixture of LaH3 and La2O3. All lanthanum oxyhydrides were demonstrated to function as
efficient and stable promoters for ruthenium catalysts in low-temperature ammonia synthesis, and their catalytic activities
are much higher than those of Ru/La2O3 and Ru/LaH3. Ru/LaH2.5O0.25 exhibited the highest activity (818 μmol g-1 h-1 at 0.1
MPa and 260C) with much lower activation energy than conventional Ru catalysts.

Catalytic ammonia synthesis is essential for the productionof synthetic fertilizers and chemical products. However,high temperature (400-500C) and high pressure (10-30MPa) are required for industrial ammonia synthesis(Haber-Bosch process) because the bond energy of NNbonds is extremely large. We have recently reported thathydride materials such as Ca2NH, CaH2 and LaH2+x
promote the activity of Ru catalysts significantly at low
reaction temperatures.1 These materials have very low
work function because of the formation of anionicelectrons at hydride vacancy sites. In the present study,
we focused on the lanthanum oxyhydrides2 as support
materials of Ru catalyst in ammonia synthesis.

Results and Discussion
LaH3-2xOx with various hydrogen content were prepared bycontrolling the mixing ratio of LaH3 and La2O3. XRD
analysis revealed that LaH3-2xOx has tetragonal fluorite-likestructure. Figure 1 shows the ammonia synthesis activities
of Ru/LaH3-2xOx and reference catalysts at atmosphericpressure. Although the catalytic activity is independent of
the hydrogen content in Ru/LaH3-2xOx, these activities arehigher than those of Ru/La2O3 and Ru/LaH3. The
maximum ammonia synthesis rate (818 μmol g-1 h-1) wasrecordedfor
Ru/LaH2.5O0.25.
Furthermore,the
Ru/LaH2.5O0.25 exhibits ammonia synthesis activity down
to 160°C, which is lower by 100°C than the case of
Ru/La2O3. As a consequence, the apparent activationenergy of Ru/LaH2.5O0.25 for ammonia synthesis isdetermined to be 64 kJ mol‒1, which is close to those for
Ru-loaded electrides and hydride materials (50-60 kJ mol‒
1)1. As we reported previously, the formation of anionicelectrons at hydride vacancy sites accounts for the strong

electron donation ability that facilitates efficient N2
cleavage on Ru. It is thus considered that the hydridevacancies are formed at Ru- LaH2.5O0.25 interface during
ammonia synthesis, which imparts high catalytic
performance of Ru nanoparticles. In addition, reversible
exchange between H- ions and anionic electrons
effectively takes place over Ru/LaH2.5O0.25 as comparedwith Ru/LaH3 because the LaH3-2xOx has high hydride ion
conductivity.
1000
Ru/LaH2.5O0.25

NH3 synthesis rate
[μmol g-1 h-1]

Introduction

800

600
Ru/LaH3400

Ru/La2O3

200
0
160

200 240 280 320
Temperature [°C]Fig. 1 Catalytic activity for ammonia synthesis over 2 wt%
Ru/LaH2.5O0.25, Ru/LaH3, and Ru/La2O3 at 0.1 MPa as afunction of reaction temperature.

References[1] M. Kitano, H. Hosono, et al., Chem. Sci. 7, 4036
(2016).
[2] K. Fukui, S. Iimura, H. Hosono, et al., Nat. Commun.
10, 2578 (2019).

Masaaki Kitano studied chemical engineering and received his Ph.D. degree from Osaka Prefecture
University in 2006 under the supervision of Prof. Masakazu Anpo who is an expert in photocatalysis.
After a stint with Prof. Michikazu Hara as a postdoctoral research fellow at Kanagawa Academy of
Science and Technology, he joined the Tokyo Institute of Technology in 2009 as an assistantprofessor and was promoted to associate professor in 2013. His research interests in ammonia
synthesis and various hydrogenation reactions using electride- and hydride-based catalysts, synthesisof alloy nanoparticles, and solid acid catalysts.
Masaaki Kitano
Corresponding author: Masaaki Kitano, kitano.m.aa@m.titech.ac.jp, Tel. +81-45-924-5191

43

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

EFFETS OF Ni-CONTAING POROUS CARBON SHEETS (Ni-PCS) ON THE
DEHYDROGENATION PROPERTIES OF Mg(AlH4)2Youngdon Ko1,2, Heena Yang1,2, Loris Lombardo1,2, Andreas Züttel1,2
1Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), Basic

Science Faculty (SB), École polytechnique fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland
2Empa Materials Science & Technology, Dübendorf, Switzerland

Complex hydrides have high theoretical hydrogen capacity as fuel for PEMFC automobiles. Among the complex hydrides,
magnesium alanate has high hydrogen storage capacity and releases hydrogen at low temperature (150 oC), but still notmatched to PEMFC operation temperature. Therefore, we prepared Ni-PCS catalyst with Mg(AlH4)2 to investigate the effectof catalyst and enhance hydrogen release.

Introduction

Results and Discussion

Hydrogen storage under moderate temperature andpressure is needed to commercialize and spread the useof the fuel cell system. The alkali and alkali earth metal
alanates are considered as candidate materials due tohigh hydrogen capacity and relatively low decomposition
temperature.1 Among the alkaline earth alanates,
magnesium alanate, Mg(AlH4)2, has a high theoreticalhydrogen capacity of 9.3 wt.% and decomposes below
150 oC at the first decomposition step.2 To meet the
PEMFC operating temperature, research is being
conducted to lower the decomposition temperature of
LiAlH4 or NaAlH4 using catalysts.3,4 In this study, theMg(AlH4)2 was synthesized with Ni-PCS to investigate thecatalytic effect of decomposition temperature.

In-situ XRD was conducted for confirming the crystal
phase during heating from RT to 300 oC. Hydrogen releaseamount and decomposition temperature were measured
by Pressure-composition-temperature (PCT). The
hydrogen release temperature of magnesium alanate
decreased with Ni-PCS catalytic effect.

Experimental
The synthesis of magnesium alanate proceeds via themetathesis method. The commercial LiAlH4, MgCl2, NiCl2
were used as received. The Diethyl ether was purified withsorbent to remove remaining water. LiAlH4 and MgCl2
were mixed by a high energy ball mill (SPEX sample prep8000). The porous carbon sheets (PCS) were synthesizedusing sucrose and phosphorus pentoxide. At first, sucroseand phosphorus pentoxide were ground well. The mixture
was put into the autoclave and heat to 200 oC for precarbonation. Then, the pre-carbonated black powder was
calcined to 900 oC with Ar flow. For the deposition of Ni
nanoparticle onto PCS, Ni nanoparticle was synthesized
by the polyol method.

Fig. 1 Schematic image of hydrogen release on
Mg(AlH4)2 with Ni-Porous carbon sheet

References[1] A. Züttel, Materials today, 6(9), 24-33 (2003)[2] M. Fichtner, O. Fuhr, O, O. Kircher, Journal of Alloys
and Compounds, 356, 418-422 (2003)[3] R. Varin, L. Zbroniec, Journal of Alloys andCompounds, 506(2), 928-939 (2010)[4] Z. Xueping, L. Shenglin, L. Donglin, international
journal of hydrogen energy, 34(6), 2701-2704 (2009)

Born in 1992, Republic of Korea. Youngdon Ko graduated B.Sc. and M.Sc. degree from Konkuk
University in 2019, Republic of Korea. During this time, he worked in the field of proton exchange
membrane fuel cell (PEMFC) with self-humidifying system, catalyst for oxygen reduction reaction(ORR). After finished his master degree, he joined Prof. Andreas Züttel’s group in EPFL as a doctoral
assistant. His current research focused on hydrogen storage with complex metal hydride.
Youngdon Ko
Corresponding author: Youngdon Ko, youngdon.ko@epfl.ch, +41 21 695 8212

44

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CARBON DOPING OF HYDROGEN BORIDE SHEET REDUCES H2
RELEASE TEMPERATURE*T. Kondo1,2, Y. Fujimoto3, R. Ishibiki4, T. Goto4, S. Ito1,2, T. Fujita5, A. Yamamoto2,6, S.

Saito2,3, and H. Hosono2
1

Faculty of Pure and Applied Sciences, University of Tsukuba, 2 Materials Research Center for Element Strategy, Tokyo
Institute of Technology, 3 Department of Physics, Tokyo Institute of Technology, 4 Graduate School of Pure and Applied
Sciences, University of Tsukuba, 5 School of Environmental Science and Engineering, Kochi University of Technology,6Institute of Engineering, Tokyo University of Agriculture and Technology,
We have prepared carbon-doped (C-doped) hydrogen boride sheets by using C-doped MgB2 as a starting material for
ion-exchange reaction and analyze its hydrogen release temperature by thermal desorption spectroscopy.

Introduction
Recently, we revealed that the hydrogen boride (HB)
sheet, with an empirical formula of H1B1, can beexperimentally prepared by exfoliation and complete ionexchange between protons and magnesium cations inmagnesium diboride (MgB2) at room temperature [1]. Our
extensive analysis revealed that the prepared HB sheets
did not show any long range order, but have a local
structure of a hexagonal boron network with bridgehydrogens. HB sheets release their hydrogen as H2
molecules by UV irradiation even at room temperature [2],while hydrogen can also be released by heating in a wide
temperature range from 423 to 1473 K [1]. Theoretically,
the release temperature of hydrogen by heating is
expected to be lower by electron doping to HB, becauseof the electron occupation of anti-bonding orbital of H-B
bonds by electron doping [3]. In this work, we have
prepared C-doped HB sheets by using C-doped MgB2 as
a starting material for ion-exchange reaction and analyze
its hydrogen release temperature by thermal desorption
spectroscopy (TDS).

introduced carbon atoms (~1.6 at%) by replacing boron
as substitute doping. The stabilized C-doped HB
structure was then obtained. The work function derived
from DFT calculations are 3.40 eV and 3.36 eV for HB
and C-doped (1.6 at%) HB, respectively. The lower work
function for C-doped HB is originated from electron
doping in HB and can explain the decrease of H 2 releasetemperature in Fig. 1.

Results and Discussion
Figure 1 shows TDS results of H2 from HB and thatfrom C-doped (10 at%) HB. As reported previously, there
are three H2 desorption peaks at ~500 K, ~900 K, and~1200 K [1]. In the case of C-doped HB, similar
desorption profile is observed except for the second peaktemperature position. The second peak temperature islocated at ~800 K which is approximately 100 K lower
compared to that for HB.
To understand the origin of the decrease ofhydrogen release temperature by C-doping in HB, wehave calculated the electronic structure of C-doped HB
by density functional theory (DFT), where we have

Fig. 1 TDS of HB and C-doped HB
References[1] H. Nishino, et al., J. Am. Chem. Soc. 139, 13761(2017).
[2] R. Kawamura, et al., Nat. Commun. (2019) in press(DOI: 10.1038/s41467-019-12903-1)[3] T. A. Abtew, P. Zhang, Phys. Rev. B, 84, 094303(2011).

2003

Ph.D. in Engineering, University of Tsukuba

2003-2006

Special postdoctoral researcher, Institute of Physical and Chemical Research (RIKEN)

2007-2011

Assistant Professor, University of Tsukuba

2011-2015

Lecturer, University of Tsukuba

2015-present Associate Professor, University of Tsukuba
Takahiro Kondo, takahiro@ims.tsukuba.ac.jp, +81-29-853-5934

45

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

LOCAL STRUCTURE STUDY OF METAL–HYDROGEN SYSEMS BY X-RAY
TOTAL SCATTERING
Akihiko Machida1, Tetsu Watanuki1, Kouji Sakaki2, Hyunjeong Kim2, Yumiko Nakamura2
1 Synchrotron Radiation Research Center, National Institutes for Quantum and Radiological Science and Technology,
Hyogo, Japan, 2 Research Institute of Energy Frontier, National Institute of Advanced Industrial Science and Technology,
Tsukuba, Japan
Structural information of a metal hydride provides important knowledge to understand its properties. Average structural
information is not sufficient to elucidate the mechanism of hydrogen absorption, and therefore local structural informationis also necessary. Atomic pair distribution function, which can be obtained from the total scattering measurement, is oneof potential tools to investigate the local structures of materials. We have constructed a rapid acquisition pair distributionfunction experimental system at BL22XU in SPring-8. BL22XU and have applied the pair distribution function method toinvestigate metal-hydrogen systems.

Introduction

Results and Discussion

Many functional materials are inherently inhomogeneousin their compositions or structures. X-ray diffraction (XRD)
analysis is the most popular method to determine a crystal
structure. In metal-hydrogen systems, the absorbedhydrogen atoms largely expand the metal lattice andinduce a structural phase transition on the hydrogenation
reaction. From a nanoscale structural point of view, a large
number of crystallographic defects, such as dislocations,and lattice distortion are formed during hydrogenation
reaction, and are considered to influence the properties ofthe metal hydrides. However, the conventional XRD
method is insufficient for the analysis of these
inhomogeneous or heavily disordered structures. An
atomic pair distribution function (PDF) is suitable toanalyse the local- to middle-range structure. We
developed the rapid-acquisition (RA)-PDF measurement[1] system in BL22XU at SPring-8 and applied the PDF
analysis to investigate metal hydrides [2-4].

Under the standard PDF measurement setup in BL22XU,
the maximum Q range of the obtained total scattering
pattern reaches 20 Å−1. Obtained PDFs show peaks even
above ~100 Å allowing us to investigate even middlerange structural features. Developed in-situ measurement
setup with hydrogen gas pressure up to 1 MPa enables us
to study change in both average and local structures ineither equilibrium or non-equilibrium states. We
succeeded in measuring the total scattering patterns
during hydrogenation process of some hydrogen
absorbing alloys, such as LaNi4.5Al0.5, V-Ti-Cr, and etc.
The XRDs and PDFs of LaNi5-based alloys suggest
formation of the intermediate state with locally distorted
structure during hydrogenation.

Experimental / Computational
PDFs are obtained by a Fourier transformation of the total
scattering data of specimens. BL22XU enables us toperform RA-PDF experiments using a large-area twodimensional detector and high-energy X-rays up to 70 keV(wavelength of approximately 0.177 Å). Powdered sample
was sealed in the polyimide capillary with an innerdiameter of 1 mm.

References[1] P. J. Chupas, X. Qiu, J. C. Hanson, P. L. Lee, C. P.
Grey, and S. J. L. Billinge, J. Appl. Crystallogr. 36, 1342
(2003).
[2] K. Sakaki, N. Terashita, H. Kim, E. H. Majzoub, A.
Machida, T. Watanuki, S. Tsunokake, Y. Nakamura, andE. Akiba, J. Phys. Chem. C, 118, 6697 (2014).
[3] K. Sakaki, H. Kim, A. Machida, T. Watanuki, Y.
Katayama, and Y. Nakamura, J. Appl. Crystallogr. 51, 796(2018).
[4] K. Asano, H. Kim, K. Sakaki, K. Jimura, S. Hayashi, Y.
Nakamura, K. Ikeda, T. Otomo, A. Machida, and T.
Watanuki, Inorg. Chem., 57, 11831 (2018).

Senior Principal Researcher, High Pressure Science and Stress Research Group, Synchrotron
Radiation Research Center, Kansai Photon Science Institute, Quantum Beam Science Research
Directorate, National Institutes for Radiological Science and Technology. Doctor of Engineering,
Nagoya University, Japan (2002). Research fields are materials science, structural analysis and highpressure. Investigate structural properties of metal hydrides under high pressure (2003-), transient
structural change of hydrogen absorbing alloys during hydrogenation process using in-situ XRD
measurement (2010-), local structure using x-ray PDF measurement (2011-).
Akihiko Machida
Corresponding author: Akihiko Machida, machida.akihiko@qst.go.jp, +81-791-58-0996.

46

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

LOW TEMPERATURE HYDROGEN ION BEAM IRRADIATION FOR
EXPLORING EXOTIC PHYSICAL PROPERTIES
Mitsuhiko Maesato1, Ryo Nakayama1,2, GyeongCheol Lim1, Takahito Terashima1, Hiroshi
Kitagawa1
1 Kyoto University, 2 Tokyo Institute of Technology
Abstract
We have developed a compact low temperature hydrogen ion irradiation apparatus with in situ physical property
measurements. This apparatus allowed us to perform heavy hydrogen doping into materials of interest and explore exotic
physical properties. We succeeded in heavy interstitial hydrogen doping into SrTiO 3 and ZnO. These insulators turned into
degenerated semiconductors by heavy hydrogen doping, and showed unprecedented irreversible thermal hysteresis inelectrical resistivity.

Introduction
Hydrogen doping can drastically change physicalproperties of materials, although the doping amount islimited in the case of conventional doping methods suchas hydrogen gas pressure and electrochemical sorption.
The low temperature hydrogen ion beam irradiation is a
powerful method for heavy hydrogen doping. To evaluate
the doping effects, in situ physical property measurements
are necessary. We have developed a low temperaturehydrogen ion beam irradiation apparatus with in situ
transport measurement and explored exotic physicalproperties of oxides induced by heavy hydrogen doping.

300 K, indicating partial desorption of doped hydrogen by
thermal annealing [2]. In the case of ZnO, we observed agiant isotope effect. The hydrogen irradiation at 7 K
instantly induced very large decrease in resistivity, while
the deuterium irradiation at 7 K resulted in only slightdecrease in resistivity of ZnO. The subsequent heating
caused huge irreversible thermal hysteresis in theresistivity of deuterium doped ZnO.

Experimental
Epitaxial thin films (~100 nm thick) of SrTiO3 and ZnO(wurtzite) were fabricated on LSAT (001) and -Al2O3(001) substrates, respectively, by pulse laser deposition
and RF magnetron sputtering, respectively. The hydrogenion beam was irradiated on the thin films with the low
acceleration voltage (≤ 5kV) at room temperature or low
temperatures down to 7 K by using the home-madeapparatus (Fig.1) [1]. The resistivity of thin films wasmeasured in situ by van der Pauw method.

Results and Discussion
Both insulating oxides showed metallic temperaturedependence of resistivity after the heavy hydrogen doping.
The hydrogen ion irradiation on SrTiO3 at 150 K induced
larger decrease in resistivity than that of 300 K irradiation,
but the resistivity irreversibly increased upon heating at

MaesatoFig. 1 Hydrogen ion beam irradiation
apparatus
References[1] R. Nakayama, N. Suzuki, M. Maesato, T. Nagaoka, M.
Arita, H. Kitagawa, Rev. Sci. Instrum. 88, 123904 (2017)[2] R. Nakayama, M. Maesato, T. Yamamoto, H.
Kageyama, T. Terashima, H. Kitagawa, Chem. Comm. 54,
12439 (2018)

Mitsuhiko Maesato was born in Okinawa, Japan in 1973. He graduated from the University of Tokyo(1995), Japan, and received his Ph.D. from the University of Tokyo (2000) under the guidance ofProf. Seiichi Kagoshima. He moved to Kyoto in 2000 to assume a position of Assistant Professor in
Prof. Gunzi Saito’s group, Kyoto University. He joined Prof. Hiroshi Kitagawa’s group in 2009.
Since 2013 he has been an Associate Professor in Division of Chemistry, Graduate School of Science,
Kyoto University. Maesato pioneered the uniaxial strain method for artificial control of materials’
properties, and discovered the first quantum spin liquid in a triangular lattice. His research interests
include superconductors, spin liquids, and emergent phenomena in strongly correlated materials.
**********************************************************

Corresponding author: Mitsuhiko Maesato, maesato@kuchem.kyoto-u.ac.jp, Tel +81-75-753-4036.

47

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

ANALYSIS OF
BOROHYDRIDEAMMONIA

Sapporo, Hokkaido, Japan, 2020

ABSORPTION

STATE

OF

METAL

Hiroki Miyaoka1, Seiki Sugino2, Takahiro Ide2, Masakuni Yamaguchi3, Norio Ogita4,
Takayuki Ichikawa1,2
1 Natural Science Center for Basic Research and Development, Hiroshima University, 2 Graduate School of Engineering,
Hiroshima University, 3 Graduate School of Advanced Sciences of Matter, Hiroshima University, 4 Graduate School ofIntegrated Arts and Sciences, Hiroshima University
Abstract
In this work, the NH3 absorption state of alkali(-earth) metal borohydride M(BH4)x is analysed by pressure-compositionisothermal measurements and various spectroscopy such as nuclear magnetic resonance (NMR), infra-red, and Raman
spectroscopy. Although NaBH4 forms liquid NH3 absorption state in all region, Mg(BH4)2 and Ca(BH4)2 shows solid ones.
On the other hand, LiBH4 shows complicated NH3 absorption process. 1, 2, and 3 mol NH3 absorption state is solid, liquid,and solid phase, respectively. From the NMR analyses, H− in (BH4)− and H+ in NH3 are clearly distinguished. With increasein the amount of absorbed NH3, the chemical states of both H are simultaneously changed, suggesting that the interaction
between H− and H+ would be related to the NH3 absorption state of NaBH4.

Introduction

Results and Discussion

Alkali(-earth) metal borohydrids M(BH4)x are studied ashydrogen storage materials with high capacity so far.
Recently, various functional properties of M(BH4)x as
ammonia (NH3) absorption materials and ion conductors
are reported[1-3]. Some M(BH4)x absorb NH3 as molecularstate to form ammine complex phases by following
chemical reactions,

In the case of NaBH4, the plateau corresponding toformation of liquid Na(NH3)2BH4 appeared at 0.09 MPa.
After the plateau region, the liquid solution of NH3 andNaBH4 Na(NH3)xBH4 (x>2) is formed. When NH3 in thesolution independently exists, the 1H NMR signal of NH3should be split into three peaks by N-H coupling due tonuclear spins of 14N (1, 0, −1). However, the peak splitting
was not observed for the Na(NH3)xBH4 solution phasealthough the peak split was observed in pure liquid NH 3.
Furthermore, the positions of signals corresponding toboth of H in NH3 and in (BH4)− are synchronously shiftedwith increase in NH3 composition. The above results
suggest that H+ in NH3 interacts with H− in (BH4)− eachother, and the chemical states are changed with the NH 3
concentration.

M(BH4)x + nNH3  M(NH3)n(BH4)x.
It is expected that the interesting behaviors are revealed
for ammine complexes of borohydrides due to interaction
between coexistent H− in (BH4)− anion and H+ in NH3.
However, detailed states of the hydrogens, reaction
mechanism, and the fundamental properties of theamminecomplexesarenotunderstoodyet.
In this work, the variation of chemical state of H in M(BH4)x
with NH3 absorption are investigated by various
spectroscopy and discussed.

This work was partially supported by JSPS KAKENHI
Grant-in-Aid for Scientific Research on Innovative Areas“Hydrogenomics”, No. JP19H05059

Experimental

References

The NH3 absorption reactions of various M(BH4)x (M=Li,
Na, Mg, Ca) are investigated by pressure-compositionisotherm (PCI) measurements, in-situ nuclear magnetic
resonance (NMR), Fourier transform infrared (FT-IR), andRaman spectroscopy under NH3 pressure.

[1] T. Zhang, et al., ACS Applied Energy Materials 1, 232242 (2018).
[2] T. Zhang, et al., Joule 2, 1522-1533 (2018).
[3] K. Nakajima, et al., Chem. Commun. 55, 2150-2153(2019).

Hiroki Miyaoka

2008: PhD, Graduate School of Advanced Sciences of Matter, Hiroshima University, Japan
2007-2009: Research Fellow of JSPS, Institute for Advanced Materials Research (IAMR), Hiroshima
University, Japan
2009-2011: Assistant Professor (Special appointment), IAMR, Hiroshima University, Japan
2011-2016: Lecturer, ISSD, Hiroshima University, Japan
2016-2017: Associate Professor, IAMR, Hiroshima University, Japan
2016-present: Associate Professor, Natural Science Center for Basic Research and Development,
Hiroshima University, Japan

Corresponding author: Hiroki Miyaoka, Email: miyaoka@h2.hiroshima-u.ac.jp, Tel: +81-82-424-4604

48

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

LOCAL DIFFUSION COEFFICIENT OF DEUTERIUM
THROUGH STAINLESS STEEL MEMBRANEPERMEATING

N. Miyauchi1, T. Iwasawa1,2, Y Murase1, S. Takagi3, Akiko N. Itakura1
1. National Institute for Materials Science, 2. University of Tsukuba, 3. Toho University
We have developed an operando hydrogen microscope to visualize hydrogen permeation. Deuterium was supplied fromthe back of the stainless steel sample for a long period of time during the experiment to visualize the deuterium
permeation. After 65-hour experiment, we found that the deuterium showed different permeation volume and diffusion
speed depending on the grains. We calculated the diffusion coefficient of each grain from the time-dependent deuterium
permeation.

Introduction
It is important to clarify the behaviour of hydrogen inmetals to understand the mechanisms of hydrogen
embrittlement and storage. There are various models ofhydrogen diffusion in metal, none of which are definitive.
We have studied the behaviour of hydrogen in metals by
visualizing sequentially spatial distributions of hydrogen
permeated through a stainless-steel membrane.
It is crucial to understand a permeation phenomenon ofhydrogen in a metal that is formed from many crystal
grains and grain boundaries, to develop fine structural
materials for hydrogen production, storage and transport.

Experimental

opposite side of the sample in UHV room, and observed
deuterium by DIET method.

Results and Discussion
Permeated deuterium was visualised in 520 hydrogenmaps during the 65-hour experiment. We couldn't define
any patterns that reflected local difference of deuterium
until 20 hours after exposure. The difference in theamount of permeation, which depends on the grain
shape, appeared in maps around 40 hours later.
We found a significant difference in the diffusion
coefficient of deuterium at local position by focusing on
the permeation speed and volume of deuterium at eachregion.

The experiment was performed in the operandohydrogen microscope1,2, which visualized hydrogen
permeated through metal in ultrahigh vacuum condition(UHV). We exposed hydrogen or deuterium to the backside of the metal sample. After being absorbed into thesample, the hydrogen or deuterium diffused to the
opposite side, then it was visualized in two dimensions bydesorption induced by electronic transition (DIET)
method.
The experimental setup is shown in Fig.1. Twodimensional pulse counting system is synchronized withthe scanning electron beam. The sample is SUS304
stainless steel which has austenite structure withmartensite dislocations made by cold working. The
diameters of austenite grains are 50-150 m and thethickness of the sample is 100 m.

Fig. 1 Experimental set up
References

The sample temperature was 473 K. The pressure of
deuterium introduced to the back side of the sample was
1×105 Pa. We waited for the permeated deuterium on the[2] N. Miyauchi, et al., Applied Surface Science 492,
280–284 (2019)[1] N. Miyauchi, et al., Scripta Materialia 144, 69–73(2018)NIMS Special Researcher
Surface Physics and Characterization Group, National Institute for Materials Science
Received a Doctor's degree from Toho University in the field of atom and molecular physics in 2007.

Dr.NaoyaMiyauchiHas careers in Hokkaido University (2007-09), KEK (2009-11) and Riken (2009-11, 2012-19), Tokyo
Metropolitan University (2012), Gakushuin University (2012-13), The University of ElectroCommunications (2013-14), Toho University (2014-17).

Corresponding author: Naoya MIYAUCHI, Email, MIYAUCHI.Naoya@nims.go.jp

49

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ANHYDROUS PROTON CONDUCTIVITY OF
IMIDAZOLIUM HYDROGEN DICARBOXYLATES
H. MORI1, Y. Sunairi1, S. Dekura1, A. Ueda1,2, T. Ida3, M. Mizuno3, Y. Hori4, and Y. Shigeta4
1 The University of Tokyo, 2 Kumamoto University, 3 Kanazawa University,4 University of Tsukuba
In order to obtain the strategy towards high-performance anhydrous organic proton conductors, the proton-conductivity
measurements, the X-ray structure analyses, and the solid-state 2H-NMR experiments were performed by using single/powdered crystals of the three imidazolium hydrogen dicarboxylates, (1) succinate, (2) glutarate, and (3) fumarate salts.
The results revealed that i) the hydrogen (H)-bond network structures, ii) small ΔpKa between constituent acid and basemolecules, and iii) the libration motion of imidazolium molecules are the key factors for the anhydrous proton conductivity.
This study suggests that not only the “static” H-bond network structures but also the “dynamics” of the constituent
molecules synergistically play important roles in the anhydrous proton conduction.

Introduction
Anhydrous proton conductors are important materials
owing to not only their potential applications for solid
electrolyte above 100 °C but also scientific interests for the
proton conduction mechanism mediated not by watermolecules. The rich designability of organic materials
enable us to design and synthesize proton conductors,
and to systematically investigate structure-property
relationship and proton conduction mechanism fordevelopment of anhydrous purely organic proton
conductors with high performance. In this study,
anisotropic proton conductivity reflecting moleculararrangements [1], effects of proton donating abilities (pKa)of constituent molecules, and molecular dynamics effects
on anhydrous proton conductivity were investigated using
high-quality single/powdered crystals of a series of theimidazolium hydrogen dicarboxylates.

directions of (1)-(3) indicates that the proton conduction
occurs more readily in the H-bond networks than in its
perpendicular direction. About (ii), in comparison with (1)(3), the proton donating ability of dicarboxylic acids isturned to be a key factor for tuning the proton conductivityof these salts, that is, small ΔpKa between constituent acidand base molecules is one of the important factors toachieve the anhydrous proton conductivity. For (iii), theclear positive correlation between proton conductivity andlibration angle of imidazole by solid-state 2H-NMR
measurement indicates that the libration motion of
imidazolium cations promotes anhydrous proton
conduction in imidazolium hydrogen dicarboxylates.
These results demonstrate that both of the H-bondnetwork structures and the dynamics of organic molecules
synergistically play important roles in the anhydrous
proton conduction. *Experimental / Computational
Single crystals of imidazolium hydrogen dicarboxylates,(1) succinate, (2) glutarate, and (3) fumarate salts wereobtained by slow evaporation. The crystal structure
analyses at T = 23−103 °C, the measurements of thermal
stability by DSC, proton conductivity by an ac impedance
analyser, and solid-state 2H-NMR were performed.

Results and Discussion
In this research, the effects of (i) the arrangements, (ii)proton donating abilities, and (iii) dynamics of constituent
molecules on the proton conductivity were investigatedusing high-quality single crystals of a series of theimidazolium hydrogen dicarboxylates. As for (i), the large
anisotropy of the conductivity between the intra and interFig. 1 Molecular arrangement in the high-T structure of
imidazolium hydrogen succinate. The orange belt, reddashed lines, brown dashed lines, gray dashed lines, andblue arrows represent the possible proton conducting path,H-bonds, disordered atom···O contacts, C−H···O contacts,and direction of the libration motion.

References[1] Y. Sunairi et al., J. Phys. Chem C, 122, 11623 (2018).

Hatsumi MORI is the Director and professor at the Institute for Solid State Physics (ISSP), theUniversity of Tokyo. She obtained her D. Sc. degree from the University of Tokyo in 1992. She wasa technical associate at ISSP (1986-1989), a researcher at International Superconductivity
Technology Center (1989-2001), and an associate professor at ISSP (2001-2010). Since 2010, she
has been a professor at ISSP. She has worked on the development and the characterization ofmolecular functional materials by utilizing molecular degrees of freedom, e.g. novel molecularelectron-proton coupled conductors, purely organic proton conductors for fuel cell, etc..*
Hatsumi MORI
Corresponding author: Hatsumi MORI, hmori@issp.u-tokyo.ac.jp, 81-47136-3201

50

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ADVANCED MOLECULAR MATERIALS BASED ON PHOTOCHROMIC
DIARYLETHENES BEARING HYDROGEN-FUNCTIONAL UNITS
Masakazu Morimoto1, Ayaka Ishizeki1, Masahiro Irie1
1 Department of Chemistry, Rikkyo University, 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan
Toward the development of molecular devices with advanced hydrogen functions we synthesized photochromic
diarylethene molecules having hydrogen-bonding or proton-accepting units and examined their photochemical andphotophysical properties. Diarylethene derivatives having imidazole rings formed intermolecular hydrogen-bonding chain
structures in single crystals. A fluorescent diarylethene derivative having a dimethylamino group changed the fluorescent
properties in response to pH change.

Introduction
Photochromic molecules, which reversibly change theircolors as well as other physical and chemical properties
upon photoisomerization, have a potential for
applications to optoelectronic devices, such as opticalmemory media, optical switches, and displays. Among
various types of photochromic molecules, diarylethene [1]is one of the most promising candidates for practicalapplication because of its outstanding properties, such as
thermal stability of two isomers, fatigue resistance, andrapid response (Fig. 1). Here we examined theintegration of photochromic reactions with hydrogen
functions, such as photochromic crystals having
intermolecularhydrogen-bonding
networks
andphoto/proton-responsive fluorescent molecules, toward
the development of advanced molecular functional
devices.
UV
Vis.
Open-ring isomer(Colorless)

Closed-ring isomer(Colored)Fig. 1 Photoisomerization of photochromic diarylethene.

Experimental
Single crystals of diarylethene derivatives were preparedby recrystallization from appropriate organic solvents andwere subjected to X-ray crystallographic analysis andpolarized
absorption
spectralmeasurement.
Fluorescence spectra and fluorescence quantum yields

in solutions were measured with a fluorescence
spectrophotometer or an absolute PL quantum yieldmeasurement system.

Results and Discussion
Diarylethene derivatives possessing imidazole rings ashydrogen-bonding units were synthesized. X-Ray
crystallographic analysis revealed that most of thederivatives form one-dimensional chain structures of theimidazole rings via intermolecular hydrogen-bonding
interactions in the crystal. Upon alternate irradiation withultraviolet (UV) and visible light the diarylethenemolecules underwent reversible photoisomerization evenin the hydrogen-bonding networks.
A fluorescent diarylethene derivative [2] having a
dimethylamino group underwent turn-on mode switchingof fluorescence upon UV induced ring-closing
isomerization and also changed the fluorescent
properties in response to pH change. Upon addition ofstrong acid, the fluorescence spectrum of the closed-ringisomer showed a significant hypsochromic shift and thefluorescence intensity dramatically increased. Such pHresponsive property is ascribed to the suppression of
intramolecular charge transfer character upon the
protonation of the electron-donating dimethylamino group.

