th

7 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory
and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materials
The 7th symposium “Hydrogen & Energy” serves as an information platform of
the fundamental science and the frontiers of research in Sciences andTechnology of Hydrogen & Energy (Hydrogen Production, Hydrogen Storage,
Hydrogen Applications, Theory and Modelling, Fuel Cells, Batteries, Synthetic
fuels).
The symposium consists of invited keynote lectures reviewing the key elementsof the hydrogen cycle, i.e. the hydrogen production, hydrogen storage andhydrogen combustion and fuel cells. Furthermore, contributions on theconversion of renewable energy in general and energy carriers beside andbeyond hydrogen are very welcome. The world leading experts present thecurrent research challenges and most important results in invited andcontributing talks. Early stage and experienced researchers present their newest
results and the open questions on posters as well as in a one slide presentation.
The conference will take place in the conference and wellness hotel Stoos in thebeautiful small village Stoos on 1'270 m above see level. The village is free oftraffic on a alp above Schwyz in central Switzerland.
The number of participants is limited to 80.

21. - 25. January 2013
Seminar- und Wellnesshotel Stoos
Ringstrasse 10
CH-6433 Stoos
Tel.: +41 (0)41 817 44 44
Fax.: +41 (0)41 817 44 45
info@hotel-stoos.ch
http://www.hotel-stoos

7th Hydrogen & Energy Symposium

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7th Hydrogen & Energy Symposium

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7th Hydrogen & Energy Symposium

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

CONTENTS
Timetable
Abstracts
MONDAYafternoon

Chair: Andreas ZÜTTEL

17:10 - 18:00

Katsuhiko HIROSE, 'Hydrogen as energy vector for fuelfor future transport and energy optimization'

TUESDAY
morning

Chair: Hans GEERLINGS, Giulio PARCIANELLO

09:00 - 09:40

Craig JENSEN, 'Development of Liquid, High Capacity
Hydrogen Carriers'

17

09:40 - 10:00

Elsa
CALLINI,'PHYSICALANDCHEMICALPROPERTIES OF VOLATILE COMPLEX HYDRIDES'

19

10:00 - 10:20

Jianjiang HU, 'Reducing the Incubation Period of
Dehydrogenation for the MgH2-LiBH4 Hydrogen Storage
System'21

10:20 - 10:40

Georgios KALANTZOPOULOS, 'From Theory to
Experimental Study and Synthesis Optimization of Mg
and Zn Mixed Borohydrides'

23

11:10 - 11:30

Arndt REMHOF, 'Controlling the hydrogen release ofborohydrides'25

11:30 - 11:50

Yigang YAN, 'FROM YH3 VIA Y(BH4)3 TO Y2(B12H12)3'

27

11:50 -12:10

Luca
PASQUINI,'MAGNESIUM-BASEDNANOPARTICLESANDNANODOTS:SYNTHESIS,STRUCTURE AND THERMODYNAMICS '29

12:10 - 12:30

Hubert H. GIRAULT, ‘no title’

TUESDAY
afternoon

Chair: Craig JENSEN, Jan ROSSMEISEL

14:00 - 14:40

Ronald GRIESSEN, 'Two new applications ofhydrogenography:
Directintrinsichydrogenpermeability measurements and enthalpy-entropy
correlation.'33

14:40 - 15:00

Martin DORNHEIM, 'Novel Materials and Systems for
Hydrogen Storage'35

15:00 - 15:20

Torben R. JENSEN, 'NEW MATERIALS FOR HYDROGEN
STORAGE'37

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7th Hydrogen & Energy Symposium

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15:50 - 16:10

Meltem SEZEN, 'Advanced Focused Ion Beam
Nanostructuring of Energy Materials for TEM Analysis
and Electron Tomography '39

16:10 - 16:30

Nicholas STADIE, 'Thermodynamics of High Pressure
Physisorption'

41

16:30 - 16:50

Olivier GILLIA, 'Modelling of the thermomechanicalbehaviour of the breathing hydride powders threatening
the integrity of their containers.'

43

16:50 - 17:10

Julian RANDALL, 'How can European Fuel Cell andHydrogen opportunities fit into my strategy?'45

17:10 - 17:30

Olaf JEDICKE, 'H2FC, European Research Infrastructure
to support Science and Development in Hydrogen and
Fuel Cell Technologies'

47

WEDNESDAY
morning

Chair: Björgvin HJÖRVARSSON, Elsa CALLINI

09:00 - 09:40

Hans GEERLINGS, 'EFFICIENT PRODUCTION OF
SOLAR FUEL USING EXISTING LARGE SCALE
PRODUCTION TECHNOLOGIES'49

09:40 - 10:00

Petra DE JONGH, 'CARBON-CONFINED COMPLEXMETAL HYDRIDES – TOWARDS FULL HYDROGENSORPTION REVERSIBILITY'

51

10:00 - 10:20

Inge LINDEMANN,
Alanate'53

10:20 - 10:40

Mattia GABOARDI, 'HYDROGEN ABSORPTIONALKALI AND ALKALIEARTH METAL FULLERIDES'

IN

55

11:10 - 11:30

Petra SZILAGYI, 'Metal infused particles in MILs,
hydrogen storage and spillover effect'57

11:30 - 11:50

Angeloclaudio NALE, 'Confinement of LiBH4 in
nanoporous materials: size and interface effects onhydrogen release and ion mobility'59

11:50 -12:30

Jeroen VAN BOKHOVEN, 'Catalysis research in the 21st
century'

61

THURSDAY
morning

Chair: John Bøgild HANSEN, Ulrich VOGT

09:00 - 09:40

Jan ROSSMEISL, 'ELECTROCATALYSIS WITH ATOMICSCALE SIMULATIONS'

63

09:40 - 10:00

Maria ESCUDERO-ESCRIBANO, 'Pt5Gd AS A HIGHLY
ACTIVE AND STABLE ELECTROCATALYST FOROXYGEN REDUCTION'

65

PROCEEDINGS'NanoconfinementofLithium4

7th Hydrogen & Energy Symposium

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10:00 - 10:20

Dirk HUFSCHMIDT, 'CATALYTIC HYDROLYSIS OF
NABH4 IN A CONTINUOUS REACTOR FOR LONG TIMESTABLEANDVERSATILE
GENERATIONOF
HYDROGEN'67

10:20 - 10:40

Fadime HOSOGLU, 'Production of 1-propanol and 1butanol from the mixture of MeOH and EtOH by Guerbet
reaction in the presence of hydrotalcite'69

11:10 - 11:30

Romain MOURY, 'SODIUM HYDRAZINYLBORANE, A
CHEMICAL HYDROGEN STORAGE MATERIAL'

71

11:30 - 11:50

Gábor LAURENCZY,BATTERY ?'HYDROGEN73

11:50 -12:10

Ulrik GRØNBJERG VEJ-HANSEN, 'ADSORPTIONPROPERTIES AND SURFACE STABILITY OF PLATINUM
BASED ALLOYS'

75

12:10 - 12:30

Daniele PONTIROLI, 'IONIC CONDUCTIVITY IN LIGHTMETALS FULLERIDES'77

THURSDAYafternoon

Chair: Ronald GRIESSEN, Fadime HOSOGLU

14:00 - 14:40

John Bøgild HANSEN, 'SOLID OXIDE ELECTROLYSIS:A KEY ENABLING TECHNOLOGY FOR FUTURE
ENERGY SYSTEMS BASED ON RENEWABLE ENERGY '79

14:40 - 15:00

Ulrich VOGT, 'High Temperature Steam Electrolysis(HTSE): Aging mechanisms and corrosion behaviour ofinterconnects & coatings'

81

15:00 - 15:20

Jürgen SCHUMACHER, 'NUMERICAL MODELING OFPEM FUEL CELLS AND PHOTOELECTROCHEMICALWATER-SPLITTING'

83

15:50 - 16:10

Maria OLEA, 'Catalysts and catalysis for bio hydrogenproduction'

85

16:10 - 16:30

Bernard DAM, 'Oxide photo-anodes for water splitting'87

16:30 - 16:50

Lennard MOOIJ, 'Hysteresis, nucleation and growth in
the hydrogenation of magnesium nanolayers'89

16:50 - 17:10

Samuele SANNA, 'Hydrogen Diffusion in Defective
Graphene'91

17:10 - 17:30

Amelia MONTONE, 'MgH2-Based Composite Compacted
Powders upon Hydrogen Cycling'

93

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FRIDAY
morning

Chair: Valentina HERZOG, Andreas ZÜTTEL

09:00 - 09:40

Liuzhang OUYANG, 'HYDROGEN STORAGE
HYDROLYSIS PROPERTIES OF MG3RE'

AND

95

09:40 - 10:00

Chaoling WU, 'Research on Hydrogen storage materials
and technology in Sichuan University'97

10:00 - 10:20

Marc LINDER, 'NEW H2 STORAGE TANK CONCEPT FORCOMPLEX HYDRIDES'

99

10:20 - 10:40

Andreas PEDERSEN, 'Hydrogen mobility and crystalline
defects, a computational study'

101

11:10 - 11:30

Feray BAKAN, 'Comprehensive AFM investigations onenergy materials'

103

11:30 - 12:10

Björgvin HJÖRVARSSON, 'ENERGY EFFICIENCY: THE
MISGUIDANCE OF COMMON SENSE'

105

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TUESDAY
evening

Chairs: Arndt REMHOF, Dinesh PALATTY KOONATHANAUGUSTINE

P01

AsunciónFERNÁNDEZ,'UNDERSTANDING
THE
BEHAVIOUR OF CO-RU-B CATALYSTS FOR SODIUM
BOROHYDRIDEHYDROLYSIS:ANELECTRONMICROSCOPY STUDY '

107

P02

Moreno DE RESPINIS, 'Optimization of Anneal
Procedure in Metal Oxides: Case Study ofNanostructured Tungsten Processed via Low-Energy
Helium-Ions'

109

P03

Thomas BIBIENNE, 'Study of Body-Centered Cubictitanium-based alloys for hydrogen storage '

111

P04

Mariana SPODARYK, 'INFLUENCE OF CHEMICALCOMPOSITION AND PARTICLE SIZE ON THE
ELECTRODE CHARACTERISTICS OF GAS ATOMIZEDAB5-TYPE HYDROGEN STORAGE ALLOYS'

113

P05

Michal GORBAR, 'COMPOSITE MEMBRANES FORCONVENTIONALHIGHPRESSURE
ALKALINE
ELECTROLYSERS'

115

P06

Mauro RICCO', 'Hydrogen interaction with graphene
probed by muons'

117

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WEDNESDAY
evening

Chairs: Philippe MAURON, Elsa CALLINI

P07

Georgia
VLACHOPOULOU,'Metal-derivativesofchemically produced graphene; synthesis andcharacterization'

119

P08

Philippe MAURON, 'Reversible hydrogen absorption of
metal intercalated fullerenes'

121

P09

Jeffrey GEHRIG, 'HYDROGENATIONSUBSURFACE HYDROGEN'

BY

123

P10

Chiara CAVALLARI, 'HYDROGEN ON
INVESTIGATEDBYINELASTICSCATTERING'

GRAPHENE
NEUTRON

125

P11

Alexander BONK, 'Ceria based redox reactions for the
production of fuels from CO2 and H2O.'

127

P12

Andreas BLIERSBACH, 'The influence of metal atoms
on the hydrogen adsorption properties of graphene'

129

P13

Arndt REMHOF, ‘Hydrogen Dynamics in Nanoconfined
Lithiumborohydride’131

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OF

CO2

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7th Hydrogen & Energy Symposium

Participants:

Stoos, Switzerland 2013

Matteo ARAMINI
Yvonne BRANDT ANDERSSONPeter CENDULA
Andrea DE SIMONE
Maximilian FICHTNER
Hubert GIRAULT
Bjorn C HAUBACKReto HOLZNER
Jiri MULLER
Hardy RAUCHFUSSAndreas ZÜTTEL
Corinne GIANOLA
Valentina HERZOG
Edoardo PUOZZOGiulio PARCIANELLO
Dominik ZIMMERMANN
Urs CABALZAR
Dinesh PALATTY KOONATHAN AUGUSTINESCIENCE OF HYDROGEN & ENERGY AWARD

133

List of Participants

147

Information

157

Notes

165

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Timetable

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Abstracts

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7th Int. Symposium Hydrogen & Energy

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HYDROGEN AS ENERGY VECTOR FOR
TRANSPORT AND ENERGY OPTIMIZATION

FUEL

FOR

FUTURE

Katsuhiko Hirose
Toyota Motor Corporation
Abstract; History shows vehicle’s evolution is also promoted by the several environmental restraints similar to theevolution of life has been. Latest environmental strain is sustainability, transport vehicle are now faced to advanceagain to tackle with the clean and sustainable demand and lead to use the sustainable fuel such as hydrogen. Practicalprogresses for preparation of both vehicles and infrastructures to ward 2015 commercialization have been made at
Japan and Europe. Vehicle cost reduction and durability development have well advanced in recent years. Currently theindustries-government collaborative efforts to prepare the hydrogen infrastructure are initiated in many countries such as
Germany, Japan, UK. Progress of those activities and challenges to be solved will be shown and discussed in thepresentation. In addition to this movement hydrogen is being re-recognized as energy storage for the fluctuating
renewable energy and vector for energy and society optimization.

HyGrid Concept

Electric Propulsion Technology
EV

motor

PCU

battery

engine

HV

PHV

PCU
motor

Hydrogen
EV

Fuel tank

Surpluselectricity

PCU
motor

battery

battery

generator

generator

Fuel tankengine Fuel tank

Heat

PHV

Electrolysis

Emergency
power feeding

FCV

Thermal power
generation

Residential cogeneration
system (ENE FARM)

Gas supply

Heat utilizationengineElectricity

Electricity grid

RenewableenergyFossil fuelHydrogen grid
PCU
motor

Energy Storage

battery

Biomass, etc.

FC bus
FC
stack

FCV

FC forklift

Hydrogen tank

New Evolution of Vehicle technologies

Local production for
local consumptionof energy

Mass introduction ofrenewable energy
and stored energy

Independent disasterprevention centerfor emergency

Job creation andindustrial
development

Hydrogen acts as enhancer for energy system
Source: HyGrid Study Group

Short CV
Graduated Nagoya University with Msc applied physics and Bsc in physics..
Joined Toyota Motor Corporation in 1981, then working as engineer inproduction engines and advanced engine systems. Later working as Toyota
Engine representative at Toyota Europe in Brussels. Involved for first hybrid(Prius) development as manager for emission and fuel economy. In later
years working as a planner for world hybrid deployment.
From 2004 fuel cell development manager.
Currently project general manager at R&D management division and Energy
Affairs department.

Name Katsuhiko Hirose
Corresponding author: Katsuhiko HIROSE hirose@katsuhiko.tec.toyota.co.jp.

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7th Int. Symposium Hydrogen & Energy

Development of Liquid, HighCapacity Hydrogen Carriers
Craig M. Jensen1,2*, Daniel Brayton,2 Scott
Jorgensen,3 Marina Chong,1 Junzhi Wang4and Shin-ichi Orimo51

Dept. of Chemistry, University of Hawaii, Honolulu, HI
96822, USA

2

Hawaii Hydrogen Carriers, LLC, Honolulu, HI 96813,
USA

3

General Motors Technical Center, Warren, MI, 48090
USA

4

Department of Material Science and Nano Technology,
Peking University, Beijing, P.R. CHINA 100871

5

Institute for Materials Research, Tohoku University,
Sendai 980-8577, JAPAN

Abstract Two projects focusing on liquid hydrogen
carriers are currently underway in our laboratories. The
first project entails the development of liquid organic

Craig Jensen

Stoos, Switzerland 2013hydrogen carriers (LOCs). The barrier to utilization ofclass of materials for automotive applications is
significantly lower than other storage media because they
are cheap, abundant, and can be distributed using
existing infrastructure. Additionally, the reversibly
released, 7-8 wt% H2 from these materials is free of thethermal management problems commonly associatedwith solid-state hydrogen absorbing materials. Our
approach utilizes the PCP pincer complex, IrH2{C6H3-2,6(OPBut2)2} as a catalyst for the dehydrogenation of theliquid organic hydrogen carriers. Screening studies ofthepincercomplexcatalyzed,
reversible
dehydrogenation of a variety candidate LOCs underpractical conditions have revealed a number of insights
and reactivity trends. Additionally, our efforts include theoptimization of the design of a reactor for thedehydrogenation of solutions of the pincer complexes in
LOCs that would provide hydrogen to power an onboard
PEM fuel cell. In a second project, we are also exploringthereversible
dehydrogenationofmagnesiumborohydrides. We have observed rapid dehydrogenationand hydrogenation kinetics for these materials in the 100200 °C which are due, at least in part, to their low melting
points (ie Mg(B3H8)2, 60 °C. The details of these studies
as well as their implications of the mechanism of the lowtemperature, reversible dehydrogenation of Mg(BH4)2 will
be discussed.

Dr. Jensen is a full professor in the Department of Chemistry of the University of Hawaii. He is an
inorganic chemist with broad experience in catalyst development and the synthesis andcharacterization of novel inorganic and organometallic materials. He obtained his PhD at the
University of California at Los Angeles and was a postdoctoral fellow at the University of California at
San Diego. He has authored or co-authored 131 peer-reviewed publications and seven U.S. patents.
Dr. 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 has been a member of the expert
groups of the International Energy Association’s tasks aimed at the development of improvedhydrogen storage since 1997. He has served as a co-chairman of the 2006 International Symposium
on Metal-Hydrogen Systems and the 2007 Hydrogen-Metal Systems Gordon Research Conference.
He founded of Hawaii Hydrogen Carriers, LLC in 2003 and has since served as the company
president.

Corresponding author: Craig Jensen, jensen@hawaii.edu 1-808-956-2769

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PHYSICAL AND CHEMICAL PROPERTIES OF VOLATILE COMPLEXHYDRIDES
E. Callini1, A. Borgschulte1, I. Lindemann2, A.J. Ramirez-Cuesta3, M. Chong4, C.M.
Jensen4, O. Gutfleisch2,5, and A. Züttel1
1Empa, Swiss Federal Laboratories for Materials, Testing and Research, CH-8600 Dübendorf, Switzerland
IFW Dresden, Helmholtzstrasse 20, D-01069 Dresden, Germany
3
ISIS Facility, Rutherford Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX, United Kingdom
4
Univ Hawaii Manoa, Dept Chem, Honolulu, HI 96822 USA
5Technische Universität Darmstadt, Petersenstrasse 23, 64287 Darmstadt, Germany
2

In the route of finding suitable materials to store hydrogen, light and complex hydrides as solid storage solutions havebeen extensively explored. However, at present, no single material fulfilling all requirements for on board applications is
in sight. The storage of hydrogen in liquid complex hydrides is an attractive option, since these materials contain up to 20
mass% of hydrogen.

Gas Phase Analysis of Complex Hydrides
Synthesis and handling these materials is not simple.
This therefore yields to difficulties in their characterizationand the identification of the decomposition reactions withparticular emphasis on gaseous products. The presented
investigation method uses a thermogravimetric balance
to monitor the sample weight loss, while thedecomposition gas is detected by an infrared
spectrometer. In this way we provide a real time in situ
composition analysis of the desorption gas.

Selected materials
One of the most promising materials in the class of theroom temperature liquid complex hydrides is Ti(BH4)3,
since it can store around the 13 mass% of hydrogen. We
investigate metasynthesis of Ti(BH4)3 by ball milling
powders of TiCl3 and LiBH4. The result is an extremely
unstable compound which decomposes within few hours
at room temperature. This observation and thecomputational modelling connect this system to the roleof Ti halides frequently used as additives to enhance
desorption kinetics. The exchange of Ti-ions with Li-ionscatalyses the desorption of LiBH4 via the intermediate

formation of Ti(BH4)3. We demonstrate the required highionic mobility by exchange experiments. Similar
investigations are presented for Al(BH4)3: this is anotherinteresting element of this new class of materials (melting
point of -65 °C) because of its high gravimetric hydrogendensity (17 mass%) and the highest known volumetric-3hydrogen density of 150 kg*m . Nevertheless, it is shownthat the analysis of the gas phase fundamental also forsolid complex hydrides, in order to understand theirdecomposition reactions: these materials emit toxic andpossibly explosive hydrogen containing species, such asdiborane, which is a drawback for their reversibility and asevere safety issue. Recent developments in theutilisation of nano-structured cages to confine complex
hydrides, give us a promising path to alter the reaction
mechanisms reducing the emission of toxic compounds
and a possible way to reversible handle them.

References[1] E. Callini, et al., Dalton Transaction, DOI:
10.1039/c2dt31608k.
[2] A. Borgschulte, et al., J. Phys. Chem. C, 2011, 115(34), pp 17220–17226

Born 13.1.1982 in Varese, Italy. In 2011 she graduated in Physics in Bologna, Italy, with Prof. E.
Bonetti. During her studies she collaborates with the Danish Technical University in Copenhagen,Denmark, with Prof. T. Bohr; the Department of Chemistry of the Aarhus University in Denmark, with
Prof. T. R. Jensen and with the California Institute of Technology in Pasadena (CA), with Prof. B.
Fultz and Dr. C. Ahn. Since 2011 she is PostDoc in the Complex Hydrides Group in the Laboratory
Hydrogen & Energy at Empa, Dübendorf, Switzerland.
Elsa Callini
Corresponding author: Elsa Callini, elsa.callini@empa.ch, +41 587654933.

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REDUCING THE INCUBATION PERIOD OF DEHYDROGENATION FOR
THE MGH2-LIBH4 HYDROGEN STORAGE SYSTEM
Jianjiang Hu1*, Raiker Witter1, 2, Huaiyu Shao3 and Maximilian Fichtner1
1

Karlsruhe Institute of Technology, Institute of Nanotechnology, P.O.Box 3640, 76021 Karlsruhe, Germany
Technomedicum, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, Estonia
3
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr, Germany
2

Theoretically, the hydrogen storage system of MgH2-2LiBH4 can release 11.4% H with an enthalpy change of 46 kJ/mol
H2 which is by one third lower than LiBH4. Nevertheless, the dehydrogenation without catalyst shows a very longincubation period prior to the formation of MgB2. Furthermore, the hydrogen amount reported so far lies below 10%. By
adjusting stoichiometry between the two components, it is found in this work that the dehydrogenation efficiency wasincreased, and at the same time, the incubation period was significantly shortened. The reactivity of the starting materials
plays also a role in the dehydrogenation. With highly reactive nanoscaled MgH2, an enhanced dehydrogenation wasobserved without formation of the byproduct Li2B12H12, which is important for the reversibility.

Introduction
Metal borohydrides are a category of materials thatpossess potential as high performance hydrogen storage
materials due to their high hydrogen contents. Dependingon the properties of metal cations in the borohydrides,
these compounds show different stabilities in thermal
1decomposition. In recent years, a concept wasdeveloped that lower enthalpies and thus lower
dehydrogenation temperatures are expected if ametastable product of dehydrogenation is formed, which2
can be exemplified by the MgH2-2LiBH4 system.

1:0.2. Highly reactive nanoscaled MgH2 obtained via
organometallic synthesis was also effective in reduction
the incubation periods (Figure 1).

Suppression of Li2B12H12 formation
It was found that the formation of Li2B12H12 waseffectively suppressed in the dehydrogenation products,
using nanoscaled MgH2 instead of commercial product(Figure 2), which might hint a different reaction
mechanism.

Shortened Incubation periods

Dehydrogenation [wt%]

10

*MgH2

BH4

MgB2
B12H12

8

0.2

1

1

2

2

0.6

6

120

100

80

60

*MgH2

40

20

0

-20

-40

-60

ppm

4

Figure 2 Solid-state 11B NMR spectra of desorbed
products with (red) and without (black) active MgH2

2

400C 3bar H2
0
0

5

10

15

20

Time [h]Figure 1 Dehydrogenation isotherms of MgH2-xLiBH4(x=0.2 – 2.0)
The incubation period was reduced by varying the molar
ratio of MgH2 to LiBH4, from over 10h at 1:2 to 1h at

References[1] Y. Nakamori, K. Miwa, A. Ninomiya, H. Li, N. Ohba,
Phys. Rev. B 74, (2006), 045126.
[2] J. J. Vajo, S. L. Skeith, F. Mertens, J. Phys. Chem. B,
Lett 109, (2005), 3719-3722.

Dr. Hu obtained his Ph. D degree at the Technical University of Dresden. He started working on
solid-state hydrogen storage materials in 2004. He is a scientific staff at KIT since 2008.