References[1] M. Irie, T. Fukaminato, K. Matsuda, S. Kobatake,Chem. Rev. 114, 12174 (2014).
[2] M. Irie, M. Morimoto, Bull. Chem. Soc. Jpn. 91, 237(2018).

Masakazu Morimoto received his B.S. (2001), M.S. (2003), and Ph.D. (2006) degrees from Kyushu
University. From 2006–2007, he engaged as a postdoctoral researcher at the Graduate School of
Science, Tohoku University. In 2007, he moved to the Department of Chemistry, Rikkyo University,
as an assistant professor. He was appointed as an associate professor at the same university in2010 and was promoted to a full professor in 2017. His research interests include the developmentof advanced photofunctional molecules and materials based on photochromic diarylethenes.
Masakazu Morimoto

Corresponding author: Masakazu Morimoto, m-morimoto@rikkyo.ac.jp, +81-3-3985-4695

51

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HIGH-PRESSURE AND HIGH-TEMPERATURE SYNTHESIS OF NOVEL ALTM (TM=ZR, HF) HYDRIDES
Shin Murakami1,2, Hiroyuki Saitoh1,2, Tetsu Watanuki1,2
1 National Institutes for Quantum and Radiological Science and Technology, 2 University of Hyogo
For the purpose of synthesizing novel Al-TM (TM = Ti, Zr, and Hf) hydrides with high Al composition, starting materials(sintered compacts with molar ratios with Al:Zr = 2:1, 3:2, 1:1, 2:3 and 1:3, Al3Hf, and Al2Hf alloys) were hydrogenated at
9 GPa and 750°C. Novel hydride Al2HfH~4.7 with high Al composition was synthesized. For Al-Zr system, novel hydrides
with high Al composition have not been achieved yet, though novel Al2Zr3H~5.6 was obtained.

Introduction
We have searched for novel hydrides with high Al
composition and have synthesized several kinds of themat high-pressures and high-temperatures, where reactivity
of hydrogen is increased. For Al-TM (TM = Ti, Zr, and Hf)hydrides, hydrides with low Al compositions have beenreported [1-3], but those with high Al compositions havenot been reported. The purpose of the present study is tosynthesize novel Al-TM hydrides with high Al composition.

For Al-Hf system, novel hydride Al2HfH~4.7 with high Al
composition was obtained by hydrogenating Al2Hf alloy(Fig. 1 bottom). The formed hydride was a single phase,
which was confirmed by a SEM-EDS measurement.
X-ray diffraction profiles of Al2Zr3H~5.6 and Al2HfH~4.7
seems to be similar as shown in Fig. 1, though atomic ratioof Al and TM are different. Now we are trying to evaluate
crystal structures of the hydrides.

Experimental
For Al-Zr system, the starting materials were sinteredcompacts with molar ratios of Al:Zr = 2:1, 3:2, 1:1, 2:3, and1:3. They were prepared by sintering powdered mixture at
1200°C for 1 h using an IR furnace. For Al-Hf system, Al3Hfand Al2Hf alloys that were prepared by an arc melting
furnace were used. A cubic-type multi-anvil press wasused to generate high-pressure and high-temperature
conditions. Starting materials were compressed to 9 GPa,then heated to 750°C, and kept in hydrogen fluid. The
hydrogenated samples were cooled to the room
temperature and depressurized to the ambient pressure.
The recovered samples were analysed by a powder X-ray
diffractometer and a SEM-EDS.

Results and Discussion

Fig. 1 X-ray diffraction profiles of Al2Zr3H~5.6 and Al2HfH~4.7.

For Al-Zr system, a novel hydride Al2Zr3H~5.6 was obtained
when the sintered compact with the molar ratio of Al:Zr =2:3 was hydrogenated (Fig. 1 top). This hydride was amodification of known Al2Zr3H~3.0 [2] with higher hydrogenconcentration. Partial formation of Al2Zr3H~5.6 wasobserved when other starting materials were used. A
formation of novel hydride with high Al composition was
not achieved.

References[1] K. Hashi, K. Ishikawa, K. Suzuki, and K. Aoki, J.
Alloys Compd., 356-357, 91-95 (2002).
[2] A. B. Riabov, V. A. Yartys, R. V. Denys, and B. C.
Hauback, J. Alloys Compd., 356-357, 91-95 (2003).
[3] B. Mishra, M. Ionescu, and T. Chandra, Materials
Science Forum, 783-786, 1686-1691 (2014).

Short CV
April, 2014 - March, 2018, Faculty of science, University of Hyogo, Japan
April, 2018 - Present, Graduate School of material science, University of Hyogo, Japan
Research topics
Shin Murakami“High-Pressure and High-Temperature Synthesis of novel Al-TM (TM=Ti, Zr, and Hf) hydrides”

Corresponding author: Saitoh Hiroyuki, saito.hiroyuki@qst.go.jp, Tel. +81-791-58-1014

52

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROGEN ON AND IN CERIAUNSATURATED HYDROCARBONSAND

HYDROGENATIONOF

Hans-Joachim FreundFritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin
Inspired by the report that oxides, and in particular ceria may be used as hydrogenation catalysts[1], depending on the
degree of reduction, we have started surface science studies on well-defined CeO2(111) films grown on a Ru(0001) single
crystal metal surface and studied the interaction of a fully oxidized ceria surface in comparison with a partially reduced
surface with respect to its interaction with hydrogen from the gas phase. We will show that a hydride is formed in the subsurface region in the case of reduced ceria leading to a re-oxidation of the ceria sublattice.[2-4] Also, the interaction withpropyne, both, regular and isotopically labelled with the ceria surface has been studied.[5]Introduction
Two mechanisms for H2 dissociation on metal oxidesurfaces have been identified:[6; 7] One is the homolytic
dissociation, which produces two hydrogen atoms at twooxygen sites, leading to the formation of two OH groups
and the concomitant reduction of two surface metal ions;the other one is the heterolytic (polar) dissociation, which
entails the formation of a hydride, H-, and a proton, H+, at
metal and oxygen sites, yielding M-H and OH species,
respectively. The H ad-atoms on metal oxide surfaces canmigrate into the subsurface region and further into the bulk
to form hydroxyl and hydride species therein.

Experimental / Computational
CeO2-x(111) thin film preparation, H2 treatment, andcorresponding XPS and Electron Energy Loss
Spectroscopy (EELS) measurements and Low Electron
Energy Diffraction (LEED) were performed in two ultrahighvacuum (UHV) systems with a base pressure of ~110-10mbar, which are described in detail elsewhere.[2]Results and Discussion
Figure 1 shows Ce 3d and O 1s X-ray Photoelectron
Spectroscopy (XPS) results on the freshly preparedCeO2-x(111) thin film. Spectra where recorded in bothnormal (=0°) and grazing (surface-sensitive) emission
geometry (=60°), which differ in the angle  between
surface normal and XPS analyzer.

Fig. 1 Ce 3d and O 1s XP spectra of CeO2-x(111) thinfilm in normal (0°) and grazing (60°) emission geometry:(a) Freshly prepared CeO2-x(111), (b) CeO2-x(111)
exposed to 10 mbar D2 at 300 K.
Figures 1 shows XP-spectra of reduced CeO2-x(111) films
upon interaction with molecular hydrogen. The clean
CeO2-x(111) thin film was exposed to 10 mbar D2 at 300 K
for 15 min. Figure 1 shows Ce 3d and O 1s XP spectra
obtained after D2 exposure. In the Ce 3d spectra, the Ce3+
concentration significantly decreases after 10 mbar D2
exposure in both normal and grazing emission modes.
This phenomenon occurs both in surface-near and deeper
layers. First experiments on acetylene and propyne
adsorption and reaction have been performed on thevarious oxidized and reduced Ceria films.

Acknowledgments
The presenting author acknowledges the collaboration on
the presented scientific projects with: S. Shaikhutdinov, K.
Werner, A. Plucienik, H. Kuhlenbeck, J.-Q. Zhong from the
FHI as well as W. Huang and his group from the USTC.

References
[1]
[2]
[3]
[4]
[5]
[6]
[7]

G. Vilé, et al., Angew. Chem. Int. Ed. 53, 1206912072 (2014).
K. Werner, et al., J. Am. Chem. Soc. 139, 1760817616 (2017).
Z. Li, et al., Angew. Chem. Int. Ed. 58, 14686-14693(2019).
A. Plucienik, et al., submitted, (2019).
J.-Q. Zhong, et al., submitted, (2019).
V.E. Henrich, et al., in, Cambridge University Press,
Cambridge, UK, 1994, p. 247.
J.L.G. Fierro, Metal Oxides: Chemistry andApplications, CRC Press, Boca Raton, FL, 2006.

Hans-Joachim Freund is a scientific member at the Fritz-Haber-Institut der Max-Planck-Gesellschaft
in Berlin where he was the head of the Department of Chemical Physics from 1995 until March
2019. The department was dedicated to the study of model catalysts, applying a large number oftechniques and instruments, some of which were newly developed within the department toinvestigate oxide surfaces and oxide metal interfaces. He received the Gaede-Langmuir Award of
the American Vacuum Society and is the recipient of the 2015 Michel Boudart for the Advancementof Catalysis by the North American Catalysis Society and the European Federation of Catalysis
Societies. In 2019 he received the prestigious ACS Award in Surface ChemistryHe has held a
Hans-Joachim
number of named lectureships around the world. He has educated more than 130 PhD students andFreundcollaborated with more than 80 postdoctoral associates.
Corresponding author: Hans-Joachim Freund, freund@fhi-berlin.mpg.del, Tel. +49 30 8413 4100
53

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CATALYST DESIGN FOR PRODUCTION AND DECOMPOSITION OFAMMONIA AS A HYDROGEN CARRIER
Katsutoshi Nagaoka1
1Department of Chemical Systems Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa,
Nagoya 464-8603, JAPANDevelopment of a H2 storage and transportation system using NH3 has been motivated by the desire to achieve a carbonfree society. To establish such a system, we found that composite rare-earth oxide supported Ru catalysts like
Ru/La0.5Ce0.5O1.75 and Ru/Ba0.1La0.45Ce0.45O1.68 exhibit high ammonia synthesis rates under mild reaction condition. On
the other hand, we demonstrated H2 production process by supplying ammonia and oxygen at room temperature to a pretreated Ru/γ-Al2O3 catalyst without external heating.

Introduction
Ammonia is an important chemical feedstock, andmore than 80% of the synthesized ammonia is used to
produce fertilizer. Ammonia is also being considered as a
H2 carrier for utilizing renewable energy (1) because it has
a high energy density (12.8 GJ m -3) and a high hydrogencontent (17.6 wt%), (2) because infrastructure forammonia storage and transportation is alreadyestablished, and (3) because CO2 is not emitted whenammonia is decomposed to produce H2. To establish sucha system, development of advanced catalytic process forammonia synthesis and decomposition is strongly
demanded.

among oxide-supported Ru catalysts reported so far (350oC, 1.0 MPa)3.
On the other hand, we discovered that H2 is producedby supplying ammonia and oxygen at room temperature toa pre-treated RuO2/γ-Al2O3 catalyst without external
heating4. The heat evolved by ammonia adsorption onto
the catalyst increases its temperature to the catalytic autoignition temperature of ammonia, and subsequently H2production by ammonia oxidative decomposition begins.
NH3 synthesis(H2 storage)

Transportation

NH3 decomposition(H2 production)

Fuel Cell

Results and Discussion
At first, we investigated influence of reduction
temperature on the ammonia-synthesis activity of
Ru/La0.5Ce0.5O1.75, a catalyst consisting of Ru supported
on a La0.5Ce0.5O1.75 solid solution1. After pre-reduction at
the unusually high temperature of 650 oC, the catalyst
exhibited high ammonia synthesis activity from 300 to 400
oC at 1.0 MPa. This catalyst consisted of fine Ru particles
anchored on a heat-tolerant complex-oxidic support.
During pre-reduction, the particle size of the Ru particles
remained unchanged, but the particles became partiallycovered with partially reduced La0.5Ce0.5O1.75. A strong
interaction between the Ru active sites and the reduced
support accelerated the rate-determining step, N2
dissociation, of ammonia synthesis. By using this strategy,
we found that Ru/Pr0.5La0.5O1.5 reduced at 650 oC shows
comparable activity with Ru/La0.5Ce0.5O1.752. Furthermore,
we discovered that Ru/Ba0.1La0.45Ce0.45O1.68 pre-reduced
at 700 oC catalyses ammonia synthesis at the highest rate

EngineNH3

O2

Room temperature> 300 ºC

RuO2

Ru

γ-Al2O3

γ-Al2O3NH3 adsorption
and heat evolution

Oxidative
decomposition

N2
H2

H2O
External heat supply

Fig. 1. Renewable H2 storage and transportation systemusing NH3 as a hydrogen carrier.

References[1] Y. Ogura et al. Chem. Sci., 9 (2018) 2230.
[2] Y. Ogura et al. ACS Sustain. Chem. Eng., 6 (2018)17258.
[3] K. Sato et al. ChemRxiv, doi.org/10.26434/chemrxiv.
7763657.v1.
[4] K. Nagaoka et al. Sci. Adv., 4 (2017) e1602747.

Katsutoshi
Nagaoka

Katsutoshi Nagaoka received his Ph. D. at Tokyo Institute of Technology in 2001. After Post Doctor
in the university and Humboldt fellow in Technical University in Muenchen, he moved to Oita University
as a Lecturer in 2004. Next year he was promoted to an Associate Professor. Since April in 2019, hehas been appointed as a Full Professor in Nagoya University. His reserch interests involve
heterogeneous catalysis for solving global energy and environmental issures. He was awarded The
Japan Petroleum Institute Prize for Encouragement (2009) and Catalysis Soxiety of Japan Prize for
Encouragement (2010).

Corresponding author: Katsutoshi Nagaoka, nagaoka.katsutoshi@material.nagoya-u.ac.jp, Tel.+81-(0)52-789-3388

54

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

THE ROLE OF HYDRIDES IN N2 REDUCTION AND NH3 FORMATION
Jianping Guo, Wenbo Gao, Peikun Wang, Fei Chang and Ping Chen
Dalian Institute of Chemical Physics, Chinese Academy of Sciences
Abstract: Catalytic ammonia synthesis from dinitrogen and dihydrogen is usually carried out over Ru or Fe metal surface
where active centers composed of multiple metals mediate electron and mass transfers. The adsorption energies andreaction barriers of reacting species on the active centers are correlated resulting in effective ammonia synthesis under
mild conditions unattainable. In this talk I will show that alkali or alkaline earth metal hydride can be actively involved in
the activation and conversion of dinitrogen and change the scenario of catalytic ammonia synthesis.

Introduction
Ammonia is a promising carbon-free energy carrier, but itis synthesized industrially under harsh conditions.
Synthesizing ammonia under lower temperature andpressure could therefore improve its prospects as achemical means to store and transport energy.
Tremendous research efforts have been devoted to this
topic over decades, which significantly enrich thefundamental understanding of heterogeneous catalysis.
Conventional catalysts are based on Fe and Ru metals,
additives such as oxides of alkali or alkaline earth metals
play important roles in modifying the electronic/structuralproperties of Fe or Ru.

Results and Discussion
With the understanding of the interactions of
hydrides/imides of alkali and alkaline earth metals (AMfor short) with 3d metals and their nitrides, we recently
developed a catalyst system, i. e., AMH-3d transition
metals, for NH3 synthesis. Both early and late 3d metals
are highly active upon combining with hydrides. The
unique chemistry among transition metals, alkali/alkaline
earth metals, N and H creates an energy-favourable
pathway allowing NH3 synthesis under mild conditions,
i.e., catalytic NH3 formation is detectable at 150 °C over
the Mn-, Fe- and Co-LiH (or BaH2) composite catalysts,
respectively (Figure 1).[1, 2]
We further identified alkali and alkaline earth metal
imides as nitrogen carriers that mediate ammonia
production via a two-step chemical looping process.
Nitrogen is first fixed through the reduction of N2 by alkali
or alkaline earth metal hydrides to form imides andsubsequently, the imides are hydrogenated to produce
NH3 and regenerate the hydrides. The oxidation state ofhydrogen therefore switches among -1 (hydride), 0 (H2),and +1 (imide and NH3). Late 3d metals especially Ni andCo can accelerate the reaction rates of both steps. The
chemical loop mediated by BaNH and catalyzed by Ni
produces NH3 with unprecedented rates in thetemperature range of 100-300 °C and atmosphericpressure (Figure 1).[3]Fig. 1 Ammonia production via thermal catalytic
process catalyzed by 3d TM-LiH (Upper panel) andchemical looping process mediated by alkali or
alkaline earth imides (Bottom panel)

References[1] J. P. Guo, P. K. Wang, G. T. Wu, A. Wu, P. Chen etal., Angew. Chem. 54, 2950 (2015)[2] P. K. Wang, F. Chang, W. B. Gao, J. P. Guo, G. T.
Wu, T. He and P. Chen, Nature Chem. 9, 64 (2017)[3] W. B. Gao, J. P. Guo, P. K. Wang, Q. R. Wang, F.
Chang, Q. J. Pei, W. J. Zhang, L. Liu, and P. Chen, Nat.
Energy 3, 1067 (2018)*

Ping Chen is a professor and division head of Hydrogen Energy and Advanced Materials, Dalian Instituteof Chemical Physics (DICP), Chinese Academy of Sciences (China).

PING CHEN

Her primary research interests include the materials development for hydrogen storage andheterogeneous catalysis. She pioneered the research in the amide-hydride system for hydrogen storage
and the alkali/alkaline earth hydride-transition metal composite catalyst system for NH 3 synthesis. She has
more than 170 peer-reviewed journal articles, delivered ca. 70 invited/keynote speeches.

Corresponding author: Ping Chen, pchen@dicp.ac.cn, Tel 86-411-84379905.

55

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROGENATION OF FORMATE ON THE Pd-Cu SINGLE ATOM ALLOY
MODEL CATALYSTS
Jun Yoshinobu, Shion Nakano, Takuma Tokunaga, Shunsuke Tanaka and Kozo Mukai
The Institute for Solid State Physics, The University of Tokyo
Abstract
We investigated the adsorption of formic acid, the decomposition into bidentate formate and the subsequent hydrogenationof bidentate formate on the Pd-Cu(997) single atom alloy model catalyst using SR-X-ray photoelectron spectroscopy (XPS).
The present XPS results indicate that hydrogenation of bidentate formate occurs below 300 K.

Introduction

Results and Discussion

Methanol synthesis from carbon dioxide has been of greatinterest from the viewpoint of a renewable carbon source
and global environmental problems. Cu/ZnO-based
catalysts have been used to synthesize methanol from H2and CO2 [1]. In the reaction process, formate is formed asa stable intermediate on the catalyst surface. The
hydrogenation of formate on the Cu substrate is importantfor methanol synthesis, but Cu is not very active for H2
dissociation due to the high activation energy (0.4 eV).
Here, we have used Pd as a cocatalyst on the Cu surface
for H2 dissociation because the activation energy of the
dissociation on Pd(111) surface is almost no barrier [2].
We have prepared a Pd single atom alloy model catalyst
on the Cu substrate, where a small amount of Pd atoms
were deposited and embedded in the first layer of Cu
surface. This Pd atom provides the active site for hydrogendissociation without losing the catalytic nature of Cu. In thisstudy, we investigated the formation of formate from formic
acid and the hydrogenation of formate on the single atom
alloy Pd-Cu model catalyst using high-resolution X-ray
photoelectron spectroscopy (XPS).

We measured C1s, O1s, Pd3d XPS spectra for theadsorption and decomposition processes of formic acidinto bidentate formate on Pd-Cu(997). The peakassignments were referred to our previous study about theadsorption and decomposition of formic acid on Cu(111)and Cu(997) [3]. At 80 K, a dominant peak was observed
at 290.0 eV, which is assigned to molecular formic acid. A
small component was also observed at 288.4eV, which is
assigned to monodentate formate. By heating to 150 K, apart of formic acid was desorbed and the amount of
monodentate species was increased. By heating to 300 K,
all adsorbed species become bidentate formate (287.5 eV).

Experimental
After the preparation of the Cu(997) clean surface, wedeposited Pd atoms on the Cu(997) clean surface at 380K.
Next, the Pd-Cu(997) surface was exposed to gaseous
formic acid at 80 K, and the sample was heated to 300 K
to form bidentate formate species. The bidentate formate
on Pd-Cu(997) was exposed to gaseous hydrogen at 80 K.
Finally, the H/formate/Pd-Cu(997) surface was heated tohigher temperature. We have measured XPS spectra foreach process. All XPS measurements were carried out
using the Phoibos100 system at BL-13B in KEK-PF.

Thus prepared bidentate formate on Pd-Cu(997) was
exposed to 800 L H2 at 80 K and subsequently heatedto
300 K. By this process, the bidentate formate O1s peak at
531.0 eV was decreased in intensity by ~20% and atomic
oxygen was newly observed at 529.4 eV (~10% of theoriginal bidentate formate). The C1s peak of bidentate
species was also decreased by ~20%. We propose that apart of bidentate species are reacted with adsorbedhydrogen atoms on Pd-Cu(997) and the desorption ofhydrogenated species (probably, formaldehyde andmethanol) occurs below 300 K.

References[1] J. Nakamura, et al., Topics in Catalysis. 22, 277(2003).
[2] G. Kyriakou, et al., Science. 335, 1209 (2012).
[3] Y. Shiozawa et al., submitted to J. Chem. Phys.
(2019).

Short CV 1989: Dr. Sci., Kyoto University, Department of Chemistry.
1989-1991: Postdoc., University of Pittsburgh, Department of Chemistry.
1991-1992: Postdoc., The Institute of Physical and Chemical Research (RIKEN).
1992-1997: Staff researcher, The Institute of Physical and Chemical Research (RIKEN).
1997-2007: Associate professor, The Institute for Solid State Physics, The University of Tokyo.
Jun Yoshinobu

2007-: Full professor, The Institute for Solid State Physics, The University of Tokyo.

Corresponding author: Jun Yoshinobu, Email: yoshinobu@issp.u-tokyo.ac.jp

56

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

DINITROGEN ACTIVATION BY MOLECULAR MULTIMETALLIC TITANIUM
POLYHYDRIDES
Takanori Shima,1,2 Zhaomin Hou1,21Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama

351-0198, Japan, 2Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako,
Saitama 351-0198, Japan
Abstract
Dinitrogen activation and hydrogenation by transition metal complexes have attracted much current attention. Here we
report the N2 activation by multinuclear titanium polyhydride complexes. We found that N 2 activation and hydrogenation
are achieved by the cooperation of the multiple metal sites, and the hydride ligands serve as the source of both electron
and proton, thus enabling the cleavage and hydrogenation of dinitrogen without extra reducing agents and proton sources.

Introduction
Dinitrogen activation and functionalization by moleculartransition metal complexes have attracted extensive
attention. This work presents multimetallic titanium
polyhydride complexes that react with N2 through N≡Nbond cleavage and N–H bond formation under mild
conditions. The activated nitrogen species can react witha wide range of organic acyl chlorides, leading to formationof the corresponding organic nitriles.

such as aromatic C−X (X = Cl, Br, I) bonds, nitro group,
aldehyde and chloromethyl moieties.

Results
Hydrogenolysis of the titanium trialkyl complex[Cp’Ti(CH2SiMe3)3] (Cp’ = C5Me4SiMe3) with H2 afforded
the trinuclear titanium heptahydride complex [(Cp’Ti)3(3H)(-H)6] (1) (Fig. 1). Complex 1 readily reacted with N2 (1atm) at room temperature, giving an imido/nitrido complex
2 via N–N bond cleavage and N–H bond formation.
Monitoring the reaction by 1H and 15N NMR revealed theinitial formation of a dinitrogen complex 3 with release of
two molecules of H2, followed by N–N bond cleavage to
give a dinitrido complex 4, and hydride migration fromtitanium to the -nitrido unit to give 2. Obviously, thehydride ligands in 1 served as the source of both electron
and proton for the dinitrogen cleavage and hydrogenation.
When the hydrogenolysis of [Cp’Ti(CH2SiMe3)3] with H2
was carried out in the presence of N2, a tetranuclear
diimido/tetrahydrido complex 5 was obtained. Complex 5
reacted with N2 (1 atm) to afford a mixed diimido/dinitrido
complex 6 with release of two molecules of H2 (Fig. 1).
Remarkably, the imido and nitride species in 6 could be
easily converted to nitriles through reaction with acidchlorides (Fig. 1). This transformation did not require any
extra reagents and was compatible with functional groups

Takanori ShimaFig. 1. Dinitrogen cleavage and hydrogenation by titanium
polyhydride complexes.

References[1] T. Shima, S. Hu, G. Luo, X. Kang, Y. Luo, Z. Hou,
Science 340, 1549 (2013).
[2] Guru, M. M.; Shima, T.; Hou, Z. Angew. Chem. Int.
Ed. 55, 12316 (2016).
[3] Shima, T.; Luo, G.; Hu, S.; Luo, Y.; Hou, Z. J. Am.
Chem. Soc. 141, 2713 (2019).

Takanori Shima was born in Osaka, Japan, in 1972. He obtained his Ph.D. degree in 2001 from Tokyo
Institute of Technology on a study of multinuclear polyhydrido complexes, under the supervision ofProf. Hiroharu Suzuki. He undertook postdoctoral research in the group of Prof. John A. Gladysz(Erlangen, Germany) as an Alexander-von-Humboldt fellow in 2002. In 2004, he joined RIKEN as a
special postdoctoral researcher in the Dr. Zhaomin Hou’s group. He was promoted senior researchscientist in 2011. His current research interests include development of new multimetallic polyhydrido
complexes and their use for activation of small molecules.

Corresponding author: Takanori Shima, Email: takanori_shima@riken.jp, Tel.+81-48-467-9380

57

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

DETERMINATION OF BCX HYDROGEN BINDING ENERGIES BY HIGHPRESSURE, VARIABLE TEMPERATURE 1H NMR SPECTROSCOPY
Bryson Nakamoto,1 Steve Christensen,2 Thomas Gennett,2 Craig M. Jensen1
Affiliation 1) University of Hawaii, Honolulu, HI, USA. 2) National Renewable Energy Laboratory, Golden, Colorado, USA.
Abstract. Boron doped graphene (BCx) has received considerable attention as a potential hydrogen storage material.
Notably, researchers at the National Renewable Energy Laboratory (NREL) have reported detection of strong (> 10 kJ.mol)hydrogen binding sites in BCx.[1] However, there have been conflicting reports regarding the hydrogen storage properties
of BCx materials. This follows a general trend that has persisted in efforts to quantify hydrogen capacities and binding
energies associated with physi-sorbed hydrogen. Typically, PCT and TGA analysis have been used to study the physicalproperties of physi-sorbed hydrogen. These methods have been shown to require very exacting procedures to obtainreproducible results. Additionally, BCx materials contain multiple types of hydrogen sorption sites which are difficult todifferentiate by PCT or TGA analysis. Alternatively, we have studied hydrogen binding by BCx materials using variabletemperature 1H nuclear magnetic resonance (NMR) spectroscopy. Our studies, conducted at ambient conditions andabove, allow us to focus on solely the strong hydrogen bindings sites. Monitoring the equilibrium populations of bound andfree hydrogen over the temperature range of 25 to 125 ˚C has allow the determination of a 11.4 kJ/mol binding energy forhydrogen in the sites of interest in NREL produced BCx. We will present the details of our studies as well as the implications
out results bring to bear on the nature of the strong hydrogen binding in BCx. The possible application of our novel
technique to other classes of hydrogen storage materials will also be discussed.
.

Fig. 1 1H NMR spectrum of BCx under 2000 psi ofhydrogen at 125 ˚C showing the line fitting analysis used
for deconvolution and quantification of the overlapping
signals of free and bound hydrogen.

Fig 2. Van’t Hoff plot of relative populations of free andbound hydrogen above the 25-125 ˚C temperature range
indicating a hydrogen binding energy of 11.4 kJ/mol.

References[1] J. Bult, J. Lee, K. O’Neill, C. Engtrakul, K.E. Hurst, Y.
Zhao, L. Simpson, P.A. Parilla, T. Gennett, J. Blackburn
J. Phys. Chem C. 116, 26138 (2012)

Dr. Craig Jensen is a full professor in the Department of Chemistry of the University of Hawaii. He has
authored or co-authored 148 peer-reviewed publications and 10 U.S. patents which have received
over 10,000 citations. Prof. Jensen was named the U.S. Department of Energy Hydrogen program’s“1999 Research Success Story” and presented with their “R&D” award in 2004. He was a co-chairmanof the 2006 International Symposium on Metal-Hydrogen Systems and the 2007 Hydrogen-Metal
Systems Gordon Research Conference. In 2003, Dr. Jensen founded Hawaii Hydrogen Carriers, LLC
and has since served as the company president.
Craig Jensen
Corresponding author: Craig Jensen, jensen@hawaii.edu 1-808-4457248.

58

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

NOVEL SPECTROSCOPY USING FAR UV LIGHT APPLIED FOR
ELECTRONIC STATES ANALYSES OF INTERFACIAL ELECTROLYTE AND
HYDROGEN STORING MATERIALS
Masaya Imai1, Ichiro Tanabe1,Tomonori Kakinoki1, Aki Suyama1, Taiki Sato1, Kenji
Miyatake2, Kenichi Oyaizu3, Ken-ichi Fukui1
1Grad. Sch. Engineer. Sci., Osaka Univ., 2Clean Research Energy Center, Univ. Yamanashi, 3Dept. Appl. Chem., Waseda

Univ.
Abstract : A novel spectroscopic method which can measure absorbance spectra close to the electrode underelectrochemical conditions in the far UV region (EC-ATR-FUV) was developed and successfully applied to the analyses ofpotential dependent behaviour of electrolyte close to the electrode and to the identification of electrolytic hydrogen storingmaterials.

Introduction
Identification of the electronic states of chemical species
at the electrode interfaces is important for understanding
the electron transfer (ET) process and the chemicaltransformation occurring in accordance with the ET
process for the electrochemical devices. Recently, we
have developed a novel spectroscopic method which canmeasure absorbance in the far UV region close to theelectrode under electrochemical conditions (EC-ATRFUV) and reported its application to such interfacial
analyses [1,2]. In the far UV region with the attenuatedtotal reflection (ATR) configuration (Fig.1), thepenetration depth, which corresponds to the evanescentwave length, is short (<50 nm), thus enabling one tochoose the interfacial electronic transition. In the present
study, we report some examples of this novel analysis
including the behavior of electrolytic hydrogen storing
polymers [3].

Experimental / Computational
The developed EC-ATR-FUV (Fig. 1) was used formeasuring the interfacial absorbance in far UV and UV
region. Experimentally obtained spectra were analyzed bytime-dependent density functional theory (TD-DFT)
calculation.

Results and Discussion
As an example of electrode potential dependent
behavior, inter-ion electron transition for the ionic liquid

which is particularly enhanced at positive electrodepotential, will be explained [1].
Then, the hydrogen storing behaviour in accordance withthe electrolytic transformation of ketone/alcohol polymer(fluorenone /fluorenol) (Fig.1).
tFig. 1 Schematic of EC-ATR-FUV and its application to ahydrogen storing material.

References[1] I. Tanabe, A. Suyama, T. Sato, K. Fukui, Anal. Chem.
91, 3436 (2019).
[2] I. Tanabe, A. Suyama, T.Sato, K. Fukui, Analyst 143,
2539 (2018).
[3] R. Kato, K. Yoshimasa, T. Egashira, T. Oya, K.
Oyaizu,H. Nishide, Nat. Commun., 7, 13032 (2016).

Ken-ichi Fukui received his Doctor of Science from the University of Tokyo in 1994. He has been a
Professor in Chemistry at Osaka University since 2008 after his research career at the University ofTokyo and Tokyo Institute of Technology. His present research interests cover the microscopic
mechanism of catalyses at solid surfaces/interfaces and the molecular view of electric double layer atliquid/solid interfaces for efficient energy conversion. He has also been working as an Editor of Surface
Science (Elsevier) since 2015.

Ken-ichi Fukui

Representative awards he received are Young Researcher Award in Surface Science from the KaoFoundation for Arts and Sciences (2006), Fellow of the Surface Science Society of Japan (2012), ,Nanoprobe Technology Award from the JSPS (2015), and the CSJ Award for Creative Work from
Chemical Society of Japan (2017).

Corresponding author: Ken-ichi Fukui, E-mail: kfukui@chem.es.osaka-u.ac.jp, Tel.:+81-6-6850-6235

59

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ELECTRODEPOSITED COPPER CATALYST FOR CO2 REDUCTION
REACTION
Jinqiu Zhang, Rui Zhang, Xin Zong, Yueping Xiong, Peixia Yang, Maozhong An
MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry andChemical Engineering, Harbin Institute of Technology, Harbin, 150001, PR China
Abstract Using electrochemical methods to reduce CO2 has the advantages of mild reaction conditions and clean energy
sources. Metallic copper as the catalyst for the reduction of CO2 to hydrocarbons is attractive to researchers. Nanoporous
copper films were prepared by electrodeposition and electrochemical etching. The catalytic properties of electroreductionof CO2 to ethylene and ethane were investigated.

Introduction
The concentration of atmospheric CO2 has risen
continuously due to accelerated burning of fossil fuel year
by year. Electrochemical reduction of CO2 has someadvantages such as reacting in mild conditions and using
clean energy sources. Cu-based catalysts, including Cu
nanoparticles, nanoporous Cu and Cu alloys, werestudied by many researchers for improving the catalyticalconversion efficiency of CO2 to chemical fuels. In this work,
Nanoporous copper films were electrodeposited and thecatalytic performances were measured.

Experimental
Cu-Zn alloy was electrodeposited on a carbon paper or astainless steel plate from the electrolyte containing CuSO4
and ZnSO4. And then the sample was put into a dilute
sulfuric acid for dissolving Zn in the Cu-Zn alloy andremaining nanopores in the Cu film. The catalytic
performance of nanoporous copper was tested in anelectrolyte of 0.1 mol/L KHCO3 at a constant potential byusing graphite electrode and Ag/AgCl electrode were usedas the counter electrode and the reference electrode,
respectively.

Results and Discussion
Cu-Zn alloys with different Zn contents and different film
thickness could be obtained by adjusting electrodepositon
process. After dissolving Zn, the porous structure of themetal layer was observed as Fig.1 (b) shown. The content
of Cu and Zn in the porous metal layer after de-alloying
was 92.51 at% and 1.07 at%. CO2 was electroreductively
reduced at a constant potential of -1.4 V, and the Faraday
efficiency of the C2 product (ethylene and ethane) was
more than 10%.

Fig. 1 (a) and (b) SEM images of porous
copper on carbon paper; (c) contents of porous
copper; (d) products of CO2 reduction reaction
at -1.4V vs. RHE.
References[1] D. Kim, J. Resasco, Y. Yu, A.M. Asiri, P. Yang, Nat.
Commun. 5，4948 (2014)[2] Z. Weng, X. Zhang, Y. Wu, S. Huo, J. Jiang, W. Liu,
G. He, Y. Liang, H. Wang, Angew. Chem. Int. Ed. 56，
13135 (2017)[3] T.T.H. Hoang, S. Ma, J.I. Gold, P.J.A. Kenis, A.A.
Gewirth, ACS Catal. 7, 3313 (2017)

Associate Prof. Dr. Jinqiu ZHANG was born in 1979 in Heilongjiang, China. Jinqiu Zhang graduatedwith a Ph.D in Chemical Engineering and Technology from Harbin Institute of Technology (HIT) in2009. She works at Department of Electrochemical Engineering of HIT and her research filed iselectrodeposition of functional materials.

Jinqiu Zhang
Corresponding author: Jinqiu ZHANG, zhangjinqiu@hit.edu.cn, +86-451-86413721.

60

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

NUCLEAR QUANTUM EFFECTS OF HYDROGEN IN MATERIALS
Motoyuki Shiga
Center for Computational Science and e-Systems, Japan Atomic Energy Agency
Ab initio path integral molecular dynamics (PIMD) is a first-principles technique, which is able to compute the thermal
equilibrium of a system where the whole entity of many electrons and nuclei are assumed to be quantum mechanicalparticles. Here I will introduce two recent applications of the method; the structure of liquid water in the ambient condition,and the hydrogen diffusion in face-centered-cubic palladium, focusing on their isotope effects. The results of PIMD werein better agreement with experimental data available compared with those of the standard ab initio molecular dynamics,
showing the importance of nuclear quantum effects.

The isotopologs of liquid water, H2O, D2O,
and T2O, were studied systematically by abinitio PIMD simulations (Fig.1). The simulation
results are in reasonable agreement withavailable experimental data on isotope effects,
in particular, on the peak shift in the radial
distributions of H2O and D2O and the shift inthe evaporation energies. It is found that, due
to differences in nuclear quantum effects, theH atoms in the OH bonds more easily accessthe dissociative region up to the hydrogenbond center than the D (T) atoms in the OD(OT) bonds.
Hydrogen diffusion in metals is a recurrent
theme in materials physics. The results fromthe PIMD simulations revealed that, forpreferential H location at octahedral sites, as in
unstrained Pd, the activation barrier for H
migration was drastically increased withdecreasing temperature owing to nuclear
quantum effects [2]. This implies that thenature of the diffusion mechanism graduallychanges from quantum- to classical-like as thestrain is increased.
It was also found that the temperaturedependence of H isotope diffusivities in facecentered-cubic (fcc) Pd has an unconventional“reversed S” shape on Arrhenius plots [3]which leads to a peculiar situation, where theheavier T diffuses faster than the lighter H in

the limited temperature range of 80-400 K.
This mechanism explains the anomalous
crossovers between the normal and reversed
isotope effects observed in the experiments athigh and low temperatures.

Fig. 1: A snapshot from PIMD of liquid water:
Black: oxygen atoms, white: hydrogen atoms.
References[1] M. Machida, K. Kato, M. Shiga, J. Chem. Phys. 148,
103324 (2018).
[2] H. Kimizuka, S. Ogata, M. Shiga, Phys. Rev. B 97,
014102 (2018).
[3] H. Kimizuka, S. Ogata, M. Shiga, Phys. Rev. B 100,
024104 (2019).

Dr. Motoyuki Shiga has received Ph.D from Tokyo Institute of Technology in 1999. He became astaff member in Japan Atomic Energy Agency in the same year. He won Humboldt Research
Fellowship in 2007. He received Distinguished Young Scientist of Japan Society for Molecular
Science (2010) and Academic Award of The Molecular Simulation Society of Japan (2010). He is
now Principal Researcher in Japan Atomic Energy Agency.

Corresponding author: Motoyuki Shiga, shiga.motoyuki@jaea.go.jp

61

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020MISCIBILITY IN LIBH4
E.Dematteis*, V.Gulino, C.Nervi, M.Baricco
Department of Chemistry and NIS, University of Turin, via P. Giuria 9, I-10126 Torino, Italy*present address: Université Paris Est, ICMPE (UMR7182), CNRS, UPEC, 2-8 rue Henri Dunant, 94320 Thiais, France
An overview of miscibility of LiBH4 with other compounds will be presented to tailor H2 storage properties and Li-ion
conductivity. Solubility in both cationic and anionic sublattices, as well as in the liquid phase, will be outlined, highlighted
the role of chemical bonds and coordination in the crystal structure. A limited miscibility with oxides will be reported.

Introduction
LiBH4 is a promising material for future energystorage applications, both for attractive H2storage capacity and for Li-ion superionic
conductivity in the hexagonal phase. Mixtureswith other compounds in the solid state may
show the formation of solutions or can form
compounds. In some cases, only a limited
miscibility is observed. The tailoring ofproperties of LiBH4 by mixing with othercompounds, both in solid and liquid phases,
will be presented.
Experimental / Computational
Parent materials have been mixed by ball
milling, sometimes followed by a thermal
treatment.
Phasetransformations
andproperties have been characterized by a
combination of experimental techniques (e.g.
PXD, ATR, TPD, TGA, EIS).
Results and Discussion
Binary, ternary, quaternary and quinary
mixtures of LiBH4 with other borohydrides inthe solid state shows full or partial miscibility,
as well as the formation of compounds,
whereas a full miscibility in the liquid phase isalways observed (Fig. 1) [1-3]. For selected
systems, thermodynamic properties and phase
diagrams have been assessed, allowing thedetermination of the enthalpy of mixing in solidand liquid phases [4-5]. The eutectic mixturesof LiBH4 show interesting hydrogen desorption

Marcello
Bariccoproperties [6-7]. Anion substitutions in LiBH4
brings to the formation of an extended
hexagonal solid solutions (I-, Br-, Cl-) [8], as
well as the formation of compounds (NH2-,
NH2-) [9-10]. The mixture of LiBH4 with various
oxides develops the formation of highconductive layers at the interface, to be
explored as solid state electrolytes [11].

Fig. 1. Summary on the cation interactions of LiBH4 with
NaBH4, KBH4, Mg(BH4)2 and Ca(BH4)2, both in the solid(A) and liquid (B) phases. From ref. [3].

References[1] E.Dematteis et al., ChemPysChem 20, 1 (2019)[2] E.Dematteis et al., Int. J. Hydr. Ener. 43, 16793(2018)[3] C.Milanese et at., Int. J. Hydr. Ener. 44, 7860 (2019)[4] E.Dematteis et al., RSC Adv. 6, 60101 (2016)[5] E.Dematteis et al., Phys. Chem. Chem. Phys. 19,
25071 (2017)[6] Y.Liu et al., Int. J. Hydr. Ener. 42, 22480 (2017)[7] E.Dematteis et al., Crystals 8 (2018) 90[8] V.Gulino et al., Chemistry of Materials 31, 5133
(2019)[9] A.Wolczyk et al., Int. J. Hydr. Ener. 41, 14475 (2016)[10] A.Wolczyk et al., J. Phys. Chem. 121, 11069 (2017)[11] V.Gulino et al., submitted.

Marcello BARICCO obtained the PhD in Chemistry in 1987 and he is full professor in Materials
Science and Technology at the University of Turin. He has been responsible for the University ofTorino in several European projects on hydrogen storage materials (COSY, FLYHY, BOR4STORE,
SSH2S, ECOSTORE). He is an expert in the Task 40 of the IEA HIA, coordinator of JU-FCH project
HyCARE and responsible of the sub program on “Hydrogen Storage” at the European Energy
Research Alliance (EERA). The scientific contributions have been presented in about 300 papers,
published in international and national journals, and in several invited talk in international meetings.

Corresponding author: Marcello Baricco, e.mail: marcello.baricco@unito.it, Tel. +39 366 7877 947

62

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

HYDROGEN FUNCTIONSCOMPOUNDS

IN

Sapporo, Hokkaido, Japan, 2020

2D

NANOSHEETSANDRELATED

Minoru Osada1,2
1Institute of Materials and Systems for Sustainability (IMaSS), Nagoya University, Nagoya 464-8601, 2International Center for

Materials Nanoarchitectonics (WPI-MANA), National Institute for Materials Science (NIMS), Tsukuba 305-0044, Japan

Abstract
We present soft-chemical approaches for designing functional layered metal oxides and exfoliated 2D nanosheets withhydrogen properties. Soft-chemical reactions such as ion-exchange and acid-base reactions have been utlized tosynthesize novel metastable layered inorganic solids, to exfoliate them into individual 2D nanosheets, and to reassemble
them as thin films and nanocomposite materials. Such soft-chemical approaches enable the design of hydrogen materials
for diverse applications.

Introduction
Two-dimensional (2D) nanosheets, which possess
atomic or molecular thickness, have been emerging asimportant new materials due to their unique properties.
In particular, the recent development of graphene has
opened up the possibility of isolating and exploring thefascinating properties of 2D nanosheets of other layeredmaterials, which upon reduction to single/few atomic
layers, will offer functional flexibility, new properties andnovel applications. In this talk, we review the progress
made in the synthesis, characterization and propertiesof 2D oxide nanosheets and related layered compounds,
highlighting emerging functionalities in hydrogenmaterials.
*

Results and Discussion
Soft-chemical reactions such as ion-exchange and acidbase reactions have been extensively investigated tosynthesize novel metastable layered inorganic solids, toexfoliate them into individual nanosheets, and toreassemble them as thin films and nanocomposite
materials [1]. These reactions proceed at most room
temperature and enable the synthesis of a rich variety ofstructures by stepwise reactions. A variety of 2D oxide
nanosheets (such as Ti1-dO2, MnO2, TiNbO5 andperovskites) were synthesized by delaminating layered
precursors into their single sheets via softchemical process. Protonic oxides (such as HTi1-dO2,

Minoru OsadaHMnO2, HTiNbO5, HCa2Nb3O10) were used as the starting
point for soft-chemical synthesis of 2D nanosheets by acidleaching and exfoliation. These H+-exchanged layeredoxides are promising materials for use as a solid acidcatalyst due to the generation of strong acidity within theinterlayer space. In these materials, H+ ions are highly
accumulated into the interlayer space, which will allow us
to induce the high-order functions of hydrogen bycontrolling proton conduction and multi-electron transfer
processes inside materials and at their interfaces.
Soft-chemical reactions have also been utilized torationally design and tailor the properties of functional
layered metal oxides [2]. Layer-by-layer assembly haveprovided insight into covalent interactions that stabilize
oxide-supported nanoparticle catalysts. In addition,
topochemical reactions have been utilized to tune thecompositions of layered perovskite oxides in order tobreak inversion symmetry, resulting in ferroelectric
properties. Such soft-chemical approaches enable thedesign of functional materials for diverse applications that
include catalysis, energy storage, fuel cells, opticalsensors and ferroic materials.

References[1] M. Osada, T. Sasaki, Dalton Trans. 47, 2841 (2018).
[2] B.-W. Li, M. Osada, Y. Ebina, S. Ueda, T. Sasaki, J.
Am. Chem. Soc. 138, 7621 (2016).

Minoru Osada is a full professor at Institute of Materials and Systems for Sustainability (IMaSS) and
Department of Materials Chemistry, Nagoya University, Japan. He received his PhD in Materials
Science from Tokyo Institute of Technology in 1998. He worked as a special postdoctoral fellow at
RIKEN and a PRESTO researcher at JST. In 2003, he became a senior researcher in National Institutefor Materials Science (NIMS) and later a Principal Investigator at International Center for Materials
Nanoarchitectnics (WPI-MANA), NIMS. In 2018, he joined Nagoya University. He has been working
on the creation of new nanoscale materials and the exploration of their novel functionalities. His recent
focus is put on 2D oxide nanosheets.

Corresponding author: Minoru Osada, Email. mosada@imass.nagoya-u.ac.jp, Tel. +81-52-789-2750

63

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

LIGHT-DRIVEN C—H CARBOXYLATION BY CARBON DIOXIDE
Akinobu Nakada,1 Kanae Abe,1 Ho-Chol Chang1
1Faculty of Science and Engineering, Chuo University, Japan

Here we report direct photochemical C–H carboxylation of aromatic compounds with various combinations of substituent.
They showed distinct photoreactivity (e.g., carboxylation by CO2, dimerization and oligomerization) depending on not only
kinds and numbers of the substituent but also their combination and position.

Introduction

Results and Discussion

CO2 fixation utilizing light energy have been extensively
developed owing to global energy and environmental
issues such as shortage of energy/chemical resources
and increasing atmospheric CO2 concentration. Many of
the researches have represented photocatalytic CO2
reduction to produce C1 compounds.1 Meanwhile,carboxylation of organic compounds using CO2 as thesubstrate is also an important process.2 The researchinterests have been expanded to develop mild andatom/step economical systems without the use ofadditives such as reductant and base.

Aromatic compounds substituted by heteroatomic
functional groups showed distinct photoreactivity
depending on not only kinds and numbers of thesubstituent but also their combination and position (Fig. 2).
Their photochemical and photophysical properties will also
be discussed in detail.

We have reported photochemical H2 production using[Fe(opda)3](ClO4)2 (opda: ortho-phenylenediamine) atroom temperature.3 Photoexcitation of opda activates theamine N–H bond producing hydrogen atom as the key
intermediate for H2 formation (Fig. 1a). Furthermore,another intermediate, i.e., anilino radical of opda, wasfound to proceed carboxylation of its aromatic C–H bondin the presence of CO2 (Fig. 1b).4 These findings allow us
to expand variation synthesis of carboxylic acids driven by
light energy.

R

HH
EH
R

H
E
E

R

R

E

R
R
EH
CO 2H

R

R
E

n

E

E

Fig. 2 Photochemical reactivities of various substituted
aromatic compounds under CO2 atmosphere.

References[1] Y. Yamazaki, H. Takeda, O. Ishitani, J. Photochem.
Photobiol. C 2015, 25, 106 (2015)[2] Maeda, C.; Miyazaki, Y.; Ema, T. Catal. Sci. Technol.
2014, 4, 1482−1497.
[3] Matsumoto, T.; Chang, H.-C.; Wakizaka, M.; Ueno, S.;
Kobayashi, A.; Nakayama, A.; Taketsugu, T; Kato, M. J.
Am. Chem. Soc. 2013, 135, 8646−8654.
Fig. 1 Photochemical reaction of [Fe(opda)3](ClO4)2 under(a) N2 and (b) CO2 atmospheres.

Akinobu
Nakada[4] Matsumoto, T.; Uchijo, D.; Koike, T.; Namiki, R.;
Chang, H.-C. Sci. Rep. 2018, 8, 14623.

Akinobu Nakada is Assistant Professor at Department of Applied Chemistry, Faculty of Science andEngineering of Chuo University. He received his PhD in 2017 from Tokyo Institute of Technology
under the supervision of Profs. Osamu Ishitani and Kazuhiko Maeda. In 2014, he visited The
University of North Carolina at Chapel Hill (Prof. Thomas J. Meyer) as a research scholar for threemonths. In 2017, he joined the group of Prof. Ryu Abe at Kyoto University as a Postdoctoral Fellow
and was promoted to an Assistant Professor (special appointment with CREST/JST) in the same year.
In 2019, he joined the group of Prof. Ho-Chol Chang at Chuo University as an Assistant Professor.
He received the Seiich Tejima Doctoral Dissertation Award at Tokyo Institute of Technology in 2018.
His research interests include metal complex and semiconductor photocatalysts for energy andchemical conversion.

Corresponding author: Ho-Chol Chang, chang@kc.chuo-u.ac.jp, +81-3-3817-1897.

64

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ENHANCEMENT OF LITHIUM ION CONDUCTIVITY OF COMPLEXHYDRIDES BY BORON NITRIDE ADDITIVES
Yuki Nakagawa1, Tomoharu Kimura2, Shigehito Isobe1, Tamaki Shibayama1
1 Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Japan
2

Graduate School of Engineering, Hokkaido University, Sapporo 060-8628, Japan

Abstract Lithium ion conductivity and H2 desorption properties of LiAlH4/BN composites were analyzed in this study.
Effects of boron nitrides with different structures (hexagonal BN(h-BN), turbostratic BN(t-BN), cubic BN(c-BN)) on theproperties were investigated. Among all the composites, LiAlH4/t-BN composite showed the highest conductivity. The
conductivity of 40wt% t-BN composite at 90 °C reached as high as 1.4×10-3 S cm-1. Also, B-H bond formation wasobserved during H2 desorption process of t-BN composite, suggesting the boron edge site of BN would have a catalytic
effect on H2 desorption kinetics. In the c-BN composite, a large amount of stainless impurity was introduced by ballmilling, which caused the H2 release without melting.

Introduction
Hexagonal boron nitride (h-BN) is known as an effective
additive to improve H2 ab/desorption properties ofcomplex hydrides. The remarkable ab/desorption
properties were achieved in ball-milled LiBH4/BN
composites, probably due to the enhancement of H2
dissociation, H－ diffusion and Li+ diffusion by nanoscale
BN [1]. In our previous study, we added h-BN to LiAlH4
system. The addition of h-BN caused the decrease ofmelting point, the delay of desorption kinetics in the 1ststep, and the enhancement of kinetics in the 2nd step [2].
The decrease of melting point suggests that h-BN would
have an interaction with Li+ cation rather than [AlH4] －anion. In this study, three kinds of boron nitrides(h-BN, tBN(turbostratic BN) and c-BN(cubic BN)) were added to
LiAlH4. The effect of each BN addition on Li ion
conductivity and H2 desorption properties were evaluated.

Experimental
h-BN (Sigma Aldrich, 98%) and c-BN (Tomei Diamond,
99.9%) was used as received. Turbostratic BN(t-BN) was
synthesized by ball-milling of h-BN for 2hr. LiAlH4/BN
composites were prepared by ball-milling with 400 rpm
for 2 hr. The ion conductivity was evaluated by AC
impedance measurements and H2 desorption properties
were analyzed by Thermogravimetry - Differential
Thermal Analysis - Mass Spectrometry (TG-DTA-MS).
Microstructures of the composites were observed by
Scanning Transmission Electron Microscope (STEM).

Results and Discussion

enhanced the conductivity by 2-3 orders of magnitude
compared to that of pristine material. The conductivity of
LiAlH4/h-BN composite was 10 times higher than that ofmilled LiAlH4. The increase of carrier concentration would
be the origin of conductivity enhancement. Among all thecomposites, LiAlH4/t-BN composite showed the highest
ion conductivity. The conductivity of 40wt% t-BNcomposite at 90 °C reached as high as 1.4×10-3 S cm-1.
In the case of c-BN composite, a large amount of
stainless impurity (Fe, Cr, Ni) was introduced by ballmilling due to the hardness of c-BN, thus it is difficult todistinguish the effect of c-BN on the conductivity. Fromthe investigation of H2 desorption process, the melting
peak at 127 °C was observed in the LiAlH4/tBN
composite. Also, the B-H bond formation after the melting
peak suggests the boron edge of BN would have acatalytic effect on H2 desorption kinetics of LiAlH4.

References[1] J. Zhu et al., Int. J. Hydrogen Energy 42, 1579015798 (2017).
[2] Y. Nakagawa et al., Inorganics 5, 71 (2017).

Acknowledgement
This work was supported by JSPS KAKENHI Grant
number 19K15304. A part of this work was conducted as
joint-use facilities in Hokkaido University, supported by“Nanotechnology Platform” and “Microscopic Analysis for
Nano materials science and Bio science Open Unit
(MANBOU)” program of the Ministry of Education, Culture,
Sports, Science and Technology (MEXT), Japan.

First, we investigated Li ion conductivity of ball-milled
LiAlH4 without BN additives. Ball-milling of LiAlH4 for 2 hr
Born in 1988, Sapporo, Japan. Yuki Nakagawa graduated with Ph.D degree in the Division ofMaterials Science and Engineering from Hokkaido University in 2016. During this time, he worked in
the field of B-N based reactive hydride composites for hydrogen storage. His current research is
focused on complex hydrides for ion conduction, transmission electron microscope (TEM) analysis
of light-element hydrides, and ion implantation effects on energy conversion materials at Hokkaido
University in the group of Prof. Tamaki Shibayama.
Yuki Nakagawa
Corresponding author: Yuki Nakagawa, Email: y-nakagawa@eng.hokudai.ac.jp, Tel: +81-11-706-7167

65

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

EFFECT OF HYDROPHOBIC CATIONS ON THE HYDROGENOXIDATION/EVOLUTION REACTIONS ON SINGLE-CRYSTAL PT
ELECTRODES
Masashi Nakamura1, Tomoaki Kumeda1, Nagahiro Hoshi1, Kenji Miyatake2
1 Chiba University, 2 University of Yamanashi
Abstract *******************************************************************************************************************************
We evaluated the activity for the hydrogen oxidation/evolution reactions (HOR/HER) on Pt single-crystal electrodes
modified with hydrophobic cations. The HOR/HER activities on Pt(100) and Pt(110) were enhanced by the hydrophobicorganic cations. The hydrophobic polymer electrolytes also activate the HOR/HER on Pt(110). The hydrogen-bonding
structure in the electrical double layer affects the HOR/HER activity, and hydration water of hydrophobic cation may
facilitate the proton transfer to the Pt(110) surface. *******************************************************************************

Introduction
Efficient hydrogen production from water is necessary todevelop the new energy source such as fuel cell. Water
electrolysis is one of the important methods for hydrogen
evolution. Platinum (Pt) is used as electrocatalysts for fuelcells and water electrolysis. Recently, we found asignificant enhancement of oxygen reduction reaction(ORR) by the addition of small amount of
tetrahexylammonium cations that have a stronghydrophobicity because of long alkyl chains [1]. In thisstudy, activities for the ORR on Pt single-crystal electrodes
were investigated in acid/alkaline solutions containinghydrophobic cations (tetraalkylammonium cation (TMA+),
tetraalkyl phosphonium cation (TMP +) and hydrophobicpolymer electrolytes. ***************************************

Pt(100) and Pt(110). The hydrophobic polymer
electrolytes also activate the HOR/HER on Pt(110). We
found that the ORR on Pt(111) was activated by THA+
because the ORR inhibitor (OHad) was destabilized by thehydrophobic cation [1]. However, no OHad is adsorbed on
the surface in the HOR/HER potential region. Therefore,hydrogen-bonding structure of hydration water withhydrophobic cation may facilitate the proton transfer to thePt(100) and Pt(110) surface. **** **Experimental / Computational
A single crystal bead of Pt was prepared with the Clavilier’s
method. The crystal was oriented using the reflection
beam of He–Ne laser from (1 1 1) and (1 0 0) facets on the
crystal [2], and then mechanically polished with diamondslurries. The polished surface was annealed in H2/O2
flame at about 1300 °C. Electrolytic solutions wereprepared from ultrapure water and suprapur grade
chemicals. The activity for the HOR/HER was estimatedby the exchange current density using Butler–Volmer
approximation in the low overpotential region.

Results and Discussion
Fig. 1 shows the HOR/HER activity on Pt(hkl) electrodes
modified by hydrophobic cations in acidic solution.
Tetrahexylammonium cation (THA+) and tetrabutyl
phosphonium cation (TBP+) activates the HOR/HER on

Fig. 1 HOR/HER activity on Pt(hkl) modified withhydrophobic organic cations

References[1] T. Kumeda, M. Nakamura et al., Nat. Commun. 9,4378 (2018).
[2] J. Clavilier et al., J. Electroanal. Chem. 107, 205(1980).

Short CV: Keio University (B.S. 1998); Keio University (Ph.D. 2002); Keio University (AssistantProfessor 2002-2004); Chiba University (Assistant Professor 2004-2013, Associate Professor
2013-)**********************************************************************************************************
Research fields: Surface electrochemistry, fuel cells ******** ********** ************** *************************************************************************************************************************************************************************************************************************************************************

Corresponding author: Masashi Nakamura, E-mail: mnakamura@faculty.chiba-u.jp, Tel: +81-43-290-3382

66

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

SOFT
X-RAY ABSORPTIONSPECTROSCOPICHYDROGENATED TITANIUM DIOXIDESTUDIESON

Takashi Nakamura1, Ryota Shimizu2, Taro Hitosugi2, Naoki Nagatsuka3, Katsuyuki Fukutani3
1

IMRAM, Tohoku University, 2 School of Materials and Chemical Technology, Tokyo Institute of Technology, 3Institute of Industrial
Science, The University of Tokyo
Black hydrogenated TiO2 prepared by the hydrogenation treatment is a promising narrow band-gap material showing high photocatalytic activity. To understand the nature of hydrogenous species in the black hydrogenated TiO2, in this study, electronic andlocal structure of the hydrogenated TiO2 specimens were investigated by soft X-ray absorption spectroscopy. The absorption
spectra of Ti L-edge shifted to the lower energy position. These spectral changes indicate that TiO2 was reduced by thehydrogenation treatment, indicating that the major part of incorporated hydrogen is considered to become proton and provides
electron to the host structure.

Introduction
Hydrogen production using renewable energy sources likesolar light and wind is a key for the realization ofsustainable development and green society. For theefficient solar-driven hydrogen production from watermolecules, TiO2 is a promising photo catalyst. To improveinsufficient photo absorption in visible and infrared ranges
due to wide band gap, metal- and nonmetal-doping was
examined widely [1-3]. Among these attempts, excellent
photo absorption properties and photo-catalytic activity ofthe black hydrogenated TiO2 was reported by Chen et al.
[3]. Although black hydrogenated TiO2 showed excellent
optical and photo-catalytic properties, true roles ofincorporated hydrogenous species in the host structure is
not understood well so far. In this study, we synthesized
black hydrogenated TiO2 and investigated the electronic
and local structures by soft X-ray absorption spectroscopy.
The function of incorporated hydrogenous species isdiscussed.

changes strongly indicate that TiO2 are reduced by thehydrogenation treatment. Since the nonstoichiometricvariation of the oxygen/metal ratio in TiO2 is negligibly
small, the major part of the incorporated hydrogenous
species is considered to be proton and provide electron to
the host structure [4].

Experimental
Hydrogenated TiO2 specimens were prepared byexposing the pristine TiO2 to atomic hydrogen using aheated W filament in 1.3 × 10-1 Pa H2 atmosphere at 573
K for 15 h. For powder samples, intermediatehomogenizations were performed every 1h. X-ray
absorption spectroscopy was carried out at BL27SU,
SPring-8, Japan. Ti L-edge (453-473 eV) and O K-edge(525-555 eV) spectra were recorded by both total electron
yielding and partial fluorescence yielding modes.

Results and Discussion
Figure 1 shows the X-ray absorption spectra at the Ti Ledge of the commercial anatase TiO2 powder, bluehydrogenated TiO2 and black hydrogenated TiO2 single
crystal (Rutile) recorded by the total electron yielding
mode. In Ti L-edge spectra, lower energy peaks indicatedby c-e are Ti-LIII edge and those indicated by f and g are
Ti-LII edge. In hydrogenated specimens, lower energy
peak of the LII and LIII edge shifted to the lower energy
position compared with the pristine TiO2. These spectral

Takashi Nakamura

Figure 1. Ti L-edge X-ray absorption spectra of thecommercial TiO2 powder (TiO2(anatase)), the bluehydrogenated TiO2 powder (H-TiO2(powder)) and theblack hydrogenated TiO2 single crystal (H-TiO2(Single
crystal)).

References[1] W. Choi, A. Termin, M. R. Hoffmann, Angew. Chem.,
1994, 106, 1148.
[2] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga,
Science, 2001, 293, 269.
[3] X. Chen, L. Liu, P. Y. Yu, S. S. Mao, Science, 2011,
331, 746.
[4] D. K. Lee, J. I. Jeon, M. H. Kim, W. Choi, H. I. Yoo, J.
Solid State Chem., 2005, 178, 185.

Acknowledgement
This work was financially supported by KAKENHI, grantNo. 18H05514, 18H05518 and 19H05044.

Dr. Takashi Nakamura received his Ph. D. degree in 2010 at Graduate School of Engineering, Tohoku
University, Japan. From April 2010 to July 2012, Battery Research Lab., Sumitomo Metal Mining Co. Ltd.,
From August 2012 to September 2019, Assistant Professor, IMRAM, Tohoku University. From October
2019, Associate Professor, IMRAM, Tohoku University (Present post). Now, he is working on the energy
conversion and storage technologies such as fuel cells and batteries based on solid state ionics, solidstate chemistry and electrochemistry. His research interests are the investigation of functionalities ofenergy materials, understanding electrochemical phenomena in energy devices and developing insitu/operando observation techniques for energy materials and devices.

Corresponding author: Takashi Nakamura, takashi.nakamura.e3@tohoku.ac.jp,

67

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

EFFECTIVE COULOMB INTERACTION IN STRONTIUM VANADIUMOXYHYDRIDES EVALUATED BY THE CONSTRAINED RANDOM-PHASE
APPROXIMATION
Masayuki Ochi1 and Kazuhiko Kuroki1
1 Department of Physics, Osaka University, Machikaneyama-cho 1-1, Toyonaka, Osaka, 560-0043
Abstract
Transition metal oxides have been one of the central objects in the studies of electron correlation effects
because of their rich variety of physical properties. Recently, it was pointed out that oxyhydrides can offer a uniqueplayground of strongly correlated low-dimensional electronic structure, where the s orbitals of hydrogen break a chemicalbond between the cation t2g orbitals. In this study, we evaluate the effective Coulomb interaction in low-energy effectivemodels for strontium vanadium oxyhydrides Srn+1VnO2n+1H n (n = 1 and ∞) using the constrained random-phaseapproximation. We find unique screening effects take place in strontium vanadium oxyhydrides.

Introduction
Transition metal oxides have been one of thecentral objects in the studies of condensed matter physics
because of their rich variety of physical properties.
Recently, oxyhydrides, where oxygen atoms in oxides are
partially replaced with hydrogen atoms, have attracted
much attention as a new platform of materials science [1].
In transition metal oxyhydrides, the low dimensionality
caused by the H-1s orbital, which breaks the chemicalbond between the cation t2g orbitals, together with apeculiar crystal field, can offer a unique playground ofstrong correlation effects. Although some theoreticalstudies reported first-principles band structures of someoxyhydrides, a detailed study on their correlation effects
has still been missing because parameters in theireffective Hubbard models are unknown.

Experimental / Computational
In this study [2], we evaluate the effective
Coulomb interaction strength in strontium vanadium
oxyhydrides Srn+1VnO2n+1H n (n = 1 and ∞) [3-4], which areprototypical transition metal oxyhydrides, where theantiferromagnetic order [3] and a pressure-induced metalinsulator transition [5] were experimentally observed. First,
we perform first-principles band calculation, and thenextract the Wannier functions. After that, we evaluate theeffective Coulomb interaction parameters among theWannier orbitals using the constrained-random-phaseapproximation with the RESPACK software [6]. We also

investigate the transfer integrals among the Wannierorbitals.

Results and Discussion
We find that the effective interaction in the t2g
model, where only the t2g orbitals are explicitly considered,is strongly screened by the eg bands compared with thatfor oxides, because the eg bands are strongly entangledwith the t2g bands in the oxyhydrides. On the other hand,the effective interaction is rather strong in the d model,
where all the vanadium d orbitals are explicitly considered,owing to a large energy separation between the V-d bands
and the anion bands (O-p and H-s). These findings
suggest that nontrivial and unique correlation effects cantake place in strontium vanadium oxyhydrides.

References[1] H. Kageyama, K. Hayashi, K. Maeda, et al., Nat.
Commun. 9, 772 (2018).
[2] M. Ochi and K. Kuroki, Phys. Rev. B 99, 155143(2019).
[3] F. D. Romero, A. Leach, J. S. Møller, et al., Angew.
Chem. Int. Ed. 53, 7556 (2014).
[4] J. Bang, S. Matsuishi, H. Hiraka, et al., J. Am. Chem.
Soc. 136, 7221 (2014)[5] T. Yamamoto, D. Zeng, T. Kawakami, et al., Nat.
Commun. 8, 1217 (2017).
[6] https://sites.google.com/view/kazuma7k6r

He obtained his Ph.D. degree from the University of Tokyo in 2014. He was a postdoctoral researcher
at RIKEN CEMS (2014—2015). Since 2015, he has been an assistant professor at Osaka University.
He has worked on condensed matter physics by means of first-principles calculation.