Dr. Jianjiang Hu
Corresponding author: Jianjiang Hu, email: jianjiang.hu@kit.edu , Tel. +49 721 6082 8915

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FROM THEORY TO EXPERIMENTAL STUDY AND SYNTHESISOPTIMIZATION OF MAGNESIUM AND ZINC MIXED BOROHYDRIDES
G.Kalantzopoulos1, E.Albanese2, J.G.Vitillo2, E.Pinatel2, B.Civalleri2, S.Deledda1, Richard
H. Heyn3, S.Bordiga2, M.Baricco2 and B.C.Hauback1
1

Department of Physics, Institute for Energy Technology, Instituttveien 18, NO-2007, Kjeller, Norway

2

Dipartimento di Chimica and NIS, Università di Torino, Torino, Italy

3

SINTEF Materials and Chemistry, P.O. Box 124, Blindern, NO-0314 Oslo, Norway

Abstract
Ab initio calculations have been used to predict the thermodynamic behaviour of Mg and Zn mixed borohydrides systems. In order toverify the results of calculations, mixtures of Mg(BH4)2 and ZnCl2 with 1:0.7 ratio have been ball milled in different conditions.
Samples have been analyzed with a combination of experimental techniques (PXD, NMR, IR-ATR, TGA, TPD with RGA, PCI). The
phase mixture obtained after the synthesis strongly depends on the milling conditions. A significant hydrogen release has been
observed for temperatures close to 100 °C, suggesting a significant decrease of the decomposition temperature with respect to pureMg(BH4)2. For prolonged times, the formation of Zn and MgCl2 has been observed, suggesting the delivering of B-containing species
during the milling. The effect of milling atmosphere (Ar or H2), of milling time and of milling type (planetary or cryo-mill) on thesystem with 1:0.7 ratio will be discussed.

Motivation
In comparison to other metal borohydrides, Mg(BH4)2
possesses lower decomposition temperature andrelatively high hydrogen gravimetric capacity. Mg(BH4)2
decomposes at 300 °C, a temperature that is still high to
be considered a promising material to be coupled with aproton-exchange membrane fuel cell (PEMFC). Various
different approaches can be utilized to de-stabilize purecomplex hydrides like anion or cation substitution, mixed
metal borohydrides formation, nanoconfinement andreactive hydride composites [1-3].
Ball milling techniques are widely used as a synthesis
technique of potential hydrogen storage materials. The
produced compounds can exhibit altered thermodynamic
properties. [4].

Theoretical and Experimental Methods
The theoretical investigation of Mixed-Metal Borohydrides
was carried out with density functional theory (DFT)
calculations employing the PBE exchange-correlation
functional and the PBE-D* method.
Powder mixtures of α-Mg(BH4)2 and ZnCl2 in ratio of
1:0.7 were ball milled in Ar or H2 using a Fritsch P6
Planetary mill or cryo-milled in a SPEX 6770 Freezer/Mill
using a specially designed stainless steel vial, in order tominimize oxygen and nitrogen contaminations. The-1
Infrared spectra (2 cm resolution, average on 1024
scans) were collected in Attenuated Total Reflection(ATR) mode on loose powder on a Bruker Alpha-P
spectrometer equipped with a germanium detector incontrolled atmosphere. Gas release was examined using
a home-made apparatus for Thermal Programmed

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Desorption (TPD) coupled with a MULTIVISION IP
detector system for residual gas detection analysis(RGA). Measurements were carried out in vacuum (10-5ombar) between RT and 600 C. Thermo GravimetricAnalysis (TGA) experiments were performed with a
Netzsch STA 449 F3 Jupiter instrument between 30 °C
and 600 °C, with a heating rate of 2 °C min-1 under argongas (50 ml/min).

Results
Results for α-Mg(BH4)2 and ZnCl2 in ratio of 1:0.7 will bepresented. Data from diffraction analysis and nuclear
magnetic resonance spectroscopy will be discussed withrespect to phase selection processes that occur duringball-milling. The existence of amorphous phase(s) andtheir effect on the sorption properties of the examined
systems will be discussed. The effect of milling conditions
on the selective release of H2 instead of B2H6 which isinvestigated by residual gas analysis will be also
discussed. Finally, the reversibility of the examined
systems will be critically assessed.

References[1] L.H. Rude, T.K. Nielsen, D.B. Ravnsbaek et al.,Physica Status Solidi a-Applications and Materials
Science, 208 (2011) 1754-1773.
[2] S.I. Orimo, Y. Nakamori et al., Chemical Reviews,
107 (2007) 4111-4132.
[3] H.W. Li, S. Orimo, Y. Nakamori et al., Journal of
Alloys and Compounds, 446 (2007) 315-318.
[4] Zhang, et al., J. Alloys Compounds, 393, (2005), 147.

23

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Stoos, Switzerland 201324.11.2006

Graduation from Materials Science & Engineering, University of
Ioannina, Greece

20.02.2009 – 15.05.2009

Visiting Researcher, Max Planck Institute for Metals Research,
Stuttgart, Germany, Dr. Michael Hirscher group

09.12.2009

Ph.D in Physics, University of Calabria, Italy, ph.D Dissertation in“Hydrogen Physisorption Processes on Porous Solids”.

Georgios
Kalantzopoulos

Supervisor: Prof. Raffaele G. Agostino
10.12.2009 – 01.10.2010

Post-Doctoral fellow, University of Calabria, Italy

02.10.2010 till present

Post-Doctoral fellow, Institute for Energy Technology (IFE),
Department of Physics, Kjeller, Norway in the group of Prof. Bjørn
C. Hauback.
Involved in the EU project: SSH2S (No. 256653).

Corresponding author: Georgios Kalantzopoulos, georgiosk@ife.no, Tel.: +47 6380-6181

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HYDROGEN RELEASE FROM LiBH4/Ca(BH4)2 EUTECTIC SYSTEM
Arndt Remhof1, Yigang Yan1, Philippe Mauron1, Young-Su Lee2, Hyun-Sook Lee2, Young
Whan Cho2, Daniel Rentsch3, and Andreas Züttel1
1

EMPA, Hydrogen & Energy, Dübendorf, Switzerland
High Temperature Energy Materials Research Center, KIST, Seoul, Republic of Korea
3
EMPA, Functional Polymers, Dübendorf, Switzerland
2

Controlling the dehydrogenation process in a suitable reaction route by choosing the appropriate reaction conditions is
crucial for a hydrogen storage system. Stable hydrogen containing intermediates reduce the usable amount of hydrogen;volatile intermediates contaminate the H2 and may poison the fuel cell. We discuss and compare different reaction
pathways of LiBH4 and of LiBH4/Ca(BH4)2 eutectic mixtures and present parameters for the hydrogen release that favor
the reabsorption of hydrogen.

Introduction
Lithium borohydride (LiBH4) is currently one of the most
discussed hydrogen storage materials. On the exampleof LiBH4 the perspectives as well as the challenges ofsolid hydrogen storage become visible. LiBH4 melts at
277°C and releases considerable amounts of hydrogenfrom the melt according to the following overall reaction:

present in the final dehydrogenation products, leading to
the improved cycling performance, as depicted in fig.1.

LiBH4 → LiH + B + 3/2H2 (1)Different reaction pathways leading to the final products
have been discussed in the past [1,2].
The reverse reaction requires elevated temperature andpressure, it has been observed at 600°C under 150 to
350 bar H2. To improve the reversibility, the formation of
stable intermediate phases such as Li2B12H12 has to beprevented.
One way to improve the reversibility are combined
systems of LiBH4 with alkali earth metal borohydrides
such as Ca(BH4)2.

Results
We prepared the eutectic system of LiBH4−Ca(BH4)2 withmolar ratio of 0.68 to 0.32 (labeled 0.68L032C in fig.1).
The hydrogen emission starts from the eutectic melt at
200 °C and the dehydrogenation process is completed
below 400 °C with hydrogen release of more than 10
wt%, as shown in fig.1. Solubility isotherms measured indesorption reveal a two-step process. First, Ca(BH4)2
decomposes into CaH2, CaB6, and H2, with traces of
CaB12H12. Subsequently CaH2 reacts with LiBH4 to CaB6,
LiH and H2. Li2B12H12 has been identified as a byproduct. The lower dehydrogenation temperature, themore CaB6 and the less [B12H12]2− containing phases are

Fig.1: Hydrogen desorption measurements of therecharged samples after isothermal dehydrogenation at
330, 350, 375 and 425 °C, respectively.
References:[1] Ph. Mauron, F. Buchter, O. Friedrichs, A. Remhof, M.
Bielmann, C. N. Zwicky and A. Züttel, J. Phys. Chem.
B, 2008, 112, 906.
[2] Y. Yan, A. Remhof, S.-J. Hwang, H.-W. Li, Ph.
Mauron, S.-I Orimo and A. Züttel, Phys. Chem.
Chem. Phys., 2012, 14, 6514.
[3] Y. Yan, A. Remhof, Ph. Mauron, D. Rentsch, Y.-S.
Lee, H.-S. Lee, Y. W. Cho, A. Züttel, in preparation

1994
University Diploma with distinction of the University of Kent at Canterbury, UK.
1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France.
1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany.
1999
Guest scientist at the Universidade São Francisco in Itatiba, São Paulo, Brazil.
2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands.
2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum.
From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.”
2010
Guest scientist at the Tohoku University in Sendai, Japan
Arndt Remhof
Corresponding author: Arndt Remhof, arndt.remhof@empa.ch +41587654369

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FROM YH3 VIA Y(BH4)3 TO Y2(B12H12)3
Yigang YAN1, Arndt Remhof1, Daniel Rentsch2, Andreas Züttel1
1

EMPA, Hydrogen & Energy, Dübendorf, Switzerland.
EMPA, Functional Polymers, Dübendorf, Switzerland

2

We achieved the direct solvent free synthesis of Y(BH4)3 and of Y2(B12H12)3 via reactive ball milling of YH3 and of Y(BH4)3
in H2/B2H6 atmosphere. The reaction can be controlled by the applied temperature. At room temperature, YH3 reacts with
B2H6, forming Y(BH4)3 with a yield of more than 75%. Exposing the as prepared Y(BH4)3 to B2H6 at 150°C, Y2(B12H12)3 isformed.

Introduction
Y(BH4)3 exhibits a high hydrogen density of 9.1 wt%, a
relatively low dehydrogenation temperature with an onset
below 200 °C and it releases pure hydrogen as the only
volatile decomposition product [1]. So far, no B12H12containing phase has been reported among thedecomposition products of Y(BH4)3. Therefore, Y(BH4)3
has been suggested as a solid hydrogen storage material.
Y(BH4)3 can be synthesized by metathesis reaction
between LiBH4 and YCl3, which leaves 50 wt% of LiClremaining as a byproduct [2]. For further applications,high purity Y(BH4)3 is needed. The dehydrogenation ofY(BH4)3 proceeds through multistep reactions. Details of
the hydrogen release and the intermediates involved are
topics of current discussion.

The 11B MAS NMR spectrum of the as-synthesized
Y(BH4)3 is shown in Fig. 1. Y(BH4)3 exhibits a resonanceat -19 ppm. No other boron containing species wereobserved. Only solid yttrium hydride was contained in the
product as the remaining contaminant [1]. After heating in
B2H6 atmosphere at 150 ºC, the resonance of Y(BH4)311
shifts to -13 ppm. Further solution state B NMR
measurements indicate that Y2(B12H12)3 as well as
Y2(B10H10)3 is formed by the reaction between Y(BH4)3and B2H6 [3].
abHere, we demonstrate a direct, solvent-free synthesis of
Y(BH4)3 and Y2(B12H12)3 and discuss the hydrogen
release reaction.

Experimental
Metallic Yttrium, ZnCl2 (anhydrous), LiBH4, andpressurized H2 are used as starting materials. The
synthesis was carried out using a custom made millconnected to a gas/vacuum supply. The B2H6 source
LiZn2(BH4)5 was prepared by ball milling the mixture of
LiBH4 and ZnCl2.

Results
Through gas solid reaction during the reactive ball millingof YH3 in a H2/B2H6 atmosphere at room temperature,
Y(BH4)3 was synthesized with a yield above 75 %. The
product was identified by XRD and NMR spectroscopy.
2001-04
2004-072007-08
2008-09
2009-11
2011-

40

20

0

-20

-40

-60

ppm
11

Fig. 1 B MAS NMR spectra of (a) as-synthesized
Y(BH4)3 and (b) the product from the reaction between
Y(BH4)3 and B2H6 at 150 ºC.

References[1] A. Remhof et al, Scritpa Mater., 2012, 66, 280.
[2] Y. Yan et al, Int. J. Hydrogen Energy, 2009, 34, 5732.
[3] Y. Yan et al., to be submitted

Master theses at Institute of chemistry science and engineering, Sichuan University, China.
PhD student at Institute of materials science and engineering, Sichuan University, China.
Senior engineer at SAE Magnetics (H.K.) Ltd in Dongguan, China.
Postdoctoral Fellowship at Institute for Materials Research, Tohoku University, Japan.
JSPS Postdoctoral Fellowship at Institute for Materials Research, Tohoku University in
Sendai, Japan.
Postdoctoral Fellowship at EMPA, Switzerland.

YIGANG YAN
Corresponding author: Yigang YAN, yigang.yan@empa.ch, +41 58 765 40 82

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MAGNESIUM-BASED NANOPARTICLES AND NANODOTS: SYNTHESIS,STRUCTURE AND THERMODYNAMICS
Luca Pasquini1, Mattia Sacchi1, Alan Molinari1,2, Horst Hahn2, Christiaan Boelsma3,
Bernard Dam3
1 Department of Physics and Astronomy, University of Bologna, v. Berti-Pichat 6/2, 40127 Bologna, Italy
2 Institute of Nanotechnology, Karlsruhe Institute of Technology, 76344 Eggenstein-Leopoldshafen,Germany
3 Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628BL Delft, The Netherlands
Abstract: The thermodynamics of hydrogen sorption in nano-sized objects is a matter of intense research. We describe
two different physical methods for the synthesis of Mg-based nanostructures and report on the thermodynamics ofhydrogen absorption/desorption studied by hydrogenography.

Synthesis of Mg nanostructures

Structural analysis

Magnesium (Mg) nanoparticles (NPs) were synthesized
by Inert Gas Condensation: Mg was thermallyevaporated in a ultra-high vacuum chamber in thepresence of a Helium flow, which induces condensationof the metal vapours into NPs and deposits them onto asuitable substrate. The NPs size can be controlled bytuning the source temperature and the helium flow,whereas the degree of agglomeration and the NPs
coalescence on the substrate strongly depends on theamount of evaporated material and on the nature of thesubstrate itself [1].

The morphology of the nanostructures was studied byelectron microscopy and atomic force microscopy. The
NPs prepared by IGC exhibit a characteristic six-foldsymmetry and a distribution of particles size, partly
resulting from coalescence on the substrate. Conversely,
the NDs are highly monodisperse with a size dictated by
the pore size of the UTAM: their spatial arrangement
displays an hexagonal in-plane symmetry again reflecting
the original geometry of the UTAM. The surface chemical
state was studied on the Mg NPs by X-ray Photoelectron
Spectroscopy, confirming the core/shell picture anddemonstrating the absence of significant Mg-Pd alloying[2].

Mg nanodots (NDs) were grown by Molecular Beam
Epitaxy (MBE) onto an MgO substrate coated by aporous, ultra-thin alumina mask (UTAM). The NDs size
and aspect ratio can be tuned by using UTAM withdifferent geometrical parameters. The UTAM can be
eventually removed by mechanical or chemical methods.
In order to facilitate the dissociation / recombination of
the H2 molecule at the surface of these Mg-based
nanostructures, they were partially coated by a Pd layer
evaporated in situ in the synthesis chamber [2]. In someexperiments and intermediate Ti layer was also
deposited.
Finally, a thin layer of MgO (5 nm) was formed aroundthe nanostructures by slow admission of oxygen into thesyntheis chamber. The MgO shell protects the NPs
against further oxidation and provides a spontaneously
formed confinement medium.

Thermodynamics of hydrogen sorption
The equilibrium pressure for hydrogen absorption anddesorption at relatively low temperatures (60 – 90 °C)
was studied by pressure/ transmission isotherms (opticalhydrogenography). We discuss the observed remarkablevariations -with respect to bulk Mg- which concern theplateau pressures of hydrogen absorption/desorption,
taking into account a possible effect of elastic
confinement by the stiff MgO shell [3].

References[1] L. Pasquini et al., IOP Conf. Series: Materials Scienceand Engineering 38, 012001 (2012)[2] L. Pasquini et al., Phys. Rev. B 83, 184111 (2011)[3] A. Baldi et al, Phys. Rev. Lett. 102, 226102 (2009)

Born 16/05/1970. 1994: Master Degree in Physics, University of Bologna, summa cum laude. 1999:
Ph.D. in Condensed Matter Physics, University of Bologna. 1999: Research fellow at Institut fürTheoretische und Angewandte Physik, Universität Stuttgart. 2001: Visiting scientist at the European
Synchrotron Radiation Facility, Grenoble. 2002-2007: Post-Doctoral fellow at the Department of
Physics, University of Bologna. 2008-: Assistant Professor at the Department of Physics andAstronomy, University of Bologna.
Luca Pasquini
Corresponding author: Luca Pasquini, e-mail: luca.pasquini@unibo.it, Phone: +39 051 2095149

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The Study of Low Co-Content and Pr/Nd-Free Mn(Ni, Co, Mn, Al) 5
Alloy
Fangming Xiao, Tai Sun, Renheng Tang

Division of Rare Metals Research, Guangdong General Research Institute of Non-ferrous Metals,Guangzhou

E-mail of the corresponding author: xfmworld@163.com
Nickel-metal-hydride(MH-Ni) secondary battery is preferred in manufracturing HybridElectrical Vehicle (HEV) because of its high capacity, high power and pollution freecharacteristics. However, the increase price of rare-earth metals cause the increase of thecost of producing the AB5 hydrogen storage alloy, which is the main material in the
manufracture of cathode. The development of Pr/Nd-Free Mn(Ni, Co, Mn, Al) 5 Alloy
will help reducing the cost of producing the MH-Ni secondary battery for HEV.
In this paper, we investigate the hydrogen storage properties and electrochemical
characteristics of the LaxCe1-x(NiCoMnAl)5 (x=0.8、0.6、0.4) prepared by combining
medium frequency induction smelting and melt spinning methods. Results show that boththe hydrogen storage capacity and the discharge capacity decrease with the reduction of x,
while the plateau of the PCT curve become broader and flater with smaller hysteretic
between hydrogenation and dehydrogenation process. When the La content decrease
from 0.8 to 0.4, the high rate discharge ability (HRD) increases from 95.65% to 96.72%,
while the 2C cycle life increase from 181 times to 239 times(80% capacity retain). The
alloy electrode shows better comprehensive electrochemical with a discharge capacity of
314.57mAh/g and a cycle life of 215 times when x=0.6. Optimizing the content of Mn,
Al and Co of the B side of the alloy can also increase the performance of the alloy
electrode. A discharge capacity of 319.01mAh/g and a cycle life of 216 times wasachieved with lower Co and higher Al content. The anneal treatment can greatly
improves the crystallinity, the homogeneity and the cycling life. However, the discharge
capacity was lightly decrease after annealing. The B-side optimized LaxCe1x(NiCoMnAl)5 (x=0.8) after annealing at 950°C/2h has a maximium discharge capacity of

328 mAh/g with a cycling life of 364 times.

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Two new applications of hydrogenography: Direct intrinsic hydrogen
permeability measurements and enthalpy-entropy correlation.
R. Griessen1, C. Boelsma2 S. De Man1, D. Visser1,
H. Schreuders2, A. Baldi3,4 , B. Dam2.
1

Physics Department, Faculty of Sciences, VU University,
De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands (r.p.griessen@vu.nl)
2
MECS, Chemical Engineering, Faculty of Applied Science,
Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
3
FOM Institute AMOLF, Science Park 104,1098 XG Amsterdam, The Netherlands
4
Department of Materials Science and Engineering,
Stanford University, 496 Lomita Mall, Stanford CA 94305, USA
One of the great advantages of Hydrogenography is that it makes it possible to investigate
simultaneously specific properties of large numbers of alloys. This eliminates statisticalerrors to a large extent and general trends become apparent. In my talk I shall describe two
new applications of Hydrogenography 1.
Hydrogen purification membranes: The purification of hydrogen from gas mixtures is an
essential step in the use of hydrogen as fuel in mobile applications and as feedstock inchemical technology 2 .The most commonly used purification membranes are made of Pd or
alloys of Pd. As Pd is a rare and expensive material there is a clear need to look for othermembrane materials. The exploration of binary and ternary alloys with standard permeation
techniques is however prohibitive as it requires at least one membrane per alloy
composition 3. We show that hydrogenography provides a highly efficient way to measure
simultaneously the intrinsic H permeability in hundreds of alloys. For this we use thesample geometry shown in Fig.1. It consists
essentially of: i) the membrane material M
Fig.1
deposited on a substrate (S), which does not need
to be optically transparent, ii) a thin layer of
Yttrium (Y) that acts as H absorber and H
indicator, iii) a thin oxide layer on the Yttrium
indicator that prevent direct absorption of H, andiv) a narrow strip of Palladium (Pd) as entrance
gate for hydrogen. At time t = 0 a desired pressureof hydrogen gas is applied. The permeation of H in
M colours the indicator blue and is easily recordedwith a CCD camera. The diffusion of hydrogen is
described with a model in which the H-particle
current depends on the gradient of the H chemical
potential in the membrane material. The chemical
potentials of H in the membrane and the Y layer
are locally equal. In the technologically importantsituation where the H concentration in the
Fig.2
membrane material is much smaller than in the Ylayer the permeability k, is given by

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2
cI d I  x f k ≡ DK S =  where cI is the H concentration in the indicator layer and p is
4d S p  t 

the H2 gas pressure used for the experiment. This implies that k can be directly determinedfrom the slope of a plot of the square of the front position x f as a function of time t . The
important feature of this equation is that the permeability is obtained directly without theneed of separate measurements of the Sieverts constant KS and the H diffusion coefficient.
For H in Pd-Cu alloys the values obtained with this hydrogenographic method at room
temperature (open circles in Fig.2) are in good agreement with the few published data
(filled squares) 4. The method described above is readily generalized to ternary alloys. One
uses then a sample with Pd dots as shown on the left. Results on Pd-Cu-Mo alloys showthat in all alloys, the permeability decreases with increasing Mo content in contradiction
with a suggestion made by R.C. Benn 5
Enthalpy-entropy correlation: In Fig.3 the compilation of a large number of enthalpy ∆Hand entropy ∆S values made by G. Thomas 6 on the basis of the Sandia data base shows ageneral trend. However, all theses data points have been obtained in different
investigations and it is questionable whether the observed correlation is real or just merely
a statistical phantom effect 7. In MgyTi1-y alloys it is possible to demonstrate that the0∆H (kJ/KmolH2)∆H(kJ/molH2)

-20
-40
-60
-80
-100
-120

-55

y=0.82

-56
-57
-58

Fig.3

-200

-150 -100-50∆S(J/KmolH2)

0

Fig.4

y=0.78

-59
-126

-124

-122

-120

-118

-116

∆S (J/K molH2)

enthalpy-entropy correlation is genuine and definitely not due statistical uncertainties. The
proof is that at the temperature Tcomp = d ( ∆H ) d ( ∆S ) = 433K determined from theenthalpy ∆H vs. entropy ∆S plot (Fig.4) the isotherms have all the same plateau pressure.
This implies that all Van ‘t Hoff plots are crossing each other at the temperature Tcomp. The
physical origin of this clear correlation still needs to be elucidated.
1

R. Gremaud, C. Broedersz, D. M. Borsa, A. Borgschulte, P. Mauron, H. Schreuders, J. H. Rector, B.
Dam, and R. Griessen, Adv. Mater. 19, 2813 (2007).

2

Y. S. Lin, Sep. Purif. Technol. 25, 39 (2001).

3

P. Kamakoti, B. D. Morreale, M. V. Ciocco, B. H. Howard, R. P. Killmeyer, A. V. Cugini, and D. S.
Sholl, Science 307, 569 (2005).

4

L. Yuan, A. Goldbach, and H. Xu, J. Phys. Chem. B 111, 10952-10958 (2007).

5

R.C. Benn, Patent (2008) WO 2008/105770 Al
G. Thomas, private communication
7
A. Cornish-Bowden, J. Biosci. 27, 121 (2002).
6

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7th Int. Symposium Hydrogen & Energy

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MATERIALS AND SYSTEMS FOR HYDROGEN STORAGE
M. Dornheim, J. Jepsen, C. Pistidda, F. Karimi, S. Börries, N. Herbst, O. Metz, C.
Horstmann, K. Taube, J. Bellosta von Colbe, T. Klassen
Abteilung für Nanotechnologie, Institut für Werkstoffforschung, Helmholtz-Zentrum Geesthacht, Max-Planck-Straße 1,
21502 Geesthacht
In this presentation results concerning reaction mechanism and sorption behaviour of complex hydrides and reactive
hydride composites are presented. The progress in the optimisation of reaction kinetics and the potential of different
hydrides and hydride composites is discussed. Results of hydrogen storage tank testing based on selected hydridematerials are shown.

Novel light weight Materials for Hydrogen
StorageIn recent years several novel materials for hydrogenstorage with significantly increased gravimetric hydrogenstorage capacities and rather low to excellent reversibility
have been identified. In this presentation the differencesin cyclability will be discussed in relation to differences inreaction mechanics.

Low Cost Materials for Hydrogen Storage
In the strong emphasis on gravimetric and volumetricstorage densities of hydrides one key requirement formost applications is the cost of the storage materials andthe tank systems. A preliminary study on storage
materials with low purity will be shown.

Hydrogen Storage Tank TestingIn addition to the optimization of the storage material
itself the total storage tank system has to be optimized.
The presentation will show results of tank simulation andtank tests.