Masayuki Ochi
Corresponding author: Masayuki Ochi, ochi@phys.sci.osaka-u.ac.jp, 06-6850-6749

681st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CHALLENGE OF DETERMINATION OF HYDROGEN POSITIONS IN
HYDRIDES BY WHITE NEUTRON HOLOGRAPHY
K. Ohoyama1, Y. Kanazawa1, T. Yamamoto1, S. Uechi1, K. Sugimoto1, S. Arase1, S. Noda1,
T. Ishizaki1, K. Hayashi2, N. Happo3, M. Harada4, K. Oikawa4, Y. Inamura4, T. Sato5,
S. Orimo5,6
1 Ibaraki Univ., 2 Nagoya Inst. Tech., 3 Hiroshima City Univ., 4 J-PARC Center, 5 IMR Tohoku Univ., 6 WPI-AIMR, Tohoku
Univ.
Abstract
We will show advantages and recent results of newly developed white neutron holography, which is an powerful probe todetermine H positions in hydrides, even though H has no translation symmetry. We succeeded in visualising H around B
in 0.26% B doped Si.

Introduction
We have developed a novel technique to visualise atomic
images around a selected atom in materials with atomic
resolution, called white neutron holography in J-PARC.
This method is a powerful probe to determine the positionsof dopants in materials [1,2]. We have already establishedthe technique to determine B positions in functional
materials, such as semiconductor B doped Si,
thermoelectric materials B doped Mg2Si, LED material B
doped SiC, and so on. Based on this progress, we aredeveloping a technique to apply this method to hydrides
under the support of Hydrogenomics. If it will be practical,
one can observe the atomic structure around H in
principle; thus, H positions in hydrides can be determinedeven for the case that H has no translation symmetry.
Since this method is quite unique as a prove of H, it can
provide strong impacts to science of hydrides. On theother hand, since the present neutron holography requires
single crystalline samples with a size of ~1 cc, we aretrying to develop a technique for powder samples to apply
this method to hydrides.

Experimental
Experiments are performed at BL10 in Japan Proton
Accelerator Research Complex (J-PARC) at Tokai, Japan
under strong support of the instrumental team.

dopants. Since the signals from H is weak in comparison
with B, we are trying to observe H around B in B doped Si
as the first step in this project in Hydrogenomics.. We will
also show results of hydrogenated B doped Si, andpresent status of powder neutron holography in Poster 33
and 34.

Fig. 1 Local atomic structure around B (Green) in 0.26at%
B doped Si. (Reproduced from Ref.2 with permission[2].)Results and Discussion

References* Fig.1 shows a recent result, which is the atomic imagearound B in 0.26 at% B doped Si, indicating that B is
located at Si positions in the diamond structure, as wellknow. This indicates that neutron holography is aneffective probe to determine positions of light element[1] K. Hayashi et al., Sci. Adv., 3, e1700294 (2017).
[2] K. Ohoyama and K. Hayashi, Phys. Status Solidi B
255, 1800143 (2018).

Kenji Ohoyama was born in Tokyo, Japan in 1961. He obtained his B.Sc.(1986) and M.Sc. (1988)
degrees from Tohoku University and Ph.D. from Tohoku University in 1992. He worked in Tohoku
University as a research associate (1992–2003) and associate professor (2003–2015). He moved to
Ibaraki University as a full professor in 2015. His main research fields are investigations of materials
science and magnetism in strongly correlated electron systems using neutron scattering. In particular,
he has been developing the novel technique, white neutron holography.
Kenji
OHOYAMA
Corresponding author: Kenji OHOYAMA, kenji.ohoyama.vs@vc.ibaraki.ac.jp、029-287-7871

69

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

Poly(dihydroxybenzoquinone): Its High-density and Robust Charge Storage
Capability in Rechargeable Acidic Polymer-air Batteries
Kouki Oka1, Shuhei Furukawa1, Hiroyuki Nishide1,2, Kenichi Oyaizu1,2※
1 Department of Applied Chemistry and 2 Research Institute for Science and Engineering, Waseda University, 3-4-1 Okubo,
Shinjuku, Tokyo 165-8555, Japan.
Abstract
2,5-Dihydroxy-1,4-benzoquinone (DHBQ) undergoes a two-electron, two-proton redox process in a single step at apotential of +0.2 V (vs. Ag/AgCl) in acidic aqueous electrolyte at pH 1, which suggests that DHBQ is a potential candidate
for use as an anode-active material with high energy density. Furthermore, simple addition condensation of DHBQ yields
poly(2,5-dihydroxy-1,4-benzoquinone-3,6-methylene) (PDBM). For the first time, a rechargeable acidic polymer-air battery
was fabricated with PDBM as the anode, the conventional Pt/C cathode catalyst, and an acidic aqueous electrolyte (pH 1).
This battery yielded a discharge voltage of 0.70 V and a high discharging capacity of 352 mAh/g polymer with a long-lifetimeof 500 cycles and high rate capabilities (up to 10 C), maintaining the moderate energy density of 172 mWh/g anode.

Introduction

Results and Discussion

Recently, electrochemical energy storage devices havebeen intensively pursued for the future energy network, tobuffer the unpredictable energy generation, to facilitate theefficient use of renewable energy sources, and to reduce
environmental impact. Aqueous air batteries have gained
revived interest to achieve much larger energy density forthe increasing demand and lower environmental burden[1]. Aqueous air batteries combine the design features ofboth conventional batteries and fuel cells and are
fabricated with a metal anode and an air-breathing
cathode in a proper aqueous electrolyte. The rechargeable
air batteries are still under development due to the low
cycle performance as a result of the formation of dendrites
on the metal anodes. In addition, the use of a basic
aqueous solution often causes the carbonate clogging
problem, which arises from the CO2 reaction in the air [2].
On the other hand, organic materials, with theirinexpensive, abundant and readily available building
blocks (H C O N S) and tunable properties, have been
proposed as replacements for inorganic electrode-active
materials. Especially, organic redox polymers haveprogressed significantly, which are composed of redoxactive groups as a repeating unit and are characterized byhigh charge transport and storage capability based on
their densely populated redox sites [3].
In the current work, organic redox polymer and acidic
aqueous solution were used as an anode-active material
and electrolyte, respectively, for the rechargeable airbattery. They released the rechargeable air battery fromits particular problems.

Simple addition condensation of DHBQ yielded PDBM. A
rechargeable acidic polymer-air battery was fabricatedwith the PDBM electrode as the anode, the conventional
Pt/C cathode catalyst, and an acidic aqueous electrolyte(pH 1). The charging-discharging curves of the battery at
5 C exhibited a plateau voltage at 0.7 V and their
coulombic efficiencies were ˃99%, demonstrating thereversible charge storage property of the cell. The capacity
for the anode used in the battery was 349 mAh/gpolymer,
suggesting that almost all of the DHBQ moieties
contributed to the charge storage. The battery kept thealmost full discharging capacity of 348 mAh/gpolymer evenat a rapid discharging of 10 C which corresponded to thefull discharging within 360 s. The high capacities of 88%
after 500 cycles were still maintained, which demonstrated
the long-life ability.
e-

e-

-

H+
e-

-

+

H+

eH+

eO

HO

H+
O H

e-

OH

n
O

Polymer electrode

H+
Electrolyte Pt/C

e-

O H

O2

+

e-

O2

H O

n
O H

Polymer electrode

(Air)

H+
Electrolyte Pt/C

References[1] Y. Li, et al. ACS Energy Lett. 2, 1370 (2017).
[2] L. Li, et al. Adv. Energy Mater. 6, 1502054 (2016).
[3] K. Oyaizu, et al. Adv. Mater. 21, 2339 (2009).

PhD student, Supervisor: Prof. Kenichi Oyaizu, Waseda University
Experience
2019-2021 JSPS Research associate (DC1), 2018- Visiting Researcher, Department of Engineering
Sciences, Nanotechnology and Functional Materials, Uppsala University, Supervisors: Prof. Maria
Strömme and Prof. Martin Sjödin.

Kouki OkaAwards2017 Poster Presentation Award; 17th IUPAC International Symposium on MacroMolecularComplexes, Japan.

Corresponding author: Kenichi Oyaizu, oyaizu@waseda.jp, Tel +81-3-5286-3214.

70

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CRYSTAL STRUCTURE PREDICTION OF LI(CB9H10) BY XRD-ASSISTED
MOLECULAR DYNAMIC SIMULATION
Ryuhei Sato1, Toyoto Sato2, Takashi Honda3 Toshiya Otomo3, Shin-ichi Orimo2, Shinji
Tsuneyuki1
1 Department of Physics, The University of Tokyo, Japan, 2 Institute for Materials Research, Tohoku University, Japan, 3Institute of Materials Structure Science, High Energy Accelerator Research Organization, Japan
Abstract
Crystal structure of complex hydrides, Li(CB9H10), has been studied by XRD-assisted molecular dynamic (MD) simulation.
Hcp-like trigonal structure of (CB9H10)− anions is obtained from these MD simulations as an candidate, whose calculated
XRD pattern almost agrees with that of experimental one.

Introduction
All-solid-state battery is one of the most promising
candidates to resolve the intrinsic drawbacks of current
lithium-ion batteries, such as electrolyte leakage,
flammability, and limited energy density. Recently, a classof complex hydrides, represented as Li(CB9H10) andNa(CB9H10), is paid considerable attention, because of its
high ionic conductivity and stability against metal anode [1].
Conductivity measurement and structure analysis suggestthat the disorder of (CB9H10)− anions plays a critical role ofthis high ionic conductivity, whereas the exact orientationof these anions has not been clarified yet. Under suchcircumstance, recently, our group develop an efficientapproach to predict the crystal structure by combining
molecular dynamic (MD) simulation and data-assimilation
utilizing XRD pattern [2]. Here, we report the result of
crystal structure prediction of Li(CB9H10) based on the
XRD-assisted MD simulation.

of 50 simulations, suggesting that this XRD-assisted MD
simulation potentially could predict the crystal structure of
Li(CB9H10). 4 out of 50 MD simulations for (CB9H10)−
anions with XRD pattern of Li(CB9H10) show the hcp-like
trigonal structure, as shown in Figure 1. (Note that thepositions of Li+ ions are determined by subsequent XRDassisted ab initio MD simulations.) Although more than
60% of simulations show the almost same center of gravity
positions of CB9H10− anions as that of figure 1, theorientation of anions is different and the obtained XRD
patterns less agree with the experiment. In addition, it isconfirmed that the potential energies of those simulations
are almost comparable suggesting the effectiveness ofdata-assimilation to find the crystal structure where theorientation of cluster is important.

Simulation Methodology
LAMMPS and VASP codes are employed for Molecular
dynamic (MD) simulation and ab initio calculation,
respectively. Reax-FF potential are employed for classicalMD simulation. PBE-GGA is employed for exchange
correlation function in ab initio calculation. the dataassimilation approach to combine XRD pattern with MD
simulation follows that in ref. [2].

Results and Discussion
As a test calculation, the configurations of (B10H10)2−
anions in the reported crystal structure of Li2(B10H10) [3]has been predicted from the random configuration of(B10H10)2− anions by MD simulation with XRD pattern ofLi2(B10H10). these MD simulations could predict theconfigurations of B10H10 in Li2(B10H10) crystal 8 times out

Fig. 1 Li(CB9H10) structure predicted from XRD-assisted
MD simulation

References[1] W. S. Tang et al, Adv. Eng. Mater., 6, 1502237(2016).
[2] N. Tsujimoto et al. Phys. Rev. Mater., 2, 053801(2018).
[3] H. Wu et al., J. Phys. Chem. C, 119, 6481 (2015).

Ryuhei Sato received his Ph. D. in 2018, at the department of Materials Engineering, The Universityof Tokyo. After half-year Postdoctoral research fellow in Japan Society for the Promotion of Science,
he joined Prof. Tsuneyuki’s group as Postdoctoral researcher. His research topics have centeredaround the protons. In previous position, he mainly studies the proton conduction phenomenon onoxide surface and, in current position, the crystal structure prediction including the position ofhydrogen, proton, hydrides.
Ryuhei Sato
Corresponding author: Ryuhei Sato, Email: rsato@cms.phys.s.u-tokyo.ac.jp, Tel. +81-3-5841-4174

71

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

THEORETICAL ANALYSIS ON STRUCTURES OF RESTING OXIDIZEDSTATES OF [NIFE] HYDROGENASE
1K. Ishikawa, 1,2 M. Shoji, 1,2 Y. Hori, 3T. Hiromoto, 4Y. Higuchi, and 1,2 Y. Shigeta,
1Graduate School of Basic and Applied Sciences, University of Tsukuba, 2Center for Computational Sciences, Universityof Tsukuba, 3National Institutes for Quantum and Radiological Science and Technology, 4Graduate School of Life
Science, University of Hyogo.
Abstract
We performed QM/MM analysis of structures of resting oxidized states and compared with the X-ray
crystallography experimental data. We assigned the bridge ligand and charge/spin state for known Ni-A and Ni-B states
as –O– bridge with Ni(III) spin state and OH bridge and Ni(III) low spin state, repsecively. We also found that the novel
resting structures for two different charge states were theoretically reproduced.

Introduction[NiFe] hydrogenase
COCO
plays an importantrole in anaerobic
S
S
S
S
H
H
metabolism
and
?
S
S
catalyzes
theSSreversible
redox?
reaction of H2. For
resting oxidized states, Glu34
Glu34
Ni-A and Ni-B states
were obtained by X-ray
Fig. 1 Active site structures.
crystallographic analysis (Fig. 1) [1]. Recently,
novel Ni-A like structure (Ni-A'), where sulphenyl
ligand bridges Ni and Fe, is obtained by Higuchi'sgroup. However, the electronic state of Ni and Fe
atoms and oxygen species contained in the active
site are unknown for this structure. In this study, we
access these structures by changing the valence
state and oxygen species using QM/MM calculation.
Cys84

Cys549

Cys84

Cys546

Cys81

included. NWChem (ver. 6.3) was used for the
calculations [2]. A stable state was obtained bymeasuring root mean square deviation (RMSD)
measured from new crystal structure.

Cys549

Cys546

Cys81

Computational details
QM/MM calculations were performed for –O–, OH, and -H2O coordination between Ni and Fe
atoms and 3 different charge states. For QM part,amino acids and ligands within 9 Å around theactive site and a few additional amino acids were

Results and Discussion
For the Ni-A state, we evaluated all possiblecombinations of the ligands, charge states, and spinstates and concluded that the Ni-A state ispresumably characterized by –O–bridge between Fe
and Ni and Ni(III) low spin state considering the
EPR experimental result. However, further analysis
is needed to determine it by considering
methodology dependency of calculation. For the
Ni-B state, we assigned the state as OH bridge andNi(III) low spin state by comparing local structurearound metal site with X-ray structure. For the NiA' structure, we optimized the structure using
QM/MM model and obtained stable structures fordifferent charge states. For Ni(II) and Ni(III), highand low spin states are ground states.
References[1] H. Ogata, et al. Structure 13, 1635 (2005).
[2] M.Valiev, et al., Comput. Phys. Commun. 181, 1477
(2010).

Yasuteru Shigeta, a Theoretical Chemist and Biophysicist, graduated from Department ofChemistry, Osaka University and obtained a Doctor of Science degree at there in 2000. He pursued
his postdoctoral researches at Osaka University, Kansas State University, and the University ofTokyo from 2000 to 2004. He worked at the University of Tokyo during 2004-2007 as an assistantprofessor, University of Tsukuba during 2007-2008 as a lecturer, University of Hyogo during 20082010 as a research associate professor, Osaka University during 2010-2014 as an associate
professor, and now joined University of Tsukuba as a full professor since 2014. He has publishedmore than 200 scientific papers and received international awards such as PCCP award of Royal
Society of Chemistry (UK) in 2007 and QSCP Promising Scientist Prize of CMOA (France) in 2017.
Y. SHIGETA
Corresponding author: Yasuteru Shigeta, Email: shigeta@ccs.tsukuba.ac.jp, Tel: +81-29-853-6496

72

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

HYDROGENATION PROPERTIESMODIFICATION BY CARBON

Sapporo, Hokkaido, Japan, 2020

OF

TITANIUM

WITH

SURFACE

Keita Shinzato1, Norio Ogita2, So Hamamoto1, Hiroki Miyaoka3, Takayuki Ichikawa1,2,3
1 Graduate School of Engineering, Hiroshima University 2 Graduate School of Integrated Arts and Sciences, Hiroshima
University 3 Natural Science Center for Basic Research and Development, Hiroshima University.
Abstract
Titanium (Ti) requires effective surface modification to improve the hydrogenation kinetics. From previous works about Ti
milled with acetone, it is suggested that carbon is important element for surface modification of Ti. In this work, weinvestigated the effect of graphite for surface modification of Ti. The Ti milled with graphite is able to be hydrogenatedaround room temperature. It is noteworthy that the high reactivity is preserved even after 7 days although the reactivity of
Ti milled with acetone is lost during only few days. Raman scattering spectra revealed a similarity between Ti milled withgraphite and acetone, indicating that the surface modification mechanism of both cases is similar.

Ti and Ti-based alloys are promising materials as afunctional materials such as hydrogen storage, hydrogenchemical compressor, and thermochemical heat storage.
However, Ti is easily oxidized, and its oxide layer inhibits
the reaction with H2. Recently, we reported that the Ti
milled with acetone shows high reactivity and selectivity forhydrogen although the surface modification effects are lost
after few days [1]. It was suggested from previous resultsthat carbon is important element for surface modificationof Ti. Thus, in this work, we investigated the effect ofcarbon for hydrogenation and reaction selectivity of Ti.

Experimental
Graphite (99.995%, 2-15 micron, Alfa Aesar) was used as
the carbon additive. 1:0.5 molar ratio of Ti (99.7%, 100
mesh, Sigma Aldrich) and graphite were mixed, and thenthe mixture and 20 of balls made of ZrO2 were put into
milling pot. The samples were ball-milled for 3 hours. To
avoid temperature increases, the milling was stopped
every 10 min for 1 min. The hydrogenation properties ofthe sample were investigated by thermogravimetry
analysis after keeping in glovebox. The degradation withtime of sample were evaluated day-by-day.

Results and Discussion
The hydrogenation curves of Ti + graphite were shown in
Figure 1. The hydrogenation temperature of Ti milled withacetone was increased to 125 C after keeping for 7 days
[1]. On the other hand, the Ti milled with graphite showshigh reactivity even after 7 days. This result indicates thatgraphite is effective for the improvement of thehydrogenation properties on Ti. In other words, thegraphite suppressed surface oxidation of Ti. The chemical
state of carbon of Ti milled with graphite and acetone wereanalysed by Raman scattering. As a result, characteristic
peaks corresponding to graphite structure (G- and Dbands) were observed for both of samples, suggesting that
hexatomic structure affects the surface modification. In
fact, in the case of Ti milled with acetone, the above peaks
disappeared with lost of the surface modification effects.
@50 C4

TG curves (wt. %)Introduction

3
2
0d
1d
2d
3d

4d
5d
6d
7d

4
6
Time (min)

8

1
0
0

2

10

Fig. 1 Hydrogenation curves of Ti + graphite at 50 C under
1 atm H2 flow.

References[1] K. Shinzato, S. Hamamoto, H. Miyaoka, T. Ichikawa,
J. Phys. Chem C. 123(32), 19269(2019).

~2016. 03. 31

University of the Ryukyu, Faculty of Science, Department of Chemistry~2018. 03. 31

Hiroshima University, Graduate School of Integrated Arts and Sciences

2018. 04. 01~

Hiroshima University, Graduate School of Engineering

Research
Surface Modification of Ti, Hydrogen Exchange between MgH2 and LiBH4, N2 dissociation by Li-Alloy
Keita Shinzato
Corresponding author: Takayuki Ichikawa, tichi@hiroshima-u.ac.jp, 082-424-4604.

73

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

DEVELOPMENT OF MULTICOMPONENT QUANTUM CHEMISTRY
METHODS FOR ACCURATE PREDICTION AND ELUCIDATION OF
HYDROGEN-FUNCTIONAL MECHANISM
Masanori Tachikawa1, Yusuke Kanematsu1
1 Graduate School of Nanobioscience, Yokohama City University, Yokohama 236-0027, Japan

Abstract: Nuclear Quantum Effect (NQE), such as zero-point vibrational energy, tunneling, and its H/D isotope effect, is quite
important in various systems from small molecules to material or biochemical complex species. Especially, in the case of “LowBarrier Hydrogen Bonding (LBHB) systems”, NQE of proton (or deuteron) is indispensable. To elucidate such hydrogen-functional
mechanism, we will develop some ab initio approaches for multi-component systems including both electrons and nuclei quantummechanically: (I) Multi-component density functional theory (MC_DFT) and (II) ab initio path integral molecular dynamics (PIMD)
methods.

Introduction
Recently, Mori et al. [1, 2] developed the κ-H3(Cat-EDT-TTF)2(H-TTF, Figure 1) with a hydrogen-bonded π-electron system,
which was found to reveal C2/c symmetry in 50-293 K, while
its isotopologue, κ-D3(Cat-EDT-TTF)2 (D-TTF), showed thephase transition at 185 K from C2/c to P-1. To elucidate theorigin of such difference, we have theoretically analyzed thedifference between H-TTF and D-TTF using quantum
chemistry approaches.

to mention that the phase transition temperature of D-TTF isdetermined by the π-π interaction and the nuclear quantum
effect [3].

Computational
First, we calculated the potential energy curves (PECs) withrespect to hydrogen-transfer coordinate for model systems by
conventional DFT method, to analyze which inter-molecularinteraction would be dominant for the contribution to the shapeof PEC. The shape of PEC for 3-unit model including b1
interaction between nearest neighboring units was drasticallychanged from that for 1-unit model. On the other hand, theshapes of the PECs of other models including b2, p, and q
interactions did not drastically change from those of 3-unit
model. Thus, we have found that the interaction by b1 (π-πstacking) shows the dominant contribution to shape of PEC,
which explicitly demonstrated the coupling of H-bondedhydrogen/ deuterium dynamics and the π-electron.

Results and Discussion
Then, we performed multicomponent density functional theory(MC_DFT) calculations, taking account of the nuclear
quantum effect with the 3-unit model that consideringinteraction by b1 (π-π stacking). In the H-TTF, the shape ofthe eff-PEC becomes single-well potential, since the energy
barrier obtained with conventional DFT is removed by protonic
quantum effect. This is in reasonable agreement with thecorresponding experimental observation that the hydrogen islocated at the center of H-bond in X-ray structures of H-TTF
both at 50 and 293 K. On the other hand, in the D-TTF, theeff-PEC still holds double-well. This means that deuterium islocalized at one side of oxygen rather than the center of Hbond in low temperature phase, due to the small thermal effect.
Therefore, it is expected that the phase transition in D-TTF
occurs due to the localization of the deuterium. We would like

Masanori
Tachikawa

Fig. 1 a) Molecular structure of H(D)-TTF and b) its schematic
illustration and the definition of H-bonding geometrical parameters.
c) The arrangement of H(D)-TTF unit. Two units are colored by
the pink and light blue spheres. d) View of the 2D crystal structurein the layer shown in c). There are four kind of inter-molecularinteractions in two-dimensional layer, b1 (face-to-face π-πstacking), b2, p, and q. All hydrogen atoms are omitted forsimplicity of the figure.

References[1] T. Isono, H. Kamo, A. Ueda, K. Takahashi, A. Nakao, R.
Kumai, H. Nakao, K. Kobayashi, Y. Murakami, and H. Mori,Nat. Commun., 4, 1344 (2013).
[2] A. Ueda, S. Yamada, T. Isono, H. Kamo, A. Nakao, R.
Kumai, H. Nakao, Y. Murakami, K. Yamamoto, Y. Nishio, H.
Mori, J. Am. Chem. Soc., 136, 12184 (2014).
[3] K. Yamamoto, Y. Kanematsu, U. Nagashima, A. Ueda, H.
Mori, and M. Tachikawa, Phys. Chem. Chem. Phys.
(Communication), 18, 29673 (2016).

Short CV: Dr. Masanori Tachikawa got Ph.D. in Waseda University in 1995, became a JSPS(PD) in Emory
University, and a Special Postdoctoral Researcher (SPDR) in RIKEN in 2000. In 2003 he moved to Yokohama City
University as an associate professor, became a professor in 2006, and now director of Department of Materials
System Science, Graduate School of NanoBioScience. His research area is “Computational Chemistry” and“Quantum Chemistry”. He is developing new quantum simulation methods, in which both electrons and hydrogen
nuclei are treated quantum mechanically. He has applied these methods to the various systems from materialscience to biochemistry. He has earned the awards for “Young Scholar Lectures of the Chemical Society of Japan,
2006”, “The Young Scientists’ Prize, The Commendation for Science and Technology by the Minister of Education,
Culture, Sports, Science and Technology 2007”, and, recently, “Award of Society of Computational Chemistry,
Japan, 2017”.

Corresponding author: Masanori Tachikawa, tachi@yokohama-cu.ac.jp, +81-45-787-2188

74

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CONTROL OF ELECTRICAL PROPERTIES ON TRANSITION METALOXIDES VIA PROTONIC-ELECTRONIC COUPLING
Hidekazu Tanaka1, Azusa N. Hattori1, Takashi Yamanaka1, Daiki Kawamoto1, Keiichiro
Hayashi1
1 Institute of Scientific and Industrial Research, Osaka University, Japan

Abstract : We report hydrogen doping into NdNiO3, SmNiO3, EuNiO3 thin films. All films exhibited large enhancement ofelectrical resistance by hydrogen doping. Furthermore, a SmNiO3 microwire with asymmetric Pt and Au microgap electrodeand microwire EuNiO3 with symmetric Pt electrodes showed electric field induced resistance change of about 10% in thein-plane two terminal device geometry.

The electrical properties of materials such as transition
metal oxides, are quite sensitive to the valence state of thetransition metals, which can be easily changed bychemical doping. A range of ionic species can be used tomodify the properties of materials or design metastablephases. Use of protons is particularly suited, and as astrong reducer can be used to realize powerful control overthe valence states in materials.1) For example, it wasreported that hydrogenation into SmNiO3 film causes
huge increase on resistivity by eight orders of magnitude,
owing to electron doped Mott transition. 2)

reduction of the hydrogenated area. With this property,
proton-based resistive memory devices can be fabricated.
Also in NdNiO3 it was reported similar proton-based
resistive switching memory devices.3) We will report thedependence of materials and microstructure of device(gap distance) on on/off ratio of electrical conductivity inhydrogenation in gas/solid interface doping and electricfield assisted proton migration.
Au/Ti

H dopedRegionAu/Ti

Experimental / Computational
The NdNiO3, SmNiO3, EuNiO3 thin films were depositedon SrTiO3 (001) substrate, and hydrogen was doped byusing the Pt catalytic spill over method in the 5%H2/Ar gas
atmosphere. a SmNiO3 microwire with asymmetric Pt andAu microgap electrode (gap distance 8m) and microwire
EuNiO3 (gap distance 10m, wire width 1m) fabricatedusing photolithography with symmetric Pt electrodes.

Results and Discussion
Hydrogen doping into NdNiO3, SmNiO3, EuNiO3 thin films
bring large enhancement of electrical resistance.
Furthermore, a SmNiO3 microwire with asymmetric Pt andAu microgap electrode and microwire EuNiO3 withsymmetric Pt electrodes showed electric field induced
resistance change of about 10% in the in-plane twoterminal device geometry as shown in Fig. 1. The
application of a positive bias at the Pt electrode leads tothe enlargement of the hydrogenated area (which is thehigh resistive state) due to the migration of protons into theentire film, while the negative bias application results in the

50µm SmNiO3

After ±20V (1sec)
After ±15V (1sec)

Resistance /MW

Introduction

4.5

4.0
After ±2V (10sec)

Pt
1

5

10 Trial

Fig. 1 Optical microscope image of a SmNiO3 microwire withasymmetric Pt and Au micro gap electrode fabricated using
photolithography(Left). Resistance modulation applying byalternating positive/negative bias voltage in the SmNiO3
microwire device (Right)

References[1] H.-T. Zhang, Z.Zhang, H. Zhou, H. Tanaka, D. D.
Fong and S. Ramanathan, Adv. Phys. 4 (2018) 1523686[2] J. Shi, Y. Zhou and S. Ramanathan, Nat. Commun. 5(2014) 4860
[3] C. Oh, S. Heo, H.M. Jang, J. Son, Appl. Phys. Lett.
108 (2016) 122106

Short CV
1997-2003: Research Associate, The Institute of Scientific and Industrial Research, Osaka University
2001-2004: Researcher, Precursory Research for Embryonic Science and Technology (PRESTO),“Nanostructure and Material Property”, Japan Science and Technology Agency (JST)2003 -2008: Associate Professor, The Institute of Scientific and Industrial Research, Osaka University.
2008-: Professor, The Institute of Scientific and Industrial Research, Osaka University
Research interests: Nanotechnology (Thin Film, Heterostructure, Nano-dot/wire), Functional Materials(Functional Oxide, ferromagnetic, ferroelectric, strongly correlated system)
Hidekazu Tanaka, h-tanaka@sanken.osaka-u.ac.jp: +81-6-68789-4280

75

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CALCULATING THE pKW OF SUBCRITICAL AND SUPERCRITICAL H2O
AND D2O
Bo Thomsen1, Motoyuki Shiga1
1 Simulation Technology Research and Development, Japan Atomic Energy Agency
In this study we seek to calculate the pKw of Sub- and Critical water using Path Integral Molecular Dynamics (PIMD). Using
this method, we are able to capture both the dynamical effects of solvent relaxation and the isotope substitution effect.
This makes this method ideal for studying the large change in pKw water undergoes at the temperature and pressure isincreased towards supercritical levels, and the isotope effect on these changes.

Introduction
The auto ionization product of water changes
drastically as the pressure and temperature isincreased [1]. The increased acidity ofsupercritical water is hypothesized to have arole in driving reactions under these conditions.
It is therefore important to understand both theclassical and quantum effects driving thischange, and we therefore wish to study both theclassical Ab-initio molecular dynamics and thequantum PIMD behaviour by elucidating theeffect of isotope exchange on the pKw ofsubcritical and supercritical water.
Experimental / Computational
A water box containing 32 water molecules were used forall simulations, the size of the box was modified to fit theexperimentally reported density of water at different
temperatures and pressures. We used the PIMD program[2] to propagate the Ab-initio and PIMD trajectories. The
electronic structure energies and gradients were provided
by DFTB+ using the ob-3 set of parameters for DFTB.

Results and Discussion
We present here our preliminary findings for
H2O, D2O and T2O at 300 K, the free energy
differences for the breaking of the O-H/D/T
bond can be found in Fig. 1. We also carried out
a calculating using only one bead, which
resulted in almost identical free energy profiles
across isotopes. The calculated pKw values forthe 12 bead PIMD calculation were 14.02, 14.85
and 14.87 for H2O, D2O and T2O respectively.
This matches well with the reported
experimental difference between light andheavy water of 0.87 pKw units. We hope toreport further results on the temperaturedependence and structural differences in waterand heavy water at the meeting.

Fig. 1 The calculated difference in free energy withrespect to bond length of the O-H/D/T bond in a solutionof H2O, D2O and T2O at 300K/1bar.

References[1] T. Yagasaki, K. Iwahashi, S. Saito, I. Ohmine, J.
Chem. Phys. 122, 144504 (2005)[2] PIMD 2.1.0, M. Shiga (2019),
https://ccse.jaea.go.jp/ja/download/pimd/index.en.html

2014 – PhD in Chemistry, Aarhus University, “Developments and Generalizations in MolecularVibrational Structure Theory”.
2014-2016 – Postdoctoral Researcher at Riken, Theoretical Molecular Science Laboratory, working
on calculating IR spectra of reverse osmosis membranes.
2016-2019 – Special Postdoctoral Researcher at Riken, Theoretical Molecular Science Laboratory,working on modelling the proton transport pathways in Bovine Heart Cytochrome c Oxidase.
Bo Thomsen

2019-now – Special Topic Researcher, Japan atomic energy agency, working on acid-base reactions
in water under subcritical and critical conditions.

Corresponding author: Bo Thomsen, thomsen.bo@jaea.go.jp, Tel. +81 070-1407-8343

76

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDROSILYLATION OF BENZOPHENONE DERIVATIVES CATALYZED BY
RARE-EARTH METAL COMPLEXES: IMPORTANCE OF AGOSTICINTERACTION BETWEEN RARE-EARTH METALS AND HYDROSILANE
Hayato Tsurugi, Koichi Shinohara, Kazushi Mashima
Department of Chemistry, Graduate School of Engineering Science, Osaka University
Rare-earth metal complexes, LnL[N(SiHMe2)2](THF) (Ln = La (1), Ce (2), Y (3); L = N,N’’-bis(pentafluorophenyl)diethylenetriamine dianion), were synthesized by treating LH2 with Ln[N(SiHMe2)2]3(THF)2. X-ray analysis of 1-3
reveals that there is agostic interaction between the metal center and Si-H moiety of the silylamido ligand:complexes 1 and 2 possess stronger agostic interaction than yttrium complex 3. Complexes 1 and 2 showed highcatalytic activity for hydrosilylation of benzophenone derivatives with HN(SiHMe2)2.

Introduction

Results and Discussion

Hydrosilylation of carbonyl compounds is importantorganic transformation to convert the carbonyl functionality
to the reduced form. The key step for the hydrosilylation is
activation of a Si-H bond of hydrosilanes: oxidative
addition of hydrosilanes to late transition metals affords
silylmetal hydrides, and subsequent insertion of the
carbonyl group into the M-H bond gives the hydrosilylation
products after reductive elimination, while Lewis acidactivation of a Si-H bond in the presence of carbonylcompounds produces the hydrosilylation product via
generation of the cationic silyl intermediate. Herein, we
report hydrosilylation of benzophenone derivatives with
HN(SiHMe2)2 catalyzed by rare-earth metal complexes, inwhich agostic interaction of the rare-earth metal centers
and Si-H moiety is a key for improving the catalytic activity.