"Hydrogen Storage in Magnesium-Based Hydrides
and Hydride Composites", Viewpoint Set on Mgbased hydrogen storage materials, Scripta Materialia
56 (2007) 841-846[2] M. Dornheim, N. Eigen, G. Barkhordarian, T. Klassen,
R. Bormann, "Tailoring Hydrogen Storage Materials
Towards Application", Advanced Engineering
Materials 8 (2006) 377-385[3] P.K. Pranzas, U. Bösenberg, F. Karimi, M. Münning,
O. Metz, C. Bonatto Minella H.-W. Schmitz, F.
Beckmann, U. Vainio, D. Zajak, E. Welter, T. J.
Jensen, Y. Cerenius, R. Bormann, T. Klassen, M.
Dornheim, and A. Schreyer, “Characterization of
Hydrogen Storage Materials and Systems with
Photons and Neutrons“, Advanced Engineering
Materials 13 (2011)730-736.
[4] José M. Bellosta von Colbe, Oliver Metz, Gustavo A.
Lozano, P. Klaus Pranzas, Heinz W. Schmitz, Felix
Beckmann, Andreas Schreyer, Thomas Klassen,
Martin Dornheim,“ Behavior of scaled-up sodium
alanate hydrogen storage tanks during sorption“,International Journal of Hydrogen Energy, Volume 37,
Issue 3, February 2012, Pages 2807-2811

References[1] M. Dornheim, S. Doppiu, G. Barkhordarian, U.
Boesenberg, T. Klassen, O. Gutfleisch, R. Bormann,
Education:
Dr. rer. nat. (PhD) Universität Göttingen, Göttingen, Germany 2002.
Dipl.-Phys. (Master degree) Universität Göttingen, Göttingen, Germany 1998.
Vordiplom (~bachelor) Universität Hamburg, Hamburg, Germany 1994
Employment records:
Lecturer at Helmut-Schmidt University, Hamburg, Germany 2012Martin
Dornheim

Scientific responsible Materials for Hydrogen Technology, HZG, 2009Head of Nanotechnology Department, Helmholtz-Zentrum Geesthacht 2005Lecturer at Hamburg University of Technology, Hamburg, 2005-2010.
Deputy Head of Nanotechnology Department, HZG, 2003-2005.

Corresponding author: Martin Dornheim, martin.dornheim@HZG.de, +49 4152 87 2604

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NEW MATERIALS FOR HYDROGEN STORAGE
Torben R. Jensen
Center for Materials Crystallography (CMC), Interdisciplinary Nanoscience Center (iNANO) and Department ofChemistry, Aarhus University, Denmark.
Hydrogen is recognized as a potential and extremely interesting energy carrier system, which can facilitate efficientutilization of unevenly distributed renewable energy. A major challenge in a future ‘hydrogen economy’ is thedevelopment of a safe and efficient means of hydrogen storage, in particular for mobile applications. Here we report an
overview of our recent results within different experimental approaches for (i) synthesis of novel metal borohydrides andstudies of their properties, (ii) tailoring materials properties by anion substitution or nano-confinement, and (iii) in situ
powder X-ray diffraction for studies of hydrogen release and uptake reactions.

Metal borohydrides

Nanoconfinement

We have recently explored mechano-chemical andsolvent based methods for synthesis of new hydrides andhave discovered new series of metal borohydridesMM’BH4, typically containing an alkali metal, M, and adi- or tri-positive cation, M’. Apparently, the structuralcomplexity increase with the increasing size of the alkali
metal and also the tendency to form mixed chlorideborohydride compounds and ternary chlorides. The latter
illustrate a fundamental drawback for mechano-chemical
synthesis method [1-3], which, on the other hand, haslead to the discovery of a new type of combined fast Liion conductors and H2-storage materials based on heavy
metals [4]. Systematic ball-milling synthesis experiments
will also be presented, which reveal new information on
the wide parameter space for this synthesis technique[5]. Both synthesis and hydrogen release and uptake
reactions often occur via several coupled chemical
reactions, which can be utilized to stabilize boron in thesolid state.

Nanoconfined chemical reactions has a high degree ofreversibility and stability and possibly also improved
thermodynamic properties as compared to bulk
conditions. This new scheme of nanoconfined chemistry
may have a wide range of interesting applications in the
future, e.g. within the merging area of chemical storageof renewable energy [7]. Reversible chemical reactions
can take place at the nano-scale, e.g. LiBH4-MgH2
system or NaAlH4 in Ti-nano-particle functionalised nanoporous carbon aerogels. Systematic studies where poresize and scaffold surface area are varied will bepresented [8-10].

A fascinating structural chemistry is discovered within
metal borohydrides, e.g. interpenetrated ‘MOF-like’
networks or zeolite-type structures with up to 30% ‘empty’
space in the porous structures with chemical bonding
ranging from ionic to more covalent and containing
composite polynuclear complex anions in the solid state[6]. Magnesium borohydrides form the most open3
structured material ( = 0.55 g/cm ), which is the first
hydride storing both chemically bonded hydrogen (14.9
wt% H2) and additionally physisorped molecularhydrogen, i.e. Mg(BH4)20.80H2, m = 17.4 wt% H2 [6].

In this talk, we will also illustrate that in situ powder X-ray
diffraction is a unique, sensitive and informativetechnique for probing gas-solid reactions.

References[1] Rude, et al, Physica Status Solidi 2011, 208(8) 1754.
[2] Ravnsbæk, et al, Z. Kristallogr. 2010, 225, 557–569.
[3] J. Huot, et al. Prog. Mater. Sci. 2013, 58, 30–75.
[4] Ley et al. Chem. Mater. 2012, 24, 1654−1663.
[5] Ravnsbæk, et al. Chem. Int. Ed. Angew. 2012, 51,
3582.
[6] Filinchuk, et al, Angew. Chem. Int. Ed. 2011, 50,
11162.
[7] Nielsen, et al, Nanoscale, 2011, 3, 2086 (review).
[8] Nielsen, et al, ACS Nano, 2011, 5, 4056–4064.
[9] Nielsen, et al, J. Phys. Chem. C, 2012. [10] Nielsen,
et al, submitted, 2012.

Torben received his Ph.D. degree in materials chemistry and did postdoctoral research at Risø
National Laboratory and DESY, Hasylab, Hamburg. He became Assistant Professor (2000) andResearch Associate Professor (2002) at the Interdisciplinary Nanoscience Center (iNANO) and
Department of Chemistry, Aarhus University. He was awarded a Steno research stipend (2002) by
the Danish research council and a Carlsberg research stipend (2005) form the Carlsberg
Foundation. His research interests are focused on synthesis, structural, physical and chemical
properties of inorganic materials and utilisation of synchrotron X-ray radiation for materials
characterization.
Corresponding author: Torben R. Jensen, trj@chem.au.dk, +45 87155939 (mobile: +45 2272 1486).

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Advanced Focused Ion Beam Nanostructuring of Energy Materials for
TEM Analysis and Electron Tomography
Meltem Sezen1, Harald Plank2, Toni Uusimaki2, Wernfried Haas2
1

Sabanci University Nanotechnology Research and Application Center, Orhanli, Tuzla, 34956, Istanbul Turkey

2Institute for Electron Microscopy, Graz University of Technology, Steyrergasse 17, A-8010 Graz, Austria

The shrinkage in the dimensions of the novel materials, structures and systems down to atomic scale as an output ofnanotechnology has assigned “Electron Microscopy” as the inseparable part of this field. In particular, tomography
applications are recently becoming more popular for imaging of three dimensional energy materials such as, solid oxide
fuel cells, hydrogen storage materials and solar cells. Especially, in order to reveal the geometric and elemental
distribution of material systems that are based on nanostructures, advanced TEM and FIB imaging and tomography
applications are being widely used. For this reason, ion milling based specific samples preparation techniques that keep
the original structures of the sections to be investigated at the TEM are often required. Dual-beam technologies, which
are becoming more popular everyday for its applications on diverse fields of science, provide material dependent andTEM analysis spectrum based solutions that are highly rapid, practical, creative and reliable.

Dual-beam instruments; consisting of Scanning Electron
Microscope (SEM) and Focused Ion Beam (FIB) columns
are versatile tools that are capable of performing
structuring, modification and prototyping from microdown to nanometer scale. Especially, when hardmaterials and material systems with hard substrates areconcerned, FIB is the only technique for site-specific
TEM specimen preparation. For an efficient TEM
tomography analysis, the specimen has to be precisely
structured so that, it has to be representing the entire
morphological properties of the original material in 3D atthe nanoscale. Such samples can be successfully
structured using the capabilities FIB-SEM systems, e.g.
ion milling, metal deposition, manipulation and polishing.
Another application of dual-beam instruments is FIB
tomography, where the material is cross-sectioned by ion
milling sequentially and from each sliced surface anelectron image (e.g. SE) or EDS data is acquired.
Consequently, the collected serial 2D data can bestackedandreconstructedtoform
ultimatecomprehensive 3D data. Using this procedure, different
material systems can be characterized for theirmorphological and elemental distributions in 3D.
Energy materials, such as, fuel cells, solar cells andhydrogen storage materials are often constructed on hardsubstrates and matrices and those materials need to be

Meltem Sezen

processed by ion milling techniques. In this study, dualbeam instruments are utilized to develop novel sample
preparation methodologies for TEM imaging andtomography applications, as well as FIB tomography
could be applied on similar material systems. The
complimentary analysis on corresponding materials arepresented using HR-TEM imaging coupled with HR-SEM
imaging for varying scales, such as from micron toatomic.

Figure 1. Preparation of pin-like TEM tomography
sample by ion milling in dual-beam instruments andrelated HR-TEM tomograph.

Meltem Sezen received her PhD degree from Institute for Electron Microscopy of Graz University ofTechnology, Austria in 2009. From 2009 to 2011, Dr. Sezen continued working as a postdoctoral
research fellow in Graz Centre for Electron Microscopy (ZFE). She is currently employed as a
researcher at the Sabanci University Nanotechnology Research and Application Center (SUNUM).
Her primary research interests include Focused Ion Beam technologies; Dual-Beam (FIB-SEM)
instruments; correlative electron/ion beam irradiation damage analysis on conjugated polymers andorganic semiconductors; nanocharacterization, nanomodification and nanostructuring of organic
optoelectronic devices, nano-scale prototyping and machining using in-situ dual-beam applications,
FIB based tomography and advanced TEM sample preparation techniques, ceramics processing andcharacterization, energy materials, Raman Spectroscopy and Wavelength-Dispersive Spectroscopy.

Corresponding author: Meltem Sezen, meltemsezen@sabanciuniv.edu, +90-216-4839886

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THERMODYNAMICS OF HIGH PRESSURE PHYSISORPTION
Nicholas P. Stadie,1 Channing C. Ahn,2 and Brent Fultz2
1

Empa, Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2

California Institute of Technology, Pasadena, CA 91125, USA

Abstract: A thermodynamic study of the enthalpy of adsorption of hydrogen and methane on high surface areacarbonaceous materials was carried out from 77-526 K. The adsorption of methane on zeolite-templated carbon (ZTC)
shows an increase in isosteric enthalpy with methane occupancy, an anomalous behaviour that significantly improvesdeliverable adsorptive capacity.

Zeolite-Templated Carbon

Results

Microporous carbon materials can be obtained via a[1]
templating procedure. Using a zeolite template, theyield (ZTC) is a highly microporous carbon with zeoliteanalogue structure, extremely high surface area (>3000
m2 g-1), and periodic pore-pore spacing (~1 nm).

The enthalpy of methane adsorption on ZTC-3 rises from-1
14 to 15 kJ mol at ambient temperature, and then falls
to lower values at very high loading (above a relative site
occupancy of 0.6), indicating that methane-methaneinteractions within the adsorption layer become
significant. Hydrogen adsorption in ZTCs is typical ofother carbonaceous materials.

Adsorption Experiments
We measured H2 and CH4 adsorption on ZTC-3, CNS201, and MSC-30 at 77-298 (H2) and 238-526 K (CH4).

Thermodynamic Model of Adsorption
The absolute quantity of adsorption was determined byfitting isotherms to a generalized Langmuir-type
equation.[2],The isosteric enthalpy of adsorption is calculated without
the ideal gas assumption:∆,

References[1] Nishihara, H.; Kyotani, T. Adv. Mater. 2012, 24, 4473.
[2] Mertens, F. O. Surf. Sci. 2009, 603, 1979-84.

Nick was born in 1985 in Calgary, Alberta, Canada. He received a BS in chemistry from ArizonaState University in Tempe, Arizona, USA in 2007, focusing on synthesis of novel metal-organic
framework materials with Prof. Michael O’Keeffe. He recently received a PhD in materials science at
the California Institute of Technology in Pasadena, California, USA with Prof. Brent Fultz and Dr.
Channing Ahn. In 2013, he joined Empa as a post-doc. The focus of his graduate research wassynthesis and characterization of high surface area materials for hydrogen storage applications.
N. Stadie
Corresponding author: Nicholas P. Stadie, nicholas.stadie@empa.ch

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MODELLING THE THERMOMECHANICAL BEHAVIOUR OF THE
BREATHING HYDRIDE POWDERS THREATENING THE INTEGRITY OF
THEIR CONTAINERS
B. CHARLAS1,2, O. GILLIA1, P. DOREMUS2, D. IMBAULT2, A. CHAISE1
1 : CEA Grenoble LITEN/DTBH/LTH, 17 Rue des Martyrs, F-38054 Grenoble Cedex 9, France
2 : G-INP, UJF, CNRS UMR 5521, 3SR Lab, Domaine Universitaire, BP53, 38041 Grenoble Cedex 9, France
Abstract : In this communication, the problem of dimensioning hydride vessels is addressed. The mechanical integrity ofvessels is threatened by the swelling/shrinking, named "breathing", of hydride powder materials. Engineers need to havepredictive laws to handle this problem. Some recent results about modelling are given in this paper.

The storage of hydrogen by hydride materials involves a
medium that shows in a granular state, whatever thismedium is a metallic or a complex hydride. In all cases,
this medium is introduced in a container that has both
functions of holding it and helping heat transfer related toexo(endo)thermicity of the (un)hydriding reaction.
Sometimes, the hydride is mixed or co-compacted withanother material (metallic foam [1], carbon flakes [2]…)]…) in order to improve its thermal conductivity, but its
nature remains granular. In addition, the material isswelling when absorbing hydrogen, and is shrinking
during the release of hydrogen. This latter effect may
cause severe solicitation of the container, threatening its
mechanical integrity [3]. Modelling aims at providing
predictive models that will be used to design efficiently
hydride hydrogen tanks.

Experimental characterization
Observation of the physical phenomena is a goodstarting point to modelling. The "breathing" phenomenon
has not been very well identified to date, it is thus
essential to have a precise experimental investigation
about it. This has led to the development an instrumented
cell operating between 0-150 bars of hydrogen and 20200°C that permits to measure the swelling/shrinking of apowder bed under different axial loads. Experiments
were performed on a TiVCr compound. Progressive
densification of the breathing hydride bed was observed[4]. Then, an instrumented compaction die in a low stressstate range (0-10MPa) has been set up. It allows thedetermination of the mechanical powder behaviour.

Modelling by the Discrete Element Method
Modelling by the discrete element method is a close way

Olivier GILLIA

to try and reproduce the behaviour of a multi-particle
medium. Some simulations have been performed andgive good results since they allow reproducing themeasured slow densification of the granular hydride bed,by re-arrangement mechanisms. It also permits to predict
stresses created when cycling the hydride in a cylindricalcontainer (Fig. 1). A strong effect of the ratio between
height and width of the granular volume has beenhighlighted, leading to emit recommendation on thegeometry of cells containing hydrides.
2
1,8
1,6

Radial Stress (MPa)Introduction

1,4
1,2
1
0,8
0,6
0,4
0,2
0
0

25

50

75

100

125

150

Time (s)Fig. 1 : Simulated cyclic stress appearing of the container vessel

References[1] M. Botzung, S. Chaudourne, O. Gillia, C. Perret, M.
Latroche, A. Percheron-Guegan, P. Marty, Int. J.
Hydrogen. Energy., Vol. 33(1), pp. 98-104, 2008
[2] A. Chaise, P. de Rango, P. Marty, et al., Int. J.
Hydrogen Energy, Vol. 34(20), pp. 8589-8596, 2009[3] F. Qin, L.H. Guo, J.P. Chen, Z.J. Chen, Int. J.
Hydrogen Energy, Vol. 33, pp. 709 – 717, 2008.
[4] B. Charlas, O. Gillia, P. Doremus, D. Imbault, Int. J.
Hydrogen Energy, Vol. 37(21), pp. 16031–16041(2012).

Born 17-04-1971, studies at Ecole Normale Supérieure de Cachan (1991), Agrégé de Mécanique(1995), Doctor of Institut National Polytechnique de Grenoble (2000), Postdoc at University ofLeicester, UK (2000), Lecturer at Institut National Polytechnique de Grenoble (2001), Research
position at CEA/LITEN - Grenoble since 2002. Activities in powder metallurgy, materials, brazing,
rupture mechanics for space and aeronautic applications, fusion (ITER) and hydrogen storage. Headof Hydrogen Storage Group of Hydrogen Technologies Laboratory since 2009.

Corresponding author: Olivier Gillia, olivier.gillia@cea.fr, 00 33 4 38 78 62 07

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HOW CAN EUROPEAN FUEL CELL AND HYDROGEN OPPORTUNITIESFIT INTO MY STRATEGY?
Julian Randall
Euresearch
Abstract
The Euresearch presentation will address these questions:•

What European funding opportunities are available today, with a focus on Fuel Cell & Hydrogen?

•

What European projects have been funded, with a focus on Switzerland (e.g. CHIC, FITUP)?

•

What further European opportunities should I be aware of?

Why attend the presentation?

Why work with Euresearch?

Whilst you may know of the significant funding at theEuropean level, finding the ideal funding strategy for yourorganisation can be challenging. Euresearch aims to be
the key access point in Switzerland for European
research and innovation. Euresearch will be represented
at the 7th International Symposium on Hydrogen &Energy by Julian Randall who can advise you on how tobenefit from European opportunities for your Fuel Cell
modelling activities.

Trust Worthiness: You get a professional and timely
service from our team, who are always ready to share
up-to-date and in-depth knowledge with you

Who are Euresearch?
The mission of Euresearch is both to increase thesuccess of Swiss researchers and companies in
European R&D&I projects and to facilitate internationalinnovation & technology cooperation. The Euresearch
network is present in Switzerland’s main scientific andinnovation centres as well as in Brussels. Euresearchcollaborators provide targeted information, expert advice
and hands-on support in all phases of applying for andmanaging European projects and technologicalcooperation with generally free of charge services.

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Commitment: We have an entrepreneurial spirit and look
for solutions
Networked expertise: You benefit from our trustworthy
personal contacts with all relevant national andinternational stakeholders

How to contact Euresearch?
Please call Julian Randall on 031 380 6010.
This number forwards to his mobile phone.

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Bachelor in Production Engineering, 7 years in industry as engineer, Ph.D. EPFL (Microtechnique),Postdoc at ETHZ in Electronics, Energy & Transport Swiss National Contact Point since 2006
What I do: Support those based in Switzerland to access European opportunities such as funding
and partners
How I do it: Provide free services such as checking ideas and/or application forms. Partner on
information events.
Julian Randall
Corresponding author: Julian Randall, Euresearch, Effingerstrasse 19, 3001 Bern, julian.randall@euresearch.ch

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H2FC EUROPEAN INFRASTRUCTURE; SCIENCE AND DEVELOPMENT
ALONGSIDE THE TECHNOLOGICAL HYDROGEN CHAIN
Olaf Jedicke
Karlsruher Institute for Technology (KIT); Institute for Nuclear and Energy-Technologies (IKET), Herrmann-vonHelmholtz Platz 1; 76344 Eggenstein-Leopoldshafen, Germany
Abstract

The European Strategy Forum on Research Infrastructures (ESFRI) recognizes in its roadmap for Research Infrastructures that “in thenear future hydrogen, as an energy carrier derived from various other fuels, and fuel cells as energy transformers, are expected to comeinto a major role for mobility but also for different other mobile and stationary applications” |1|. Actually it appears, that such modernhydrogen driven society lags far behind the reality. So it is allowed to question the current situation. The belief, that already most iscomprehensively investigated and developed concerning hydrogen technology is incorrect. In fact, the hydrogen technology is market
ready only partial and not prepared in a sufficient way to get finally included and adopted in a modern hydrogen driven society.
Nevertheless it is possible to foster furthermore science and development on hydrogen technology. The “Integrating European
Infrastructure” was created to support science and development of hydrogen and fuel cell technologies towards European strategy forsustainable, competitive and secure energy. Its acronym is H2FC European Infrastructure and was formed to integrate the European
R&D community around rare and/or unique infrastructural elements that will facilitate and significantly enhance the research anddevelopment of hydrogen and fuel cell technology.

Introduction
The widespread adoption of hydrogen and fuel cell
technologies will support the broader utilization ofotherwise lost renewable energy. However,hydrogen technologies including fuel cells currently
do not achieve the required cost and performancetargets for an immediate and broad market
introduction. Also safety aspects are still an issue
and public acceptance needs wider and moreconsistent information. A number of these issues
are partially addressed by the European Fuel Celland Hydrogen Joint Undertaking (FCH-JU) whichmainly supports the demonstration and adoption of
the currently available technologies. However, as
the current state and demonstration clearly showsthat there are still major open issues requiring
further investigation. Thus much additional researchwork, both on the fundamental and applied levels,need to be done. Without this R&D, the prospect ofcommercial success is pushed further into the
future |2|. H2FC European Infrastructure aims atfitting this gap and supporting the necessary
research by providing the required world classresearch infrastructure for external users. In brief,
H2FC European Infrastructure complements parallelto the European Joint Undertaking activities andfacilitates tackling major R&D bottlenecks in thefield by making available the necessary advanced
infrastructures to the EU research community.

Infrastructure Project
H2FC European Infrastructure is an European
Infrastructure Project funded by the European
Commission. The project combines Europe’s leading

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R&D institutions together supporting research anddevelopment on i.e. hydrogen production technologies,
pureness of hydrogen, storage materials and systems,
storage and distribution possibilities, final use throughfuel cells in a safe manner in stationary and mobile
systems etc. The project is coordinated by Karlsruher
Institute of Technology (KIT) and consists of 19
European partners, collected from European’s research
centers, universities and industry. With a total cost of €10.147.583,60, H2FC European Infrastructure activities
are subdivided into 25 work packages, fully interrelated,devoted to network activities, transnational accessactivities and joint research activities and oriented
towards the resolution of identified scientific bottlenecks.
Main support to European’s hydrogen and fuel cellcommunity will be given through the transnational accessactivities of the project, while opening very different
technical and experimental facilities to external users. A
further strong international support will be given toscientists and also to students by a continuous
researchers exchange program and four technicalschools. The prospects, education and the user access,will be announced by continuous calls through the H2FC
European Infrastructure consortium.
Furthermore main objective of the project will be to
generate a coordinated and integrated alliance based oncomplementary, state-of-the-art, or even beyond state-ofthe-art unique infrastructures to serve the needs of thescientific hydrogen and fuel cells community and facilitateworld class research. The current key research topics
identified are:
- Reducing degradation and increasing performance ofelectrolyser, hydrogen storage systems and fuel cells- Assessing and reducing hazards and risks associatedwith the use of hydrogen or hydrogen blended fuels andthereby ensuring the appropriate safety level of systems

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- Improving current storage technologies, in particularthrough advanced materials research- Central databases and libraries of safety, performanceand durability data and modeling codes- Coordination of relevant education and training actions;- Integration, enhancement and improvement of theexisting infrastructures- Coordination with national and international bodies aswell as academic and industry demands.

Conclusion[fig.1] thematic structure of H2FC European Infrastructure
Objectives of the project are to provide:Asingleintegrated
virtualinfrastructureaccommodating H2FC communities’ test and analysis
facilities;- Transnational access for the H2FC R&D communities tomember state infrastructures- Expert working groups to enhance work at the provided
facilities and coordination in the aspects of safety,
performance, durability

The structure proposed in H2FC European Infrastructure
will realize an alliance of the European scientificcommunity for serving the necessities of the scientificcommunity itself. Over the next 4 years, duration of the
project, the H2FC consortium expects that external
European experts will take up the opportunity tocollaborate concerning identified scientific and technicalbottlenecks, to strengthen hydrogen and fuel cell
technologies, to support the adoption by industry and at
least, to enlarge related knowledge.

References[1] ESFRI, European Road Map for Research
Infrastructures (Report 2006)[2] EC, DG RTD. “European funded research on Fuel
Cells and Hydrogen: review, assessment and future
outlook”. Report from the conference Hydrogen and Fuelthth
Cell Review Days – 2007, Bruxelles, 10 -11 2007

Olaf Jedicke; physicist and mathematician; 12 years Fraunhofer Community (Institute for Chemical
Technology, Pfinztal) to developed digital high speed measurement techniques to investigate
practically fast dynamic deformation processes of polymeric materials. Modeling of polymericmaterial behavior. Parallel investigation and application of sub- and super critical water, to use its
properties to extract fine chemicals from biomass and especially lignocelluloses materials. In 2005
Olaf Jedicke took up a lead position at Project Management Agency, which acts in behalf of the
National Ministry of Education and Science (BMBF), to develop national research and investigation
programs. Teaching Fluid Dynamics at the University of Cooperative Education since 1994 andMathematics since 2000 and Energy Technologies (Hydrogen Society) in 2012. Olaf Jedicke startedrdworking with EU Framework programs already in the 3 FP, was coordinator of BIONIRS, cocoordinator of HySafe, NanoHy, ScinTax, RELATE, and is coordinator / co- coordinator of theEuropean infrastructure projects H2FC and EUMINAfab. Since 2011 member of Institute of Nuclearand Energy- Technologies, “Hydrogen Safety Group” in 2011.
Olaf Jedicke; olaf.jedicke@kit.edu; Phone +49 (0) 721 6082 5274

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EFFICIENT PRODUCTION OF SOLAR FUEL USING EXISTING LARGESCALE PRODUCTION TECHNOLOGIES
Hans Geerlings and Wim Haije
Delft University of Technology, Department of Chemical Engineering, Julianalaan 136, 2628 BL Delft, The Netherlands
Abstract
Solar fuels will play an important role in our future global energy system, which arises after its transformation from thecurrent system based on fossil fuels to a more sustainable alternative largely based on contemporary solar energy. This
notion is well appreciated by the scientific community and the number of studies in this area is increasing rapidly. Manyof these studies are investigating advanced routes for synthesizing solar fuels including for instance modified
photosynthesis or solar thermal routes. Though interesting from a scientific point of view, none of these routes offer theprospect to be realized in practice within a decade from now. Fortunately relatively simple schemes to synthesize solar
fuels, which could be realized on commercial scale within 10 years, are existing today. For instance liquid hydrocarbon
fuels production from CO2 and water with efficiencies approaching 10% -from solar energy to fuel- is technically feasible
today. The challenge for further research is to reduce costs and further improve efficiency through optimized processschemes, which could enable commercial production of solar fuels within a decade. Such development would provide anenormous boost to all other lines of research in the area of solar fuel production, when these hold the promise of evenmore energy and cost efficient schemes. In this paper some of the routes to synthesize solar fuels will be reviewed withthe emphasis on those schemes that can be realized in practice in the very near future.

Hans Geerlings studied experimental physics in Amsterdam, where he received his
PhD degree in 1987. In that year he moved to Shell, where he worked in research
on a number of topics including synthesis gas conversion, hydrogen storage andCO2 capture and storage. In 2007 he was appointed as a part time professor at theDelft University of Technology. His current research interests are in the area of‘Solar Fuel synthesis’ and ‘Mineralization of CO2’.

Hans Geerlings

Corresponding author: Hans Geerlings, j.j.c.geerlings@tudelft.nl

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CARBON-CONFINED COMPLEX METAL HYDRIDES - TOWARDSFULL HYDROGEN SORPTION REVERSIBILITY
Jinbao Gao, Peter Ngene, Rien van Zwienen, Petra de Jongh
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials
Utrecht University, Universiteitsweg 99, 3584 CG Utrecht, The Netherlands

Science,Complex metal hydrides have a high hydrogen content, and hence are interesting hydrogen storage
materials, but often show limited hydrogen cycling efficiency under mild conditions. In this contribution we
focus on which factors limit the reversibiliy in carbon-nanoconfined complex metal hydrides, and discuss
effective strategies towards full hydrogen sorption reversibility.

Background
Complex metal hydrides, most notably alkali
metal alanates and borohydrides, have highhydrogen contents, but their applicability islimited by slow release kinetics, and poor
reversibility. A general approach to improve
the kinetics is nanosizing and confining in for
instance a carbon scaffold.1,2 This generally
leads
to
lower
hydrogenreleasetemperatures, but the amount of hydrogen
release usually decreases significantly in thefirst few cycles.

Results
For a range of complex metal hydrides incarbon scaffolds we studied in detail thefundamental reasons underlying the capacity
fading, especially in the first few cycles.3-5
Structural characterisation was essential tofollow the phase transformations andmorphology changes during cycling. We will
discuss some general strategies to combat
capacity fading upon cycling, and treat a few
specific examples. Especially the chemicalcomposition of the scaffold, its poremorphology, and nature of the interface
between the metal hydride and scaffold porewall determine the reversibility of thehydrogen release process.

Calorimetric measurements (left) andhydrogen release in the second cycle(right) for 20 wt% NaAlH4 in differently
treated carbon matrices.

References[1] J.J. Vajo et al, JPCC 112 (2008), 5651.
[2] P.E. de Jongh, P. Adelhelm, ChemSusChem 3(2010), 1332.
[3] P. Ngene, M. van Zwienen, P.E. de Jongh,
Chem. Comm. 46 (2010), 8201.
[4] P. Ngene et al, EES 4 (2011), 4108.
[5] Gao et al, J. Mat. Chem. 22 (2012) 13209.

Petra de Jongh received her PhD in photoelectrochemistry in 1999, andworked 5 years as a senior scientist at Philips Research. She is now associate
professor at Utrecht University, where she (co)-supervises researchers
working on supported nanoparticles, especially for applications in catalysis andenergy storage and conversion.

P.E. de Jongh
Corresponding author: Petra de Jongh, email: P.E.deJongh@uu.nl, Tel. +31 6 22736345

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NANOCONFINEMENT OF LITHIUM ALANATE
Inge Lindemann1,2, Markus Klose1, Christian Bonatto Minella1,2, Katja Pinkert1, Lars
Giebeler1, Ludwig Schultz1,2, Oliver Gutfleisch3
1

Leibniz Institute for Solid State and Materials Research Dresden (IFW), 01069 Dresden, Germany
TU Dresden, Materials Science, Helmholtzstr.10, D-01069 Dresden, Germany.
3
TU Darmstadt, Materials Science, Petersenstr. 23, D-64287 Darmstadt, Germany.
2

LiAlH4 is a metastable hydride which can be produced from organometallic synthesis route only. Due to the solvationenergy involved in the formation of the complex hydride, regeneration is possible in several steps. The nanoconfinementof LiAlH4 into a carbonaceous mesoporous structure with uniform diameters (3 nm) seems to lead to its successful
regeneration at moderate conditions without further addition of transition-metal based additive.

Introduction
Alanates have attracted great attention as hydrogenstorage materials for mobile applications due to theirlarge hydrogen content combined with moderatehydrogen desorption temperatures. Concerning NaAlH4,
the lack of reversibility can be overcome by the additionof catalyst.[1] Among the alanates, LiAlH4 has the highesthydrogen content (10.5 wt. % H2). Its hydrogen
desorption pathway follows a 3-step mechanism as
observed for NaAlH4. In case of LiAlH4, the addition of adopant (e.g. TiCl3) contributes to accelerate thedesorption reaction but no significant effect on the reabsorption reaction is observed in contrast to NaAlH4.
The first step is considered irreversible due to thenegative reaction enthalpy value. The re-hydrogenation
reaction was successful only in solution.[2] Additional Ti
doping could lower the required re-hydrogenationpressure and temperature extensively. However, thehydrogen capacity fades away over subsequent
cycles.[3]Nanoconfinement of complex hydrides into a porous
carbon structure represents a good strategy to alter
thermodynamics as well as to improve kinetics of theactive material. In this work, LiAlH4 was incorporated bysolution infiltration technique in an ordered mesoporous
carbon matrix in order to promote its reversible rehydrogenation reaction.

Experimental

LiAlH4/THF. The loading can be varied by the number ofsteps and the drying temperature. The structuralcharacterisation was carried out by XRD and MAS-NMR
as well as depth profiles from AES measurements. The
desorption reaction was monitored by simultaneous
thermogravimetry and mass spectrometry analysis of thegas phase. Sorption properties were further investigatedby a Sieverts Type apparatus.

Results
Due to a complexation reaction between LiAlH4 and THF,
the residual solvent could be only removed by fulldesorption upon the first cycle. By using several
activation cycles, the nanoconfinement strategy indicates
eventually, successful reversible formation of LiAlH4
occurring under moderate conditions without the additionof any transition-metal based additive.

References[1] B. Bogdanovic, M. Schwickardi, J. Alloys Compd.
253–254 (1997) 1–9.
[2] E. C. Ashby, G. J. Brendel, H. E. Redman, Inorg.
Chem. 2 (1963) 499-504.
[3] J.Graetz, J. Wegrzyn, J. Reilly, J. Am. Chem. Soc.
130 (2008) 17790-17794., X. Liu, G. S. McGrady, H.
W. Langmi, C. M. Jensen, J. Am. Chem. Soc. 131(2009) 5032-5033.

A multistep dry infiltration approach was used for solution
impregnation of ordered mesoporous carbon with 2M
Born 8.4.1984 in Cottbus, Germany
2006 Exchange student at Advanced Nanotechnology Ltd. in Perth, Australia
2009 Diploma in Materials Science at Dresden University of Technology, Germany
Inge Lindemann

Since 2009 PhD student at IFW Dresden in the group “Functional magnetic materials and hydrides”

Corresponding author: I.Lindemann@ifw-dresden.de, Tel.: (+49) 351 4659337

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HYDROGEN ABSORPTION IN ALKALI AND ALKALI–EARTH
METAL FULLERIDES
Mattia Gaboardi1, Daniele Pontiroli1, Matteo Aramini1, Georgia Vlachopoulou1,
Marcello Mazzani1, Mauro Riccò1, Chiara Cavallari2, Philippe Mauron3 andDenis Scheptiakov4.
1

Dipartimento di Fisica e Scienze della Terra, Università di Parma, 43124 Parma, Italy
Institut Laue Langevin, BP 156 38042 Grenoble, France
3
Empa. Swiss Federal Laboratories for Materials Science and Technology, Division ‘‘Hydrogenand Energy’’, Überlandstrasse 129, 8600 Dübendorf, Switzerland
4
Laboratory for Neutron Scattering, Paul Scherrer Institute, 5232 Villigen PSI, Switzerland
2

Abstract: we report our work on the hydrogen interaction in alkali and alkali-earth metal intercalated
fullerides. The treatment of MxC60 (M = Na, Li, Ca) in pressure of hydrogen brings to formation of metalintercalated hydrofullerides MxC60Hy through the intermediate formation of the metal hydride.

Introduction
BCC hydrofullerite

0.35
0.30

NaH

0.25

FCC

0.20
0.15

FCC

0.10

Results
Alkali and alkali-earth metal intercalated
fullerides MxC60 (M= Li, Na, Ca) weresynthesized via solid state reaction (using a
metal azide precursor) or by the intercalationof pure metal dissolved in liquid-ammonia
solution into fine grinded C60. The assynthesized
sampleswerethenhydrogenated/deuterated in 100-200 bar of
H2/D2 pressure at temperatures up to 400°C
for obtaining the metal intercalatedhydrofullerides. The characterization wasmade by making use of X-ray diffraction,
Nuclear Magnetic Spectroscopy, Muon Spin
Resonance, Neutron diffraction and Inelastic
Neutron Scattering.

Mattia Gaboardi

Na8C60 RT 100bar
Na8C60 150°C 100bar
Na8C60 250°C 100bar
Na8C60 350°C 100bar

0.40

Intensity (a.u.)

Hydrogen storage in carbon nanostructures
is a very promising area of research. Some
theoretical works shows that metal-decorated
C60 can absorb hydrogen up to 9.5 wt% [1,2].
Recently, was experimentally evidenced thehydrogen absorption in Na10C60 [3] and LixC60
systems [4].

0.00

STEEL

FCC

0.05

10

15

20

25

30

35

40

45

50

55

60

65

70

2θ (deg)

Fig.1: in-situ neutron diffraction of Na8C60

References:[1] K.R.S. Chandrakumar et al., Nano Lett. 8(1),13-19 (2008)[2] T. Yildirim, et al., Phys. Rev. B 72, 153403(2005)[3] P. Mauron et al., Int. J. Of Hydrogen andEnergy 37(19) 14307-14314 (2012)[4] J. A.Teprovich et al., Nano Lett. 12, 582 (2012)

1986: Born on in Reggio Emilia, Italy.
2010: Degree in Material Science.
Actually: PhD student in Physics at University of Parma in the Carbon
Nanostructures Laboratory headed by Prof. Mauro Riccò. His research activity is
focused on the synthesis, structural characterization and magnetic properties ofcarbon nanostructures.

Corresponding author: Mattia Gaboardi, email: mattiagianandrea.gaboardi@fis.unipr.it, Tel.(+39)0521
906067

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METAL INFUSED PARTICLES IN MILS, HYDROGEN STORAGE AND
SPILLOVER EFFECT
Petra Á. Szilágyi1, Jana Juan-Alcañiz1, Pablo Serra-Crespo1, Jorge Gascon1, Hans
Geerlings1,2 and Bernard Dam1
1 Delft University of Technology, Delft, The Netherlands
2 Shell Technology Centre, Amsterdam, The Netherlands

Abstract
Metal particles were infused into MIL-type metal-organic frameworks and their hydrogen-storage properties monitoredwith regards to the metal and the specific interactions the frameworks can allow for. Hydrogen-spillover effect was
detected and its extent will be discussed.

Introduction
Hydrogen storage is arguably the biggest challenge indeveloping a hydrogen economy. While different types ofmaterials are being explored as hydrogen carriers,
porous materials have the advantage of offering fast
kinetics for hydrogen sorption as well as reversibility overmultiple cycles. Among them, metal-organic frameworks(MOFs) are being increasingly considered as promisingmaterials for non-dissociative hydrogen adsorption. They
display high crystallinity as well as high and regularporosity. In addition, their syntheses can be carried out
under mild conditions, allowing for their rational design
and facile pre- or post-synthetic modification.
Furthermore, hydrogen-storage properties of MOFs were
improved by addition of metal particles due to hydrogen[1-4]
spillover.

Results and Discussion
Different metal particles, such as Ni and Pd were infused
into various MIL-type metal-organic frameworks (such as[5]
MIL-101 (Cr) ), using the solution-infiltration method andsubsequent reduction (with wet chemical methods as wellas in gas phase). The frameworks were equipped withdifferent functionalities, which may allow for specificinteractions with the metal sites prior and/or after
reduction.

and with respect to their pore-volume – hydrogen-storage
capacity relations at various temperatures. The variationof the hydrogen-storage properties of the MOFs upon
metal infusion will be dicussed.

Conclusions
Hydrogen-spillover effect was triggered in a number ofmetal-particle
infused
MIL-type
metal-organic
frameworks. The enhancement of hydrogen-storage
capacity was prevalent at higher temperatures (fromambient temperature) and showed an interplay with thenature of the metal infused as well as the supporting
frameworks.

References[1] Int. J. Hydr. Energ. 2007, 4005
[2] Langmuir, 2007, 12937[3] J. Am. Chem. Soc. 2006, 8136
[4] J. Am. Chem. Soc. 2006, 726[5] Science, 2005, 309

The so-obtained materials were characterised using
various structural, spectroscopic, microscopic methods

Petra Ágota
Szilágyi

Dr Petra Ágota Szilágyi obtained her PhD degree in chemical and materials sciences in 2007 fromthe University Eötvös Loránd (Budapest, Hungary) and the University Paul Sabatier (Toulouse).
After a short postdoctoral contract at the CNRS, in Toulouse, on coordination chemistry, she started
to work on hydrogen-storage materials at the University of Edinburgh, where she was involved withthe pressure study of chemical hydrides as an AXA research fellow. Currently she’s working as a
postdoctoral researcher at TU Delft on enhancing MOFs hydrogen-storage properties by the design,synthesis and characterisation of metal/metal-oxide/metal-hydride – metal-organic framework
composite materials.

Corresponding author: Dr Petra Ágota Szilágyi, email: P.A.Szilagyi@tudelft.nl, Tel. +31 152782637.

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CONFINEMENT OF LIBH4 IN NANOPOROUS MATERIALS: SIZE AND
INTERFACE EFFECTS ON HYDROGEN RELEASE AND ION MOBILITYAngeloclaudio Nale1, Tamara M. Eggenhuisen1, Margriet H. W. Verkuijlen2, Arndt Remhof3
and Petra E. de Jongh1
1 Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands
2 Institute for Molecules and Materials, Radboud University, The Netherlands
3 Hydrogen and Energy group, EMPA, Dübendorf, Switzerland
Nanosizing of hydrogen storage materials enhances sorption kinetics and reversibility. Nanoconfinement of LiBH4 inside
different porous structures is associated with absence of long range structural order, and a strong interaction with thehost material. This affects not only hydrogen release but also other fundamental physical chemical properties.

Nanosizing is a well known technique to reduce thedecomposition temperatures and enhance reactions
kinetics of metal hydrides, thanks to large fraction of
surface atoms and to reduced diffusion distances [2].

SiO26,7 nm [x5]8,3 nm12,3 nm

8 nm

CarbonLithiumborohydride attracts much attention as apromising material for hydrogen storage (the totalhydrogen content is 18.5 wt%) but the elevatedtemperatures required to release the gas and the limited
reversibility are important obstacles for practicalapplication [1].

LiBH4 in the high temperature phase. NMR shows+increased Li mobility for nanoconfined materials even at
low temperatures, confirming the strong interaction
between LiBH4 and host material [4].

Heat Flow
3 [W/g]Introduction

13 nmExperimental
Taking advantage of the low melting temperature of
LiBH4 can be infiltrated into porous scaffolds [3,4], with
N2 physisorption allowing quantification of the volume
and feature size of the LiBH4 in the scaffold. In situ DSC
was used to study the melt infiltration process, andchanges in phase transitions. Quasi Elastic Neutron
Scattering (QENS) and solid state NMR allowed proving
changes in hydrogen dynamics and Li and B translational
mobility as a result of the nanoconfinement.

Results
Surprisingly nanosizing affected not only the melting
temperature and enthalpy of LiBH4 but also the LiBH4
solid-solid phase transition (see Figure). The temperature
shift depends on pore size, but also on the chemicalcomposition of the scaffold, indicating that the pore wallLiBH4 interface plays an important role. .
QENS highlighted changes in hydrogen dynamics, withthe similar highly mobile BH4 units observed in
nanoconfined LiBH4 at room temperature as seen in bulk

solid solid
phase transition
50

100

Exo up150

melting
200

250

300

Temperature [°C]

Figure – Calorimetric measurements of phasetransitions upon heating LiBH4 confined in
nanoporous silica and carbon materials with different
diameters. Dashed lines indicate phase transitions
temperatures for bulk LiBH4.
Better understanding of the impact of nanoconfinement
on fundamental properties migth allow tuning of therelevant physico-chemical material properties forapplications in different fields.
References[1] A. Züttel et al, J. Power. Sources 118 (2003), 1.
[2] P.E. de Jongh, P. Adelhelm, ChemSusChem 3 (2010), 1332.
[3] A.F. Gross, J.J. Vajo et al, JPCC 112 (2008), 5651.
[3] X. Liu, E.H. Majzoub et al, Chem. Mater. 23 (2011), 1331.
[5] M. Verkuijlen et al, J. Phys. Chem. C, (2012) in press

Born in 1979, he studied Materials Science by University of Milano-Bicocca (IT) and graduated in thesame University under the supervision of Prof. M. Catti with a project titled “Synthesis andcharacterization of Mg-Al-Ni alloys and Li-Mg borohydrides for hydrogen storage”; he is actually a
postdoctoral fellow of Prof. Dr. P.E. de Jongh by Utrecht University.

Angeloclaudio
Nale
Corresponding author: Angeloclaudio Nale, ac.nale@uu.nl ; phone : +31 6 22736392

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Catalysis research in the 21st century
Catalysis is one of the major technologies for production of energy carriers, chemicals,
and pollution abatement. From hydrogen production, solar energy conversion via processintensification, to sustainable chemicals and fuel production, new and better systems
must be developed. An essential component is the development of better catalysts.
Catalyst development in the 20th century focused on achieving maximal activity; that inthe 21st century on maximizing the yield, thus also improving on the selectivity. Thisrequires the development of defined catalysts in which (multiple) active sites are definedand oriented in space. Such endeavor is greatly helped by the understanding how thecatalyst functions.
Any catalytic reaction can be analyzed at various time and length scales. The moving ofatoms is described at the femto-second time scale; catalyst deactivation at the multi day
or month scale. Angstrom length scales define the molecular structure of the active site;that of nano-, micro-, and millimeter the diffusion of reactant, intermediate, and product.
Some of these scales can be readily characterized, others remain a challenging task. In
my talk, I will focus on the functioning of a catalyst and how modern characterization
tools continue to be developed and applied to determine the structure of a functioning
active site.

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ELECTROCATALYSIS WITH ATOMIC SCALE SIMULATIONS.
Jan Rossmeisl
Center for Atomic scale Materials design, Department of Physics, Technical University of Denmark. DTU, building 311,
2800 Lyngby, Denmark
Abstract; For energy conversion the oxygen reduction and oxygen evolution reactions are of extreme interest. For bothreactions a huge over potential is needed to obtain a reasonable current, and in both cases this is mainly due to sluggish
catalysis. I study the reasons for the over potential on the basis of density functional simulations and determine activity
descriptors, which are easy to calculate and therefore suited for computational screening for more active catalystmaterials. I will show examples on rational design of electrocatalyst materials. Furthermore, I will discuss the challenges
related with atomic scale modelling of the electrochemical interface.

Jan Rossmeisl

Short CV: Jan Rossmeisl is since 2009 Associated Professor at Department of Physics at theTechnical University of Denmark (DTU). He is heading the Theoretical Electrochemistry Group, partof the Center for Atomic scale Materials Design. He is the author or co-author of around 80 peerreviewed scientific articles and has mentored approximately 20 postdoctoral fellows and graduate
students. His research interests include: Density functional theory simulations, Photo and electrocatalysis for energy conversion, modeling of charged interfaces and charge transfer reactions,material design of catalysis of the oxygen reduction/evolution and hydrogen evolution/oxidation
reactions.

Corresponding author: jross@fysik.dtu.dk

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Pt5Gd AS A HIGHLY ACTIVE AND STABLE ELECTROCATALYST FOROXYGEN REDUCTION
María Escudero-Escribano,1 Arnau Verdaguer-Casadevall,1 Paolo Malacrida,1 Ulrik
Grønbjerg,1,2 Brian P. Knudsen,1 Jan Rossmeisl,2 Ifan E.L. Stephens,1 Ib Chorkendorff*,1
1

Center for Individual Nanoparticle Functionality, Department of Physics, Technical University of Denmark (DTU), 2800
Lyngby, Denmark; 2Center for Atomic-Scale Materials Design, Department of Physics, DTU, 2800 Lyngby, Denmark.

Abstract The activity and stability of Pt5Gd for the oxygen reduction reaction (ORR) have been studied, by combining
electrochemical measurements, angle-resolved XPS (AR-XPS) and density functional theory (DFT) calculations. Pt5Gdshows a five-fold increase in ORR activity, relative to Pt at 0.9 V versus a reversible hydrogen electrode (RHE). AR-XPS
profiles after electrochemical measurements show the formation of a thick Pt overlayer on the bulk Pt5Gd. The enhanced
ORR activity appears to be due to compressive strain effects. Furthermore, these novel bimetallic electrocatalysts arehighly stable, which, in combination with their enhanced activity, makes them very promising for the development of newcathode catalysts for proton exchange membrane fuel cells (PEMFCs).

Introduction
The main obstacle to the development of PEMFCs as acommercially competitive reality is the high overpotential
required for the ORR to proceed at an adequate rate. In
order to improve the kinetics for the ORR and reduce thePt loading we need to develop more active catalysts. Thiscan be achieved by alloying Pt with other metals [1-3].
Herein, we present experimental and theoretical studies
concerning the activity and stability of a new catalyst,
Pt5Gd, for the ORR.

Results and discussion
Rotating disk measurements show that sputter-cleaned,polycrystalline Pt5Gd shows a five-fold increase in ORR
activity [4], relative to Pt at 0.9 V in 0.1 M HClO4,
approaching the activity of Pt3Y (the most active catalyst
in the literature, prepared in this way [2,3]). We use ARXPS and DFT to elucidate the origin of this high activity.
AR-XPS measurements taken after measuring the ORR
show that a Pt overlayer with a thickness of few Pt layers
is formed [4]. Accordingly, the effect of alloying Pt is to
impose strain onto the Pt overlayer. DFT calculations
suggest that a perfect defect-free Pt overlayer on bulk
Pt5Gd would be compressed by 6 %, relative to Pt(111),
which would result in an excessive weakening of the OH
binding energy, relative to Pt(111), of ~0.3 eV. It is likelythat this strain relaxation would be relaxed by defects.

Not only is the catalyst highly active, but also very stable,
losing only 14% of its initial activity after 10,000 cycles
between 0.6 V and 1.0 V vs. RHE. Furthermore, theelectrode maintains a significant activity enhancement
even when cycling to potentials as positive as 1.6 V [4].
These results make Pt5Gd very promising for thedevelopment of new highly active and long term stable
cathode catalysts for fuel cells.

Conclussion
In summary, we present a novel highly active and stableelectrocatalyst for the ORR. The activity of Pt5Gd issimilar to that obtained on Pt3Y in previous studies, which
was identified as the most active Pt-based polycrystalline
alloy for the ORR. Moreover, Pt5Gd electrodes are
extremely stable. For all these reasons, we expect thatalloying Pt with Gd and other rare earths will be a fruitfulstrategy towards the development of highly active anddurable cathodes for PEMFCs.

References[1] H. A. Gasteiger, et al. Appl. Catal. B 2005, 56, 9.
[2] J. Greeley, et al. Nature Chem. 2009, 1, 552.
[3] I. E.S. Stephens, et al. Energy Environ. Sci. 2012, 5,
6744.
[4] M. Escudero-Escribano, et al. J. Am. Chem. Soc.
2012, accepted.