Solid-state structures of 1-3 (Figure 1 for 2) clarify thepresence of agostic Si-H interaction between theN(SiHMe2)2 ligand and the rare-earth metal center: thelarger value of Si1—N4—Si2 indicates agostic interactionof two Si—H moieties of the N(SiHMe2)2 ligand to the metal
center in 1 and 2, while the smaller value of Si1—N4—Si2
and Y—N4—Si1 suggests one Si—H moiety interactingwith yttrium in 3. In the IR measurement, two separated
absorptions were observed at 2051 cm-1 and 2107 cm-1 foryttrium complex 3, the latter of which was typical for a SiH bond without any significant agostic interaction, whereas
one broad absorption was observed at 2002 cm-1 for 1 and2017 cm-1 for 2, respectively. It is interesting to note thatthe complexes 1 and 2, having two agostic Si-H interaction,
exhibited high catalytic activity for hydrosilylation of
benzophenone derivatives with HN(SiHMe2)2. According
to the generally accepted hydrosilylation mechanism, we
propose that strong Si-H agostic interaction facilitates
insertion of the C=O moiety of benzophenone derivatives
due to the formation of cationic silicon center. Further
mechanistic study of the catalytic reaction is presented.

Experimental
ReactionofLn[N(SiHMe2)2]3(thf)2
with
N,N“bis(pentafluorophenyl)diethylenetriamine ligand (LH2)yielded mononuclear rare-earth metal complexes,
LnL[N(SiHMe2)2](THF) (Ln = La (1), Ce (2), Y (3); L =N,N’’-bis(pentafluorophenyl)diethylenetriamine dianion)
along with two equivalents of HN(SiHMe2)2.
The
complexes 1-3 were characterized by 1H and 19F NMR
spectra and IR measurement as well as X-ray diffraction
study of the single crystals.
Upon combined with
HN(SiHMe2)2, complexes 1-3 (5 mol%) were used as
catalysts for hydrosilylation of benzophenone derivatives,
and their catalytic activities were evaluated by comparing
the yield of the corresponding diphenylmethanol
derivatives obtained after hydrolysis of the reaction
mixture.

Fig. 1 Molecular structure of cerium complex 2.

Osaka University (Ph.D., 2006), Graduate School of Engineering, Osaka University (Assist. Prof.
2006-2008), Graduate School of Engineering Science, Osaka University (Assist. Prof. 2008-2010,
Lecturer 2010-2012, Assoc. Prof. 2013-present).
[Field of research] Organometallic Chemistry, Coordination Chemistry, Catalysis

Hayato Tsurugi
Corresponding author: Hayato Tsurugi, tsurugi@chem.es.osaka-u.ac.jp, +81-6-6850-6247

77

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ROLE OF HYDROGENS AROUND HETEROINTERFACES IN IMPROVINGPASSIVATION PERFORMACE OF SOLAR CELLS
K. Gotoh1, S. Miyagawa1, Y. Nakagawa1, Y. Kurokawa1, T. Hojo2, Y. Shibayama2, E.
Akiyama2, M. Wilde3, S. Ogura3, K. Fukutani3, and N. Usami1
1 Graduate School of Engineering, Nagoya University, 2 Institute for Materials Research, Tohoku University, 3 Institute ofIndustrial Science, The University of Tokyo
We report on the role of hydrogens around heterointerfaces in improving passivation performance of silicon-based
heterojunction solar cells. Thermal desorption spectroscopy of atomic layer deposited TiOx with hydrogen clarified thatsilicon dihydride bonding energy increases when passivation performance is improved. In addition, nuclear reaction
analysis of hydrogenated amorphous Si deposited on crystalline Si suggested that local rearrangement of hydrogens at
the molecular level is responsible for the improved passivation performance. The both examples indicate the importanceof controlling hydrogens around heterointerfaces to increase conversion efficiency of heterojunction solar cells.

Introduction

Results and Discussion

High passivation performance of the surface of crystalline
silicon (c-Si) is one of prerequisites to realize highefficiency silicon-based heterojunction solar cells.
Hydrogenated amorphous Si (a-Si:H) is known to provide
excellent passivation performance. Recently, atomic layer
deposited metal oxide such as TiOx (ALD-TiOx) attracts
attention as carrier selective passivating contacts.
Passivation performance could be modified by surface
treatment of the c-Si substrate prior to deposition,
conditions of deposition, and post-deposition process.
Therefore, it is important to understand underlying physics
during the process to establish the guideline how to
improve passivation performance.

The effective carrier lifetime was largely improved whenultra-thin SiOx interlayer was formed by so-called SC-2
solution (HCl:H2O2:H2O=1:1:5) prior to deposit ALD-TiOx.
We speculate that low-density SiOx enhanced diffusion ofTi and O atoms during post deposition annealing [1],leading to formation of mixed-oxides with hydrogens. In
fact, higher silicon dihydride bonding energy wasconfirmed by TDS, suggesting that hydrogens play a rolein improving passivation performance.[2]Experimental
All experiments were carried out on double-side mirrorpolished float-zone grown c-Si(100) substrates. Aftervarious chemical treatments to form SiOx interlayer withdifferent densities, TiOx layers including hydrogens were
deposited at 150 ºC by a thermal ALD (GEMStar-6,
Arradiance). In addition, the intrinsic a-Si:H was depositedby plasma enhanced chemical vapor deposition (PECVD)
at various temperatures followed by post-annealing.
Effective carrier lifetimes were measured by WCT-120
lifetime tester (Sinton Instruments) to investigate
passivation performance. For a part of samples, thedesorption of hydrogens was characterized by thermal
desorption spectroscopy (TDS), and nuclear reaction
analysis (NRA) was performed to investigate hydrogen
depth profiles.

Effective carrier lifetime in a-Si:H/Si increased withincreasing deposition temperature or increasing post
deposition annealing up to 200 oC. NRA clarified that thehydrogen concentration decreases with increasing
deposition temperature, while no significant change wasobserved after post deposition annealing at 200 oC. Thesesuggest that local rearrangement of hydrogens at themolecular level that results in enhanced hydrogenation of
dangling bonds would be responsible for the improved
passivation performance [3].

References[1] T. Mochizuki et al., Adv. Mater. Interfaces 5, 1801645(2018).
[2] K. Gotoh et al., in preparation.
[3] K. Gotoh et al., AIP Advances 9, 075115 (2019).
*

Noritaka USAMI received the B.E. M.E., and D.E. degrees from the University of Tokyo in 1991, 1993,
and 1998, respectively. From 1994 to 2000, he worked as a research associate at the University ofTokyo. From 2000 to 2013, he worked as an associate professor at Tohoku University. Since April
2013, he has been with Nagoya University as a professor. His research interest covers a new
methodology for materials development by utilizing data science, materials and process for siliconbased solar cells, and so on. He has received various awards, including the best paper award at
PVSEC (2009), JSPS Innovative PV Award (2017), and so on. He has authored over 420 publicationsin international journals.
Noritaka Usami
Corresponding author: Noritaka Usami, usa@material.nagoya-u.ac.jp, +81-52-789-3620

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

APPLICATION OF PROTON-COUPLED ELECTRON TRANSFER
REACTION TOWARD THERMOCELL WITH HIGH SEEBECK COEFFICIENT
Teppei Yamada
Kyushu University, Faculty of Engineering
Abstract
Seebeck coefficient of thermocell, a kind of thermoelectric conversion devices, is improved by the utilization of protoncoupled electron transfer reaction of ruthenium complexes. [Ru(H xbiim)3] (H2biim = 2,2’-biimidazole, x = 0-2) shows 1e/0H,
1e/1H, 1e/2H and 1e/3H redox reactions by changing pH and solvent ratio, and the Se is improved up to −3.7 mV K−1. The
increment of the Seebeck coefficient is proportional to the dissociated proton, which is in good agreement with the theory.

Thermocells are a class of thermoelectric conversion
devices capable of recovering waste heat and convertingit to electrical energy using the offset of the redox potential.
The low cost and the high Seebeck coefficient (voltage
difference per unit temperature, Se) have recently aroused
great interest; however, the efficiency of the thermoelectric
conversion, or figure-of-merit, of the thermocell remains
lower by an order of magnitude than that of conventional
thermoelectric devices, and the thermocells require a newprocess to improve the performance of it.
We reported improved SE from ca. 2.0 mV K−1 byintroducing host-guest chemistry and found that theconcentration of redox-active species varied with thechange in temperature.[1]-[5] Ring-opening reaction ofpolysulfide was also utilized.[6]In addition to them, we utilized proton-coupled electrontransfer reaction of ruthenium complexes (Figure 1) thathave large redox entropy according to the association or
dissociation of proton accompanying to the redox reaction.
[Ru(Hxbiim)3] (H2biim = 2,2’-biimidazole, x = 0-2) shows
1e/0H, 1e/1H, 1e/2H and 1e/3H redox reactions bychanging pH and solvent ratio, and was used as a redox
species of thermocells.
Thermocell measurement revealed the high Se of −3.7 mV
K−1, which was in good agreement with the shift of peakvoltage in various-temperature square-wave voltammetry.
The Se of thermocell increases with the increase of
dissociating proton along with the redox reaction. One
proton dissociation corresponds to roughly 1.0 to 1.5 mV/K,

which is in good agreement with the protonation entropy of
buffer chemicals.

Fig. 1 The chemical structure of Ru(biim)3 and a schematic
figure of thermocell consisting of Ru(biim)3.

References[1] H. Zhou, T. Yamada, N. Kimizuka, J. Am. Chem. Soc.,
138, 10502 (2016).
[2] Y. Liang, T. Yamada, H. Zhou, N. Kimizuka, Bull.
Chem. Soc. Jpn. 92, 1142 (2019).
[3] Y. Liang, T. Yamada, H. Zhou, N. Kimizuka, Chem.
Sci., 10, 773 (2019).
[4] T. Yamada, X. Zou, Y. Liang, N. Kimizuka, Polymer J.,
50, 761 (2018).
[5] H. Zhou, T. Yamada, N. Kimizuka, Sustainable
Energy and Fuels, 2, 472 (2018).
[6] Y. Liang, T. Yamada, N. Kimizuka, ChemSusChem, 12,4014 (2019).

He received his BS (2001) and MS (2003) degrees in Science from the University of Tokyo under thesupervision of Professor Hiroshi Nishihara. After he worked at Mitsubishi Chemical Corporation(2003–2004), he moved to Kyushu University as a researcher and an assistant professor (2005-2010).
He received his Ph.D. in Science from Kyushu University under the guidance of Professor Hiroshi
Kitagawa in 2010. He then moved to Kyoto University as an assistant professor (2010-2012). Thenhe moved back to Kyushu University as an associate professor in Faculty of Engineering. His current
research focuses on the combination of electrochemistry and nanoporous materials. Supramolecular
thermocells, Ionics in metal-organic frameworks, MOF battery, asymmetric plastic crystals are studied.
Teppei Yamada
Corresponding author: Teppei Yamada, teppei343@gmail.com, 092-802-2833

79

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

STUDY OF HYDROGEN POSITION IN HYDRIDES USING WHITE
NEUTRON HOLOGRAPHY
T. Yamamoto1, S. Uechi1, Y. Kanazawa1, K. Sugimoto1, K. Ohoyama1, S. Arase2, T. Isizaki2,
S. Noda2, K. Hayashi3, N. Happo4, M. Harada5, K. Oikawa5, Y. Inamura5, T. Sato6,
S. Orimo6,7
1 Grad. Sch. Sci. and Eng., Ibaraki Univ., 2 Fac. Eng., Ibaraki Univ., 3 Nagoya Inst. Technology., 4 Grad. Sch. ofInformation Sci., Hiroshima City Univ., 5 MLF, J-PARC Center., 6 IMR, Tohoku Univ., 7 WPI-AIMR, Tohoku Univ.
Abstract We are aiming at determining H positions in hydrogen strange materials. We visualized the H structure around B
in B-doped Si by newly developed white neutron holography.

Introduction
For hydrogen storage materials, determination of theposition of H is important. However, when H does not forma crystal lattice, hydrogen cannot be observed bydiffraction. A challenging method to observe H withouttranslation symmetry is newly developed white neutron
holography which can observe the local atomic structures
around H in principle. We have already established thetechnique to observe local atomic structure around doped
B in materials. The final goal of this project is visualizationof atomic images around H to determine H positions. As
the first step, we tried to observe local structures of H
around B in hydrogenated B dope Si.

Experimental
We prepared two samples of 0.26% B-doped Si with thesame cylindrical shape. One sample was hydrogenatedunder 9 MPa H2 gas in three weeks and another was nothydrogenated. We measured the two samples using white
neutrons under the same condition at J-PARC.

Results and Discussion
Fig. 1 shows atomic images around B in 0.26% B-doped
Si. The green circles indicate Si positions, indicating that
Si around B was observed in both samples. On the other
hand, for the hydrogenated sample (Fig.1 (b)), there aresome images, such as the white image with the arrow,
whose positions cannot be explained by that of Si (green
circles). This implies that we successfully visualized H
around doped B. The blue circles indicate interstitial
positions between Si, which are consistent with the whiteatomic images, indicating that H around B is probably
located at the interstitial position.

Fig. 1 Atomic image of 0.26% B-doped Si
without 𝐇 (a). An atomic image of 0.26% Bdoped Si containing 𝐇 (b).

*Takayoshi Yamamoto was born in Chiba, Japan in 1995. He obtained his B Eng.. in Ibaraki Univ. He
belongs to Ibaraki University graduate school of Sci. and Eng..His main research is the local atomic
structures around H in hydrogen storage materials using white neutron holography.

T. Yamamoto
Corresponding author: Takayoshi Yamamoto, 19nm960f@vc.ibaraki.ac.jp, 029-352-3240

80

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

FIRST-PRINCIPLES CALCULATIONS OF HYDROGEN DIFFUSION VIANONADIABATIC CARRIER CAPTURE
Yoshiyuki Yamamoto and Osamu Sugino
The Institute for Solid State Physics, The University of Tokyo
An impurity in material can diffuse through hopping via charge state change by carrier capture. This process is possibly
important for hydrogen (H) diffusion because H atom can have large non-adiabatic coupling due to its light mass. We haveinvestigated such possibility for H atom in silicon from first principles calculations. The rate for nonadiabatic carrier capture
is obtained with the Fermi’s golden rule based on DFT/HSE06 calculations. Based on the calculated rate, we will discuss
the diffusion of H impurity in silicon via nonadiabatic carrier capture.

Introduction
An impurity in material can diffuse through hopping via
charge state change by carrier capture, known as, e.g.,
Bourgoin-Corbett process [1]. This process is likely to beimportant for hydrogen (H) impurity because H atom canhave large non-adiabatic coupling due to its light mass.
Regardless of its possible importance, this process has
not been discussed thoroughly due to experimental
difficulty to detect this kind of diffusion and computationaldifficulty to treat nonadiabatic process. In this study, we
discuss hydrogen diffusion via charge state change fromfirst principles.

difference in its activation energy. The origin of thediscrepancy is likely to be 1D approximation of the PES
and inaccuracy of electronic structure methods. With thecalculated rate, we discuss the H atom diffusion in Si
including process via charge state change.

Computational
The rate for charge state change was calculated with the
Fermi’s golden rule by considering nonradiative carrier
capture via multiphonon process [2]. Within this formalism,
anharmonic effect of phonon can be taken into account by
imposing 1D approximation for ionic degrees of freedom
and solving the Schrödinger equation for the 1D potential
energy surface [3]. Treating anharmonic effect is crucial to
study H diffusion because there exists long distance
between stable sites for each charge state. We used
DFT/HSE06 method for electronic structure calculations.

Results and Discussion
Figure 1 shows the calculated potential energy surface(PES) and the calculated rate for H- → H0 + e- transition.
The PES shows large anharmonicity due to large
difference in H atom position between the two stable sites.
Compared to the experimental rate [4], the calculated rateis underestimated by 1/100 and also shows 0.2 eV

Fig. 1 Left: calculated potential energy surface for thetransition between H- and H0. Right: calculated rate forthe transition H- → H0 + e-.

References[1] J. C. Bourgoin, K. W. Corbett, J. Chem. Phys. 59,4042 (1973).
[2] A. Alkauskas, Q. Yan and C. G. Van de Walle, Phys.
Rev. B 90, 075702 (2014).
[3] S. Kim, S. N. Hood and A. Walsh, Phys. Rev. B 100,041202(R) (2019).
[4] C. Hering, N. M. Johnson and C. G. Van de Walle,
Phys. Rev. B 64, 125209 (2001).

Short CV
Ph. D in Physics, The University of Tokyo
Apr 2015 - current, postdoc in Institute for Solid State Physics, The University of TokyoL. Yan, Y. Sun, YY, S. Kasamatsu, I. Hamada and O. Sugino, “Hydrogen adsorption on Pt (111)
revisited from random phase approximation”, J. Chem. Phys. 149, 164702 (2018).
Yoshiyuki
Yamamoto

YY, S. Kasamatsu and O. Sugino, “Scaling Relation of Oxygen Reduction Reaction Intermediates at
Defective TiO2 surfaces”, J. Phys. Chem. C 123, 19486 (2019).

Corresponding author: Yoshiyuki Yamamoto, yoshiyuki.yamamoto@issp.u-tokyo.ac.jp, +81-4-7136-3292.

81

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

FAST AND SLOW DYNAMICS OF HYDROGEN CLUSTER MATERIAL
Li6NbH11
O. Yamamuro1*, Y. Ohmasa1, H. Akiba1, S. Takagi2, K. Toshima2, K. Yokoyama2, S. Orimo2,3,
H. Saitoh4，T. Yamada5, Y. Kawakita6，K. Ikeda7, T. Otomo7
1 ISSP, University of Tokyo, 2 IMR, Tohoku University, 3 WPI-AIMR, Tohoku University, 4 QST, 5 CROSS, 6 J-PARC Center,

JAEA, 7 J-PARC Center, KEK
We have performed the quasielastic neutron scattering (QENS) measurement of Li6NbH11, which contains unusual ninefold
hydrogen-coordinated clusters. Two different QENS signals, corresponding to the relaxational motions of H atoms,
appeared between 150 K and 300 K. The slower motion should be due to the classical rotation of the NbH9 clusters, while
the origin of the faster one is still under discussion.

Introduction
Recently, Orimo group (Tohoku Univ.) has synthesized aseries of novel materials LixMH11 which contain unusual
ninefold hydrogen-coordinated clusters MH9 (x = 5 or 6, M
= Nb, Mo, W, Ta) [1]. These are of interest since they havehigh hydrogen density and possible high Li ionic
conductivity. The dynamics of MH9 cluster may play
important roles in determining the physical properties ofthe materials. We have performed the quasielastic neutron
scattering (QENS) measurements of Li6NbH11.

and area of the QENS peak, the slower motion isconsidered to be due to the classical rotation of the NbH9
clusters, while the origin of the faster one is still underdiscussion.
This work was supported by JSPS KAKENHI No. JP
18H05513 and JP18H05518.

Experimental
The QENS measurements of Li6NbH11 was conductedwith a backscattering spectrometer DNA, which is installed
at MLF, J-PARC. The sample of 20 mg was checked by aneutron powder diffraction with NOVA at MLF, J-PARC.
QENS is a powerful method to study the dynamics of H
atoms since the incoherent scattering cross-section of a
H-atom is much larger than those of other atoms including
Li and Nb.

Results and Discussion
Two different QENS signals, corresponding to therelaxational motions of H atoms, appeared between 150 K
and 300 K. Figure 1 shows the Arrhenius plot of therelaxation times which were derived by fitting the QENS
spectra to Lorentz functions. For both relaxations, it isremarkable that the temperature dependence of therelaxation time is very small, implying that the activationenergy is very small. From the Q-dependence of the width

Osamu Yamamuro

Fig. 1 Arrhenius plot for the relaxation times derived fromthe QENS data of Li6NbH11.

References[1] S. Takagi, Y. Iijima, T. Sato, H. Saitoh, K. Ikeda, T.
Otomo, K. Miwa, T. Ikeshoji, and S. Orimo, Scientific
Reports 7, 44253 (2017).

Osamu Yamamuro received his Ph.D. at Graduate School of Science, Osaka University in 1987.
After working as a research associate and assistant professor at Osaka University, he moved toInstitute for Solid State Physics, The University of Tokyo as an associate professor in 2004. He got
promoted to a full professor in 2013. He is studying chemical physics of complex condensed
matters; e.g., glasses and supercooled liquids, water and related materials, ionic liquids, hydrogenstorage/conducting solids and their nano-particles. They are investigated by neutron scattering, xray diffraction, heat capacity, dielectric and rheometric measurements. The ultimate aim of his study
is to find simple rules involved in complex systems from the three different points of view, i.e.,
structure, dynamics, and thermodynamic.

Corresponding author: Prof. Osamu Yamamuro, yamamuro@issp.u-tokyo.ac.jp, +81-4-7136-3494

82

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

CATALYTIC ENHANCEMENT ON RUTHENIUM-IRON
CATALYSTS FOR AMMONIA SYNTHESISNANOALLOY

Miho Yamauchi1*
1International Institute for Carbon-Neutral Energy Research (WPI-I2CNER), Kyushu University

Despite many advancements, an inexpensive ammonia synthesis catalyst free from hydro-gen and nitrogen poisoning,and capable of synthesizing ammonia under mild conditions is still unknown and is long sought-after. Here we present anactive nanoalloy catalyst, RuFe, formed by alloying highly active Ru and inexpensive Fe, capable of activating both N 2
and H2 without blocking the surface active sites thereby overcoming the major hurdle faced by the current best
performing pure metal catalysts. This novel RuFe nanoalloy catalyst operates under milder conditions than theconventional Fe catalyst and is less expensive than the so far best performing Ru-based catalysts providing additional
advantages. Most importantly, by integrating theory and experiments, we identified the underlying mechanisms responsible for lower surface poisoning of this catalyst, which will provide directions for fabricat-ing poison-free efficient NH3synthesis catalysts in future.

Introduction
Ammonia (NH3) is a strategic chemical produced in large
quantities. NH3 is synthesized through Haber-Boshprocess which contributes around one-third to the overall
greenhouse gas emissions and many researchers
challenge to work towards finding an alternative NH3synthesis catalyst. For the enhancement of durability ofammonia synthesis catalysts, we choose a simple
strategy where we alloyed high performance Ru and Fe
catalysts.

Surprisingly, RuFe/MgO exhibited the highest catalytic
performance under 0.5 and 1 MPa whereas we could notobserve any products on Fe/MgO, suggesting that
Fe/MgO cannot promote NH3 synthesis reaction under
the conditions applied here. Under 0.1 MPa, turn overfrequencies (TOFs) on Ru/MgO and RuFe/MgO below
400 C seemed almost the same. Meanwhile, at 500 ºC,
RuFe/MgO showed twice the performance on Ru/MgO,
Furthermore, under 1 MPa at 600 ˚C, RuFe/MgO showed
three times higher performance compared to that on
Ru/MgO,

Experimental
We prepared the Ru-Fe/MgO catalysts by hydrogen
reduction of precipitates produced on MgO supports via
thermal decomposition of impregnated carbonyl
complexes of Ru and Fe ions. In this method, metalcompositions were controllable by changing a mixing
ratio of metal complexes. Both MgO supported Ru andFe nanoparticles catalysts (Ru/MgO and Fe/MgO,
respectively) were prepared in a similar way.
The NH3 synthesis rate on the catalyst was measured
using a conventional flow system (BEL-REA, BEL Japan).
An H2/N2 gas mixture with an H2/N2 molar ratio of 3 (gashourly space velocity = 18,000 mL h–1 g–1) was then fed
to the catalyst.

Results and Discussion
Scanning electron microscope (STEM) images for
Ru/MgO, RuFe/MgO, and Fe/MgO suggested that
nanoparticles are well dispersed on MgO supports (Fig.
1). Catalytic performances at 400 ˚C for Ru-Fe/MgO withvarious compositions of Ru and Fe are shown in Fig. 1.

(g)Fig. 1. STEM images for (a) Ru/MgO, (b) RuFe/MgO and(c) Fe/MgO and (d-f) EDX maps for RuFe/MgO. (d)Distributions of Ru (red) and (e) Fe (green) and (f)overlay of (d) and (e). (g) Catalytic performance of
Ru/MgO (blue) and RuFe/MgO (red) at 1.0 MPa.

References[1] K. Ghuman, K. Tozaki, M. Sadakiyo, S. Kitano, T.
Oyabe, M. Yamauchi, Phys. Chem. Chem. Phys., 21,5117-5122 (2019).

Miho Yamauchi is a professor in International Institute for Carbon-Neutral Energy Research (WPII2CNER), Kyushu University. Her research interests involve hydrogen related properties of metal
and alloy nanoparticles, selective catalysis by using the structure controlled nanoalloy catalysts
and materials development for efficient energy conversion.

Miho Yamauchi
Corresponding author: Miho Yamauchi, yamauchi@i2cner.kyushu-u.ac.jp, Tel.+81-92-802-6874

83

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

MAGNESIUM HYDRIDE ON NITROGEN DOPED GRAPHENE FOR
HYDROGEN STORAGE
Heena Yang1,2, Andreas Züttel1,2
1Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), Basic

Science Faculty (SB), École polytechnique fédérale de Lausanne (EPFL) Valais/Wallis, Energypolis, Sion, Switzerland
2Empa Materials Science & Technology, Dübendorf, Switzerland

The nitrogen doped graphene oxide was synthesized and used as a support for MgH2. The nitrogen in graphene oxide
increases the hydrogen storage capacity and reversibility, it also decrease the hydrogen release temperature due to bondwith Mg in MgH2. This material has a potential to apply in hydrogen storage at low temperature.

Introduction

under an Ar purge [2]. This nitrogen doped graphene oxide
was mixed with MgH2 by ball-milling with different time.

Hydrogen energy is one of the alternative energy sourcesthat can replace fossil fuels that can actively replace
climate change due to global warming and become
depleted. The hydrogen storage method developed so far
includes a method of storing liquid hydrogen, a method ofstoring gaseous hydrogen, and a method of storing in theform of hydrogen alloy. Gas hydrogen storage or liquidhydrogen storage method is explosion risk at room
temperature, storage cost is high [1]. Complex hydrides
are attractive hydrogen storage materials due to their highhydrogen capacity, but generally have the disadvantage ofhigh hydrogen desorption temperatures and poor rehydrogenation reactions.
In this study, MgH2 were prepared to improve the stability
and the reversibility of hydrogen adsorption/desorption bycontrolling the size of hydrides and using supports. Other
parts are that doped carbon materials are introduced todecrease hydrogen release temperature and exhibit acomplete reversibility of the hydrogen adsorption.

Results and Discussion
The MgH2 with nitrogen doped graphene oxide were thensynthesized by ball-milling and confirmed by XRD. The FTIR analysis was conducted to confirm the functionalgroups of the nitrogen doped graphene oxide and the XPS
analysis is conducted and the relative intensities. The
effect of nitrogen for bonding with MgH2 was investigatedby in-situ XRD. This MgH2 on nitrogen doped graphene
oxide decrease the hydrogen release temperaturecompared with MgH2.

Experimental
First, graphene oxide were pretreated with HNO3 solution.
After that, HNO3-pretreated graphene oxide were filtered
and washed until pH became neutral. Then, HNO3pretreated CB was added to the mixture of dicyandiamide
with deionized water while stirring. The mixture was thenplaced in a tubular furnace and heated under an Ar
atmosphere. After finalizing the heating process, thesample was allowed to naturally cool to room temperature

Fig. 1 MgH2 on nitrogen doped graphene oxide.

References[1] A. Chambers, C. Park, R.T. Baker, N.M. Rodriguez, J.
Phys. Chem. B. 102, 4253 (1998).
[2] H. Li, G. Sun, N. Li, S. Sun, D. Su, Q. Xin, J. Phys.
Chem. C. 111(15), 5605 (2007).

Born in 1986 in Seoul, Republic of Korea, Heena Yang graduated with a Ph.D. degree in Materials
Chemistry and Engineering from Konkuk university in 2016. During this time, she worked as anundergraduate research assistant in the field of nanostructured materials and proton exchange fuelcells at Konkuk university. Her current research is focused on complex hydride for hydrogen storageat Ecole Polytechnique Fédérale de Lausanne (EPFL), Switzerland
Heena Yang
Corresponding author: Heena Yang, email: Heena.yang@epfl.ch, Tel: +41 21 69 58214.

841st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

QUANTUM TRANSITION OF HYDROGEN/ELECTRONS IN SOLID AND
SURFACES-Some theoretical aspectsMasaru Tsukada1
1Emeritus Professor at University of Tokyo

Abstract: A systematic theoretical method for quantum transition is provided by energy loss spectral function (ELSF) forhydrogen and electron embedded in an interacting medium. Based on this approach hydrogen hopping rate in solids isobtained in a wide temperature range.

Introduction
In hopping processes of hydrogen in solid or liquid,
quantum nature prevails with lowering temperature.
Quantum transitions of hydrogen are similar in certain
aspects to those of electrons coupled with phonons andelectromagnetic environment and both can beunderstood by a unified theory.
This talk provides asystematic view of quantum behavior of hydrogen or
electron in solids and surfaces focusing on interacting
effects of disturbing environment medium.

Computational/Theoretical
Quantum transition of a particle (hydrogen, proton,
electron) causes disturbance of various degrees of
freedom of external medium (phonons, solvents,
electromagnetic environment,..) which governs thetransition rate and its dependence on energy balance
and temperature. The disturbances are generally
described by an energy loss spectral function (ELSF),
which is a correlation function of external medium before
and after the transition. With introducing harmonic andlinear coupling models for external medium, a generalform of ELSF can be derived. Based on analyses of
ELSF for phonons, hydrogen quantum hopping rate aswell as its temperature and energy balance dependence
can be obtained. For case of metals, the effect ofconduction electrons on the hydrogen hopping rate canbe described in a similar framework. We will show ageneral trend of temperature dependence of hydrogen
diffusion rate in a metal in a wide range.
For the case of electron, quantum transitions in nanojunctions can be formulated by ELSF. We clarified how
features of I-V curve such as zero bias anomaly, andd 2 I / dV 2 for small voltages are closely related with theenergy dependence of ELSF. Contribution of1970

electromagnetic environment to ELSF is also obtained ina similar way as the case of phonons, with introducing amodel formed of a number of tiny LC circuits. The
dissipation mechanism is related with the observation
problem in single-electron processes.
If the initial and the final state of quantum transition areof considerably different character, a semi-classicalmodel of particle motion is appropriate and gives us acomprehensive understanding of involved phenomena as
well as ELSF. We studied a Landau-Zener processembedded in disturbing random medium, and clarified
effect of medium on an adiabatic or non-adiabatic
transition probability at a point of state crossing. The
results of stochastic trajectory calculations indicatedsuppression of adiabatic pathway. The results are
consistent with a general picture obtained by ELSF.

Results and Discussion
Effects of interaction of external medium on quantum
transition of hydrogen and electron are systematicallyformulated by energy loss spectral function (ELSF).
Using the analyses of ELSF, quantum hopping rates ofhydrogen in metals are obtained in a wide temperature
range, which reproduces well many experimental results.
This theoretical method can be applied to many quantum
tunneling processes of hydrogen including, e.g., inorganic molecules, hydrogen reaction at surfaces, and soon.

References[1] M.Tsukada and K.Mitsutake, J.Phys.Soc.Jpn., 78(2009) 084701[2] K.Mitsutake and M.Tsukada, e-J. Surf. Sci. Nanotech,
4 (2006) 311[3] M.Tsukada, J.Phys.Soc.Jpn., 51 (1982) 2927

Graduated Dept. Physics, University of Tokyo, PhD

1970-1976 Res. Assoc., Dept. Physics, University of Tokyo
1976-1982 Assoc. Prof. at IMS, 1982-1991 Assoc. Prof. at Univ. Tokyo,
1991-2004 Professor at Univ. Tokyo

2004-2009 Professor at Waseda Univ.

2008-2012 Professor at WPI-AIMR, PI 2012-2018 Administrative Director AIMR
TsukadaCorresponding author: M.Tsukada, tsukada_m2004@yahoo.co.jp Tel. 03-5617-5713

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Sapporo, Hokkaido, Japan, 2020

SYSTHESIS OF SUPERHYDRIDES UNDER HIGH PRESSURE
Katsuya Shimizu1, Mari Einaga1, Daichi Takeda1, Masafumi Sakata1, Harushige Nakao1,
Saori Kawaguchi2，Naohisa Hirao2, Yasuo Ohishi2
1 KYOKUGEN, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan, 2 JASRI, Sayo, Hyogo 6795198, Japan
High-temperature superconductors with the critical temperature exceeding 200 K were recently found in highly compressedhydrides, so-called “super-hydrides”. The superconducting hydrides consist of a lot of hydrogen atoms which weresynthesized from a mother element and hydrogen under pressure above 100 GPa and laser-heat treatment. We haveinvestigated the synthesis method and the superconducting properties of the superconductive superhydrides by using
high-pressure techniques.

Introduction

Results and Discussion

The “room-temperature superconductivity” was predicted
in a metallic state of hydrogen [1]. Hydrogen is not yet
become metallic since hydrogen is a very compressive
molecular solid, and it requires very high pressure
exceeding the current experimental limit. A precompression of hydrogen is proposed which could realize
the metallic state of hydrogen in a hydrogen-rich hydridewith reducing the critical pressure of the metallization. [2]Actually the result of the superconductivity of thecompressed sulfur hydride (H3S) [3] is one of thehydrogen-rich systems. We conducted the structural
studies of the H3S and revealed that H3S was generated
from H2S through molecular dissociation as shown by thefollowing equation: [4-7] 3H2S -> 2H3S +S. To prevent the
shortage of hydrogen, the synthesis of H3S through thedirect conversion from pure H2 and S was performed underhydrogen excessive condition.