María Escudero-Escribano was undergraduate at the University of Extremadura (Spain), where she
studied Chemical Engineering. Her PhD (2007-2011) was conducted at the Institute of Physical
Chemistry “Rocasolano” (Madrid) under the supervision of Dr. Ángel Cuesta. During her PhD, shespent two research stays abroad, at the Argonne National Laboratory (U.S.) with Prof. Nenad
Markovic, and at the University of Ulm (Germany) with Prof. Wolfgang Schmickler. Since February
2012, she has been a postdoctoral researcher at the group of Prof. Ib Chorkendorff, in the Center for
Individual Nanoparticle Functionality at the Technical University of Denmark. She has 8 papers inhigh impact factor journals, including Nature Chemistry and JACS. She received prizes both as anundergraduate, for the “Most Outstanding Student”, and as a PhD student for “Suschem Young
Chemistry Reasearchers” National Award, 2011.
María Escudero
Corresponding author: María Escudero Escribano, maria.escudero@fysik.dtu.dk, Tel.: (0045) 22 77 69 88

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CATALYTIC HYDROLYSIS OF NABH4 IN A CONTINUOUS REACTOR FOR
LONG TIME STABLE AND VERSATILE GENERATION OF HYDROGEN
D. Hufschmidt1, G.M. Arzac1, A. Fernández1, B. Sarmiento2, M.A. Jiménez2
1. Instituto de Ciencia de Materiales de Sevilla (ICMS), CSIC-Univ.Sevilla, Américo Vespucio 49, Sevilla, Spain
2. Abengoa Hidrogeno, Campus Palmas Altas, Sevilla, Spain
Abstract: In this work a continuous working reactor for the production of Hydrogen based on the catalytic hydrolysis of
NaBH4 is presented. It is shown, that this system permits a permanent, versatile and safe release of Hydrogen. The
behaviour of the reactor and the catalyst under long term high performance conditions was studied. Special emphasis
was laid on the deactivation and possible regeneration of the catalyst employed in these experiments.

Introduction
Sodium borohydride (NaBH4, SBH) is a stable, nonflammable and non toxic hydride that permits a safe andversatile generation of hydrogen. SBH solutions at highpH (fuel) are stable and only produce hydrogen when incontact with suitable catalysts (on demand H2generation). The release of hydrogen can be carried out
controlled in ambient conditions, which makes it suitable
for small scale and portable applications.

Continuous reactor system
In the present work a continuous working reactor was
designed and built, which allows a constant andadaptable generation of hydrogen over a long period oftime. The system operates under the addition of the fuelto a Co-B catalyst supported on a homemade stainlesssteel monolith for the release hydrogen at a constant rate
and temperature. A stable hydrogen generation rate wasobtained in the range of 0.3-1.7 L/min feeding the reactor
with a 19 wt% SBH fuel solution added in the range of
0.8-5 ml/min. The reaction was self inducing andmaintained a constant working temperature between 95 –105 ºC. This high reaction temperature supported greatly
the constant removal of NaBO2 formed as the by-productof the hydrolysis reaction, which in previous works was
identified as responsible for the catalyst deactivation and,due to crystallisation, leads to clogging of the entire
system.

Deactivation of the catalyst
Among metal based catalysts Co-B materials are themost investigated owing to its reactivity and low cost. In
this work the Co-B based catalyst was prepared bychemical methods on bare and pre-treated stainless steel

homemade monoliths searching for high adherence andcontact with the fuel solution. Special interest was laidon the durability of the catalyst coating on the support
and the catalytic activity over long periods of intensehydrogen generation.
Adherence was tested during 60 minutes-longexperiments. Durability of supported Co-B catalyst wastested by repeating the previous experiment for 11
cycles. Long life experiments were performed during 9hours of hydrogen production. For comparison a
supported Ru-B catalyst was prepared on a pre-treatedstainless steel monolith and durability was also tested
during 11 cycles.
The adherence of the catalyst was found to be good, withrelative low losses of material during the test. A
deactivation of the catalyst was observed after long timeof use, depending largely of the mode of experiment(start/stop cycles, continuous run). The deactivation andthe intents of reactivation of both catalysts, CoB and its
noble counterpart RuB were intensely studied and will be
discussed in detailed in terms of borate formation andelimination and nanoparticle growth.

References[1] G.M. Arzac, A. Fernández, A. Justo, B. Sarmiento,
M.A. Jiménez, M.M. Jiménez. Optimized hydrogengeneration in a semicontinuos sodium borohydridehydrolysis reactor for a 60-W scale fuel cell stack.
Journal of Power Sources, 2011, 196, 4388-4395[2] B.H. Liu, Z.P. Li. A review: Hydrogen generation fromborohydride hydrolysis reaction. J. Power Sources,
2009, 187,527-534.

Worked as Investigator at the Institute for Solarenergy Hameln/Emmerthal (ISFH) and at the Institutefor Chemical Technology (TCI) of the University of Hannover, both Hannover, Germany, and,currently, at the Institute for Material Sciences of Seville (ICMS), Sevilla, Spain
Fields of interest: Catalysis, Photocatalysis, Reactor engineering (Production and application of
Hydrogen by different methods, treatment of water and gas), Coatings and Thin films,
Nanotecnology
Dirk Hufschmidt
Corresponding author: Dirk Hufschmidt, dirk@icmse.csic.es, Tel. ++34 954 48 95 00 ext. 9222

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Production of 1-propanol and 1-butanol from the mixture of MeOH and EtOH by Guerbet reaction in
the presence of hydrotalcite
Fadime Hosoglu

1,2,4, Jeremy Faye

1,2

1,2

, Mickaël Capron , Franck Dumeignil
1

1,2,3

2

Univ. Lille Nord de France, F-59000, Lille , France. CNRS UMR8181, Unité de Catalyse et Chimie du Solide, UCCS, F359655 Villeneuve d’Ascq, France. Institut Universitaire de France, Maison des Universités, 10 Boulevard Saint-Michel,
475005 Paris, France, Empa Materials Science and Technology, Dept. Energy, Environment & Mobility, Sec. Hydrogen &Energy, CH- 8600 Dubendorf, Switzerland

Abstract: Due to decreasing the fossil fuel reserves, negative impact of petroleum fuels on the environment and anincrease of oil price, biofuels became more and more interesting in the recent years. The most commonly used liquidbiofuels are bioethanol, biomethanol and biodiesel which are obtained from edible biomass sources such as sugar caneor corn and vegetable oils, respectively [1].
Guerbet chemistry has a real potential in industrial reactions to replace petrochemicals-based processes by bioalcoholsbased processes, which would further be much more economical provided a selective catalytic system can be rationally
tailored and optimized [2].
The Guerbet reaction shows a great potential to for bioalcohols-based chemistry such as n-propanol and n-butanol. In
this study, we will specifically examine a reaction which is of a great importance for enhancing the potential of thebiomass-derived chemistry: the synthesis of higher alcohols from lower alcohols via Guerbet reaction.
It occurs in the presence of a multifunctional catalyst with basic, acid and redox properties. Hydrotalcites are a layered
double hydroxide, with the general formula Mg6Al2(CO3)(OH)16.4H2O
and are known as basic catalysts or basic catalyst precursors.
Transition metals (TM, for example: Ni, Cu, Mn) can be added to thecatalytic system in substitution of Mg in order to tune the redox
properties of the catalysts. In the present work, we have studied the
production of propanol and butanol obtained from a mixture of ethanol
and methanol via the Guerbet reaction in the presence of hydrotalcitebased catalysts. The catalytic activity has been measured in the 200 °C400 °C temperature range. XRD analyses coupled with high resolution
27Al MAS-NMR spectroscopy validated the formation of a well crystallinehydrotalcite structure. After calcinations, the HT based materials aredecomposed into mixed oxides, which develop very high specific surface
areas compared to the conventional synthesis method without
sonication. The reducibility of the solids has been measured by TPR.

Acknowledgements
The financial support from National Agency of Research (ANR-09-CP2D-19-01) is gratefully acknowledged.
References
1 D. Huang, H. Zhou, L. Lin, Energy procedia, 16 (2012) 1874
2 C. Carlini, A. Macinai, M. Marchionna, M. Noviello, A.M.R. Galletti, G. Sbrana, Journal of Molecular Catalysis A:
Chemical, 206 (2003) 409-418
Fadime Hosoglu has finished University of Mersin Faculty of Engineering, Department ofEnvironmental Engineering in 2008 and received her degree. (Turkey) In 2006 she has studied in
the University of the Valencia Poly., department of Environmental Engineering by the scholarship of
the University of Mersin (Spain) .She has studied her master in the same university department of
the Geoenvironnement by the scholarship. In 2012 she has obtained her PhD in the University ofLille1 Laboratory of Catalysis and of Chemistry of Solid State with Franck Dumeignil and Mickael
Capron.

Corresponding author: Fadime Hosoglu, fadime.hosoglu@empa.ch

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SODIUM HYDRAZINYLBORANE, A CHEMICAL HYDROGEN STORAGE
MATERIAL
R. Moury, U. B. Demirci and P. Miele
IEM (Institut Europeen des Membranes), UMR 5635 (CNRS-ENSCM-UM2), Universite Montpellier 2, Place E. Bataillon,
F- 34095, Montpellier, France
Herein, we report the successful synthesis, structural and thermal characterization of sodium hydrazynilborane
NaN2H3BH3 (8.85 wt% H), a novel material for chemical hydrogen storage. It is showed that its dehydrogenation is
improved in comparison to that of the parent material hydrazine borane N2H4BH3. In addition, it is showed that it could
have a potential as energetic material (fuel of propellant).

Introduction
Chemical hydrogen storage is one of the ways much
explored to address the hydrogen storage issue, which is
detrimental to the development of fuel cell. 1 Research isvivid and that has permitted to find new materials and toenhance the knowledge in material chemistry.

Hydrazine borane
Hydrazine borane N2H4BH3 (HB) has recently shown its
potential as material for hydrogen storage.2 It stores 15.4
wt% H and 146 g H L-1. However, as ammonia borane
NH3BH3 (AB),3 it suffers from a too high dehydrogenation
temperature. Further, it releases significant amounts ofammonia and hydrazine during heating. Thereby, itcannot be used as such for hydrogen storage. An
alternate strategy has been then adopted. We envisaged
the destabilization of HB by chemical modification, i.e.
substitution of one Hδ+ by Na+; a new material was
synthesized. It showed improved dehydrogenation
properties in comparison to HB.

A hydrazine borane derivative
A derivative of HB, sodium hydrazynilborane NaN2H3BH3(NaHB), was synthesized through a mechano-chemicalroute. It was obtained by reaction of sodium hydride and+-hydrazine borane. NaHB contains 3 Hδ and 3 Hδ ; it
could thus liberate up 3 equiv H2, i.e. 8.85 wt% H.

NaHB was characterized by powder XRD. The crystal
structure was determined and indexed as a single phaseusing a monoclinic space group P21/n (a=4.97312(28) Å,
b=7.96189(42) Å, c=9.29433(49) Å, β=93.8112(26)°).
The thermal behavior of NaHB was analyzed by TGA andthe gases followed by MS. The dehydrogenation of NaHB
in comparison to that of HB is improved, with an onset
temperature of 65 °C vs. 95 °C. Further, the emissions ofammonia and hydrazine are reduced. In terms of kinetics,
NaHB liberates 1 equiv H2 in 5 min vs. 96 min for HB.
Interestingly, the behavior of NaHB under heatingchanges from temperatures <100 °C to >100 °C. At>100°C, the dehydrogenation is sudden, extremely rapid,
with ca. 2.5 equiv H2 being released within 1 min.
To sum up, our new material NaHB might have different
applications in the energy fields, i.e. as material forhydrogen storage and/or fuel of propellant. The EMPA
7th International Symposium Hydrogen and Energy will
be an opportunity to present our main results.

References[1] U. Eberle et al., Angew. Chem. Int. Ed., 2009, 48,
6608.
[2] R. Moury et al., Phys. Chem. Chem. Phys., 2012, 14,
1768.
[3] A. Staubitz et al., Chem. Rev., 2010, 110, 4079.

11

NaHB was structurally characterized by solid-state B
23
and Na MAS NMR and IR spectroscopy. It was showed+

the successful substitution of Hδ by the electron-donor+
Na and the modification of the hydrogen polarization.
Romain Moury studied inorganic chemistry at University Claude Bernard in Lyon (France), where heobtained his master degree. He is now young researcher at Institut Européen des Membranes in
Montpellier (France), in 2nd year of his doctorate. Under the co-supervision of Prof. Philippe Miele
and Assoc. Prof. Umit B. Demirci, He works on solid-state chemical hydrogen storage, with a
specialization in boron chemistry and structural determination by powder X-ray diffraction.

MOURY Romain
Corresponding author: Moury Romain, romain.moury@univ-montp2.fr, +33 (0)4 67 14 91 71

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TOWARDS A HYDROGEN BATTERY ?
Gábor Laurenczy
EPFL, École Polytechnique Fédérale de Lausanne, ISIC, LCOM, Groupe de catalyse pour l’énergie et l’environnement –GCEE, CH-1015 Lausanne, Switzerland
The interconversion of hydrogen and carbon dioxide to chemical energy carriers has attracted considerable interest forthe development of novel energy technologies, because it combines hydrogen storage and CO2 utilization. Carbon
dioxide and carbonates have been proven to be viable H2 vectors, as these widely available natural C1 sources can beeasily hydrogenated to formic acid and formates. On the other hand, formic acid can be selectively decomposed into CO
free (< 10 ppm) carbon dioxide and hydrogen.

Introduction
Efficient energy storage/delivery is currently achallenging topic. Hydrogen is one of the potential
candidates to replace fossil fuels as energy vector bothfor environmental and economic reasons. H2 has theadvantage to form only water when it is burned; andcombined with fuel cell technology a very efficientconversion of the chemical energy into electricity can beachieved.

Results and discussion
A completely rechargeable hydrogen storage device has
been developed based on the hydrogenation ofbicarbonate and decomposition of formate in aqueous
solution with the same catalyst, [{RuCl2- (mtppms)2}2] +mtppms, in both directions without the need of isolating
either the formate or bicarbonate to start a new cycle.

Figure 2. Cycles of CO2 hydrogenation (H2 recharge)
and HCOOH decomposition (H2 release).
Acknowledgment. Swiss National Science Foundationand EPFL are thanked for financial support.

References[1] C. Fellay, P. J. Dyson, G. Laurenczy*, A Viable Hydrogen-Figure 1. The reversible bicarbonate – formate cycle.
The Ru-catalysed hydrogenation of carbon dioxide, using
the [RuH2(dppm)2] complex, proceeds with anunprecedented high formic acid to amine ratio (AAR of
2.69), which results in an improved energy content. This
catalyst system allows for reversible fast hydrogenloading (even at RT) and unprecedented unloading (TONfor H2 liberation of 800 000).

Gábor Laurenczy

Storage System Based On Selective Formic Acid
Decomposition with a Ruthenium Catalyst, Angew. Chem.
Int. Ed., 2008, 47, 3966.
[2] A. Boddien, C. Federsel, P. Sponholz, D. Mellmann, R.
Jackstell, H. Junge, G. Laurenczy*, M. Beller*; A Towards
the development of a hydrogen battery, Energy Environ.
Sci., 2012, 5, 8907.
[3] G. Papp, J. Csorba, G. Laurenczy, F. Joó, A
Charge/Discharge Device for Chemical Hydrogen Storageand Generation, Angew. Chem. Int. Ed., 2011, 50, 10433.
[4] A. Boddien, D. Mellmann, F. Gärtner, R. Jackstell, H. Junge,
P. J. Dyson, G. Laurenczy*, R. Ludwig*, M. Beller*, Efficient
Dehydrogenation of Formic Acid Using an Iron Catalyst,
Science, 2011, 333, 1733.
[5] M. Grasemann, G. Laurenczy*, Formic acid as a hydrogensource – recent developments and future trends, Energy
Environ. Sci., 2012, 5, 8171.

Chemistry M.Sc. at the Univ. Debrecen, Hungary, 1978. PhD. in Physical Chemistry, Univ.
Debrecen, Hungary, 1982. Habilitation in Inorganic Chemistry, Hungarian Academy of Sciences,1991. Assistant professor, Dept. of Inorganic Chemistry, Univ. Debrecen, Hungary, 1984. Maître
d’enseignement et de recherche, Univ. Lausanne, 1997. M.E.R., EPFL, École PolytechniqueFédérale de Lausanne, 2002. Chairman of the M. C. European COST D30: High Pressure Tuning ofChemical and Biochemical Processes, 2002-2007. Visiting professor, Dept. of Chemistry, Universityof Bourgogne, France, 2007. Prof. EPFL, 2010. Head of Group of Catalysis for Energy andEnvironment – GCEE, 2010.

Corresponding author: Prof. Gábor Laurenczy, email: Gabor.Laurenczy@epfl.ch, Tel. (+41) (21) 693 9858

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DECONVOLUTING LIGAND AND STRAIN EFFECTS ON THE ACTIVITY
AND STABILITY OF PLATINUM ALLOYS
Ulrik Grønbjerg1,2, Anders K. Jepsen1,2 and Jan Rossmeisl2
1

Center for Individual Nanoparticle Functionality, Department of Physics, Technical University of Denmark (DTU), 2800
2
Lyngby, Denmark; Center for Atomic-Scale Materials Design, Department of Physics, DTU, 2800 Lyngby, Denmark.

Abstract:
An ideal catalyst should exhibit both maximal activity and stability to be technologically competitive. In this theoretical
study, we show that the two properties are fundamentally connected, and there is a limit to the extent to which the activity
can be improved for a given alloy, without destabilising the surface.

Introduction

Conclusion

The search for new improved Pt based catalysts for theoxygen reduction reaction, ORR, has resulted in the
discovery of various interesting alloys, such as Pt3Y [1]and Pt3Ni [2]. These catalysts must possess two
important properties, (a) they should exhibit moderatebinding to the intermediates, neither too strong nor too
weak, and (b) they should be stable against degradation
via corrosion, phase separation and dissolution.
Investigating and evaluating new catalysts in generalentails the assumption that the activity and stability areuncorrelated parameters.

It is possible to deconvolute the ligand and strain effectsof Pt overlayers on Pt-alloys. This shows that there arefundamental limits to the stability that is attainable for agiven catalytic activity.

Results and discussion
In this present study, we investigate the surface stabilityof Pt-terminated alloys using density functional theory.
We aim to determine whether any correlation exists
between the surface stability and the corresponding
binding energies of the adsorbates that constitute theintermediates of the ORR. The binding energy of these
adsorbates can be deconvoluted into two contributions:
1) strain effects [3] and 2) ligand effects [4]. Our results
indicate that the contribution to the binding energy fromthe ligand effect, i.e. the binding energy corrected formismatching lattice constants, scales linearly with thesurface stability. This can be rationalized on the basisthat a high surface stability implies a surface layer
bonded strongly to the second atomic layer. This, in turn,leads to a surface layer that binds weaker to adsorbates.

References[1] J. Greeley, I. E. L. Stephens, A. S. Bondarenko, T. P.
Johansson, H. A. Hansen, T. F. Jaramillo, J.
Rossmeisl, I. Chorkendorff, J. K. Nørskov, Alloys ofplatinum and early transition metals as oxygen
reduction electrocatalysts, Nature Chemistry 1, 552 556 (2009)[2] V. R. Stamenkovic, B. Fowler, B. S. Mun, G. Wang, P.
N. Ross, C. A. Lucas and N. M. Marković, Improved
Oxygen Reduction Activity on Pt3Ni(111) via
Increased Surface Site Availability, Science Vol. 315(2007), 493-497[3] M. Mavrikakis, B. Hammer, J. K. Nørskov, Effect ofStrain on the Reactivity of Metal Surfaces, PhysicalReview Letters, Vol. 81 (1998), 2819-2822[4] J. R. Kitchin, J. K. Nørskov, M. A. Barteau, and J. G.
Chen, Role of Strain and Ligand Effects in the
Modification of the Electronic and Chemical
Properties of Bimetallic Surfaces, Phys. Rev. Lett.
93, 156801 (2004)

Ulrik Grønbjerg is a PhD student at the Center for Individual Nanoparticle Functionality at the
Department of Physics, the Technical University of Denmark. His research is focused on theinterplay between environment, structure and functionality of nanoparticles and surfaces,
investigated using theoretical methods, such as electronic structure calculations.

Ulrik Grønbjerg
Corresponding author: Ulrik Grønbjerg, ulrik.groenbjerg@fysik.dtu.dk, +45 40 62 54 69

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IONIC CONDUCTIVITY IN LIGHT METALS FULLERIDES
Daniele Pontiroli1, Matteo Aramini1, Mattia Gaboardi1, Georgia Vlachopoulou1,
M. Mazzani1, M. Riccò1 and Chiara Cavallari2
1 – Dipartimento di Fisica e Scienze della Terra, Università Parma, 43124 Parma, Italy
2 - Institut Laue Langevin, BP 156 38042 Grenoble, France
Abstract: We report our recent findings on the ionic diffusion in light alkali and alkali-earth metalintercalated fullerenes (M = Li, Na, Mg). We found that fast ionic diffusion in a wide range of temperatures
is possible in these systems and that this behaviour is triggered by the polymerisation of the C60 units.

Fast-ion conduction
Fast-ion conductors are materials displaying
a very large ion conductivity in the solid state,
which could be comparable to that of liquidorganic electrolytes, commonly used in Li-ion
batteries.

Light metal C60 polymers
It is known that fullerenes are able tointercalate light alkali (Li, Na) and alkali-earth
ions (Mg) and this often leads to theformation of polymers, in which C60 units areinterconnected by covalent bonds.
In particular, either in Li or Mg intercalated
C60, the charge transfer of four electrons fromthe metal to the fullerene stabilizes a peculiar
two-dimensional polymer structure [1, 2],+2+where Li and Mg ions can easily diffuse
also at low temperature with a low activationenergy [2, 3].

Ion conductivity in fullerides
The polymer arrangement is of paramountimportance for the onset of fast ion diffusion
in such compounds; it is supported by then+presence of intrinsic unoccupied M

interstitial sites in the crystalline structure,connected by three-dimensional pathways.
In particular, we recently found that in Mg2C60
2+polymer the onset of Mg
diffusion isobserved already at T=120 K. Above thistemperature, ion conductivity increases
following an Arrhenius law and reaches the-4
noticeable value for the of 0.5⋅10 S/cm atroom temperature, with an unusual low
activation energy of only ∆Ea=100 meV [3].
Impedence measurements also evidenced
2+
that Mg diffusion follows the ideal Debye
model in this system.
This material appears very promising for the
production of the future and still unexplored
Mg ion batteries.

References[1] S. Margadonna, D. Pontiroli, M. Belli, T.
Shiroka, M. Riccò and M. Brunelli, J. Am.
Chem. Soc., 2004, Vol.126 (46), 15032.
[2] D. Pontiroli, M. Aramini, M. Gaboardi, M.
Mazzani, A Gorreri, M. Riccò, I. Margiolaki and
D. Sheptyakov, Carbon, 2012 Vol. 51, 143.
[3] M. Riccò, M. Belli, M. Mazzani, D. Pontiroli, D.
Quintavalle, A. Jánossy and G. Csányi, Phys.
Rev. Lett., 2009, Vol. 102, 145901.

Daniele Pontiroli was born 9. 3. 1977 in Piacenza, Italy. 2002 Degree in Physics. 2005
PhD in Physics at University of Parma. 2006 Post-doc fellowship financed by theEuropean NEST FP6 Project “Ferrocarbon”. 2008 Research fellowship at the Universityof Parma in the Carbon Nanostructures Laboratory headed by Prof. Mauro Riccò.
2012–today Post-doc fellowship financed by MIST-ER. His research activity deals withsynthesis, structural characterisation, dynamical and transport properties offunctionalised carbon nanostructures, such as fullerene and graphene.
Daniele Pontiroli
Corresponding author: Daniele Pontiroli, email: Daniele.Pontiroli@fis.unipr.it, Tel. (+39) 0521 905231

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TITLE: SOLID OXIDE ELECTROLYSIS: A KEY ENABLING TECHNOLOGYFOR FUTURE ENERGY SYSTEMS BASED ON RENEWABLE ENERGY
Name(s) John Bøgild Hansen
Affiliation Haldor Topsøe A/S

Solid Oxide Electrolyser Cell stacks (SOEC) are able to produce inert free synthesis gas ofany desired composition with very high efficiency from electric power, carbon dioxide andsteam, but the necessary stack area, power and required balance of plant components willvary as function of conversion and gas composition.
SOEC can thus be a key enabling technology in future energy systems providing a link
between physical, intermittent energy forms from wind or solar sources to chemical energy
in the form of fuels.
Biomass is deficient in hydrogen with respect to production of renewable fuels. This
deficiency can be covered by hydrogen from SOEC thus doubling or tripling the biomass
potential depending on the end product.
Examples of processesUpgrading of biogas
Coupling of wood gasification with SOEC to produce:o Substitute Natural gas
o Methanol
Methanol from CO2, steam and power

will be discussed with respect to efficiency and requirements to the SOEC technology.

Short CV:John Bøgild Hansen is Senior Scientist & Advisor to Management in the Company
Management of Haldor Topsøe A/S. He graduated with a MSc in Chemical Engineeringfrom DTU in 1975 and has been employed by Haldor Topsøe since then. Initially heworked in the catalyst division but in 1979 joined the R&D Division where he became
department manager in 1985. In 2000 he became senior scientist and advisor to thechairman, Dr. Haldor Topsøe and since 2012 to the company management in general.
Name:
John
Bøgild Hansen
Corresponding author: John Bøgild hansen, jbh@topsoe.dk, Tel. +4522754072

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High Temperature Steam Electrolysis (HTSE): Agingmechanisms and corrosion behaviour of interconnects & coatings
Ulrich F. Vogta,d, Ji Woo Kima,c, Yong Seok Choic, Cyril Radob, Aude Brevetb, Karine
Couturierb, Andreas ZüttelaaHydrogen and Energy, Swiss Federal Laboratories for Materials Science and Technology, CH-8600, Dübendorf, CH
CEA-Grenoble, LITEN, 17 rue des Martyrs, F-38054 Grenoble Cedex 9, FrancecDept. of Materials Science and Engineering, Seoul National University, Seoul 151-744, Republic of KoreadAlbert-Ludwigs University of Freiburg i. Br., Faculty of Crystallography, GermanybHigh temperature steam electrolysis (HTSE) in solid oxide electrolysis cells (SOEC) offers a promising way to producehydrogen with high efficiency. Compared with alkaline- or PEM based water electrolysis, HTSE reduces the required
electrical energy and thus increases the total efficiency of the process.

High temperature SOEC stacks are using Cr alloys asinterconnects, connecting each cell in series byconducting electricity, distribute active gas to the cells
and separate the hydrogen and oxygen between thecells. One efficient way of reducing the aging processes,
but also raw material and fabrication cost is to lower theoperating temperature of the SOEC from 950°C to ca.
700°C, thereby enabling the use of stainless steel
interconnects instead of high Cr alloys.
Although stainless steel interconnects can reduce thestack cost, they also introduce several challenges.
Chromium oxide-forming alloys are preferred due to theirhigh oxidation resistance associated with low electricalresistance, thus minimizing the ohmic losses within thestacks.
However, chromium oxide can react with the anodematerials and form non-catalytic and resistive
compounds. These compounds finally lead to thedegradation of the SOEC performance. In order toreduce the reaction between interconnect and anodeelectrode and to improve the electrical contact, LNF(La(NixFe1-x)O3) and LSMC ((LaxSr1-x)(MnyCo1-y)O3) areproposed as a coating layer between anode andinterconnect. In this study, material compatibility between
the proposed coating layers and interconnects (Crofer
22APU, AISI 441) is investigated for operating
temperature of 700°C with pure oxygen as anodeatmosphere.

Figure 1: Cross section of backscattered electron (BSE)
images of LNF/Mn-Co Oxide coating/Crofer 22 APU after
200h and 3000h heat treatment at 700°C with pureoxygen flow and corresponding energy dispersive
spectroscopy (EDS) line scanning profiles, showing that
no Cr concentration gradient is seen through the Mn-Co
spinel coating and LNF coating as well.

PD Dr. Ulrich Vogt is Senior Scientist at the EMPA laboratory “Hydrogen & Energy” and leader of thegroup electrolysis & membranes. He received his PhD and his P.D at the Albert-Ludwig-University
Freiburg, Germany. Topics of his research work are hydrogen production via “high temperature
steam electrolysis”, “new membrane materials for low temperature alkaline water electrolysis” andcatalytic hydrogen combustion for cooking and heating applications by a novel developed catalytichydrogen burner system. U. Vogt authored over 50 publications and he is lecturer at the University
of Freiburg, with the topic “Materials for Energy Research”.
Dr. Ulrich Vogt
Corresponding author: PD Dr. Ulrich Vogt, ulrich.vogt@empa.ch, Tel. (+41) 58 765 4160

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NUMERICALMODELING
OF
PEM
FUEL
PHOTOELECTROCHEMICAL WATER-SPLITTING

CELLS

AND

J. Schumacher, P. Cendula, D. Tilley, M. Schmid
Institute of Computational Physics, Zurich University of Applied Sciences, Wildbachstr. 21, 8401 Winterthur, Switzerland
Abstract Hydrogen technologies emerge as promising energy carrier for the future. Development of fundamental andindustrial hydrogen applications, such as proton-exchange membrane (PEM) fuel cells or photoelectrochemical (PEC)
water-splitting go hand in hand with the available numerical simulation tools to understand and optimize theirperformance. Our group specializes in specifying and implementing such numerical models.

Proton-exchange
cells

membrane

(PEM)

fuel

We have been developing models of PEM fuel cells that
describe the transport phenomena and the electrochemical
reactions. We apply these models to analyze laboratory test
cells and large-area cells for technical applications.
We developed a 1D model of the membrane electrodeassembly (MEA) that comprises five layers: the anodic gas
diffusion layer, the anodic catalyst layer, the protonexchange membrane (PEM), the cathodic catalyst layer andthe cathodic gas diffusion layer. The transport processes aremodeled by seven coupled nonlinear ordinary differential
equations that are discretized using the Galerkin finite
element method.
We simulate the pressure and velocity distribution of the gas
flow in the gas distribution channels on the anode side andthe cathode side (flow-field). It takes several hours to solve
the incompressible Navier-Stokes equations in 3D using
commercial codes since we have to consider complicatedshapes of the flow-field channels. To speed up the solution
procedure we developed a method to reduce the modeling
dimension from 3D to 2D.
Simulation of the coupled transport and reaction processes
in cells of technical size is realized by a 2+1D approach [1].
This approach is suitable to take the high aspect ratio
between the in-plane and the through-plane dimensions offuel cells into account, and to avoid expensive 3D
calculations.

Photoelectrochemical (PEC) water-splitting
Converting solar energy directly into hydrogen is the goal ofa photoelectrochemical water-splitting cell (PEC). Such asolar cell would then replace the conventional route via a
photovoltaic solar cell (or other renewable energy source)
coupled with a water electrolysis system. Even though thebenchmark PEC cells reached hydrogen production
efficiency 12% [2], the current challenge is to fabricate themcheaply enough to compete with other hydrogen production
solutions. In this respect, metal oxide semiconductors(Fe2O3, Cu2O) show good light absorption and favourable
band position for oxygen evolution, but have intrinsic
drawbacks in poor carrier mobility and large overpotentials.
We review the understanding of the energy band alignment
for the semiconductor-electrolyte interface. We describe asimple kinetic model of charge transfer from semiconductor
surface states to the electrolyte or recombination fromsurface states with conduction band electrons. The model isnumerically solved in steady-state or transient conditions
which enables extraction of the rate constants for chargetransfer and recombination processes. The effect ofnanostructured PEC electrodes on the light absorption andcharge transfer is also discussed.
References[1] J.O. Schumacher, J. Eller, G. Sartoris, B. Seyfang, T.
Colinart, Mathematical and Computer Modelling of
Dynamical Systems (MCMDS), pp 1-23, 2012
DOI:10.1080/13873954.2011.642390.
[2] O. Khaselev, and J. A. Turner, Science 280, (1998): 425–
427.

Jürgen O. Schumacher studied physics in Frankfurt/Main and Freiburg in Germany. He finished his
PhD in 2000 at the Fraunhofer Institute for Solar Energy Systems (ISE) in Freiburg/Breisgau on thesimulation and characterization of novel and high-efficiency solar cell devices. He was working as avisiting scientist at the University of New South Wales (Sydney) in the Photovoltaics Special
Research Centre headed by Prof. Martin Green. Then, he was working at the Fraunhofer ISE on themodeling and simulation of portable fuel cells.

J.O.
Schumacher

At present, he is working as a professor at the Institute of Computational Physics (ICP) in Winterthur.
His research fields are PEM fuel cells, photoelectrochemical cells for hydrogen production, and solar
cells, particularly, dye sensitized solar cells.

Corresponding author: J. Schumacher, schm@zhaw.ch, Tel. 0589346989

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CATALYSTS AND CATALYSIS FOR BIO HYDROGEN PRODUCTION
Maria Olea and Simon Hodgson
Teesside University, School of Science and Engineering, Borough Road, Middlesbrough TS1 3BA, UK
Abstract. Ni-based catalysts, with increased Ni loading, were prepared by wet impregnation of nickel acetate on to SBA15 mesoporous silica. The samples were further characterized using XRD, SEM/EDX, TEM, N2 adsorption isotherms,
XPS and a CATLAB system for temperature programmed reaction, reduction and oxidation. Very well dispersed Ni
species were prepared with high activity towards dry reforming of methane reaction, as a low-cost alternative for biohydrogen production.

Introduction
Hydrogen can be produced using a wide range ofresources, from fossil fuels to nuclear via biomass,
through an even wider range of technologies, fromconventional to renewable energy technologies. The
main challenge to hydrogen production is cost reduction.
The production of hydrogen through the dry reforming of
methane (DRM) could be a potential low-cost technology
if the reactants are produced through the anaerobic
digestion of biomass/waste and for their conversion very
active and carbon resistant catalysts are developed. All
metals of the VIIIA group on a large variety of supports
have been studied. Nickel showed good catalytic activity,
especially when well dispersed on the support. This
paper deals with the preparation and characterization of
Ni-based catalysts supported on SBA-15 mesoporous
silica.

Experimental

Catalysts preparation. 1.0 g support, SBA-15, preparedthrough an optimized sol-gel method [1], wasimpregnated with 12 ml water solution containing 0.153 g
nickel acetate tetrahydrate. After sonication for several
minutes, the mixture was stirred for 1h at room
temperature. Impregnated silica was collected and driedat 100°C in vacuum and calcined at 550°C for 2h withheating rate of 10°C min-1.This process was repeatedseveral times to increase the Ni content.
Catalysts characterization. XRD, SEM/EDX, TEM, N2
adsorption isotherms, XPS were among the techniques
used to assess the morphology, structure, and texture of

the samples. Catalytic measurements were performed
using a CATLAB microreactor – MS system from Hiden
Analytical, UK. The same system was used fortemperature programmed reduction and oxidation as
well. For this study, two samples were selected, i.e., the 5
wt% (obtained after two impregnation cycles) and 11
wt% (obtained after five cycles) Ni/SBA-15.

Results and discussion

Low-angle XRD showed that the well-ordered hexagonalmesoporous structure of SBA-15 was maintained after
impregnation, for both loadings. Wide-angle XRD
evidenced very well dispersed Ni species. The Ni/Si(surface, XPS) to Ni/Si (bulk, EDX) ratio was >1 for bothloadings. SEM images showed a fiber-like morphology
while TEM micrographs supported the well-orderedmesoporous structure. Very narrow pore size distribution
centered around 7.6 nm for the support, decreasing withloading. BET surface area from 720 m2/g (SBA-15) to2
506 m /g (11 wt% Ni). Both, fresh and reduced samples
showed high activity towards DRM reaction, higher forthe reduced ones [2]. As for example, for the 5% loading,the pre-reduced sample starts to produce H2 and CO at
480 ºC while the fresh one must to exceed 600 ºC to start
to convert the reactants.

References[1] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky,
J. Am. Chem. Soc. 120 (1998), 6024.
[2] M. Olea, S. Hodgson, T. Sasaki, N. Aoki, K. Mae,
Chemical Engineering Transactions 17 (2009) 7.

Prof Olea, who is originally from Romania and has 30 years’ experience in teaching and research,came to the Teesside University in January 2007.
After leaving Romania in 1999, where she was an Associate Professor with Babes-Bolyai Universityof Cluj-Napoca, Prof Olea spent two and a half years at the University of Tokyo, where she taught
MA students and worked on gold catalysis.
Prof Olea also spent five years at Ghent University in Belgium, where she taught MA and PhD
students and worked on a research project covering multiple aspects of heterogeneous catalysis
and its environmental applications.
Maria Olea
Corresponding author: Maria Olea, M.Olea@tees.ac.uk, +44 1642 34 2447.

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OXIDE PHOTOANODES FOR WATER SPLITTING
Fatwa Abdi, Moreno de Respinis, Bernard Dam, Roel van de Krol*
MECS, Department of Chemical Engineering, Faculty of Applied Sciences, Delft University of Technology, Julianalaan136, Delft, Netherlands*Helmholtz -Zentrum Berlin für Materialien und Energie, Institute offor Solar Fuels and Energy Storage Materials,
Glienicker Strasse 100Hahn-Meitner-Platz 1, 14109 Berlin, Germany
Abstract: The solar water splitting process depends on the quality of the photon absorption and the efficiency of thesurface catalytic reaction. Here we focus on the development of oxide semiconductors as photoanodes, using the cobalt
phosphate as an ‘ideal’ catalyst.

Hydrogen as solar fuelFluctuating sustainable energy sources necessitate thedevelopment of large scale storage options. Electricalstorage is expensive, volatile, heavy and requires a large
volume. The conversion of sunlight into fuel is an
attractive approach to this problem. Recently, it has
become popular to promote research into the productionof artificial hydrocarbons. We focus on the solar induced
water splitting. This is by far the simplest
photoelectrochemical conversion process, and thereby
serves to develop the understanding needed to develop
more complicated schemes. On the other hand, if one
aims to further develop means to convert CO2 tohydrocarbons using classical chemical pathways, thesustainable production of hydrogen is a prerequisite.

Photoanode development
The development of solar water splitting devices has
been the focus of many researchers recently. We favour
devices with separate electrodes for the production ofoxygen and hydrogen, to avoid recombination losses andseparation penalties. Recent achievements on catalysts
have resulted in various composite photoelectrodes forwhich oxygen or hydrogen evolution are no longer themain performance-limiting factors [1,2]. In those cases,
efficient light absorption and charge separation are theissues to be addressed. For example, the solar leaf
presented by Nocera et al.[3] shows that the lightabsorbing triple junction Si solar cell does not produce ahigh enough photocurrent to achieve the required solarto-hydrogen efficiency (>10%). Hence the photo-absorberis the element to be improved.
We focus on the development of oxide photo-anodes.
Although a wide range of oxides with the appropriate gap(1.8eV<Eg<2.5eV) is available, the position of the band
levels and the poor carrier transport properties have to be
optimized. Using BiVO4 as an example, we will show thata step by step improvement results in a photo-anode witha >4.3% solar-to-hydrogen efficiency. An analysis of thedevice shows that further improvements are within reach.

References[1] Abdi et al., J Phys Chem C 116 (2012) 9398
[2] Paracchino et al., Nature Mater. 10 (2011) 3017.
[3] Reece, S.Y. et al. Science 334 (2011) 645

Since 2009 Bernard Dam is the head of the MECS group at the Delft University of Technology which
focuses on Materials for Energy Conversion and Storage. In addition to the thin film metal hydride
research on storage, sensing and membranes, his group specializes in photoelectrochemical water
splitting and the development of high-efficient oxide photoanodes. His research interests on therelation between growth, (defect)structure and physical properties of thin film oxides and hydrides.

Bernard Dam
Corresponding author: B. Dam, b.dam@tudelft.nl, Tel. +31152784342

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HYSTERESIS, NUCLEATION AND GROWTH IN THE HYDROGENATION
OF MAGNESIUM NANOLAYERS
Lennard Mooij and Bernard Dam
Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands.
The origin of hysteresis broadening in Mg nanolayers is identified to be largely due to a nucleation barrier. With
Hydrogenography, we measure the hydrogenation of 10 nm Mg layers maintaining a stable hydrogen pressure within thehysteresis gap. Because only few heterogeneous hydride nucleation sites are available, we observe the two dimensional
growth of single hydride domains of up to millimetre in diameter. From an analysis of the growth based on irreversible
thermodynamics, we extract the 'true' equilibrium pressure where both hydrogen and magnesium in both metal and metal
hydride phases are in equilibrium.

Nano-hydrides and hysteresis
Many metal hydrides are very stable and require heat torelease the hydrogen. One way to destabilize metal
hydrides is through nanostructuring.1 The increased
surface or interface area per unit volume destabilizes thehydride phase, if the surface/interface energy of thehydride phase is higher than that of the metal phase.
Nanosized and nanoconfined metal hydrides have beenshown to have improved kinetics, as well as different2
reaction pathways compared to the bulk materials. We
expect that nucleation and growth processes arechanging at the nanoscale as well. If metal hydrides areto be used at low temperaturethe actual goal ofdestabilizing the hydridethe transformation kinetics
becomes of increased interest.
We have recently reported that Mg layers thinner than 10
nm are destabilized due to the increased surface-to3
volume ratio. We furthermore observed, however, thatthe hysteresis increased with decreasing Mg thickness,thus partially decimating the destabilization. We therefore
now investigate whether slow nucleation and growth
processes are the origin of this hysteresis broadening.

If we now begin with a completely dehydrogenatedsample, and increase the hydrogen pressure to 70 Pa,
the sample is still able to hydrogenate. This process isvery slowa typical hydrogenation takes several
daysbecause only very few hydride nuclei are formed.
The image below shows a 10x10 mm sample, which isilluminated with white light from below. Because MgH2 isan insulator, it transmits more light than the metal Mg.
Hence, the circular domains are hydride phase, while thegray area is still metallic. We analyze the two dimensional
growthofthesedomainsusing
irreversible
thermodynamics, and relate the metal-metal hydride
boundary velocity to the single, 'true' equilibriumpressure. This is the pressure where all elements andphases are in equilibrium, which is normally notaccessible because of the hysteresis.

Hysteresis scans and 2D-growth
The hysteresis of 10 nm Mg layers is first examined moreclosely by hysteresis scans with Hydrogenography at 90
C. We find that there is a large nucleation barrier during
absorption for the 10 nm layer, because after thehydrogenation has started (p = 130 Pa), subsequent
growth can still occur at a lower hydrogen pressure (p =70 Pa).

References[1] Fichtner, Nanotechnology, 2009, 20, 204009[2] Gao et al., J Phys Chem C, 2010, 114, 4675-4682[3] Mooij et al., Adv. Energy Mater. 2011, 1, 754-758

Born on 4 July 1983 in Woerden, The Netherlands. In 2009 he graduated at Delft University ofTechnology with a masters degree in Materials Science and Technology. He moved on to a PhDposition under supervision of prof. Bernard Dam at the Solid State Physics group at VU University
Amsterdam, headed by prof. Ronald Griessen. As prof. Dam became group leader of the Materials
for Energy Conversion and Storage (MECS) group at Delft University of Technology, from 2010
onwards he continues to work on his PhD at his alma mater.
Lennard Mooij
Corresponding author: Lennard Mooij, L.P.A.Mooij@tudelft.nl, +31(0)15 27 83 891

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HYDROGEN DIFFUSION IN DEFECTIVE GRAPHENE
Samuele Sanna1, Daniele Pontiroli2, Chiara Cavallaria3 , Matteo Aramini2,
Mattia Gaboardi2, Georgia Vlachopolou2, Marcello Mazzani2, Mauro Riccò2,
Pietro Carretta1 and Stephane Rols3
1 - Dipartimento di Fisica, Università di Pavia, 27100 Pavia, Italy.
2 – Dipartimento di Fisica e Scienze della Terra, Università Parma, 43124 Parma, Italy
3 - Institut Laue Langevin, BP 156 38042 Grenoble, France

Astract: We report our recent findings on the study of the hydrogen diffusion in chemically produced
defective graphene. By combining Nuclear Magnetic Resonance and Neutron Spectroscopy we show theexistence of a slow dynamics of the hydrogen atoms bonded to the graphene plane. Such findings indicatethat hydrogen spillover could be supported on graphene systems.

Introduction
Graphene has been considered interestingfor hydrogen storage because of its highspecific surface[1]. Moreover it has been
predicted that the hydrogenated graphene
could be a good receptor favouring thehydrogen spillover process [2]. However a
clear evidence of hydrogen diffusion ongraphene, which is a essential requisite toachieve the spillover mechanism, is stilllacking. Here we show that chemically
produced defective graphene is effective indissociatinghydrogenmolecules
andpromoting the chemisorption of hydrogenatoms, which are shown to slowly diffuse
onto the graphene plane.

Results Chemically produced defective

graphene were differently treated inhydrogen atmosphere and were investigatedwith solid state nuclear magnetic resonance(NMR) and with neutron spectroscopy. The
results show that, besides the hydrogenstrongly bounded to the lattice defects (inplane vacancies and edges), a sizeable
fraction of chemisorbed H atoms on the
C-plane is present. For the latter, NMR gives
clear evidence of a thermally activatedSamuele Sanna

NMR spectra of H-enriched defective graphene fordifferent temperatures. The narrowing observed at hightemperatures is of motional origin and it is due to thehydrogen diffusion process.

diffusion process which at room temperature
is typically on the microseconds scale.

References[1] L. Schlapbach and A. Zuttel, Nature (2001)
414, 353.
[2] K. Singh et al., ACSNano (2009) 7, 1657.

Samuele Sanna was born 23. 06. 1974 in Sassari, Italy. 1998 Degree in Physics. 2002
PhD in Physics at University of Cagliari. 2002-2006 Post-doc fellowship at the
University of Cagliari. 2006-2009 Senior Researcher at the University of Parma. 2009–
today Assistant Professor at the University of Pavia, Italy. His research activity is in thearea of Solid State Physics in the fields of Superconductivity, Magnetism and recently
Hydrogen Storage. Experimental expertise mainly in nuclear magnetic resonance andmuon spin rotation techniques.

Corresponding author: Samuele Sanna, email: Samuele.Sanna@unipv.it, Tel. (+39) 0382 987470

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MgH2-BASED COMPOSITE COMPACTED POWDERS UPON HYDROGENCYCLING
A.Montone1, A. Aurora1, D. Mirabile Gattia1, L. Pasquini2, M.Vittori Antisari1
1

ENEA, Technical Unit Materials Technology, Research Center of Casaccia, Via Anguillarese 301, 00123 Rome, Italy2

Department of Physics and CNISM, University of Bologna, V. Berti-Pichat 6/2, 40127 Bologna, Italy

MgH2-based compacted powders prepared with the addition of Nb2O5 or Fe and carbon based materials have beenstudied in view of application of MgH2-base composits inside tanks for hydrogen storage, studies were carried out with.
The pellets are subjected to repeated hydrogen sorption cycles to measure hydrogen storage properties and its stability
with cycling. The sorption kinetic of the pellets was studied revealing the material to have a similar kinetic with respect tothe powder. Electron Microscopy observations of the pellets, before and after the cycling process, point to a dramatic
modification of the material’s microstructure upon repeated hydrogen cycling. The effects of air exposure were also
investigated.

TEXT
Nanostructured composite materials obtained by ball
milling MgH2 with different additive (Fe, Nb2O5 or carbonbased materials) were studied by a microstructural andkinetic point of view. The interest is in testing theirreversibility and exploring the structural modification afteran extended number of H2 absorption and desorption
cycles.
The evolution of MgH2 ball-milled during a sequence ofhydrogen absorption and desorption reactions at different
temperature and pressure conditions was explored by the
Scanning Electron Microscopy and by the analysis of the
kinetic curves, in order to derive information about thereaction rates and the rate limiting step. The mainfeatures coming up by the cycling procedure was thepresence of micrometrical worm-like structures protrudingfrom the particle surface and of hollow particles
constituted by empty MgO shell box, at nanometric level.
Despite the evident microstructural evolution, the storage
capacity of 6.5 H2 wt % and the H2 sorption kinetics are
not strongly affected by cycling.
Focusing the attention to the application of these metallic
hydrides inside tanks for hydrogen storage, studies werecarried out with MgH2-based pellets prepared with theaddition of Nb2O5 or Fe and carbon based materials.
A powder mixture consisting of 90 wt% MgH2 and 10 wt%
microNb2O5 (or Fe) was subjected to ball milling (BM) for
10 hours in a SPEX 8000 mixer-mill, using a hardened

steel vial equipped with a special valve that allowed
evacuation and filling under a Ar overpressure of 6.0 bar.
Hardened steel balls in ball to powder weight ratio of 10:1
were employed. Afterwards, 5 wt % of Expanded Natural
Graphite (ENG) was mixed with the milled MgH2/Nb2O5
powders. Finally, cylindrical pellets with diameter = 8 mm
and height ≈ 3 mm in were obtained by cold compacting
245 mg of milled powder in a dye, under a uniaxialpressure of 195 MPa. The powders were handled underinert atmosphere by using an Ar-filled glove bag.
The kinetics of absorption and desorption reactions of
the pellets was studied revealing the material to have asimilar kinetic with respect to the powder. ScanningElectron Microscopy observations of the inner core of thepellets, before and after the cycling process, have been
performed. The effects of air exposure were also
investigated showing similar results. A modest effect of
exposure to the atmosphere was revealed: after 2 hours
under non-dry air, the pellet exhibited a 9% reduction of
the total H2-capacity and a slightly slower H2-absorption
rate, while the H2-desorption rate remained almost
unaffected.