The high purity and high crystallinity in synthesized H 3S
was successfully synthesized. It was expected that thehigher onset temperature than the previous lowtemperature compression method, however, observed Tc
was almost comparable. We expect that the direct
synthesis method can be applied to the further synthesisof hydrogen-rich systems. [8]Experimental
A diamond anvil cell (DAC) is a compact pressure device
and easy to be assembled to a refrigerator. We havedeveloped the electrical resistance measurement in thepressure range exceeding 100 GPa and the technicalachievements are widely shared with the researcher over
the world. The sample pure sulfur crystal was cut into a
rectangular shape and placed in the gasket chamber. The
chamber was filled with pure liquid hydrogen at low
temperature < 20 K in a cryostat and the pressure cell wascompressed up to 150 GPa at room temperature. The
sulfur sample became metallic and absorbed the infraredlaser light and heated. The electrical resistance as well as
the X-ray diffraction (XRD) image was monitored during
the heating.

K. Shimizu

Summary
Recently, superconductivity > 250 K at around 180 GPa in
lanthanum hydride was reported. [9,10]. The metallichydrogen-like electronic structure seemed to be stabilized
in the superhydrides in the frame of a mother element
under pressure. Comparing to the speed of progress intheoretical work, the experimental is slow. We may needto find the synthesis pathway, “a cooking recipe” ofhydrogen. The improvement of the high-pressuretechnology and the accuracy of theoretical calculation may
lead to the discovery of the room-temperature
superconductivity in the near future.

References[1] N. W. Ashcroft, Phys. Rev. Lett. 21, 1748 (1968).
[2] N. W. Ashcroft, Phys. Rev. Lett. 92, 187002 (2004).
[3] A. P. Drozdov et al., Nature 525, 73 (2015).
[4] M. Einaga et al., Nature Physics 12, 835 (2016).
[5] N. Bernstein et al., Phys. Rev. B 91, 060511(R)(2015).
[6] D. Duan et al., Phys. Rev. B 91, 180502(R) (2015).
[7] I. Errea et al., Phys. Rev. Lett. 114, 157004 (2015).
[8] H. Nakao et al., to be published in J. Phys, Soc. Jpn.
[9] A. P. Drozdov et al., Nature 569, 528 (2019).
[10] M. Somayazulu et al., Phys. Rev. Lett. 122, 027001(2019).

Our group: KYOKUGEN (Center for Science and Technology under Extreme Conditions) havedeveloped a multi-extreme condition (< 50 mK, > 3000 K, > 300 GPa, >18 T) using their original
designed diamond-anvil cells (DAC) to investigate pressure-induced phenomena in several systems
such as elemental materials, organic and inorganic molecular crystals and so on. Frontier studies anddevelopments for the pressure-induced novel properties such as superconductivity, magnetism andmetallization of simple systems. The unique experimental technique is now essential and widely
spreading to the community of materials science for future applications.

Corresponding author: Katsuya Shimizu, shimizu@stec.es.osaka-u.ac.jp, Tel.+81 66850 6675

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Sapporo, Hokkaido, Japan, 2020

QUANTUM CRYSTAL STRUCTURE IN THE 250 K SUPERCONDUCTINGLANTHANUM HYDRIDE
Ryotaro Arita1,2
1University of Tokyo, 2RIKEN Center for Emergent Matter Science

Motivated by the recent discovery of high Tc superconductivity in LaH10 under high pressure, we performed firstprinciples calculation, taking account of the effects of the zero-point motion and phonon anharmonicity. We found that
LaH10 is a ‘’quantum crystal’’ in that the quantum effects stabilize the symmetric crystalline form (Fm-3m) which favors
superconductivity, otherwise the colossal electron-phonon coupling would destroy the system. We also succeeded in
reproducing the experimental Tc accurately.

Introduction
Over the years, searching for a room temperature
superconductor has been the Holy Grail in condensed
matter physics. In 2017, Peng et al. [1] and Liu et al. [2]proposed that LaH10, a hydride of lanthanum having aclathlate-like host-guest structure, can have an extremely
high superconducting transition temperature Tc.
Recently, Somayazulu et al. [3] and Drozdov et al. [4],have reported striking evidences indicating that LaH10
subject to a pressure of 120–185 GPa indeed has Tc ashigh as 250-260 K.

ComputationalWiththestochastic
self-consistent
harmonic
approximation, we studied the effect of quantum atomic
fluctuations (i.e., zero-point energy) on the stability of thehigh-symmetric Fm-3m structure.
We also calculated Tc within the framework of anisotropic
Migdal-Éliashberg theory and superconducting theory,
taking account of strong anharmonicity of low-energy
phonons.

Fig. 1 Calculated superconducting transition
temperatures, compared with the experimental
measurements (Refs. [2] and [3]).
References

Results and Discussion[1] F. Peng, et al., Phys. Rev. Lett. 119, 107001 (2017)

We found that quantum effects are extremely large in
LaH10. They induce not just a simple hydrogen bondsymmetrization, but a full reshaping of the potential
energy landscape [5]. LaH10 is a “quantum crystal” in thatquantum fluctuations stabilize a special crystalline form
which favors superconductivity. Otherwise the colossal
electron-phonon coupling would destroy it. We also
succeeded in reproducing the experimental Tc [3,4]accurately (Fig.1).

[2] H. Liu et al., Proc. Natl. Acad. Sci. U.S.A. 114, 6990
(2017).
[3] M. Somayazulu et al., Phys. Rev. Lett. 122, 027001(2019)[4] A. P. Drozdov et al., Nature 569, 528 (2019)[5] I. Errea, F. Belli, L. Monacelli, A. Sanna, T. Koretsune,
T. Tadano, R. Bianco, M. Calandra, R. Arita, F. Mauri, J.
A. Flores-Livas, arXiv: 1907.11916

Ryotaro Arita is a Professor in the Department of Applied Physics at the University of Tokyo and aTeam Leader at RIKEN Center for Emergent Matter Science. He obtained Ph.D. from the Universityof Tokyo in 2000, and his postdoctoral work was carried out at the Max Planck Institute for Solid
State Research in Stuttgart. He is a recipient of the Ryogo Kubo Memorial Prize and Highly Cited
Researchers (Clarivate Analytics). His main interests are in first-principles studies on high Tc
superconductors, functional magnets, strongly correlated electron systems, and topologicalmaterials.
Ryotaro Arita
Corresponding author: Ryotaro Arita, arita@ap.t.u-tokyo.ac.jp, +81-3-5841-6810

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Sapporo, Hokkaido, Japan, 2020

VIOLATION OF THE SWITENDICK CRITERION IN METAL HYDRIDESEVIDENCED BY INELASTIC NEUTRON SCATTERING
Anibal (Timmy) Ramirez-Cuesta
Oak Ridge National Laboratory, Oak Ridge, TN, United States.
Abstract: Only 37.5% of the interstitial sites in the intermetallic hydride ZrV 2Hx can be occupied by hydrogen as a result of
the short-range correlations avoiding direct next H-H interaction. We present inelastic neutron scattering experiments
showing non-expected scattering at low-energy transfer. The analysis of the inelastic neutron scattering spectra reveals
that these structures originate from by hydrogen vibrations confined by neighbouring hydrogens, partially at distances as
short as 1.6 Å. This is an experimental demonstration of the violation of Switendick’s criterion, which predicts the minimal
possible hydrogen-hydrogen distance at around 2.1Å. We use DFT modelling and high performance computing (HPC) to
determine the nature of these sites and compare with experimental data.

Introduction
The Switendick limit is a consequence of the interaction
between two protons and associated electrons. In
molecular hydrogen with its H-H distance of 0.74 Å, thestrongly repulsive Coulomb force of the protons is
outweighed by the strong covalent bond. In metal hydrides,
a locally increased electron density between H-atoms is
not possible as the hydrogen electrons share bonds withthe metal electrons, and thus do not weaken the Coulomb
repulsion of the proton. As a result, the minimal hydrogenhydrogen distance in conventional metal hydrides isaround 2.1 Å under ambient conditions.

Experimental / Computational

Fig. 1 Configurational energy per 8 formula units ofZrV2H4 of with hydrogens occupying different sites.
To better understand and interpret the experimental
results, we performed atomistic first-principle calculations,using the TITAN supercomputer at ORNL, the propertiesof ZrV2 with various hydrogen stoichiometries andcoordination. Extensive combinatorial calculations of theenergetics of 3200 different minimized structures ofhydrogen-loaded ZrV2 that support the finding of
anomalous short H-H distances in the material, Fig 1.

Fig. 2 neutron scattering at various temperatures asmeasured by VISION at the ORNL. The peak at 50 meV is
the spectroscopic signature of the violation of the criteria.
These theoretical calculations allowed us to sample theconfigurational space and prove that these violations
occur and are responsible for the spectroscopic signatureobserved in Fig. 2. We estimate that the number of pairsthat break the criteria is below 5%. If so it is very difficultthat neutron diffraction will be able to measure thoseviolations. On the other hand, it paves the way to study
higher concentration using higher pressures.

Results and Discussion
Finite spectral intensity at around 50 meV occurs only
when H-H distances that are less than 2 Å. The numberof hydrogen atoms violating the Switendick criterion issmall, but strong enough to generate the unexpected peakat 50 meV. The results give insights into the creation of
new materials with novel properties such as very high Tc
superconductivity at ambient pressure. Searching theliterature, there evidence of this behaviour in other similar
compounds and materials.

Anibal J (Timmy) Ramirez-Cuesta studied Physics in Argentina and his PhD Thesis working on
computer modeling of chemical reaction on surfaces. He worked at the Rutherford Appleton
Laboratory in the UK as senior instrument scientist at the TOSCA spectrometer and developed themethodology to calculate the results of dynamical properties calculations. He is the author of the
ICEMAN software and the coauthor of the book Vibrational Spectroscopy with Neutrons: withapplications in Chemistry, Materials Science and Catalysis; World Scientific 2005. He joined Oak
Ridge National Laboratory in 2013 as Leader of the Chemical Team and currently is also thecoordinator of the Chemistry, Catalysis and Interfacial Chemistry at ORNL.
Corresponding author: AJ (Timmy) Ramirez-Cuesta, NSD, ORNL, phone: +1(865) 246 9397

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Sapporo, Hokkaido, Japan, 2020

METAL-ORGANIC FRAMEWORKS FOR THE HYDROGEN ECONOMYPetra Ágota Szilágyi
Queen Mary University of London
Metal-organic frameworks are interesting materials for the hydrogen economy as they offer multiple ways of interactingwith hydrogen (physisorption, catalytic activation), and with other materials that enable their integration in devices, suchas fuel-cell membranes. I will present my group’s latest results focussing on how to modulate the interaction strength
between the metal-organic framework hosts and guest molecules/ions with potential in facilitating the hydrogen economy.

Introduction
Metal-organic frameworks are hybrid inorganic-organic
frameworks (MOFs) are porous crystalline inorganicorganic hybrid materials with tuneable chemistry andtextural properties. [1] We have previously demonstrated
that the interaction of small molecules [2], metal atoms [3]and metal nanoclusters [4] may result in altering theproperties of the guests. This change consequently can be
exploited to tune the properties of the guest for particularfunctions, such as applications for the hydrogen economy,of which a few examples will be given.

Experimental / Computational
Metal-organic frameworks with pore sizes near and below
1 nm (UiO-66, ZIF-8) have been synthesised andfunctionalised directly or post-synthetically by grafting
various functional groups on the organic linker and/or
embedding metal nanoclusters in their pores. The samples
were screened for their interaction with hydrogen, andhydroxide ions to uncover the relevant host-guest
interactions and their impact on the materials’ function.

Results and Discussion
I will be reviewing our latest results on three different
possible applications in the hydrogen economy; i)hydrogen storage, ii) catalysis, and iii) alkaline fuel cells.
We have found that i) the functionalisation and grafting of
MOFs significantly change their hydrogen-storage
properties including the nature and strength of the storehydrogen bonds; ii) superior hydrogenation catalysts may
be obtained using systems in which nanocluster catalysts
are embedded in the pores of MOFs; and iii) selfsupporting flexible MOF membranes can be synthesised
and functionalised resulting in the possibility to engineer
their hydroxide-ion conductivity to increase by several
orders of magnitude. The last may be applied in alkaline
fuel cells.

Fig. 1 Scanning electron micrograph of aself-supporting MOF-based membrane foralkaline fuel cells
References[1] S. Kitagawa, R. Kitaura, S. Noro, Angew. Chem. Int.
Ed. 43, 2334 (2004)[2] E. Callini, P. Á. Szilágyi, M. Paskevicius, N. P. Stadie,
J. Réhault, C. E. Buckley, A. Borgschulte, A. Züttel,
Chem. Sci, 6, 666 (2016)[3] D. E. Coupry, J. Butson, P. S. Petkov, M. Saunders,
K. O'Donnell, H. Kim, C. Buckley, M. Addicoat, T. Heine,P. Á. Szilágyi, Chem. Commun. 52, 5175 (2016)[4] P. Á. Szilágyi, I. Weinrauch, E. Callini, D. M. Rogers,
S. Turner, A. Borgschulte, S. Bals, H. Geerlings, A.
Züttel, M. Hirscher, B. Dam, J. Mater. Chem. A, 5, 15559(2017)

Short CV I obtained PhD degrees in 2008 in Chemistry (University Eötvös Loránd, Budapest Hungary)and in Physics (University Paul Sabatier, Toulouse France). I previously held postdoctoral positions
at the Laboratory of Coordination Chemistry of the CNRS (France), Edinburgh University (UK), Delft
University of Technology (Netherlands), and academic positions at Curtin University (Australia),
University of Greenwich (UK). I am currently a Lecturer in Functional Materials and I am heading theAdvanced Functional Hybrid Materials research group.

Petra Ágota
Szilágyi
Corresponding author: Petra Ágota Szilágyi, p.szilagyi@qmul.ac.uk, +44 207 882 7948.

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Sapporo, Hokkaido, Japan, 2020

Phase transitions and ultra-high mechanical stress in Nb-H thin films
Philipp Klose2, Magnus Hamm1, Vladimir Burlaka1, Stefan Wagner2, Astrid Pundt2
1Göttingen University, Institute of Materials Physics, Friedrich-Hund-Platz 1, D-37077 Göttingen
2Karlsruhe Institute of Technology KIT, Institute of Applied Materials IAM-WK, Kaiserstraße 12,

D-76131 Karlsruhe

Hydrogen absorption in metals commonly leads to lattice expansion. This expansion is restricted when the metal adheres
to a rigid substrate since this does not allow for expansion at the interface. Consequently, high mechanical stresses arise
upon hydrogen uptake. Theoretically, these stresses can reach about -10 GPa for 1 H/M. Usually metals cannot yieldsuch high stresses and deform plastically by dislocation formation. Therefore,
maximum compressive mechanical stress of -2 to -3 GPa is measured for 100
nm Nb thin films adhered to Sapphire substrates. We demonstrate here thatupon size reduction plastic deformation can be hindered and even suppressed.
In this case the system behaves linearly elastic and the theoretically determined
ultra-high stress of about -10 GPa can be experimentally achieved.[1] This will
be demonstrated for epitaxial Nb-H thin films, as an example for vertical size
reduction. We suggest further strategies to maintain the coherent phasetransformation even for larger film thicknesses.[2] Such high mechanicalstresses result in changes of the materials thermodynamics.[3] In the case of
Nb-H thin films of less than 8 nm thickness, the common phase transformationfrom the α-phase solid solution to the hydride phase is completely suppressed,
Fig.1: Mechanical stress of Nb-H films
at 300 K.[4,5] This affects the storage applications of nano-sized systems.
upon hydrogen absorption .[1][1] M. Hamm, V. Burlaka, S. Wagner, A. Pundt, “Achieving reversibility of ultra-high mechanical stress by hydrogen loadingof thin films”, Appl. Phys. Lett. 106 (2015) 243108.
[2] P. Klose, M. Hamm, V. Roddatis, A. Pundt, “Influence of Fe on the mechanical stress development during hydrogenloading of ultrathin Nb-films”, Int. J. Hydrog. Energy 42 (2017) 22583.
[3] S. Wagner, A. Pundt, “Quasi-thermodynamic model on hydride formation in palladium-hydrogen thin films: Impact ofelastic and microstructural constraints “, Int. J. Hydrog. Energy 41 (2016) 2727.
[4] V. Burlaka, S. Wagner, M. Hamm, A. Pundt, “Suppression of phase transformation in Nb-H thin films below switchoverthickness”, Nano Letters 16 (2016) 6207.
[5] S. Wagner, P. Klose, V. Burlaka, K. Nörthemann, M. Hamm, A. Pundt, Structural Phase Transitions in Niobium
Hydrogen Thin Films: Mechanical Stress, Phase Equilibria and Critical Temperatures, Chem. Phys. Chem 20 (2019),
1890.

Astrid Pundt,

1985:
Abitur (A-levels), Hoffmann von Fallersleben Gymnasium (grammar school), Wolfsburg
1985 – 1991: Studied physics at Braunschweig University of Technology, Germany
1991:
Diplom degree in physics at Braunschweig University of Technology
1992 – 1995: Doctor of Natural Sciences (Dr. rer. nat.) in physics at the University of Göttingen, Germany
1995 – 1996: Postdoctoral fellow at the University of Göttingen
1996 – 2001: Habilitation (postdoctoral qualification) at the University of Göttingen2001 – 2008: Researcher and lecturer at the University of Göttingen2008 - 2018: Adjunct professor at the University of Göttingen, Heisenberg fellowship
Since 2018: full professor at Karlsruhe Institute of Technology (KIT) at Institute of Advanced Materials(IAM-WK)

Corresponding author: Astrid Pundt, astrid.pundt@kit.edu

911st Int. Symposium "Hydrogenomics" combined with
14th
Int.Symposium
Symposium"Hydrogen & Energy"
1st Int.
“HYDROGENOMICS”

Sapporo, Hokkaido, Japan, 2020

テキストを⼊力する
combined with 14 Int. Symposium “ HYDROGEN & ENERGY”
th

Sapporo, JAPAN 2020

A NEW TECHNIQUE FOR VISUALIZATION OF HYDROGEN PERMEATED
THROUGH PURE IRON USING AN IRIDIUM COMPLEX
Saya Ajito1, Tomohiko Hojo1, Motomichi Koyama1, Ken-ichi Fujita2, and Eiji Akiyama1
1 Institute for Materials Research, Tohoku University, Japan, 2 Graduate School of Human and Environmental Studies,
Kyoto University, Japan
Abstract
An in-situ technique for hydrogen visualization in a pure iron using an iridium complex was developed in this study. One
side of the iron surface was plated with palladium, and then coated with a thin film of the iridium complex. Hydrogen waselectrochemically introduced to the opposite side of the bare iron surface. The color of the iridium complex corresponding
to the hydrogen-charged area changed soon after hydrogen was introduced into the iron. This result indicates that theiridium complex can be applied for visualization of hydrogen in metals.

Introduction
In recent years, hydrogen embrittlement (HE) of steels
has been a great concern because the HE susceptibility ofsteels is highly relevant with the strength of the steels.
Since the hydrogen atoms, which induce HE, will not be
distributed homogeneously in most cases, this distribution
is of great importance for HE. Hence, there is a highdemand for visualizing hydrogen distribution.
It is known that the color of aqua (2,2’-bipyridine-6,6’dionato)(pentamethylcyclopentadienyl)
iridium(III)1(hereafter, Ir complex) changes from yellow to orange
when it reacts with hydrogen. We hypothesized that the Ir
complex on a metal substrates could visualize thehydrogen distribution. Aiming at a novel hydrogenvisualization technique using the Ir complex, we tried tosee the distribution of hydrogen permeated through an ironmembrane in this study.

hydrogen charging for 1 hour, respectively. The backsideof the left-hand side of the iron sheet was masked to avoid
hydrogen entry. The color of the Ir complex on the righthand side where hydrogen permeated was obviously
changed by hydrogen permeation.
This result indicates that the Ir complex can be applied
for the hydrogen visualization in metals. In thepresentation, quantitative analysis of the time-dependentchange in color according to hydrogen permeation will also
be introduced.

Experimental procedure
In this study, we used a 30 mm x 30 mm pure iron sheet,with a thickness of 0.25 mm. One side of the iron surface,which was used for the hydrogen-detection side, waselectroplated with palladium (Pd) to a thickness of about
400 nm. Subsequently, a thin film of the Ir complex wasformed on the Pd coated surface by putting 1 mL of amethanol solution containing 5 mg of the Ir complex andby drying. From the opposite side of the iron surface,hydrogen was electrochemically introduced. During thehydrogen charging, the Ir complex film on the ironsubstrate was monitored by a digital camera.

Results and Discussion

Fig. 1 Surface images of the Ir complex on the ironsheet (a) before and (b) after the hydrogencharging for 1 hour.

References[1] R. Kawahara, K. Fujita, and R. Yamaguchi, Angew.
Chem. Int. Ed. 51, 12790 (2012).

Figures 1 (a) and (b) show the surface images of the Ir
complex film on the iron sheet before and after the

Saya Ajito received her Ph. D. from Tokyo Institute of Technology, Japan in 2019. She is now working
in Institute for Materials Research at Tohoku University, Japan, as a postdoc. Her main interest ishydrogen absorption into steel during corrosion, which relates to hydrogen embrittlement.

Saya Ajito
Corresponding author: Saya Ajito, ajito@imr.tohoku.ac.jp, +81-22-215-2062

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Sapporo, Hokkaido, Japan, 2020

COMPLEX HYDRIDES FOR CO2 CAPTURE AND TRANSFORMATION
Lombardo Loris1,2,*, Heena Yang1,2, Andreas Züttel1,2
1 Institute of Chemical Sciences and Engineering (ISIC), École Polytechnique fédérale de Lausanne (EPFL) Valais/Wallis,

CH-1951 Sion, Switzerland.
2 Empa Materials Science and Technology, Dübendorf, Switzerland.

Abstract Ionic liquids with borohydride as anion can capture and reduce CO 2 from the atmosphere to formate, which
represents a new application to complex hydrides.

Introduction
Carbon dioxide is the main contributor for global warming,
but it also represents a cheap, abundant and safe carbon
source. During the last years, CO2 capture and utilization
has been a global intensive research area. Conversion of
CO2 to chemicals or synthetic fuels represents a promising
way to valorise this greenhouse gas[1], thus limiting theclimate change. However, mild conditions reactions ischallenging due to CO2 stability. Here we demonstrates
the CO2 reduction from air under mild conditions by
combining ionic liquids (IL) with borohydride. IL cation has
strong interaction with CO2, allowing its reduction with BH4-.

This approach represents an interesting way to capture
and reduce CO2 from the atmosphere into fuel.

Experimental
1-ethyl-1-methylpyrrolidinium borohydride ([EMPY][BH4])
was synthesized following our previous method.[2] CO2
reduction with [EMPY][BH4] was studied by NMR, FT-IR,
microbalance, and DSC.

Results and Discussion
As shown in our previous studies, the large
electronegativity of nitrogen based IL cations destabilized
BH4- anion by charge transfer, increasing the reactivity ofborohydride. When the white powder is exposed to CO2 at
atmospheric pressure and room temperature, we canobserve an increase in volume followed by a phasetransition to liquid. Based on NMR and microbalancemeasurements, the number of CO2 fixed to theborohydride was determined to be between 2 and 3 (seeFig. 1). Based on analysis and literature, the obtained
product appears to be triformatoborohydride. The reaction
can proceed at room temperature even at low CO2
concentration (6 vol% CO2, 94 vol% N2). Remarkably,[EMPY][BH4] was able to fix and reduce CO2 from air (360ppm) at 70 °C. The product can then be treated with NaOH
or HCl solution to collect formate/formic acid and the IL.

Fig. 1 CO2 reduction with [EMPY][BH4] followedby the mass change.
References
[1]

[2]

A. Gopakumar, I. Akçok, L. Lombardo, F. Le Formal,
A. Magrez, K. Sivula, P. J. Dyson, ChemistrySelect2018, 3, 10271–10276.
L. Lombardo, H. Yang, A. Züttel, Journal of Energy
Chemistry 2019, 33, 17–21.

Born in 1992, Sion, Switzerland. Loris Lombardo graduated M.S degree in Molecular and Biological
Chemistry from Ecole Polytechnique Fédérale de Lausanne (EPFL), in 2017. During this time, heworked in the fields of catalysis for CO2 reduction, water splitting, and biomass conversion. His current
research is focusing on complex hydride for hydrogen storage and CO2 reduction at EPFL,
Switzerland in the group of Prof. Andreas Züttel.

Loris Lombardo
Corresponding author: Loris Lombardo, loris.lombardo@epfl.ch, +41 21 695 82 15

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Sapporo, Hokkaido, Japan, 2020

MULTIFUNCTIONAL METAL HYDRIDES
Bjørn C. Hauback
Department for Neutron Materials Characterization, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway
This work addresses the use of neutron diffraction and synchrotron radiation X-ray scattering methods as important tools
to study the properties of functional metal hydrides. The presentation will cover determination of crystal structure,understanding of absorption and desorption processes and understanding of the effect of additives. Furthermore, recent
results using metal hydrides as a solid-state electrolyte will be presented.

Introduction
Metal hydrides form large varieties of different types ofmaterials. The traditional applications are related tohydrogen storage, but during the last decade it has foundthat these compounds are also important for battery
applications, smart windows, sensors, heat storage,
magnetism and compressors [1]During the last 10-15 years complex hydrides based onaluminum, boron and nitrogen, respectively, have been
extensively investigated. Such materials have a muchhigher gravimetric hydrogen capacity. than the traditionaltransition metal based hydrides, and thus potential
candidates for hydrogens storage application [2, 3].
Recently it has been found that boron-based complex
hydrides, for example hexagonal LiBH4 has a high Li
conduction, and thus such materials are also possible
candidates as solid-state electrolytes in Li-ion batteries [4].
Recently, high entropy alloys have been considered asinteresting compounds for hydrogen storage [5].

Results and Discussion
Hydrogen uptake and release are complicated in many ofthese compounds, with presence of several intermediate
steps and phases that can be both crystalline andamorphous. Thus, synchrotron radiation X-ray diffraction
in combination with neutron diffraction are the key
methods for detailed structural characterization. Diffraction
experiments during hydrogen desorption and absorption
are important for clarifications of the intermediate phases
and the processes for hydrogen uptake and release.
Furthermore, catalysts and additives are important toBjørn C
Hauback

promote the reactions, and therefore the combination of
XANES/EXAFS and diffraction methods are needed tounderstand the effect of additives
Selected examples of novel compounds, efforts tounderstand hydrogenation/dehydrogenation properties
including effect of selected additives will be presented.
The combination of neutron and synchrotron radiation Xray scattering will in particular be emphasized. Total
scattering methods will also be presented as an important
method to study disordered compounds.

Acknowledgements
The Research Council of Norway, EU FP7 and H2020 are
acknowledged for financial support.

References[1] R. Mohtadi, S.I. Orimo, Nature Rev. Mater. 2, 16061(2016)[2] O. Zavorotynska, A. El Kharbachi, S. Deledda, B.C.
Hauback, Int. J. Hydrogen Energy 41, 14387 (2016)[3] C. Frommen, M.H. Sørby, M. Heere, T. Humphries,
J.E. Olsen, B.C. Hauback, B.C. Energies 10, 2115 (2017)[4] A. El Kharbachi, Y. Hu, K. Yoshida, P. Vajeeston, S.
Kim, M.H. Sørby, S.-I. Orimo, H. Fjellvåg, B.C. Hauback,Electrochim. Acta 278, 332 (2018)[5] M.M. Nygård, G. Ek, D. Karlsson, M.H. Sørby, M.
Sahlberg, B.C. Hauback, Acta Mater. 175, 121 (2019)

Bjørn C. Hauback is Department Head and Chief Scientist of the Department for Neutron
Materials Characterization, Institute for Energy Technology and adjunct professor at the
University of Oslo in Norway. He has a PhD in physics from Norwegian Institute of Technology
from 1989. His main interests are structure-property relationships of hydrogen storage materials
and neutron diffraction. He is a member of Norwegian Academy of Technological Sciences.
Hauback led the Task 22 on hydrogen storage materials of the IEA Hydrogen Implementation
Agreement in 2006-2012, since then been Norwegian expert in Task 32 and 40, and he was theco-chair of the Gordon Research Conference Hydrogen-Metal Systems in July 2015.

Corresponding author: Bjørn C. Hauback, bjorn.hauback@ife.no, tel. +47 974 08 844.

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

STRUCTURAL STUDY OF HYDRIDES BY A HIGH INTENSITY TOTALSCATTERING INSTRUMENT, NOVA
Toshiya Otomo1,2,3,4, Kazutaka Ikeda1,2,3, Takashi Honda1,2,3, Hidetoshi Ohshita1,2,3, Yasuo
Kameda5
1 Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK),
Tsukuba, Ibaraki 305-0801, Japan, 2 Department Materials Structure Science, The Graduate University
for Advanced Studies (SOKENDAI), Tsukuba, Ibaraki 305-0801, Japan, 3 J-PARC Center, Tokai, Ibaraki
319-1195, Japan, 4 Ibaraki Univ., Hitachi, Ibaraki 316-8511, Japan, 5 Faculty of Science, Yamagata
University, Yamagata 990-8560, JapanA neutron total diffractometer, NOVA, which was installed at the high-intensity neutron source at J-PARC to analyse
structure of crystalline and non-crystalline materials. Hydrides are important target of NOVA and instrument developmentsfor obtaining accurate hydrogen observation are on-going.

Introduction
Neutron has large scattering cross section of lightelements, especially hydrogen, and its energy (meV) andwavelength (Å) is given by 𝑬 = 𝟖𝟏. 𝟖/𝝀𝟐 . Therefore,
neutron is unique tool to observe position and dynamics ofhydrogen in materials. A neutron total diffractometer,
NOVA, was designed to perform total scattering of
crystalline and non-crystalline materials with high intensity
and wide momentum transfer, Q, range from 0.03 Å-1 to100 Å-1 in J-PARC (Japan Proton Accelerator ResearchComplex). It is feasible to measure the static structure
factor S(Q) of the order of several ten mg samples withreasonable resolution (Q/Q ~ 0.5 %) and the atomic pair
distribution function which derived by the Fouriertransformation of S(Q) is reliable up to 200 Å [1].

Experimental
Utilizing specifications of NOVA, variety of materials suchas hydrogen storage materials, secondary battery
materials, magnetic materials, super conducting materials,
liquid and glassy materials have been investigated. Inorder to obtain accurate pair distribution function, data
reduction to absolute coherent neutron scattering crosssection is essential.
To improve the ability to observe positions of hydrogen inmaterials by NOVA following developments are on-going:
1) inelasticity correction for determination of positions of
1H atom, 2) polarized neutron apparatus for reduction of

Toshiya Otomo

incoherent scattering cross section of 1H atom, 3)
scattered neutron collimation for capillary size sample.

Results and Discussion
Inelasticity correction of hydrogen is a long-standing
problem. Adopting one of the new approaches, theintermolecular partial pair correlation functions (H-H, H-O
and O-O) of liquid water at ambient temperature wereobtained with statistically accurate diffraction data of liquid
H2O, HDO, and D2O measured by NOVA and discussed
differences the results of molecular dynamics (MD)simulation studies employing classical water-water
potentials [2]. Further approaches for inelasticity
correction and recent results of the structure analyses of
hydrides on NOVA will be presented. This work waspartially supported by the Neutron Scattering Program
Advisory Committee of IMSS, KEK (Proposal No.
2019S06) and JSPS KAKENHI Grant Numbers
JP18H05518, 18H01994, 16K05508.

References[1] T. Otomo, et al., KENS Report 17, 28 (2009-2010)[2] Y. Kameda, et al., Bull. Chem. Soc. Jpn., 91, 15861595 (2018).

1993 Dr. of Engineering, Tohoku University, Japan
1993 Post Doctoral fellow at Institute for Material Research, Tohoku Univ.
1994 Research associate, High Energy Physics Laboratory (former name of High Energy Accelerator
Research organization, KEK), Japan
2003 Associate Professor, KEK, Japan
2008 Professor, Institute of Materials Structure Science, KEK, Japan2017 Professor, Ibaraki University, Japan (Cross Appointment)2018 Deputy Head of Materials and Life Science Division, J-PARC, Japan (concurrent position)

Corresponding author: Toshiya Otomo, toshiya.otomo@j-parc.jp, +81-29-864-4333.

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

STRUCTURE AND DYNAMICS OF HYDROGEN CLUSTER MATERIAL
Li6NbH11
Y. Ohmasa1*, S. Takagi2. K. Toshima2, K. Yokoyama2, S. Orimo2,3, H. Saitoh4，T. Yamada5,
Y. Kawakita6，K. Ikeda7, T. Otomo7, H. Akiba1, O. Yamamuro1
1 ISSP, University of Tokyo, 2 IMR, Tohoku University, 3 WPI-AIMR, Tohoku University, 4 QST, 5 CROSS, 6 J-PARC
Center, JAEA, 7 J-PARC Center, KEK
Neutron powder diffraction (NPD) and quasielastic neutron scattering (QENS) measurements were performed for Li 6NbH11,
which contains unusual ninefold hydrogen-coordinated clusters. The NPD pattern shows a hexagonal structure in which
the NbH9 cluster is orientationally disordered. The QENS spectra of Li6NbH11 exhibit clear peak broadening suggesting therotational relaxation of the NbH9 clusters above 240 K.