References[1] D. Mirabile Gattia, A. Montone, L. Pasquini, Int. J.
Hydrogen Energy, 10.1016/j.ijhydene.2012.11.116[2] A. Montone, A. Aurora, D. Mirabile Gattia, M. Vittori
Antisari, Catalysts 2 (2012) 400-411

Degree in Physics, staff scientist at ENEA, Research Centre of Casaccia, Rome. Research work has
been on applications of electron microscopy methods to material science problems and on
synthesis, microstructural and thermal characterization on nanocomposite for hydrogen storage,
Author of more than 100 publications in international journals, invited speaker at congresses.
President of SISM (Italian Society for Microscopical Sciences) from 2008. Project scientific leader innational and European projects on hydrogen storage materials. ENEA scientific coordinator of
Amelia Montone Hydrostore-Industria 2015. Management board member of EERA-Joint Programme on Advanced
Materials and Processes for Energy Application (AMPEA), Chair of COST Action MP1103(Nanostructured materials for solid-state hydrogen storage), 25/10/2011-25/10/2015.
Corresponding author: Amelia Montone, amelia.montone@enea.it, +390630484762

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HYDROGEN STORAGE AND HYDROLYSIS PROPERTIES OF MG3RE
L. Z. Ouyang*1, J. M. Huang1, H. Wang1, J. W. Liu1, Q. A. Zhang2, D.L. Sun3, M. Zhu1
1

School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China
2

School of Materials Science and Engineering, Anhui University of Technology, Maanshan, Anhui 243002, China
3

Department of Materials Science, Fudan University, Shanghai 200433, China

Abstract A method is reported of in situ formation of a highly stable REH2-3-MgH2(Ni) nanocomposite, to develop an Mgbased alloy of high hydrogen storage performance. This nanocomposite structured RE3Mg based alloy demonstrates
reversible hydrogen storage capacity of more than 4.0 wt.%, low desorption temperature, fast kinetics and high stability.
The temperature for the full hydrogenation/dehydrogenation cycle is significantly decreased to about 500 K, which isabout 100 K lower than that for pure Mg. The hydrogen desorption activation energy is only about 60 kJ/mol, which islower than that of pure Mg (158±2 kJ/mol, respectively). X-ray diffraction and transmission electron microscopy wereused to reveal the mechanism which delivered this excellent stability and hydriding/dehydriding kinetics for this CeH2.73MgH2(Ni) nanocomposite. The hydriding/dehydriding process was catalyzed by the adjoining of extremely fineCeH2/CeH2.73 and Ni to Mg/MgH2. In addition, The hydrolysis mechanisms of the hydrogenated Mg3RE are also
discussed in this paper. Hydrogenated Mg3Mm (where Mm denotes La-rich and Ce-rich misch metal) has been identified
as an excellent hydrolysis material for the first time. Hydrolysis of the as-hydrogenated Mg3Mm produced 695 mL g1
hydrogen in 5 min, 828 mL g1 hydrogen in 15 min, and the highest hydrogen yield reached 9.79 wt.% at 298 K. The
hydrolysis mechanisms of hydrogenated Mg3RE are also discussed herein.

Hydrogen storage property of Mg3RE

Hydrolysis property of Mg3RE

Fig. 1 shows bright field images of the fullyhydrogenated microstructure of the CeH2.73-MgH2-Nicomposite. A very fine plate-like or lamellar mixture ofCeH2.73 (dark) and MgH2
(white) was observed,
which were identified bytheselectedarea
diffraction patterns. The
CeH2.73 platelets had an
average width of 20 nm
and a planar length ofabout 150 nm, while the
MgH2
matrixwas
nanocrystalline with anaverage grain size of
200nm
about 30 nm.

Hydrolyses of hydrogenated Mg3Mm, Mg3La, Mg3Ce,
Mg3Pr and Mg3Nd generated 1097 ml g-1, 949 ml g-1,
-1-1
-11025 ml g , 905 ml g and 657 ml g in the end, withtotal hydrogen yields of 9.79 wt.%, 8.47 wt.%, 9.15 wt.%,
8.08 wt.% and 5.86 wt.%, respectively. The fitting results
confirmed that the hydrolysis reactions of hydrogenated
Mg3Mm, Mg3La, Mg3Ce, Mg3Pr, and Mg3Nd all obey the
nucleation growth mechanism.

Fig. 1 TEM images of the fully hydrogenatedmicrostructure of in situ formed CeH2.73-MgH2-Nicomposite shows very fine platelike or lamellar mixture of
MgH2 and CeH2.73.

Fig. 2 The kinetics
curves of H2 evolution
for hydrogenated (a)Mg3Mm, (b) Mg3La,(c) Mg3Ce, (d) Mg3Pr
and (e) Mg3Nd at
298K.

Liuzhang Ouyang received his B.S. in Metallic Materials from Yanshan University at Hebei province
in 1994. He received his Ph.D. from South China University of Technology (SCUT) in 2001 andjoined SCUT faculty in 1987. Current research projects focus on hydrogen storage and hydrolysis
materials of light metal hydrides, light metal complex hydrides and their composites, La-Mg-Ni-basedhydrogen storage, nickel/metal hydrides (Ni/MH) secondary batteries electrode alloys etc..
Liuzhang OUYANG
Corresponding author: Liuzhang OUYANG, meouyang@scut.edu.cn, 00862087114253

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FACTORS TO AFFECT CYCLE STABILITY OF V-BASED HYDROGEN
STORAGE ALLOYS
Wu Chaoling1,2, Andreas Borgschulte2, Zhou Jingjing1, Yan Yigang1,Yang Fei1, Luo Linshan1, Urs
Frischknecht2, Chen Yungui1, Andreas Züttel2
1

College of Materials Science and Engineering, Sichuan University, Chengdu, 610064, China

2

Empa, Swiss Federal Laboratories for Materials Science and Technology, 8600 Dübendorf, Switzerland

Abstract The V-based BCC alloys have high reversible hydrogen capacities around 2~3mass% at room
temperature and are therefore expected to be applied as on-board hydrogen storage materials. During the first 10hydrogenation/dehydrogenation cycles, the capacities decrease markedly by about 10~15%, which hinders the largescale application of the alloys. Possible reasons are both internal (including lattice variation, strain, phase transformation,etc.) and external factors (poisoning by impurities in the gas after decades of cycles mainly). In this work, some factors
causing capacity decay of V-Ti-Cr-Fe hydrogen storage alloys were experimentally demonstrated with reasonablesuggestions.
Internal factors to cause capacity decay
H2 desorption capacity of V-Ti-Cr-Fe alloy, which isdeveloped by Sichuan University, decreases sharply
during the first 10 hydrogenation/dehydrogenation cycles,
while keeping steady afterwards. Higher V containing
alloy shows relatively better cyclic stability than lower one.
Microstrain inside the lattice relates directly with thedesorption capacity. Grain size is another importantreason to determine the desorption capacity, which isrelated to microstrain too. After 25 cycles, both BCC andBCT structures coexist in the alloy. Lattice distortion byphase transformation and consequent strain may result ina decrease of capacity.

impurities of hydrogen sources and oxygen during
manufacturing is suggested.

Prospect
V-based hydrogen storage alloy was stored in acontainer as a a hydrogen supply to a fuel cell bicycle,
who runs 47.9km with 1.17kg of alloys after fullyhydrogenated. It can be an alternative hydrogen storage
candidate for submarine or other vehicles.

External factors leading to capacity decay
In manufacturing processes, especially powder making,as well as transportation before application, oxygen isunavoidable. There are also CO, CO2, N2 and steam
impurities in H2 gas. The surface properties of V-Ti-CrFe-Mn alloy during 20 hydrogenation/dehydrogenation
cycles were investigated by XPS analysis. Duringhydrogenation/dehydrogenation cycles, the surface
becomes oxidized. Particular oxides were known to blockhydrogen uptake and might thus be responsible for thecapacity decay. Dense and passive chromia forms
thereafter on alloy particles and hinder further oxidationand therefore stops further degradation of the hydrogencapacity of the alloy. Impurities in H2 gas with different
density were studied as well. Strict control of both

Wu Chaoling

References[1] Y.G. Yan, et al. J. Alloys Compds, 2008, 454: 427.
[2]C.B. Wan, el al. Inter J Hydrogen Energy,
2009,348:944.
[3] C.L.Wu, et al. Inter J Hydrogen Energy,2010, 35:
8130.
[4] C.L.Wu, et al. MH2012 proceedings, J. Alloys
Compds, submitted.

Born 20th July,1974 in Chongqing City, China. 1997 bachelor in department of metal materials
and heat-treatment, Chengdu University of Science and Technology, Chengdu, China. 2000 Masterin College of Materials Science and Engineering, Sichuan University, Chengdu, China. 2003 Ph.D.
in College of Materials Science and Engineering, Sichuan University. 2003 Lecturer in College ofMaterials Science and Engineering, Sichuan University. 2007 Associate professor in College ofMaterials Science and Engineering, Sichuan University. 2007 Assistant director in Engineering
Research Center of Alternative Energy Materials & Devices, Ministry of Education of China.2008
Chief Engineer in Sichuan Baosheng New Energy Materials Co., Ltd. Chengdu, China. Research
field: Hydrogen production, hydrogen storage and system, electrode materials in batteries. 2012
Guest Professor in Züttel Lab in EMPA Swiss Federal Laboratories for Materials Science andTechnology, Switzerland.

Corresponding author: Wu Chaoling, wuchaoling@scu.edu.cn, 86-28-85466916

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NEW H2 STORAGE TANK CONCEPT FOR COMPLEX HYDRIDES
Inga Utz, Marc Linder, Antje Wörner
German Aerospace Center, Institute of Technical Thermodynamics, Pfaffenwaldring 38-40, 70569 Stuttgart, Germany
Complex hydrides show very high potential H2 storage densities offering the possibility to store H2 safely and lightweight
on-board of vehicles. Their slow rates of absorption at temperatures below 120°C can be improved by a new storagetank concept, where the complex hydride (CxH) is partially replaced by an interstitial metallic hydride (MeH). The fast
reaction rate of the MeH even at room temperature can initiate the reaction of the CxH in the powder bed, as theexothermal absorption reaction is heating up the total system. Simulations for two model materials (2LiNH2–1.1MgH2–0.1
LiBH4 –3 wt.% ZrCoH2 with LaNi4.3Mn0.4Al0.3) show significant improvements in performance for both, the absorption
process (fuelling) as well as the desorption process (hydrogen discharge).

Introduction
Due to the high theoretical H2 storage capacity, complex
hydrides (e.g. Metal–N-H systems) offer the possibility tostore H2 lightweight and safely for on-board applications[1]. However, the rate of reaction of these materials israther low below 120 °C leading to a slow start-up andgenerally poor dynamics of the tank. By the addition of aninterstitial metal hydride to a complex hydride tank thesetwo problems can be overcome, as metal hydrides showhigh reaction rates at room temperature. However, since
their storage capacity for hydrogen is lower, an optimized
ratio and geometry have to be identified.

necessary for the coupling to a HT-PEM fuel cell, theaddition of a fast desorbing metal hydride can also
improve the desorption performance significantly. If theplateau pressure of the MeH is lower than that of theCxH, the pressure in the tank decreases to theequilibrium pressure of the MeH. Then, the reaction of
the MeH prevents a further decrease of pressure. At thispoint both materials desorb at the same time. Therefore,
the capacity of the CxH material can be fully usedcompared to a pure Amide tank (see “star” in Fig.1).
Absorption

Simulations for Absorption
In order to charge a complex hydride tank at room
temperature, the temperature inside of the tank needs to
be increased by an external heat transfer fluid (HTF) to atleast 120-130°C. At this temperature, the absorption
reaction of the CxH is initiated and the excess heat isthen removed by the HTF. The addition of 10 vol% MeH
to the same tank improves the overall performance in two
important points (see Fig.1): First of all, the temperatureof the tank can be increased very fast and efficiently by
the heat of reaction of the MeH, therefore the reaction of
the CxH is initiated just after few seconds. Second, while
the tank is heated up for the CxH, the MeH material isalready absorbing. Thus, the heat is not provided fromthe outside, but the heat is generated directly in thereaction bed by an additional H2 uptake.

Desorption
Peq for MeH

improved fuelling
performanceextended CxH capacity

Fig. 1: Left: Absorption with mass H2 absorbed vs. time. Right:
Desorption starting from 20 bar and decreasing pressure withconstant H2 flow-rate. Blue: amide, red: mix. Simulations havebeen performed using a 2-D model in COMSOL®.

References[1] Chen et al., Metal-N-H systems for the hydrogen storage,
Scripta Materialia 56 (2007) 817-822.

Parts of this work have been funded by EUProject, SSH2S

Simulations for Desorption
As the desorption rate of a CxH is usually rather low attemperature (~165°C) and pressure (>1.5bar) conditions

Born in 1984 in Mutlangen, Germany.
2003 – 2009 Diploma in Process Engineering at the University of Stuttgart, Germany.
2008 Diploma thesis at Queen´s University in Kingston, Canada.
Since 2009 research assistant and phd student at the Institute of Technical Thermodynamics at theGerman Aerospace Center (DLR) in Stuttgart, Germany.
Inga Utz
Corresponding author: Inga Utz, inga.utz@dlr.de, +49 – (0)711 6862 492

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HYDROGEN AND CRYSTAL DEFECTS, A COMPUTATIONAL STUDY
Andreas Pedersen and Hannes Jónsson
University of Iceland, Science Institute
The interaction of hydrogen with point- and planar defects in aluminium has been studied by atomistic simulations. For apoint defect (vacancy) the presence of four H-atoms results in pinning and the lowest energy path for a diffusion hop
requires the displacement of two or more H-atoms away from the vacancy. In the low concentration limit, planar defects(grain boundaries) are found to trap H-atoms at 300 K and in most cases reduce diffusivity rather than providing apathway for high mobility as is often assumed. The lowest energy grain boundary, however, imposes an impenetrable
barrier confining the H-atoms and leads to reflection from the grain boundary, thereby increasing the diffusivity of theatoms within the grain.

Simulations

Planar defects

The migration mechanism of a vacancy in Al was studied
using the ‘Minimum-mode Following’ [1] method to locate
saddle points on the potential energy surface (DFT) andtheir connected minima. Long time scale simulations of a
H-atom in the vicinity of either a twist, a tilt or a twist+tilt
grain boundary at room temperature were carried out by
applying ‘Adaptive kinetic Monte Carlo’ [2]. The EMT
potential function was used to describe the atomic
interaction in these simulations.

The diffusion of hydrogen in the vicinity of several grainboundaries has also been simulated. The high energy,
twist+tilt boundary is found to contain closed pockets ofdeep traps where the H-atom ends up spending most of
the time. Despite being trapped, the H-atom still hops
around, but no net diffusion results. The simulated
diffusivity parallel to the grain boundary is found to be anorder of magnitude smaller than within a perfect crystal.
The mid-range energy, Σ5 tilt boundary gives similar
results, except that certain interface regions did not get
visited during the simulation. The diffusivity was a factorof two smaller than for a perfect crystal. The low energy,
Σ5 twist boundary yielded a surprising result. In this casethe H-atom never entered the boundary region but
remained within the crystalline grain in which the
trajectory started. The explanation for this behavior canbe found in the energy landscape. Close to the boundary
the potential energy increases significantly and provides
a repulsive wall, which reflects the H-atom away from thegrain boundary. The parallel diffusivity is found to beslightly higher as compared to a crystal [3]. These results
can help explain reported experimental measurements ofhydrogen degassing from nanocrystalline samples.

Point defect
Earlier computational studies have revealed that thebarrier for vacancy diffusion in aluminium is 0.63 eV.
Furthermore, it is known that 0.20 eV is gained when aH-atom moves from an interstitial site into a vacancy.
From the present calculations it appears that the binding
energy per atom increases to a maximum value of 0.23
eV/atom, when two H-atoms are present, followed by adecrease to 0.16 eV/atom for the case when eight Hatoms are within the vacancy. A net gain of 1.31 eV
results from the latter loading of the vacancy and thisalmost equals twice the vacancy creation energy of 0.73
eV/vac. At the same time as the vac-H complex
becomes energetically more stable, its mobility
decreases and the vacancy becomes pinned. The
pinning occurs when four or more H-atoms are present
within the vacancy. Then, the diffusion barrier has
increased by a factor of more than 1.5 compared withhydrogen free Al. The optimal mechanism for vacancy
hops then involves the separation of two or more Hatoms from the vacancy, thereby leading to intermediate
configurations of high energy.

References[1] A. Pedersen S. F. Hafstein and H. Jónsson;
Journal on Scientific Computing, 32, 633 2011

SIAM

[2] G. Henkelman and H. Jónsson; Journal of Chemical
Physics, 115, 9657 2001
[3] A. Pedersen and H. Jónsson; Acta Materialia, 57,
4036 20092010-Present Research Assistant Professor, Computational Science, University of Iceland. LongTime Scale Dynamics and Sampling of Rare Event Systems. 2009-2010 Post Doctoral Fellow,
Applied Mathematics, Universidad Complutense de Madrid. A computational study of UV radiation
on interstellar dust. 2008-2009 Post Doctoral Fellow, School of Science and Engineering, Reykjavik
University. Investigation of Basic Properties of Vacuum Microelectronic Devices. 2004-2008
Doctoral Student, Computational Chemistry, University of Iceland. Long Time Scale Simulations ofMaterials using Distributed Computing.
AndreasPedersen
Corresponding author: Andreas Pedersen, andreas@hi.is, (+354) 8688177.

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COMPREHENSIVE AFM INVESTIGATIONS ON ENERGY MATERIALSFeray Bakan1 and Ahmet Oral1,21Sabanci University Nanotechnology Research and Application Center, Orhanli, Tuzla, 34956, Istanbul Turkey

2

Sabanci University Faculty of Engineering and Natural Sciences, Orhanli, Tuzla, 34956, Istanbul Turkey

This study summarizes the examination of energy materials with comprehensive Atomic force Microscopy techniques fortheir surface characteristics. The AFM applications on diverse energy materials such as fuel cells and their components,
solar cells, hydrogen storage materials are presented and the outcomes and interpretations on corresponding structures
are discussed.
The Atomic Force Microscope (AFM) is a versatile,
high-resolution microscope for imaging conducting andnon-conducting materials with nanometer resolution.
AFMs are now widely used in many areas such as
materials science, nanotechnology, biophysics, andindustrial process control. Modern AFMs can be used toimage nanoparticles, single molecules, semiconductor
devices and even living cells. AFM has the advantage
of being able to image the sample with no priortreatment, in an ambient atmosphere. This makes
scanning quicker, and can also mean fewer artifacts are
introduced by the vacuum drying, or the coatingprocedure [1].
AFM techniques have proven to be a valuable tool forthe investigation of fuel cell [2-3] and Li-ion battery
components [4], since the properties are dependent on
the nanostructure to a large extend. With AFM surface
topography as well as different properties such as i.e.
conductivity, adhesion force, elasticity, dissipationenergy can be measured and statistically analyzed. The
contribution of electro catalyst layer microstructure to
the performance of gas diffusion electrodes in fuel cells
is extremely important. These structures containdifferent levels of porosity and particles ranging fromseveral nanometers to several micrometers, along with
1-10 nanometers thick coating materials. Therefore,characterization of these surfaces is crucial tounderstand the mechanisms affecting fuel cell
efficiencies. The 3-dimensional surface structure can bereconstructed from non-contact topography. In addition,
the distribution of adhesion forces can be used tomeasure surface hydrophobicity. With a conductive tip,
the size and distribution of conductive areas on the

micro porous layer of as diffusion layer can beanalyzed. The aging of microporous layers of fuel cell
can also be examined before and after fuel cell
operation by using an AFM technique.
AFM can also provide precise, qualitative andquantitative roughness measurements of surfaces. The
substrate roughness has a large effect on all aspects ofthin-film polycrystalline-Si solar cell process. The
efficiency of hydrogenated amorphous silicon solar cells
can be significantly improved when enhancing the lightabsorption in the thin layers by introducing lightscattering at rough surfaces. Therefore it is important toinvestigate the roughness of solar cell [5-6].

References[1] P. Eaton, P. West, Atomic Force Microscopy, Oxford
University Press, 2010,[2] [4] K. A. Friedrich, M. Schulze, A. Bauder, R.
Hiesgen, I. Wehl, X. Yuan, H. Wang, ECS
Transactions, 25 (1) 395-403 (2009)[3] R. Hiesgen, I. Wehl, E. Aleksandrova, E. Roduner,
A. Bauder, K. A. Friedrich, Int. J. Energy Research, 34(14) 1223-1238 (2010)[4] Shrikant C. Nagpure,Bharat Bhushan, Suresh Babu,
Giorgio Rizzoni, Scripta Materialia , 60, 933–936 (2009)[5] H. C. Hesse, J. Weickert, M. Al-Hussein, L. Dossel,
X. Feng, K. Mullen, L. S. Mende, Solar Energy
Materials and Solar Cells, 94 (3), 560-567 (2010)[6] J. Krc, M. Zeman, O. Kluth, F. Smole, M. Topic, Thinsolid films,426 (1-2), 296-300 (2003)

Feray Bakan studied chemical engineering and received her PhD degree from Ataturk University,
Erzurum, Turkey in 2010. She is currently employed as a postdoctoral researcher at the Sabanci
University Nanotechnology Research and Application Center (SUNUM). Her primary researchinterests include general Atomic Force Microscopy applications, high-resolution nc-AFM applications
in liquids, synthesis & characterization of bio ceramic materials.
Feray Bakan
Corresponding author: Feray Bakan, feraybakan@sabanciuniv.edu, +90-216-4839000-2417

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ENERGY EFFICIENCY: THE MISGUIDANCE OF COMMON SENSE
Björgvin Hjörvarsson
Uppsala University, Department of Physics and Astronomy, Box 516, 751 20, Uppsala, Sweden
The transition to alternative energy sources is one of the grand challenges of our civilisation. The development ofefficient energy-carriers is an important step, for which hydrogen has been identified as an alternative. Although this isrequired, it is not sufficient. Moving beyond the optimization of the Carnot cycle is required, which will be illustrated using
examples from the automotive and nuclear power plant industry.

Background
Collapses of societies, caused by collective choices of its
members, are well known in our history [1], and the
choices made, can often not be rationalized in retrospect.
However, these choices must have been guided bycommon sense, as the opposite is unimaginable.
The awareness of the possible extinction of our species,
as a consequence of a human intervention, was probably
initially developed during the final stage of the Manhattan
project [2]. This awareness should be omnipresent, as
we are facing a question, which will determine our role in
the future terrestrial ecosystem: How will we satisfy our
future energy needs. The guidance offered by common
sense will be argued to be misleading, highlighting theneed of moving beyond the current understanding ofenergy efficiency.

ExamplesThe energy efficiency is one of the most importantparameters to optimize, when designing future energy
systems. The efficiency is often determined in theperspective of the Carnot cycle, dictating the maximum
transformation from one form of energy to another.
Although this consideration is required, it is not sufficient
as a sole optimization parameter.
As an example, hydrogen is often hampered as being thefuture energy carrier for automobiles. Meanwhile, thecurrently obtained energy density is viewed as being tolow, as compared to gasoline. This view is an example of
how common sense can be misguiding, leading us
towards sub-optimization. The current efforts are, forexample, on the optimisation of the efficiency ofhydrogen replacing fossil fuels. The optimization is
performed using vehicles developed for combustion
engines, as a target. The effort should be replaced by an
optimization of the intended transportation, a change ofview which will give an alternative route of progress. For
example, when burning fossil fuels in combustion
engines, the maximum conversion efficiency is about

40%, depending on the type of fuel and engine design.
This efficiency does not include the efficiency of theintended work and is therefore illusive as an ultimate
optimization goal. When using the alternative route of
optimization, the use of hydrogen can become highly
beneficial. This step could result in substantial decreaseof the energy demand within the transport sector.
The second example of how common sense can lead to
sub-optimization, is the current use of nuclear power.
The utilization of nuclear power in Sweden will be used
as a benchmark here, in which an increase of efficiency
by 100 % can be obtained using known technology. This
increase in efficiency is solely hindered by the presenceof what is perceived as common sense. The example isbased on available data from the Swedish energy
authority [3].
The efficiency of the Carnot cycle is therefore not theright level of optimization. The intended function needs tobe taken into account. This step is certainly needed,considering the limited resources available and thealternatives when failing to do so. Using full optimization,
taking into account the intended work, can result in morerational optimization of the use of available resources.
This is possible by abandoning the guidance obtained bycommon sense, replacing it by scientific methodology. Bytaking this step, we might avoid some of the mistakes ofthe past [1] and substantially extend our presence in theterrestrial ecosystem.

References[1] Jared M. Diamond, Collapse: How Societies Choose
to Fail or Succeed ISBN 0-14-303655-6[2] Richard Rhodes, The making of the atomic bomb,ISBN 0-671-44133-7[3] Energiläget 2011, Enegimyndigheten, ISSN 1403-

1892

Prof. Björgvin Hjörvarsson is heading the Material Physics group at the Department of
Physics and Astronomy at Uppsala University. He has published more than 200
scientific articles on hydrogen in materials and low dimensional magnetism. He has also
published popular science articles, animations and other outreaching material for thegeneral public. He has given more than 100 invited talks at conferences and colloquia
and is frequently serving as an evaluator for funding agencies in Europe and the USA.
e-mail: Björgvin Hjörvarsson, bjorgvin.hjorvarsson@physics.uu.se

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UNDERSTANDING THE BEHAVIOUR OF CO-RU-B CATALYSTS FOR
SODIUM BOROHYDRIDE HYDROLYSIS: AN ELECTRON MICROSCOPY
STUDYG.M. Arzac1, T.C. Rojas1, L.C. Gontard1 and A. Fernández 1*
1. Instituto de Ciencia de Materiales de Sevilla (ICMS), CSIC-Universidad de Sevilla. C/ Américo Vespucio 49. Isla de la
Cartuja, 41092 Seville, Spain.
Abstract: The catalyzed hydrolysis of sodium borohydride has been proposed as a method for hydrogen production in
portable devices. In this paper Electron Microscopy (EM) is shown as a versatile tool to explain the catalytic activity,
stability and durability of a series of Co-Ru-B materials. The nanostructure, the Co surface segregation and the intermixof Co- and Ru- containing phases explain the properties of the series of catalysts.