Introduction
Recently, Orimo group (Tohoku Univ.) has synthesized aseries of materials Li6NbH11, Li5MoH11, Li5WH11, Li6TaH11
which contain unusual ninefold hydrogen-coordinatedclusters MH9 (M= Nb, Mo, W, Ta) [1]. These are of interest
since they have high hydrogen density and possible highLi ionic conductivity. The dynamics of MH9 cluster may
play important roles in determining the physical propertiesof the materials. We have performed the neutron powder
diffraction (NPD) and quasielastic neutron scattering(QENS) measurements of Li6NbH11.

intensity and the relaxation time depend on the scatteringvector and temperature, and discuss the dynamics of
NbH9 cluster more deeply.
This work was supported by JSPS KAKENHI No. JP
18H05513 and JP18H05518.

Experimental
The NPD and QENS measurements of Li6NbH11 was
conducted with a high-intensity total scattering instrument
NOVA and a backscattering spectrometer DNA,
respectively. Both instruments are installed at MLF, JPARC. Neutron scattering is a powerful method to study
materials with H atoms since the scattering cross-sectionof a H-atom, especially incoherent one, is large.

Results and Discussion
The NPD pattern of Li6NbH11 was consistent with the
hexagonal structure predicted by the DFT calculation [1],in which the NbH9 cluster is orientationally disordered.
Figure 1 shows the QENS spectra of Li6NbH11. When thetemperature is raised, the width of the spectrum increases,
indicating that the motion of the NbH9 cluster is thermally
activated. In the symposium, we will show how the QENS

Fig. 1 Quasielastic neutron scattering spectra of
Li6NbH11.

References[1] S. Takagi, Y. Iijima, T. Sato, H. Saitoh, K. Ikeda, T.
Otomo, K. Miwa, T. Ikeshoji, and S. Orimo, Scientific
Reports 7, 44253 (2017).

Yoshinori Ohmasa received his diploma and PhD in physics from Kyoto University. His doctoral
thesis is about the structure and the phase transitions of chalcogen mixed crystals under highpressure. He worked for Kyoto University from 1996 to 2008, and moved to Hiroshima Institute ofTechnology, and then to Kansai University. Since 2019 he has belonged to the Institute for Solid
State Physics (ISSP), the University of Tokyo as a project researcher. His research interest covers
the field of structurally disordered materials, such as liquid, glass, alloys and disordered crystals.
He is currently studying the dynamics of hydrogen cluster materials using neutron scattering
techniques.
Yoshinori Ohmasa
Corresponding author: Dr. Yoshinori Ohmasa, ohmasa@issp.u-tokyo.ac.jp, +81-4-7136-3298

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

RECENT DEVELOPMENTS IN HIGH TEMPERATURE METAL HYDRIESFOR THERMAL BATTERY APPLICATIONS
Terry D. Hymphries1, M. Veronica Sofianos1, Mariana Tortoza1, Arnaud Griffond1, Mark
Paskevicius1, Craig E. Buckley1
1 Physics and Astronomy, Fuels and Energy Technology Institute, Curtin University, GPO Box U1987, Perth,

WA 6845, Australia
Thermal energy storage (TES) has been developed tosolve power intermittency problems in Concentrating Solar
Thermal power (CSP) plants [1, 2]. By collecting heat
during the daytime and storing excess for use at night timeor dull periods. CSP shows considerable advantages overother renewable sources such as wind power. Although
the first generation of CSP with integrated TES has beenhighly successful, the next generation of plants will require
TES materials that can operate at higher temperatures(>600 °C) that are currently unattainable by molten nitratesalts. Metal hydrides have the potential to become the 2nd
generation TES material due to their high heat storage
capacity that is in the order of 20 times larger than molten
salts, which leads to an inherent reduction in volume ofmaterials, cost of raw materials and engineering costs.
The Hydrogen Storage Research Group at Curtin
University have been developing metal hydride materials
that reversibly absorb hydrogen at elevated temperatures.
A range of compounds have been developed using
thermodynamic stability calculations and further tuned toenable technological applications. Fluorine substitution ofhydrogen in metal hydrides has provided an approach thatallows thermodynamic stabilization of metal hydrides toform NaH1-xFx, Mg(H1-xFx)2 and NaMgH3-xFx systems, all ofwhich show significantly increased operating temperaturescompared to their hydride counterparts [3-5]. This has not
only allowed the operating temperature of these materials
to increase at moderate pressures, but has also
diminished the problems associated with metal
segregation. Upon desorption of hydrogen the metals
formed, including Mg and Na, have low vapour pressures

but the formation of metal fluorides prohibits evaporation
at elevated temperatures. Thermodynamically stable
metal hydrides, including CaH2, that are only reversible attemperatures above 850 °C, have been destabilised toallow reversibility at temperatures of ~700 °C [6, 7].
Addition of metal halides and Si have been shown to beeffective.
The development of high temperature metal hydrides will
be discussed including thermodynamic calculations,
synthesis and characterisation. Each of the systems havebeen studied by in situ X-ray diffraction andthermodynamic assessment by PCI analysis and DSCTGA. These materials have now been shown to beappropriate for upscaling towards application as thermal
batteries.

References[1] D.A. Sheppard, M. Paskevicius, T.D. Humphries, et al.,Appl. Phys. A, 122 (2016) 395.
[2] K. Manickam, P. Mistry, G. Walker, T.D. Humphries etal., Int. J. Hydrogen Energy, 44 (2019) 7738.
[3] T.D. Humphries, D.A. Sheppard, M.R. Rowles, et al., J.
Mater. Chem. A, 4 (2016) 12170.
[4] D.A. Sheppard, C. Corgnale, B. Hardy, et al., RSC Adv.,
4 (2014) 26552.
[5] M.S. Tortoza, T.D. Humphries, D.A. Sheppard, et al.,Phys. Chem. Chem. Phys., 20 (2018) 2274.
[6] A.C.M. Griffond, M.V. Sofianos, D.A. Sheppard, et al.,Appl. Energy, (2019) Submitted.
[7] M.V. Sofianos, S. Randall, M. Paskevicius, et al., J.
Alloys Compd., (2019) Submitted.

Dr. Terry Humphries is a Research Fellow at Curtin University. He is an Inorganic Chemist with aparticular interest in metal-hydrides for hydrogen storage applications. Terry excels in the synthesisof novel air/moisture sensitive compounds and the subsequent characterisation using a variety ofanalytical methods including X-ray and neutron diffraction, multi-nuclear NMR and vibrational
spectroscopy. Dr. Terry Humphries was awarded his Ph.D. in 2011 at the University of New Brunswick(UNB), Canada. He completed his first Post-doctoral role at the Institutt for energiteknikk (IFE),
Norway, and has subsequently been provided with the opportunity to be a guest researcher at the
University of Hawaii, USA, and University of Aarhus, Denmark. Dr Humphries also completed a
Research Fellowship at the Advanced Institute for Materials Research (WPI-AIMR), Tohoku
University, Sendai, Japan.
Corresponding author: Terry Humphries, terry.humphries@curtin.edu.au, +61 481 069 686.

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

NOVEL METAL HYDRIDES DISCOVERY AND APPLICATION
Martin Dornheim
Helmholtz-Zentrum Geesthacht, Geesthacht, Germany
Abstract
In this presentation results on selected hydrides and hydride composites as well as measures for scale-up of materials
synthesis and testing are reported. A newly built infrastructure for testing of scaled-up hydrogen storage systems ispresented. The potential of metal hydrides for hydrogen storage applications is discussed.

Introduction
While significant work on metal hydrides for hydrogenstorage started already in the 1980s, so far only few
materials are utilized for hydrogen storage or hydrogencompression applications.

methods and achieved results on the scale-up of synthesis
and testing of different hydrides is shown.
Advantages and limitations of their possible usage forhydrogen storage applications will be discussed.

In recent years a huge number of novel light weight
hydrides as well as so-called Reactive HydrideComposites has been discovered with many of themshowing rather good cycling stability and enhanced
gravimetric storage capacity.

Experimental / Computational
Reactive Hydride Composites were characterized bydifferent techniques as in-situ XRD, small angle X-ray
scattering, EXAFS and XANES, volumetric Sieverts’ typemeasurements, TEM, in-situ neutron radiography etc..
A novel tank testing apparatus for large scale hydrogenstorage testing has been developed. Its properties andcapability will be reported.

Results and Discussion
Insights about reaction mechanisms, sorption behaviour,cycling stability of light weight hydrides and Reactive
Hydride Composites, the influence and optimisation ofcompaction on such materials to pellets and the behaviourof such pellets under in-situ conditions are given.
The possibility for scale-up of the synthesis as well as the
kinetic and cycle behavior of larger sample batches
considering for example the effect of temperature
inhomogeneities on the performance and cycle life time ofthe storage materials has been studied. An overview about

Fig. 1 Reaction Scheme of Reactive HydrideComposites
References
1. M. Dornheim, Thermodynamic Properties ofMetal Hydrides, Chapter in Thermodynamics– Interaction Studies Solids, Liquids, Gases
edited by J.C. Moreno, InTech (2011) 891914,
ISBN 978-953-307-563-1,
http://www.intechopen.com/articles/show/title/
thermodynamics-of-metal-hydrides-tailoringreaction-enthalpies-of-hydrogen-storage-materials

Employment records:
Scientific and Strategic Deputy Director of the Materials Technology division at HZG since 2014.
Lecturer at Helmut-Schmidt University, Hamburg, Germany since 2012
Lecturer at Hamburg University of Technology since 2005.
Head of the Nanotechnology Department, at HZG since 2005.

M. Dornheim

Education:
Dr. rer. nat. (PhD) in experimental Material Physics, Universität Göttingen, Germany, 2002.
Dipl.-Phys. (~Master of Science): diploma thesis in computational solid state physics at Universität
Göttingen, Göttingen, Germany, 1998.
Vordiplom (~bachelor) in Physics: Universität Hamburg, Hamburg, Germany 1994

Corresponding author: Dr. Martin Dornheim, martin.dornheim@hzg.de, Tel. +494152872604

97

1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HYDRIDE-BASED SOLID STATE LI-ION BATTERIES FOR ENERGYSTORAGE
Michel Latroche1, Anh Ha Dao1,2, Pedro López-Aranguren2, Junxian Zhang1, Fermín
Cuevas1 and Christian Jordy2
Affiliation 1ICMPE (UMR7182), CNRS, UPEC, F-94320 Thiais, France, 2Saft, 111 Bd. A. Daney, 33074 Bordeaux, France.
Abstract : Looking for safe and efficient energy storage systems is a very high challenge for the energy transition. It istherefore necessary to develop new, affordable and safe systems able to fulfil the requirements for efficient storage
operating near ambient conditions. Metal and complex hydrides are widely studied for their astonishing properties. They
are foreseen for H2 gas storage or batteries to harvest renewable energies. In the present work, we propose the
combination of various materials, including metal and complex hydrides to develop practical solid-state Li-ion batteries.

Introduction
Solid-State Lithium-ion Batteries (SS-LiBs) are widely
studied as they offer solutions to some drawbacks ofconventional batteries such as safety issue, energy
density and power limitations. For LIBs, metallic andcomplex hydrides may act either as negative active
materials or solid electrolytes (SE) in next generation of
SS-LiBs. LiBH4-based SEs have shown recently good
properties as solid ionic conductors; however, theiroperating range remains above room temperature limiting
their application domains [1-5].

state cell operated either at 25 or 40°C using
Li6PS5Cl5/6(BH4)1/6 argyrodite as SE.

Experimental
Solid-state cells were assembled by pelletizing materials
with a 10-mm diameter die into a sealed Teflon Swagelok
cell. The cathode consisted of 25:5:70 wt% of active
material (NMC-LiNi1/3Mn1/3Co1/3 or TiS2): carbon C65: SE.
Substituted argyrodites Li6PS5X5/6(BH4)1/6 (X=Cl, Br, I)
were used as SEs [6]. Three mg of cathode material and
80 mg of SE were pressed at 2 tons to make 2-layer pellets.
A 9 mm-diameter indium-lithium double-layer disk wasplaced on top of the SE side, where indium is sandwiched
between Li and SE, and pressed with the pellet. The cell
was heat-treated overnight at 75 °C and then cycled witha battery tester (MPG-2, Biologic) near RT.

Results and Discussion
In the present work, we combined cathode materials ofdifferent potentials (NMC or TiS2) with Li-In anode using
substituted argyrodites as SE. These SEs provide highionic conductivity near RT [6]. As an example, Fig. 1 shows
the potential profiles of an NMC/C65/SE | SE | Li-In solid-Michel Latroche

Fig. 1 First charge/discharge cycles at 25 and 40°C for
an NMC/C65/SE | SE | Li-In solid-state battery.

References[1] P.E. de Jongh et al., Appl. Phys. A. 122 (2016)[2] M. Matsuo, S. Orimo, Adv. Energy Mater. 1, 161 (2011)[3] S. Sartori et al., Appl. Phys. A. 122, 135 (2016).
[4] P. López-Aranguren et al., J. Power Sources, 357, 56(2017).
[5] M. Latroche et al.; Int. J. Hydrogen Energy, 44, 7875
(2019).
[6] A. H. Dao et al., Solid State Ionics, 339, 114987 (2019).

Dr. Michel LATROCHE is currently Director of Research at ICMPE CNRS in France. He studied at
Nantes University (F) and obtained his PhD at the Institut Jean Rouxel in the field of Solid State
Chemistry. After a post-doctoral position with Prof. J. Ibers at the Chemistry Department ofNorthwestern University in Chicago (USA), he joined the group of Dr. A. Percheron-Guégan in
Meudon (F) to work in the field of metal hydrides. His research works deal with structural, physical,
thermodynamic and electrochemical properties of metals or intermetallics and their hydrides. His
research activities are devoted to fundamental aspects of these materials in relation with theirapplications such as negative electrode for NiMH and Li-ion batteries or hydrogen gas storage for fuelcells. He has published more than two hundred fifty publications in this field and filed twelve patents.

Corresponding author: Latroche Michel, michel.latroche@cnrs.fr , Tel. +33 1 4978 1210.

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

HIGH-PRESSURE
SYNGHESISOFNOVEL ALUMINUM-BASEDHYDRIDES USING SYNCHROTRON RADIATION X-RAYS
H. Saitoh1,2, M. Tanikami1,2, A. Machida1, T. Watanuki1,2, T. Sato3, S. Takagi3, S. Orimo3, K.
Ikeda4 and T. Otomo4
1 National Institutes for Quantum and Radiological Science and Technology, 2 Hyogo university, 3 Tohoku University,
4 High Energy Accelerator Research Organization
Novel aluminum-based hydrides have been synthesized using high-pressure and high-temperature techniques, where insitu synchrotron radiation x-ray diffraction measurement are effectively used to find synthetic conditions, to optimized them,and to investigate the reaction mechanisms. The obtained hydrides were recovered at ambient conditions andcharacterized by synchrotron radiation and neutron diffraction techniques to investigate their crystal structures.

Introduction
Chemical potential of hydrogen becomes extremely highat high pressure above 1 GPa and reacts with metals andalloys to form hydrides which cannot be obtained aroundambient pressure. We are trying to synthesize novel
aluminium-based hydrides with the aid of synchrotron
radiation X-ray diffraction measurement. Synchrotron
radiation X-ray diffraction measurement enables us to findsynthetic conditions of target materials, to optimize these
conditions, and to clarify these reaction mechanisms. The
obtained hydrides are recovered at ambient conditions
and characterized.

Experimental
Starting materials were pressurized to target pressures atroom temperature and then were heated to target
temperatures in hydrogen fluid. High-pressure and hightemperature conditions were generated using a cubic-type
multi-anvil high-pressure apparatus. Structural changes ofsamples were monitored by an in-situ synchrotron
radiation X-ray diffraction measurement system installed
at BL14B1 at SPring-8 [1]. The recovered samples werecharacterized by synchrotron radiation x-ray (SPring-8

Hiroyuki Saitoh

BL22XU) and neutron (J-PARC NOVA) diffraction
techniques.
.Results and Discussion
We have synthesized some novel aluminium-based
hydrides, such as Al-TM (TM = Cr, Mn, Fe, Co, Zr, and Hf)
in addition to the previously reported Al2CuHx [2]. Crystal
structures of some of them have been analysed andclarified. The detailed results will be presented.
This work was supported by JSPS KAKENHI, Grant
Numbers, JP18H05513 and JP18H05518, and the InterUniversity Cooperative Research Program of the Institutefor Materials Research, Tohoku University (Proposal Nos.
18K0032 and 19K0049). The neutron scatteringexperiment was approved by the Neutron Scattering
Program Advisory Committee of IMSS, KEK (Proposal No.
2014S06).

References[1] H. Saitoh, A. Machida, and K. Aoki, Chinese Sci. Bull.
59, 5290 (2014).
[2] H. Saitoh, S. Takagi, N. Endo, A. Machida, K. Aoki, S.
Orimo, and Y. Katayama, APL Mater. 1, 032113 (2013).

Hiroyuki Saitoh is currently a senior principal researcher at Quantum Beam Science Research
Directorate, National Institutes for Quantum and Radiological Science and Technology (QST), Japan.
He received his PhD degree in material science from Tsukuba University in 2003, where heinvestigated structural phase transitions of macromolecules using X-ray diffraction technique. He
joined Japan Atomic Energy Research Institute, the former organization of JAEA, as a postdoc. He
became a tenured scientist at JAEA in 2011. He moved to the present position due to a reorganization.
His research interests focus on high-pressure synthesis of functional materials, especially metal
hydrides, with the aid of synchrotron radiation X-ray diffraction techniques.

Corresponding author: Hiroyuki Saitoh, saito.hiroyuki@qst.go.jp, +81-791-58-1014.

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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

MATERIAL DEVELOPMENT OF H– CONDUCTIVE OXYHYDRIDESGenki Kobayashi1,2
1 Institute for Molecular Science, National Institutes of Natural Sciences, 2 The Graduate University for Advanced Studies(SOKENDAI)
Hydrogen transport in solids is a key technology for electrochemical devices such as fuel cells, batteries, and chemical
reactors. Recently, hydride (H–) has come to be recognized as a new charge carrier for hydrogen transport, which opened
up a new frontier in solid state ionics and electrochemistry. Here, we report on the current states and prospects for thematerial exploration for H– conductors, targeting H– conductive oxyhydrides we have developed so far.

Introduction

Results and Discussion

A hydride ion (H–) is an attractive charge carrier
because it exhibits promising features for fast ionic
conduction; namely, monovalence, suitable ionic size
similar to that of F– and O2–, and high polarizability.
Furthermore, hydride ions exhibit strong reducing
properties through the standard H–/H2 redox potential (–2.3 V vs. SHE), which can be expected to be applied tonovel electrochemical devices. In 2016, H– conduction inoxide-based flamework structure has been realized in2016 by finding a series of H– conductive oxyhydrides La2–
(LSLHO)1 with the K2NiF4-typex–ySrx+yLiH1–x+yO3–ystructure, possessing capability of H– solid electrolytes.
The discovery of LSLHO has triggered materials
exploration for H– conductors, and several H– conductive
oxyhydrides with the K2NiF4-type and fluorite-type
structures have been reported so far2-4. In the presented
study, I would like to introduce our material developmentof H– conductors, focusing on K2NiF4-type oxyhydrides.

In the K2NiF4-type oxyhydrides represented as A2BX4(X = H, O), anion configuration depends on the valance of
cations at the A- and B-sites. Hydride ions in the Sc-based
oxyhydride occupy the apical site rather than theequatorial site in the ScX6 octahedra, which is clearly
contrasted to that of Li-series1-3. This tendency can beunderstood by electrostatic argument; the less charged H–(compared to O2–) ions prefer the site showing the smaller
bond strength sums. The relationship between
conductivity and structure will be discussed in thepresentation.

[LiHO][Ln2O2][LiHO]

Ln3+Li+HO3 (Ln = La, Nd, Pr)

Experimental
Hydride conducive oxyhydrides were synthesized bysolid state reaction using oxides and hydrides of eachelement as the starting materials. As needed, highpressure was applied to the synthesis system tosuppress loss of hydrogen source. The crystal structures
for the obtained compounds were determined by Rietveld
analysis to X-ray and neutron diffraction data. Ion
conductivities for the samples were measured byelectrochemical impedance spectroscopy (EIS). The
transport number for each sample was confirmed by the
Hebb-Wagner polarization method and electromotive
force measurements using hydrogen concentration cells.

G. Kobayashi

Equatorial H –Apical H–[ScO2][Ba2HO][ScO2]
Ba2+Sc3+HO3

Fig. 1 Comparison of the crystal structure of Ln2LiHO3 (Ln= La, Pr, Nd) and Ba2ScHO3

References[1] G. Kobayashi et al., Science, 351, 1314 (2016).
[2] Y. Iwasaki, G. Kobayashi, R. Kanno et al., J. Mater.
Chem A, 6, 23457 (2018).
[3] F. Takeiri, G. Kobayashi et al., Inorg. Chem., 58, 4431
(2019).
[4] S. Iimura, H. Hosono et al., Nat. Comm., 10, 2578
(2019).

Genki Kobayashi currently an Associate Professor based at the Department of Materials Molecular
Science at the Institute for Molecular Science, Japan, where I have held this position since 2018.
Based on fundamental studies into solid-state chemistry, I have been investigating materials for use
in electrochemical energy storage/conversion devices since 2006. His current research focuses on
hydride ion (H−) conduction in solids. He recently developed H– conductive oxyhydrides, anddemonstrated the first battery reaction based on H− diffusion. In addition, he received the several
research awards, such as the Spriggs Phase Equilibria Award in 2010 from the American CeramicSociety, the 39th Honda Memorial Young Research Award in 2018 from the Honda Memorial
Foundation, 7th Ishida Award in 2018, from Nagoya Univ., and Tagawa Memorial Young ResearcherAward in 2019 from Electrochemical Society of Japan.

Corresponding author: Genki Kobayashi, gkobayashi@ims.ac.jp, Tel. +81-564-55-7440

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HETEROGENEOUS CATALYTIC REACTIONS FROM VAN DER WAALSDENSITY FUNCTIONAL
Ikutaro Hamada
Department of Precision Science and Technology, Graduate School of Engineering, Osaka University
Accurate description of molecular surface interaction is prerequisite for microscopic understanding of molecular adsorption
and chemical reaction that take place on the surface and interface. Herein I present recent results of theoretical study onmolecular adsorptions and chemical reactions on metal surfaces by using the van der Waals density functional that is able
to describe both covalent and noncovalent interactions accurately, including carbon dioxide hydrogenation and formic aciddehydrogenation on a metal surface. The mechanisms of these reaction are discussed in detail.

Introduction
Understanding of the microscopic mechanisms of theheterogeneous catalytic reactions that take place atsurfaces and interfaces is crucial to develop efficientenergy and material conversion devices, such as fuel cells
and three way catalysts for automotive exhaust. Density
functional theory within the semilocal approximation, i.e.,
generalized gradient approximation (GGA), has been used
for this purpose. However, it is well known that thesemilocal approximation fails to accurately describe
dispersion, or van der Waals (vdW) forces, which isessential in inter-molecular and molecule-surface
interactions. The development of the van der Waals
density functional [1] and its offsprings [2,3], and theirefficient implementation [4,5] enables one to describe thevdW forces accurately and efficiently, which leads to more
precise description of molecular adsorption andheterogeneous catalytic reactions on solid surfaces.

Hydrogenation of CO2 on Cu(111)
Adsorption and reaction of CO2 on solid surfaces are oftechnological importance concerning the energy andenvironmental management. Elucidating the reaction
mechanism is crucial to develop more efficient catalysts
for CO2 utilization. We study the CO2 adsorption andreaction on Cu(111) by means of vdW-DF. We proposethat the CO2 hydrogenation to formate takes place via the
Eley-Rideal mechanism[6]. Furthermore, we predict thatvibrational O-C-O bending mode of CO2 enhances thehydrogenation of CO2 [6], which has been verified
experimentally [7].

mechanism is important for utilization of HCOOH. We use
vdW-DF to study adsorption and decomposition of HCOO
on Cu(111). We found that vdW-DF improves theadsorption energy of HCOOH on Cu(111) over GGA andthe calculated adsorption energy agrees well with theexperiment. We then investigated the decomposition of
HCOOH and found that the activation barrier is lower thanthe desorption (adsorption) energy, implying that
decomposition is preferred over desorption, in
contradiction with the experiment at room temperature. To
resolve the contradiction, we performed the reaction rate
analysis base on the vdW-DF calculations. We found thatat room temperature, the calculated desorption rate ishigher because of larger preexponential factor, suggestingthat no HCOOH decomposition takes place [8].

Acknowledgment
This work was partially supported by Grant-In-Aid for
Scientific Research on Innovative Area “Hydrogenomics”(contract No. JP19H05519). This work has been done incollaboration with Yoshitada Morikawa, Kouji Inagaki, Yuji
Hamamoto, Fahdzi Muttaquin, and Septia Eka Marsha
Putra.

References[1] M. Dion et al., Phys. Rev. Lett. 92, 246401 (2004).
[2] J. Klimeš, et al., Phys. Rev. B 83, 195131 (2011).
[3] I. Hamada, Phys. Rev. B 89, 121103 (2014).
[4] J. Wu and F. Gygi, J. Chem. Phys. 136, 224107(2012).

Formic acid adsorption and decomposition
on Cu(111)[5] Y. Hamamoto, et al., Phys. Rev. B 93, 245440 (2016).

Formic acid (HCOOH) has been considered as a potential
material for hydrogen storage for proton exchange
membrane fuel cells, and elucidating its decomposition[7] J. Quan, et al., Nat. Chem. 11, 722 (2019).

[6] F. Muttaqien, et al., Chem. Comm. 53, 9222 (2017).
[8] S. E. M. Putra, J. Chem. Phys. 150, 154707 (2019).

Ikutaro Hamada received his PhD from Osaka university in 2003. After working in Institute for Scientificand Industrial Research, Osaka University as a specially appointed Assistant Professor/postdoc
researcher, he joined WPI-AIMR, Tohoku University as an Assistant Professor and then moved to
National Institute for Materials Science as a senior researcher. In 2017, he joined Osaka University
as an Associate Professor. His research interest is the electronic structure theory and its application
to surface and interface problems.
Ikutaro Hamada
Corresponding author: Ikutaro Hamada, e-mail: ihamada@prec.eng.osaka-u.ac.jp

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Sapporo, Hokkaido, Japan, 2020

SCIENCE OF
HYDROGEN & ENERGY
AWARD

The “Science of Hydrogen & Energy” award is a price, just similar to the Nobel price, for an
extraordinary contribution to the sciences of hydrogen. The aim is to award a prize to a
distinct scientist for their scientific work of a life time.

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2007

2008

2009

Prof. Dr. Ronald Griessen

Prof. Dr. Louis Schlapbach

Dr. Gary Sandrock

2009

2010

2010

Prof. Dr. Jens Norskov

Prof. Dr. Rüdiger Bormann

Prof. Dr. Ivor Rex Harris

2010

2011

2012

Prof. Dr. Rainer Kirchheim

Prof. Dr. Koji Hashimoto

Prof. Dr. Mogens Mogenson105

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2013

2014

2014

Mr. Katsuhiko HIROSE

Prof. Dr. Hans GEERLINGS

Prof. Dr. Qidong WANG

2014

2015

2015

Prof. Dr. Andreas ZÜTTEL

Prof. Dr. Bernard DAM

Prof. Dr. Shin-Ichi ORIMO

2015

2015

2016

Dr.Michael HIRSCHE

Prof. Dr. Bjørn HAUBACKDr. Young Whan CHO

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2016

2016

2016

Prof. Dr. Craig JENSEN

Prof. Dr. Torben R. JENSEN

Prof. Dr. Min ZHU

2017

2017

2018

Prof. Dr. Ping CHEN

Dr. Robert BOWMAN

Prof. Dr. Michael GRÄTZEL

2019

Prof. Dr. Henning Zoz

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SCIENCE OF HYDROGEN & ENERGY AWARD 20202014-now Deputy Research Director of the Institute of Materials
Technology and Centre for Hydrogen Technology at theHelmholtz-Zentrum Geesthacht, Germany
2005-now Headofthe
Department
ofNanotechnology
and the Hydrogen Storage Activities at the HelmholtzZentrum Geesthacht
2003-2005 Deputy Head of the Department of Nanotechnology,
Helmholtz-Zentrum Geesthacht
2002-2003 Deputy Group Leader “Hydrogen in Metals”, Georg-AugustUniversität, Göttingen
2002

PhD., Material Physics, „Impact of stress and strain on
thermodynamics of metal hydride systems“, Georg-AugustUniversität, Göttingen

1998

Dipl.-Phys, Theoretical Solid State Physics, “atomistic
simulations of misfit dislocations in semiconductor
heterostructures”, Georg-August-Universität, Göttingen

1994

Phys.-Vordipl., Universität Hamburg

Dr. Martin Dornheim

After his early work on the effect of stress and strains on the phase boundaries of hydride phases in yttrium and niobium
thin films he moved to the Helmholtz-Zentrum Geesthacht where he continued to work on hydrides and the effect ofadditives on nucleation and growth as well as on the grain sizes and grain size stability in magnesium hydride. He wasinvolved in the discovery of the formation of different borohydrides (LiBH4, NaBH4 and Ca(BH4)2) starting from MgB2 andthe respective alkali(ne earth) metal hydrides and led the comprehensive investigations on the reaction mechanisms inReactive Hydride Composites (RHCs). He started, developed and led new comprehensive in-situ measurements on thereaction mechanism and the effect of additives in RHCs, which led to an enormous increase of cycling stability of RHCs
and composites of RHCs and polymers. Under his leadership, HZG started in 2005 the development and characterisationof hydrogen stores based on interstitial hydrides, complex hydrides and hydride composites for a wide range of applications
from the gram scale of hydrogen up to the tens of kg of hydrogen scale.
We award Dr. Martin Dornheim for outstanding work in the science of hydrides, the discovery and characterization ofreaction mechanisms of new hydride systems as well as the development and characterization of hydrogen storage tanksystems based thereon with the Science of Hydrogen & Energy prize 2020.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2020

Dr. Michel LATROCHE

2015

Representative Officer for the Energy Research Coordination
at the Institute of Chemistry at CNRS.

2012

Director of ICMPE, CNRS, Thiais, France.

2010

Member of the International Steering Committee of theInternational Symposium on Metal-Hydrogen Systems

2009

Adjunct Director of ICMPE, CNRS, Thiais, France.

2006

Expert member at International Energy Agency IEA-HIA; Task
22, 32 and 40.

2005

Director of Chemical Metallurgical Chemistry of Rare Earth Lab,UPR 209, Thiais, France.

1988

Postdoctoral Fellow, Northwestern University, Chemistry
Department, Evanston, Illinois, USA.

1994

Habilitation to Direct Research (HDR), University of Paris Sud,
Material Science, 1994.

1988

PhD University of Nantes, Solid Chemistry.

Dr. Michel Latroche main scientific interests are focussed on metallic compounds obtained by combining various metals
such as rare earths, transition elements, or p-elements. These intermetallics have original physical and chemical properties
with the ability to reversibly absorb hydrogen over a wide range of temperature and pressure to form metal hydrides. Dr.
Michel Latroche had developed in the nineties new experimental set-up to follow in-situ the hydrogenation reaction of thesematerials using neutron diffraction. These experiments have been later extended to the electrochemical reactivity of thesematerials allowing to elucidate the complex mechanisms involved in the reversible hydrogenation reaction and leading to
improved materials for energy storage applications. Dr. Michel Latroche has also investigated the properties of metallic
hydrides dispersed at the nanoscale in various porous materials (Carbon, MOFs) to form composites with peculiar
properties combining ad- and absorption of hydrogen. More recently, Dr. Michel Latroche has developed the use of metallic
hydrides as anode materials for Li-ion batteries showing the high capacity of these materials by using a conversion reaction
with lithium. He has set up a prototype for an electrochemical cell combining hydrides used both as anode and electrolyte.
We award Dr. Michel LATROCHE for outstanding work in the science of hydrides, the discovery of new hydride systems,
reaction mechanisms and tunable properties of hydrides with the Science of Hydrogen & Energy prize 2020.

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1st Int. Symposium "Hydrogenomics" combined with
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Sapporo, Hokkaido, Japan, 2020BEST POSTER AWARDS
2007

2012

2013

Ms. Alondra Torres Trueba

Mr. Andreas Bliersbach

Mr. Moreno De Respinis

2014

2015

2015

Mr. Yixiao Fu

Dr. Shunsuke Kato

Mr. Nikolai Biliskov

2016

2016

2017

61

Ms. Efi Hadjixenophontos

Ms. Guanqiao Li

Ms. Marina Chong110

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2017

2018

Ms. Katherine Hurst

Ms. Stavroula (Alina) Kampouri

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Sapporo, Hokkaido, Japan, 2020BEST POSTER AWARD 2019
Dr. Young-Su Lee“INTERFACE ENHANCED LITHIUM ION CONDUCTION IN LIBHAOXIDE MIXTURES”
High Temperature Energy Materials Research Center,
Korea Institute of Science and Technology, Seoul, Republic of Korea
Young-Su Lee majored in materials science and engineering and her
specialty is first-principles simulation. She received PhD degree in2006 from Massachusetts Institute of Technology, and started hercareer as a senior research scientist at Korea Institute of Scienceand Technology in 2007. Ever since she joined KIST, her research
activities have centered around the materials for hydrogen energy,
such as structural/thermodynamical properties of metalborohydrides, nanostructuring of hydrides for hydrogen storage,
metallic hydrogen separation membranes, etc. Current research
focuses are room temperature hydrogen storage materials and ionic
conduction in hydrides.

“INTERFACE ENHANCED LITHIUM ION CONDUCTION IN LIBHA-OXIDE MIXTURES”
A solid-state Li ion conductor composed of LiBH4 and SiO2/Al2O3 was synthesized by a simple ball-milling
process. The ionic conductivity of the mixture reached as high as 2x10-4 S cm-1 at room temperaturewhen the volume fraction and the particle size of the oxide material were optimized. The interface
between LiBH4 and oxides is likely to support such high ionic conductivity. By applying a continuum
percolation model, the interface conductivity was estimated to be 104~105 times higher than that of pure
LiBH4. The increase in conductivity is accompanied by the lowered activation energy for the Li ion
conduction. First-principles calculation demonstrated that the Li ion migration barrier in LiBH4 is as small
as ~0.2 eV and suggested that Li ion defect accumulation at interface may deliver the remarkable rise in
conductivity.

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Sapporo, Hokkaido, Japan, 2020BEST POSTER AWARD 2019Dr. Marco Calizzi“FeCO NANOPARTICLES FOR CO2 HYDROGENATION”
Laboratory of Materials for Renewable Energy (LMER), Institute ofChemical Sciences and Engineering (ISIC). Basic Science Faculty(SB), École polytechnique fédérale de Lausanne (EPFL) Valais/Wallis,
Energypolis, Sion, Switzerland
Bom in October 1989 in Bologna.
2013 - Master degree in Physics at University of Bologna, Italy, thesis"The nanostructured Mg-Ti system for solid state hydrogen storage",supervisor Prof. Luca Pasquini in collaboration with ICMPECNRS in
Paris, France with Dr. F. Cuevas.
2017 - PhD in Physics at University of Bologna, Italy, with thesis"Advances in nanoparticle condensation from the gas phase: Mgbased and TiO2-based materials for energy applications", supervisor
Prof. Luca Pasquini.
Since July 2017 - Post-doc in Prof. Andreas Züttel's Laboratory ofMaterials for Renewable Energy (LMER), École PolytechniqueFédérale de Lausanne (EPFL) Valais / Wallis, Sion, Switzerland,
working on thermal CO2 reduction.

“FeCO NANOPARTICLES FOR CO2 HYDROGENATION”
The idea of producing synthetic fuels is a very attractive option: retaining all the benefits of fossil fuels
and, at the same time, having a closed and sustainable energy cycle, where the CO2 produced fromcombustion is captured and converted into fuel again. In this framework, the need of a material that
efficiently catalyzes the synthesis of hydrocarbons is of key importance. For such world scale application,
heterogeneous catalysis is the preferred one because of its high throughput capability. In this work wesynthesized FeCo alloy nanoparticles (NPs) at different Fe/Co ratio via Inert Gas Condensation.
Structural and morphological properties like NPs size distribution, Fe/Co ratio are determined by SEM,
STEM, EDX, and XRD. The reaction conditions, stability, catalytic activity, and selectivity towards
products of CO2 hydrogenation are studied, with special focus on C2+ hydrocarbons, with a lab-scale
reactor coupled with a mass spectrometer and gas chromatograph for products analysis. The alloy NPs
have new catalytic properties compared to pure Fe and pure Co NPs, showing activity towards thecatalysis of C2+ hydrocarbons.

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PARTICIPANTS

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INFORMATION

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14th Int. Symposium "Hydrogen Energy"

Sapporo, Hokkaido, Japan, 2020

Name

AdressTel., E-mailDr. Saya AJITO

Tohoku University
2-1-1 Katahira Aoba-ku Sendai,Japan

T: +81-22-215-2062
E: ajito@imr.tohoku.ac.jp

Dr. Hiroshi AKIBAThe University of Tokyo
ISSP, University of Tokyo 5-1-5 Kashiwanoha Kashiwa,
Chiba 277-8581
Japan

T: +81-4-7136-3298
E: h-akiba@issp.u-tokyo.ac.jp

Prof. Eiji AKIYAMA

Tohoku University
Institute for Materials Research, Tohoku Univ. 2-1-1
Katahira Aoba-ku SendaiJapan

T: +81-22-215-2060
E: akiyama@imr.tohoku.ac.jp

Dr. Elvis F. ARGUELLESThe University of Tokyo
7-3-1 Hongo Bunkyo-ku TokyoJapan

T: +81-3-5841-1286
E: elvisarguelles@cello.t.u-tokyo.ac.jp

Prof. Ryotaro ARITA

The University of Tokyo
7-3-1 Hongo Bunkyo-ku TokyoJapan

T: +81-3-5841-6810
E: arita@ap.t.u-tokyo.ac.jp

Prof. Marcello BARICCO

Dipartimento di Chimica and NIS Universita' di Torino
Via P.Giuria, 9 I-10125 TORINO
Italy

T: + 39-11-670-7569
E: marcello.baricco@unito.it

Prof. Craig BUCKLEY

Curtin University
Physics and Astronomy Curtin University Perth,WA
Australia

T: +61-401-103-602
E: c.buckley@curtin.edu.au

Prof. Ho-Chol CHANG

CHUO UNIVERSITY
T: +81-3-3817-1897
Department of Applied Chemistry 1-13-27 Kasuga Bunkyo- E: chang@kc.chuo-u.ac.jp
ku TokyoJapan

Dr. Martin DORNHEIM

Helmholtz-Zentrum Geesthacht
Max-Planck-Str. 59 Geesthacht
Germany

T: +49-4152-87-2604
E: martin.dornheim@hzg.de

Prof. Hans-Joachim FREUND

Fritz Haber InstituteFaradayweg 4-6 .... Berlin
Germany

T: +49-30-8413-4100
E: freund@fhi-berlin.mpg.de

Prof. Ken-ichi FUJITA

Graduate School of Human and Environmental Studies,
Kyoto University
Yoshida Nihonmatsu-cho, Sakyo-ku Kyoto
Japan

T: +81-75-753-6827
E: fujita.kenichi.6a@kyoto-u.ac.jp

Prof. Ken-ichi FUKUIOsaka University
C308, School of Engineering Science, Osaka Univ. 1-3
Machikaneyama Toyonaka, OsakaJapan

T: +81-6-6850-6235
E: kfukui@chem.es.osaka-u.ac.jp

Prof. Katsuyuki FUKUTANIThe University of Tokyo
Institute of Industrial Science, Univ. of Tokyo, Meguro-ku,
Komaba4-6-1 Room Be308 TokyoJapan

T: +81-3-5452-6132
E: fukutani@iis.u-tokyo.ac.jp

Prof. Jianping GUO

Chinese Academy of Sciences
457 Zhongshan Road Dalian
China

T:
E: guojianping@dicp.ac.cn

Dr. Ikutaro HAMADA

Osaka University
2-1 Yamada-Oka Suita, OsakaJapan

T: +81-6-6879-7289
E: ihamada@prec.eng.osaka-u.ac.jp117

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Name

AdressTel., E-mailDr. Jun HARUYAMA

Institute for Solid State Physics, The University of Tokyo
5-1-5 Kashiwanoha Kashiwa, Chiba
Japan

T: +81-4-7136-3291
E: haruyama@issp.u-tokyo.ac.jp

Prof. Bjorn C. HAUBACKInstitute for Energy Technology (IFE)
IFE, P.O. Box 40 Kjeller, Norway
NorwayT: +47-9740-8844
E: bjorn.hauback@ife.no

Prof. Yoshiki HIGUCHI

University of Hyogo
3-2-1 Koto Kamigori-cho Ako-gun, Hyogo
Japan

T: +81-791-58-0179
E: hig@sci.u-hyogo.ac.jp

Dr. Michael HIRSCHER

Max Planck Institute for Intelligent Systems
Hesienbergstrasse 3 Stuttgart
Germany

T: +49-711-689-1808
E: hirscher@is.mpg.de

Prof. Taro HITOSUGITokyo Institute of Technology
2-12-1 Ookayama Meguro Tokyo
Japan

T:
E: hitosugi.t.aa@m.titech.ac.jp

Dr. Terry David HUMPHRIES

Curtin University
Building 301, Curtin University Kent Street Perth
Australia

T: +61-489-069-686
E: terry.humphries@curtin.edu.au

Dr. Soshi IIMURATokyo Institute of Technology
203 S8-bldg. Tokyo Institute of Technology 4259
Nagatsuta-cho Midori-ku YokohamaJapan

T: +81-45-924-5197
E: s_iimura@mces.titech.ac.jp

Dr. Munehiro INUKAI

Tokushima University
2-1 Minami-Josanjima-Cho Tokushima, TokushimaJapan

T: +81-88-656-7550
E: inukai.munehiro@tokushima-u.ac.jp

Dr. Takayoshi ISHIMOTO

Yokohama City University22-2 Seto Kanazawa-ku, YokohamaJapan

T: +81-45-787-2165
E: tishimo@yokohama-cu.ac.jp

Prof. Craig JENSEN

Department of Chemistry, University of Hawaii
2545 McCarthy McCarthy Mall Honolulu, HI
United States of America

T: +1-808-445-7248
E: jensen@hawaii.edu

Mr. Yuki KANAZAWA

Ibraki univ.
Ibaraki quantum beam research center 162-1, Shirakata,
Naka Gun Tokai Mura, Ibaraki Ken,Japan

T: +81-29-352-3240
E: 18nm914r@vc.ibaraki.ac.jp

Prof. Hiroyuki S. KATO

Osaka University
1-1 Machikaneyama Toyonaka, OsakaJapan

T: +81-+6-6850-6570
E: hirokato@chem.sci.osaka-u.ac.jp

Dr. Kazuaki KISU

Advanced Institute for Materials Research
Tohoku University
2-1-1 Katahira, Aoba-ku, Sendai Miyagi
Japan

T: +81-22-215-2094
E: k.kisu@imr.tohoku.ac.jp

Prof. Masaaki KITANOTokyo Institute of Technology
4259 Nagatsuta, Midori-ku Yokohama, Kanagawa
Japan

T: +81-42-924-5191
E: kitano.m.aa@m.titech.ac.jp

Mr. Youngdon KO

EPFL
Rue de l'industrie 17 CP 440 Sion
Switzerland

T: +41-21-695-8212
E: youngdon.ko@epfl.ch

Prof. Genki KOBAYASHI

Institute for Molecular Science, National Institute of Natural T: +81-564-55-7440
Science
E: gkobayashi@ims.ac.jp
S303 38 Nishigonaka, Myodaiji Okazaki, Aichi
Japan

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Name

AdressTel., E-mailProf. Takahiro KONDO

Faculty of Pure and Applied Sciences, University ofTsukuba
1-1-1 Tennodai, Tsukuba IbarakiJapan

T: +81-29-853-5934
E: takahiro@ims.tsukuba.ac.jp

Dr. Michel LATROCHEINSTITUT DE CHIMIE ET DES MATERIAUX PARIS-EST- T: +33-149-78-1210
UMR 7182
E: michel.latroche@icmpe.cnrs.fr
ICMPE-CMTR, CNRS UMR 7182, 2-8, rue H. Dunant,
THIAISFranceProf. JongChoo LIM

Dongguk University-Seoul
Dept. of Chemical and Biochemical Eng. Dongguk
University Seoul
Republic of Korea

T: +82-2-2260-3707
E: jongchoo@dongguk.edu

Mr. Loris Giovanni LOMBARDOEPFL
Rue de l'industrie 17 CP 440 Sion
Switzerland

T: +41-21-695-82-15
E: loris.lombardo@epfl.ch

Dr. Akihiko MACHIDA

National Institutes for Quantum and Radiological Scienceand Technology
1-1-1 Kouto, Sayo-cho Sayo-gun, Hyogo
Japan

T: +81-791-58-0996
E: machida@spring8.or.jp

Dr. Mitsuhiko MAESATO

Kyoto University
Kitashirakawa Oiwake-cho, Sakyo-ku Kyoto
Japan

T: +81-75-753-4036
E: maesato@kuchem.kyoto-u.ac.jp

Dr. Hiroki MIYAOKA

Natural Science Center for Basic Research andDevelopment, Hiroshima University
1-3-1 Kagamiyama Higashi-HiroshimaJapan

T: +81-82-424-4604
E: miyaoka@h2.hiroshima-u.ac.jp

Prof. Kenji MIYATAKE

University of Yamanashi
4 Takeda KOfu, YamanashiJapan

T: +81-55-220-8707
E: miyatake@yamanashi.ac.jp

Dr. Naoya MIYAUCHI

National Institute for Materials Science
1-2-1 Sengen Tsukuba, Ibaraki
Japan

T:
E: MIYAUCHI.Naoya@nims.go.jp

Prof. Hatsumi MORI

The Institute for Solid State Physics, The University ofTokyo
A301 ISSP, The Univ. of Tokyo 5-1-5 Kashiwanoha
Kashiwa, Chiba
Japan

T: +81-4-7136-3201
E: hmori@issp.u-tokyo.ac.jp

Prof. Masakazu MORIMOTO

Rikkyo University
3-34-1 Nishi-Ikebukuro Toshima-ku TokyoJapan

T: +81-3-3985-4695
E: m-morimoto@rikkyo.ac.jp

Mr. Shin MURAKAMI

National Institutes for Quantum and Radiological Scienceand Technology
1-1-1, Kouto, Sayo-cho Sayo-gun, Hyogo
Japan

T: +81-791-58-1014
E: murakami.shin@qst.go.jp

Prof. Katsutoshi NAGAOKA

Department of Chemical Systems Engineering, Graduate
School of Engineering, Nagoya University
Furo-cho, Chikusa Nagoya CityJapan

T: +81-52-789-3388
E: nagaoka.katsutoshi@material.nagoyau.ac.jp

Dr. Akinobu NAKADA

Department of Applied Chemistry, Faculty of Science andEngineering, Chuo University
1-13-27 Kasuga, Bunkyo-ku TokyoJapan

T: +81-3-3817-8551
E: nakada.773@g.chuo-u.ac.jp

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Name

AdressTel., E-mailDr. Yuki NAKAGAWA

Hokkaido University
N-13 W-8, Kita-ku Sapporo, HokkaidoJapan

T: +81-11-706-7167
E: y-nakagawa@eng.hokudai.ac.jp

Prof. Masashi NAKAMURA

Chiba University
Yayoi-cho 1-33, Inage-ku Chiba
Japan

T: +81-43-290-3382
E: mnakamura@faculty.chiba-u.jp

Dr. Takashi NAKAMURA

Tohoku University
2-1-1, Katahira Aoba-ku Sendai
Japan

T:
E: takashi.nakamura.e3@tohoku.ac.jp

Dr. Chikashi NISHIMURA

National Institute for Materials Science
5F Main Bidg 1-2-1 Sengen Tsukuba, IbarakiJapan

T: +81-298-59-2652
E: NISHIMURA.Chikashi@nims.go.jp

Dr. Masayuki OCHI

Osaka University
H614 1-1 Machikaneyama-cho Toyonaka, OsakaJapan

T: +81-6-6850-6749
E: ochi@presto.phys.sci.osaka-u.ac.jp

Dr. Yoshinori OHMASAInstitute for Solid State Physics, University of Tokyo
Institute for Solid State Physics, Univ. of Tokyo 5-1-5
Kashiwanoha Kashiwa-shi, Chiba
Japan

T: +81-4-7136-3298
E: ohmasa@issp.u-tokyo.ac.jp

Prof. Kenji OHOYAMA

Ibaraki Univ.
Frontier Research Center Shirakata 162-1 IbarakiJapan

T: +81-29-287-7871
E: kenji.ohoyama.vs@vc.ibaraki.ac.jp

Mr. Kouki OKA

Waseda University
55S-701 3-4-1 Okubo Shinjuku-ku TokyoJapan

T: +81-3-3200-2669
E: pauling-japan@fuji.waseda.jp

Prof. Shin-ichi ORIMO

Advanced Institute for Materials Research
Tohoku University
2-1-1 Katahira, Aoba-ku, Sendai Miyagi
Japan

T: +81-22-215-2093
E: orimo@imr.tohoku.ac.jp

Prof. Minoru OSADA

Minoru Osada
Furo-cho, Chikusa-ku NagoyaJapan

T: +81-52-789-2750
E: mosada@imass.nagoya-u.ac.jp

Prof. Toshiya OTOMO

Institute of Materials Structure Science, High Energy
Accelerator Research Organization
1-1 Oho Tsukuba, IbarakiJapan

T: +81-29-284-4333
E: toshiya.otomo@j-parc.jp

Prof. Kenichi OYAIZU

Waseda University
65-303 Okubo 3 Shinjuku, TokyoJapan

T: +81-3-5286-3214
E: oyaizu@waseda.jp

Prof. Astrid PUNDT

Karlsruher Institut fur Technologie (KIT) Institut fur
Angewandte Materialien-Werkstoffkunde (IAM-W
KIT-Campus Sud, Geb. 10.91/Zi. 035 Kaiserstrase 12 D76131 Karlsruhe
Germany

T: + 49-721-6084-2345
E: astrid.Pundt@kit.edu

Prof. AJ (Timmy) RAMIREZ-CUESTA

Oak Ridge National Laboratory
Neutron Sciences Directorate
1 Bethel Valley Rd, Oak Ridge, TN 37831
United States of America

T: +1-865-246-9397
E: ramirezcueaj@ornl.gov

Dr. Hiroyuki SAITOH

National Institutes for Quantum and Radiological Scienceand Technology
1-1-1, Kouto, Sayo-cho Sayo-gun, Hyogo
Japan

T: +81-791-58-1014
E: saito.hiroyuki@qst.go.jp

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Name

AdressTel., E-mailDr. Toyoto SATO

Tohoku University
Katahira 2-1-1 Aoba-ku SendaiJapan

T: +81-22-215-2094
E: toyoto@imr.tohoku.ac.jp

Dr. Ryuhei SATOThe University of Tokyo
T: +47-3-5841-4174
Faculty of Science Bldg. 1 room 919 7-3-1 Hongo, Bunkyo- E: rsato@cms.phys.s.u-tokyo.ac.jp
ku TokyoJapan

Dr. Motoyuki SHIGA

Japan Atomic Energy Agency
Satellite Bldg, The University of Tokyo 178-4 Wakashiba
Kashiwa, Chiba
Japan

T:
E: shiga.motoyuki@jaea.go.jp

Prof. Yasuteru SHIGETA

Center for Computational Sciences, University of Tsukuba
1-1-1 Tennodai Tsukuba, IbarakiJapan

T: +81-29-853-6496
E: shigeta@ccs.tsukuba.ac.jp

Dr. Takanori SHIMA

RIKEN
Organometallic Chemistry Laboratory 2-1 Hirosawa Wako,
SaitamaJapan

T: +81-48-467-9380
E: takanori_shima@riken.jp

Prof. Katsuya SHIMIZU

Osaka University
KYOKUGEN 1-3 Machikaneyama Toyonaka, OsakaJapan

T: +81-6-6850-6675
E: shimizu@stec.es.osaka-u.ac.jp

Mr. Keita SHINZATO

Hiroshima University
1-3-1 Kagamiyama Higashi-HiroshimaJapan

T: +81-82-424-4604
E: keita-shinzato@hiroshima-u.ac.jp

Prof. Osamu SUGINO

Institute for Solid State Physics, the University of Tokyo
T: +81-4-7136-3290
The Institute for Solid State Physics, A511 Kashiwanoha 5- E: sugino@issp.u-tokyo.ac.jp
1-1 Kashiwa, ChibaJapan

Ms. Ivana SUTER

EPFL Valais Wallis
Rue de l'industrie 17 CP 440 Sion
Switzerland

Dr. Petra Ágota SZILÁGYI

School of Engineering and Materials Science, Queen Mary T: +44-207-882-7948
University of London
E: p.szilagyi@qmul.ac.uk
Mile End Road, E1 4NS London, UK

Prof. Masanori TACHIKAWA

Masanori Tachikawa
Yokohama City University, 22-2, Seto, Kanazawa-ku,
Yokohama CityJapan

T: +81-45-787-2188
E: tachi@yokohama-cu.ac.jp

Prof. Hidekazu TANAKAISIR-Sanken, Osaka University
8-1 Mihogaoka Ibaraki, OsakaJapan

T: +81-6-6879-4280
E: h-tanaka@sanken.osaka-u.ac.jp

Prof. Joseph TEPROVICH

California State University Northridge
18111 Nordhoff St. Northridge, CA
United States of America

T: +1-570-578-7842
E: joseph.teprovich@csun.edu

Dr. Bo THOMSEN

Japan Atomic Energy Agency
Satellite Bldg, The University of Tokyo 178-4 Wakashiba
Kashiwa, Chiba
Japan

T: +81-70-1407-8343
E: thomsen.bo@jaea.go.jp

Prof. Masaru TSUKADA

Emeritus Professor at The University of Tokyo

T: +81-3-5617-5713
E: tsukada_m2004@yahoo.co.jp

T:
E: ivana.suter@epfl.ch121

1st Int. Symposium "Hydrogenomics" combined with
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Sapporo, Hokkaido, Japan, 2020

Name

AdressTel., E-mailProf. Shinji TSUNEYUKI

Department of Physics, The University of Tokyo
7-3-1 Hongo, Bunkyo-ku TokyoJapan

T: +81-3-5841-4127
E: stsune@phys.s.u-tokyo.ac.jp

Prof. Hayato TSURUGIOsaka University
1-3, Machikaneyama-cho Toyonaka, OsakaJapan

T: +81-6-6850-6247
E: tsurugi@chem.es.osaka-u.ac.jp

Prof. Noritaka USAMI

Noritaka Usami
Furocho, Chikusa-ku Nagoya, Aichi
Japan

T: +81-52-789-3620
E: usa@material.nagoya-u.ac.jp

Dr. Colin James WEBB

Griffith University
T:
School of Natural Sciences, Griffith University 171 Kessels E: j.webb@griffith.edu.au
Rd Nathan, Queensland
Australia

Prof. Teppei YAMADA

Kyushu University, Faculty of Engineering
Motooka744, Nishi-ku FukuokaJapan

T: +81-92-802-2833
E: teppei343@gmail.com

Dr. Yoshiyuki YAMAMOTO

The Institute for Solid State Physics, The University ofTokyo
5-1-5 Kashiwanoha, Kashiwa-shi Kashiwa, Chiba
Japan

T: +81-4-7136-3292
E: yoshiyuki.yamamoto@issp.utokyo.ac.jp

Mr. Takayoshi YAMAMOTO

Ibaraki Univ.
Shirakata162-1 Tokai IbarakiJapan

T: +81-29-352-3240
E: 19nm960f@vc.ibaraki.ac.jp

Prof. Osamu YAMAMURO

Institute for Solid State Physics, University of Tokyo
ISSP, University of Tokyo 5-1-5 Kashiwanoha Kashiwa,
Chiba 277-8581
Japan

T: +81-4-7136-3494
E: yamamuro@issp.u-tokyo.ac.jp

Prof. Miho YAMAUCHI

Kyushu University
Motooka 744 Nishi-ku FukuokaJapan

T: +81-92-802-6874
E: yamauchi@i2cner.kyushu-u.ac.jp

Dr. Heena YANG

EPFL
Rue de l'industries 17 Sion/VS
Switzerland

T: +41-21-69-58214
E: heena.yang@epfl.ch

Prof. Jun YOSHINOBUThe Institute for Solid State Physics, The University of
Tokyo
ISSP A321, Univ. of Tokyo 5-1-5 Kashiwanoha Kashiwa,
Chiba
Japan

T:
E: yoshinobu@issp.u-tokyo.ac.jp

Dr. Jinqiu ZHANG

Harbin Institute of Technology
Mingde Building No. 92 Xidazhi St Harbin
China

T: +86-451-86413721
E: zhangjinqiu@hit.edu.cn

Prof. Min ZHUSouth China University of Technology
Room 237, Building 8, School of Materials Science
Wushan Campus, 381 Wushan Road 381 Wushan Road,
Tianhe District, Guangzhou
China

T: +86-20-87113924
E: memzhu@scut.edu.cn

Prof. Andreas ZUETTELEPFL Valais Wallis
I17 1 G1 Rue de l'industrie 17 CH-1950 Sion
Switzerland

T: +41-79-484-2553
E: andreas.zuettel@epfl.ch122

1st Int. Symposium "Hydrogenomics" combined with
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1st Int. Symposium "Hydrogenomics" combined with
14th Int. Symposium "Hydrogen & Energy"

Sapporo, Hokkaido, Japan, 2020

ACCESS

Sapporo

New Chitose Airport

Map from New Chitose Airport to Sapporo

Sapporo Station

Hotel Monterey Edelhof Sapporo

Map of Sapporo region125

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Travel to Hotel Monterey Edelhof Sapporo from New Chitose
Airport:
1. New Chitose Airport => Sapporo
Please take the "Rapid Airport Express" train on the JR Chitose Line to JR Sapporo
Station (about 40 minutes / JPY1,070 per adult).

Rapid Airport Express

Stops

The Rapid Airport Express is always
standing by at the New Chitose Airport.
Departing every 15 minutes during the day.

*Stops may differ depending on the train.

Get on the Elevator in theDomestic Terminal andgo to B1F.

The JR Information Desk islocated to the right of theelevator on B1F.

JR Information DeskJR New Chitose Airport
Station Ticket Gate

Overall map of New Chitose Airport (2F)

Overall map of New Chitose Airport (B1F)

Exchange rail passes andpurchase JR tickets here.

Platforms are on B2F.

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2. Sapporo Station => Hotel Monterey Edelhpf Sapporo
Please disembark at JR Sapporo station. After getting off at JR Sapporo Station, passthrough the East ticket Gate and go out the South Exit. It takes about 7 minutes by walkfrom the South Exit to Hotel Monterey Edelhof Sapporo.

Hotel Monterey Edelhof Sapporo

Map from Sapporo Station to Hotel Monterey Edelhof Sapporo (in English)

Hotel Monterey Edelhof Sapporo

Map from Sapporo Station to Hotel Monterey Edelhof Sapporo (in Japanese)127

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EMERGENCY TELEPHONE NUMBERS
Country code for Japan:+81
POLICE

110

FIRE FIGHTERS / ANBURANCE

119

Ms. Miki HINO

+81-22-215-2093 (Lab.)

Conference Secretary

Ms. Yasuko ITO+81-3-5734-2636 (Lab.)

Conference Secretary

Prof. Shin-ichi ORIMO+81-80-1846-1221 (Mobile)

Conference Chair

Prof. Andreas ZÜTTEL

+41-79-484-2553 (Mobile)

Hotel Monterey Edelhof Sapporo+81-11-242-7111

Nishi 1-1, Kita 2 Jyo, Chuo-ku,
Sapporo, Hokkaido, 060-0002, Japan
https://www.hotelmonterey.co.jp/en/ed
elhof/

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CLIMATEThe maximum snow depth between December and February can reach up to
approximately 1 m, and the annual cumulative snowfall is about 5 m. The averagetemperature in January is -3 degrees.

Average air temperature in Sapporo
Precipitation(mm)Temperature max ( °C)

Temperature average ( °C)

Temperature min ( °C)

30

200
180
160
140
120
100
80
60
40
20
0

25
20
15
10
5
0
-5
-10

Jan

Feb

Mar

Apr

May JunJul

Aug Sep

May

Jun

Jan

Feb

Temperature max ( °C)

-0.6

0.1

Temperature average ( °C)-3.6

Temperature min ( °C)-7.0

Precipitation (mm)

Mar

Apr

Oct

Nov Dec

Jul

Aug

Sep

Oct

Nov

Dec

4.0 11.5 17.3 21.5 24.9

26.4

22.4

16.2

8.5

2.1

-3.1

0.6

7.1 12.4 16.7 20.5

22.3

18.1

11.8

4.9

-0.9

-6.6

-2.9

3.2

19.1

14.2

7.5

1.3

-4.1

8.3 12.9 17.3

113.6 94.0 77.8 56.8 53.1 46.8 81.0 123.8 135.2 108.7 104.1 111.7

Clothing and footwear:
We recommend a down jacket or thick coat that is waterproof and retains heat, while also
capable of keeping the snow and cold wind out. If you plan to play in the snow or be out inthe cold for long hours, we suggest that you wear heavy winter outerwear over yourtrousers.
It is dangerous to walk the frozen winter streets of Sapporo with sneakers, high heels orleather soled shoes. For your safety, we recommend a pair of waterproof thermal bootswith non-skid soles.

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SOCIAL EVENTS
Otaru Canal Cruise:
Otaru Canal Cruise is the new must do activity for visitors to Otaru! Otaru once prospered
as the gateway to Hokkaido and retains a rich history from that time. Our captains will
each introduce that history in their own way during a leisurely, 40-minute cruise down the
Otaru Canal.

Otaru Canal Boat LLC
5-4, Minatomachi, Otaru, Hokkaido, 047-0007, Japan
Tel: 0134-31-1733
URL: https://otaru.cc/en/

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LOCAL GUIDE / SAPPORO
Hokkaido's capital city of Sapporo retains a unique mixture of modern Japanese efficiency
and technology with a more relaxed approach to daily life influenced by the environmentand climate, making any visit a pleasant change from the frenetic pace of other major
centers in the country.
Drawing its name from the indigenous Ainu terminology meaning "river-lined-with-largereed-bed", Sapporo was officially founded in 1869 - very early in Japan's Meiji Era.
Designed on a grid pattern and boasting several train and subway lines and even a tramline, Sapporo is one of Japan's easiest cities to navigate.
Adding to this distinctiveness, Sapporo is spared a rainy season, unlike the rest of Japan.
A mild spring, pleasant summer, cool autumn and snowy winter characterize a year in
Sapporo. Average temperatures during most months make Sapporo an ideal destination
and base for an outdoor or nature enthusiast, while winter brings perfect temperatures forsnow and winter sports. Ski Season generally starts in mid-December and can last as longas late April!
FOOD:
Mention Hokkaido, and especially Sapporo, and mostJapanese will inevitably mention food. Famed throughout
the country for its produce, dairy products and seafood avisitor will find a massive variety of ingredients and dishes tosample during their stay.
Some of the more famous dishes include:⚫

Genghis Khan. The dish is named after the notorious Mongol Warlord and consists ofpremium mutton grilled with vegetables at the table. Delicious Genghis khan
restaurants abound throughout Sapporo.

⚫

Fresh seafood, especially salmon, crab, and sea urchin are renowned all over Japan.
Early winter and late summer are the best time for Sapporo's famous crab while early
Autumn is salmon and sea urchin season.

⚫

Miso Ramen Noodles. Sapporo is the birthplace of this nationwide favorite andaficionados still flock to establishments in the city to sample the authentic dish.

Attractions and Local Specialties:
Sapporo city abounds in tourist attractions. Some of the highlights to consider include:⚫
Odori-koen. Running about 1.5 kilometers andapparently the starting point for Sapporo's layout when it was
being planned, this park is the city's focus in every season.
Whether acting as a host site for the famous Snow Festival in
February, transformed into a massive flower garden in May or
acting as city-wide beer garden in the summer this is first stopon every visitor's trip to the city.

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Sapporo Beer Museum, established in 1890, now offers historical and brewery tours
as well as tastings and a family friendly beer hall.

⚫

Tanuki Koji Shopping Arcade. At nearly 1 km long and offering 200 shops you can finda huge variety of restaurants and local shops as well as souvenir shops offering someof Sapporo's famous souvenirs such as Marusei Butter Raisin cookies, Shiroi Koibito
or, of course, ramen sets.

⚫

Hitsujigaoka Observation Hill. Located just outside of Sapporo main centre, thismountain top offers fantastic views of the city, set in a beautiful park.

⚫

Confectionery factory tour. For something a little different but fun for all ages, take atour of one of Sapporo's celebrated chocolate or cookie producers then try your handat making your own!

Events & Activities:
Sapporo has no shortage of events and festivals.
⚫

Sapporo Snow Festival - perhaps the most internationallynotable event in Hokkaido. Held every February andattracting participants and visitors from around Japan andthe world, Sapporo is utterly transformed into a world of
fantastic ice and snow sculptures that astound andenthral.

⚫

Sapporo White Illumination - preceding the Snow Festival from November to earlyFebruary, Sapporo becomes a celebration of lights as nearly 400 thousand orbs are
employed to brighten Sapporo during the Sapporo White Illumination.

⚫

Sapporo Summer Festival - Odori-koen again takes centre stage during this festival
which highlights Sapporo's food, people and even unique take on Japanese traditional
Bon Dancing.

Ref.:
http://www.sapporo.travel/?lang=en
https://www.hotelmonterey.co.jp/en/edelhof/localguide/132

1st Int. Symposium "Hydrogenomics" combined with
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Sapporo, Hokkaido, Japan, 2020

SOUVENIR
Hydrogenomics Original Tumbler & Portable Straw[Tumbler]⚫ Capacity: 400ml⚫ Material / Heat resistance:
Lid: Polypropylene / 90 degrees
Body: Polypropylene / 90 degrees
Packing: Silicone rubber / 130 degrees⚫

Please note the following when using.
The lid is not completely sealed with the main body.
Please note that the contents may spill if it falls over.
Do not drop or give a strong impact.
Do not put the drinks above the heat-resistanttemperature, dry ice or alcohol.
Do not use a dishwasher, microwave ovens or open
flames.
Do not place near fire or high temperatures.
There is a risk of damage if put in the freezer.
Please keep out of small children’s reach.

[Portable Straw]
A straw that can be easily carried in a special case,washed and used repeatedly. With cleaning brush.
⚫

Straw length: 21cm⚫

Material:
Straw: Stainless steel
Brush: Hair: Nylon / Handle: Stainless steel
Case: ABS resin / POM⚫

Please note the following when using.
Cold drink only. Do not use for hot drinks. Do notuse for anything other than its intended purpose.
Do not use anything other than neutral detergents.
Do not drop or give a strong impact. Do not use if
damaged or deformed.
Do not use a dishwasher.
Do not place near fire or high temperatures.
Please keep out of small children’s reach.

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NOTES

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Sapporo, Hokkaido, Japan, 2020139

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14th Int. Symposium "Hydrogen & Energy"

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Sapporo, Hokkaido, Japan, 2020142