Introduction
Catalysed sodium borohydride (NaBH4) hydrolysis(NaBH4 + 2H2O→4H2 + NaBO2) is a safe and controllable
method to produce hydrogen to feed PEMFCs (Polymer
Exchange Membrane Fuel Cells) in portable applications[1]. Co-B based catalysts are the most used because
they are cost-effective. The addition of Ru to form a CoRu-B material produces a synergistic effect in catalytic
activity. In this paper we prepared and isolated a seriesof Co-Ru-B materials with variable Ru content ascatalysts for reaction (1). We intended to explain theenhancement in catalytic activity as well as the stability
and durability of the series using mainly transmission
electron microscopy (TEM) based techniques (i.e.
scanning TEM (STEM), high angle annular dark field
detector (HAADF) and electron energy loss spectroscopy(EELS)). Also additional techniques (photoemission
spectroscopy (XPS) or surface area (BET)) have beenused. Whether or not the formation of a Co-Ru nanoalloy
occurs is also investigated using EELS with high lateral
resolution.

Results and Discussion
The analysis by BFTEM (bright field TEM) and HAADF
showed that the Co-containing catalysts have similarnanostructure than the previously reported by us for apure Co-B material [2]. XPS quantitative analyses haveshown that there is a Co surface segregation except ofcourse for the Ru-B material [3]. The plot of catalytic
activity as a function of surface Ru/Ru+Co atomic ratio isa straight line consistent with the addition of small
amounts of Ru to the same microstructure, except for the
Ru-B. For the latter a change in the microstructure
related to an abrupt increase in particle size is found. Cocontaining catalysts are stable against

ASUNCIÓN FERNÁNDEZ

oxidation what is explained by the presence of aprotective layer (veil) detected by HAADF images. The
veil is mainly composed of Co-B-O species and is notpresent for the pure RuB catalysts where also the boron
content is strongly reduced. Co-containing catalysts must
be stable against deactivation by B-O species´ deposition
during reaction (1) [2-4]. This hypothesis was further
tested in a continous reactor based on reaction (1)-1capable of producing 1L.min H2 during 30hours [5]. We
have also found that Co and Ru do not form a nanoalloy
but appear intermixed forming Ru- and Co- containing
phases.

Conclusions
Rational design of catalysts implies understanding therelationship between nanostructure, chemistry andcatalytic properties. For the Co-Ru-B series as catalysts
for hydrogen generation this understanding was achievedby combining XPS, XRD and surface area techniqueswith electron microscopy. The synergies between
techniques could also be employed in the study of therole of additives in the kinetics of hydrogen releasing
solid-gas based reactions.

References[1] B.H. Liu, Z.P. Li, J. Power Sources, 187 (2009), 527534.
[2] G.M. Arzac, T.C. Rojas, A.Fernández, Chem. Cat
Chem, 3 (2011) 1305-1313.
[3] G.M. Arzac, T.C. Rojas, A. Fernández, Appl. Catal. B
Environ,(2012) .
doi.org/10.1016/j.apcatb.2012.02.013[4] O.Akdim, U.B. Demirci, P. Miele, Int. J. Hydrogen
Energy, 36, (2011),13669-13675[5] G.M. Arzac et al, Int. J Hydrogen Energy, 37,(2012),14373-14381.

Born May 1958 in Vigo, Spain, Prof. Asunción Fernández graduated in Chemistry at the University ofCádiz (Spain) (1980) and in Physics at UNED (Spanish Open University) (1984). She carried out her
PhD work at Max-Planck Institut für Strahlenchemie in Mülheim a.d. Ruhr (Germany) obtaining theDr. rer. nat. degree at the University of Dortmund (Germany) in June 1983 on the subject ofphotocatalytic H2 production from water solutions. In 1984 she joined the Materials Science Instituteof Seville (Spain), a mix-centre of the Spanish Research Council (CSIC) and the Univ. Seville; where
she is leading the “Nanostructured Materials & Microstructure” group and the “Advanced Laboratory
for Nanoscopies and Spectroscopies”. Her actual research is devoted to the fabrication andcharacterization of nanostructured coatings by PVD and the study of materials for H2
storage/production for portable applications.

Corresponding author: Asunción Fernández, asuncion@icmse.csic.es, +34-954489531

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Optimization of Anneal Procedure in Metal Oxides: Case Study ofNanostructured Tungsten Processed via Low-Energy Helium-Ions
Moreno de Respinis1, Roel van de Krol1, Bernard Dam1; Irem Tanyeli2, Gregory De
Temmerman2, Richard van de Sanden2; Russel Doerner3
1) Delft University of Technology, Faculty of Applied Siences, Department of Chemical Engineering, Materials for Energy
Conversion and Storage; Julianalaan 136, 2628 BL Delft, The Netherlands
2) FOM-Institute DIFFER, Dutch Institute For Fundamental Energy Research, Edisonbaan 14, 3439MN, Nieuwegein,
The Netherlands
3) Centre for Energy Research, University of California at San Diego, 9500 Gilman Drive, La Jolla, USA
Abstract. One challenge in developing highly efficient nanostructured photoelectrodes is to control their morphology,
crystal phase and stoichiometry. We present a novel physical processing route that uses high-flux of low-energy heliumion to generate porous structures on tungsten targets. Optimal anneal condition to form WO3 photoanode is determined
via in-situ XRD. SEM images show mesoporous crystalline structure, and feature sizes depend on substrate temperatureand can be tuned between 30 nm and 1 µm. Our research shows that a two-step anneal procedure is optimal to oxidize
surface nanostructures into crystalline WO3, preserving the bulk as metallic W for good electrical contact. As a result,
2
2
IPCE of 20% is obtained, resulting in an AM1.5 photocurrent of 0.75 mA/cm at 1.23 VRHE (compared to 0.15 mA/cm
after standard thermal oxidative anneal). The excellent control over feature size offers an exciting new processing routeto nanostructure materials for e.g. solar water splitting.

Introduction
One of the challenges in developing highly efficient
nanostructured photoelectrodes is to achieve good
control over the desired morphology, crystal phase and[1]stoichiometry . We present a novel physical processing
technique that uses a high-flux of low-energy helium-ion
plasma-irradiation to generate a porous structure intungsten substrates heated to high temperatures. To
determine the optimal anneal conditions to form thetungsten oxide photo-anode, we use in-situ XRD.

Characterization
Scanning electron microscopy on samples before andafter anneal shows a well-defined mesoporous crystalline
structure. The feature size depends on the substratetemperature, and can be controlled between 30 nm and 1µm. Thermal anneal of W targets at 500°C<T<600°C
produces crystalline but highly oxygen deficient WO3-X
samples. Anneal at T = 700°C promotes the formation of
stoichiometric WO3, but the elevated oxidation rate leads
to thick oxide layer with increased carrier recombination
at defects. Using in-situ XRD we determine the effect oftemperature on crystal lattice parameters. Our researchshows that a low-temperature two-step anneal procedureis optimal to oxidize the surface nanostructures into

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crystalline and stoichiometric WO3, preserving the bulk as
metallic tungsten for good electrical contact. Raising thetemperature to 550°C promotes crystallinity, while asubsequent decrease to
450°C
allows for thetransformation of the WO3-X nanostructures into
stoichiometric WO3.

Performance analysis
As a result of this optimization, Incident Photon-toCurrent Conversion Efficiencies (IPCE) of 20% arereadily obtained in these photoanodes, resulting in an
2
AM1.5 photocurrent of 0.75 mA/cm at 1.23 V vs RHE.
The effect of the nanostructure is appreciated by2comparison with 0.05 mA/cm at 1.23 V vs. RHE
obtained with the polished tungsten oxide, whereas thebenefit of the optimized anneal procedure is revealed by2comparison with 0.2 mA/cm obtained after standard
thermaloxidative
anneal.
Thisphotocurrent
enhancement, along with the excellent control over thefeature size with the helium plasma technique, offers an
exciting new synthesis route to nanostructured materials
for e.g. solar water splitting.

References[1] Van de Krol et al., “Photoelectrochemical hydrogenproduction”, Springer (2012)

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Moreno de Respinis received his bachelor degree in physics at the University of Milan in 2008, andearned his master degree in sustainable energy with study line hydrogen and fuel cells at theTechnical University of Denmark (DTU) in 2011. He concluded his master with a fellowship at theLawrence Berkeley National Laboratory with Dr. Heinz M. Frei’s group, in which he performed
mechanistic studies of water photo-oxidation by visible-light driven Co3O4 catalyst. He is currently aPh.D. student at Delft University of Technology where he is researching on photoanodes for solar
water splitting.

Corresponding author: Moreno de Respinis, m.derespinis@tudelft.nl, +31-15-2782637.

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STUDY OF BODY-CENTERED CUBIC TITANIUM-BASED ALLOYS FOR
HYDROGEN STORAGE
Thomas Bibienne*, Jean-Louis Bobet+, Jacques Huot**Hydrogen Research Institute, Université du Québec à Trois-Rivières, 3351 des Forges, G9A 5H7, Trois-Rivières - Qc,
Canada+ Institut de Chimie de la Matière Condensée de Bordeaux, 87 Avenue du Dr Schweitzer, 33600 Pessac, France
Abstract
We report here our recent results on the hydrogen storage properties and microstructure of Ti-V-Cr alloys. Our goal is to
reduce the cost of alloys while keeping a high reversible hydrogen storage capacity at room temperature and low
pressure. All alloys were doped with Zr7Ni10 in order to ensure rapid activation.

Solid solution alloys with BCC structure of Ti-V-Cr and TiV-Mn composition have been reported to be interestinghydrogen storage materials [1,2]. The maximum capacityof these alloys at room temperature is about 3.5% wt.
and the reversible hydrogen capacity is around 2.3% wt.
In order to be used for practical applications, the BCC
alloys have to meet the following criteria: ease ofactivation (first hydrogenation), low cost, and plateaupressure of a few bars at room temperature. It has beenreported that the activation of these materials is difficult[3,4] but recently it has been solved by the addition ofZr7Ni10 phase (Charbonnier et al. [5]).
In their study of the 33Ti-30V-37Cr composition, Miraglia
et al. [6] found a two-phase material: a major phase – TiV-Cr rich - and minor intergranular phases – Zr-Ni rich.
The chemical composition of one minor phase has been
determined as 45Ti-10V-23Cr-9Zr-12Ni. In order to study
the specific hydrogenation behaviour of this particularphase, we synthesised by co-fusion of 52Ti-12V-36Cr
with 4% wt. of Zr7Ni10. The X-Ray diffraction study
revealed that the as-cast doped alloy is a pure body
centered cubic phase, with a lattice parameter of 3.10Å
and a crystallite size of 20.9 (+/- 0.7) nm. These
crystalline parameters have been compared to an
undoped material: it has been found that the addition of
4% wt. of Zr7Ni10 has no significant effect on the lattice
parameter of this alloy.
The as-melted sample was analysed by SEM andElectron Probe Micro Analysis. The SEM pictures
revealed a matrix with homogenous distribution of Ti, V
and Cr along with a minor phase - the intergranularphase – made of Ti, V, Cr, Zr and Ni. Mapping of eachelement have been determined using EPMA. An over-

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concentration of zirconium and nickel located into theintergranular phase was observed.
The first hydrogenation of the doped alloy is very fast,
and the hydride was found to be a pure FCC phase. The
hydrogen sorption properties of this material showed thatthe hydride material is composed of a monohydride at
low hydrogen weight percent (from 0 to 1.5 % wt) and adi-hydride at high hydrogen weight percent (from 1.5 to
3% wt). At 400°C, the desorption was complete after
3hours. The formation enthalpy of the di-hydride has
been determined as -60kJ/mol and its entropy as 169J/mol/K. The value of the enthalpy pointed out thatthe hydride is very stable, its equilibrium plateau is at
10KPa being at room temperature.
References
1: E. Akiba and H. Iba, Intermetallics, 6 (1998) 461.
2: H. Iba and E. Akiba, J. Alloys & Compounds, 253–254,
21 (1997)
3: A. Maeland et al., Journal of the Less Common Metals,
104, (1984), 361–364
4: E. Akiba and M. Okada, MRS Bulletin, 27 (2), (2002),
699–703
5: J. Charbonnier et al., Pulverulent intermetallic
materials for the reversible storage of hydrogen, US
Patent, 2012, US 8,257,464B2
6: S. Miraglia et al., Journal of Alloys and Compounds,
536, (2012) 1–6

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Stoos, Switzerland 20132011-2014 : PhD Student in Material Science and Energy, Hydrogen Research Institute, Universityof Quebec at Trois-Rivieres, Quebec, Canada
2010 : Master in Materials Chemistry, Bordeaux, France
2008 : Bachelor in Chemistry, Bordeaux, France

BIBIENNE
Corresponding author: Jacques Huot, Jacques.Huot@uqtr.ca, Tel: 1-819-376-5011 ext 3576

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INFLUENCE OF CHEMICAL COMPOSITION AND PARTICLE SIZE ON
THE ELECTRODE CHARACTERISTICS OF GAS ATOMIZED AB5-TYPE
HYDROGEN STORAGE ALLOYS
L. Shcherbakova, M. Spodaryk, Yu. Solonin, A. Samelyuk, O. Khyzhun
Institute for Problems of Materials Science (NASU), Krzhizhanovsky str., 3, Kyiv, Ukraine
A complex study of the electrochemical behavior of electrodes derived from powders of LaNi 4.5Al0.5 and (La+Mm)
Ni3.5Co0.7Al0.35Mn0.4Zr0.05 alloys, obtained by high pressure gas atomizing (HPGA) technique has been performed.
Dependence of this behavior during reversible electrolytic hydrogen absorption on particle size powders of the alloys has
been examined. For such a study XRD, SEM, XPS and several electrochemical methods have been used. The
electrodes of the large fraction powders of the both alloys reveal better kinetics, discharge capacity and ability to highrate discharge. The discharge process of electrodes, regardless of particle size and composition of alloys, is controlled
by diffusion of hydrogen in the electrode.

Introduction
Electrochemical properties of hydrogen storage alloys
are largely determined by their production technology,
therefore, this problem is widely studied in recent years.
A variety of technologies allows to obtain materials with
controlled
structure(amorphous,
nanocrystalline,
amorphous-crystalline) and grain size, that cansignificantly change their electrochemical characteristics[1,2]. Therefore, the application of new technologies for
obtaining multicomponent hydride forming alloys withadjustable non-equilibrium structure, such as highpressure gas atomizing (HPGA) technique, is relevant.

hydrogen discharge capacity than powders with larger
particle size. Unlike powders with larger particles, theelectrodes of the fine fraction are not capable to high-ratedischarge.
The
comparativeelectrochemical
characteristics of the electrodes of the investigated AB5type alloys powders are presented in Table.
Alloy

Surfacestate

Hydrogendiffusioncoefficient,
2
cm /s

≤0.05

Initial

6*10

0.63-1.0

Initial

3.5*10Initial

2*10

Activated
Initial≤0.05(La+Mm)Ni
3.5Co0.7 Al0.3
5Mn0.4 Zr0.05

75
mA/g

300
mA/g

235

232

-10

296

289

-12

-

-

1.5*10

-10

135

54

5.7*10

-11

210

-

-9

220

215

0.63-1.0
Activated

Capacity atdischarge
current*, mAh/g-12

LaNi4.5Al 0.5

Experimental results
High pressure gas atomized (HPGA) powders of
LaNi4.5Al0.5 and (La+Mm)Ni3.5Co0.7Al0.35Mn0.4Zr0.05 alloys
have been produced. In this work, two fractions of
powders of alloys have been used: small - <0.05 mm,large – 0.63-1.00 mm. Electrochemical properties ofelectrodes of all the fractions have been studied in thethree-electrode open cell with Pt counter electrode andHg/HgO reference electrode in 30% KOH solution, usinga PGSTAT4-16 apparatus. The electrodes of the large
fraction powders of the alloys under study possess better
kinetics, discharge capacity and ability to high rate
discharge. The electrodes of small fraction (≤0.050 mm)
powder of LaNi4.5Al0.5 alloy reveal improving their kinetic
and absorption characteristics and ability to high-ratedischarge during cycling. The electrodes made of small
powder fraction of (Mm+La)Ni3,5Co0.7Al0.35Mn0.4Zr0.05 alloy
are very difficult to activate and they show 15-20 % lower

Fractions,mm

3.7*10Conclusions
The difference in the electrochemical characteristics of
two fractions of alloys depending on their composition,
mainly related to the different states of the surface of thealloy particles, especially small ones. It has been
confirmed by XRD, XPS and SEM techniques.

References[1] H.Yuexiang et all. Journal of Alloys and Compounds,
V. 330-332 (2002), pp. 831-834.
[2] K. Younga et all. Journal of Alloys and Compounds,
V.509, I.14 (2011),pp.4896–4904.

PhD student.
Field of research: electrochemistry of metal hydrides.

Mariana Spodaryk

She works in a research team in electrochemical laboratory of Institute for Problems in Materials
Science of National Academy of Sciences of Ukraine.

Corresponding author: Mariana Spodaryk, email: poshtamary@ukr.net, Tel. (+38) (068) 5417935

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COMPOSITE MEMBRANES FOR CONVENTIONAL HIGH PRESSURE
ALKALINE ELECTROLYSERS.
Michal Gorbar, Ulrich F. Vogt, Alexander Bonk and Andreas Züttel
EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland
Hydrogen production via water electrolysis regained attention nowadays in the global search for energy alternatives. Oneof the favourite fields of the study for many researchers is to use electrolysis method by utilizing renewable energy
sources. Efficiency enhancement of this process by means of reducing the electric power consumption is one of the most
crucial parts in the research area. The presented work is devoted to the description of the lab-electrolyser working at
ambient conditions, the role of which is to provide efficient and quick feedback about tested commercial and newly
developing membranes for convectional type of alkaline electrolysers. Attention was paid to system development withfocus on reliability of results as well as behavior and properties of tested membranes.

Introduction

Results

An indispensable part of high-pressure alkaline
electrolysers of the type Lurgi-Zdansky is an asbestos
membrane responsible for separating hydrogen andoxygen gases. Due to health hazards, law forbids thesefabrics to be used in new electrolysers in future. The newmembranes have to be developed and to reachcomparable performance, i.e. suitable ion-conductivity
and gas separability, simplicity of processing but alsosufficient mechanical and chemical stability in a highly
corrosive environment. In addition the materials have tobe harmless, cost efficient and abundant. In the EU
Project ELYGRID, novel membranes based on inorganicorganic composites fulfilling all these aspects aredeveloped.

Processing
An industrially well-known tape casting technique isapplied for the manufacturing process. The surface ofpolymeric fibrous matrix is tape casted with slurries,
based on a mixture of inorganic filler and organic binder
in combination with a solvent. Subsequently, a phase
inversion process in a non-solvent bath follows thecasting process leading to creation a solid homogenous
layer on the top. The ratio of filler, binder and solvent isvaried to optimize the membrane performance withrespect to the final requirements.

Michal Gorbar

Electrochemical characterization at ambient conditions is
performed on a lab-scale electrolyser. Main focus lies on
the determination of the purity of produced hydrogen andoxygen and cell over-potential as an influence of themembranes state-of-the-art.

Born 14. 11. 1982 in Levoca, Slovakia. 2001 – 2007, study of chemistry at the Comenius University
in Bratislava. 2006 - 2007 Master Thesis "TiO2 surface modified ceramic foams for catalytic
applications" at Empa, Dept. of High Performance Ceramics. In 2007 graduated as Master of
Science in inorganic chemistry. 2007 - 2008 employee of Empa, at the Dept. of Internal Combustion
Engines and High Performance Ceramics in Dübendorf, Switzerland. Research focused on
production and development of ceramic foams as a support for catalytic materials. 2008 - 2012, PhD
student at University of Fribourg and in the Laboratory "Hydrogen & Energy" at Empa, Dübendorf.
Involved in the CTI project (NMAE2), BFE & SwissElectric projects and EU project ELYGRID until
present.

Corresponding author: Michal Gorbar, Michal.gorbar@empa.ch, Tel. (+41) (58) 765 4301

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HYDROGEN INTERACTION WITH GRAPHENE PROBED BY MUONSMauro Riccò1,*, Daniele Pontiroli1, Marcello Mazzani1, Matteo Aramini1, Mattia Gaboardi1,
Georgia Vlachopoulou1,Pietro Bonfà1, Oleg V. Yazyev2 and Chiara Cavallari3
1

Dipartimento di Fisica e Scienze della Terra, Università di Parma, Via G.Usberti 7/a, 43100 Parma, Italy.

2

Institute of Theoretical Physics, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland

3

Institut Laue Langevin, BP 156 38042 Grenoble, France

ABSTRACT: Here, we present the first µSR investigation of graphene, focused on chemically-produced, gram-scale
samples, appropriate to the large muon penetration depth. We have observed an evident muon spin precession, usually
the fingerprint of magnetic order, but here demonstrated to originate from muon-hydrogen nuclear dipolar interactions.
This is attributed to the formation CHMu (analogous to CH2) groups, stable up to 1250 K where the signal still persists.
The relatively large signal amplitude demonstrates an extraordinary hydrogen capture cross-section of CH units.

Introduction
Muons are spin ½ particles which could be implanted
in a fully spin polarized state into matter. The study of thetime evolution of the muon spin polarization P(t) is a
powerful tool for understanding the magnetic andelectronic properties of materials.
The low concentration of free electrons incarbonaceous materials inefficiently screen the coulomb
muon field thus inducing the capture of an electron by the
implanted muon. The bound state thus formed, calledmuonium (Mu), is totally equivalent to an hydrogen atom
(it is indeed one of the H isotopes).
Zero field μSR in graphite shows a slow muon spin
depolarization, due to the muon interaction with theconduction electrons (Korringa). The muon in this case iscovalently bound to the graphite plane. In nanostructured (ball-milled) graphite a more pronounced
lorentzian depolarization appears, induced by the
localized electron spin states at the edges. However,when graphite is exfoliated in graphene single layers aclear muon spin precession appears [1].

Results and Discussion
The coherent muon spin precession is usually thefingerprint of long range magnetic order. However in ourcase the precession has a different origin. The treatmentof graphene with H2 at 800C induces an increase of theprecession amplitude while if the same treatment isperformed with deuterium, the precession signal
disappears. This proves that the dipolar interaction
between the muon and a nearby hydrogen atom is theorigin of the observed precession [2]. The μ-H distance,

fitted from the observed spin evolution, is d-H  1.75 Åwhich matches the inter-proton distance in a CH2 group.
The detailed analysis of the dipolar precession
frequencies in samples with different defects
concentrations and different hydrogen content, combinedwith first-principle calculations, allowed to localize the
CHMu units, either in plane or at the edges.
The persistence of the observed precession up to 1250 K
witnesses an exceptional temperature stability of thismoiety. The amplitude of the precession signal indicatesthat up to 40% of the implanted muons end up in thisenvironment. The concentration of the involved defects
can be estimated on the basis of their expectedparamagnetism[2] and turns out to be a few molar %when measured by SQUID. Therefore these results
indicate an exceptionally high Mu (or H) capture crosssection by the CH defects.

Implications
The high efficiency in H (Mu) trapping by monohydrogenated carbons in graphene implies the possibility
that hydrogen atoms could diffuse on the graphene
layers. Different diffusion models will be presented andsupported by recent H-NMR and inelastic neutron
scattering measurements.

References[1] M. Riccò, D. Pontiroli, M. Mazzani, M. Choucair, J. A.
Stride, O. V. Yazyev, Nano Letters 11 (2011) 4919.
[2] J. H. Brewer et al., Phys. Rev. B 33 (1986) 781

Prof. Mauro Riccò is the coordinator of the Carbon Nanostructure Laboratory of Parma
University (www.fis.unipr.it/nanocarbon) since 1990, when it was established as one of thepioneers groups on the research on fullerenes and fullerene based materials. During the last
few years a still growing activity was devoted to graphene and to the application of carbon
nanostructures as hydrogen storage materials. He was the coordinator of the European
NEST project “Ferrocarbon” on carbon based magnetism.
Mauro Riccò
Corresponding author: Mauro Riccò, Mauro.Ricco@fis.unipr.it, Tel.+390521905217

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METAL-DERIVATIVES OF CHEMICALLYSYNTHESIS AND CHARACTERIZATIONPRODUCED

GRAPHENE;

Georgia Vlachopoulou,a,* Matteo Aramini,a Mattia Gaboardi,a Marcello Mazzani,a Daniele
Pontiroli,a Samuele Sanna,b Mauro Riccòa
aDepartment of Physics and Earth Sciences, University of Parma, Via G. Usberti 7/A, 43100, Parma, Italyb

Department of Physics “A. Volta”, University of Pavia, 27100 Pavia, Italy

Abstract: One possible way to store hydrogen can be realized by the adsorption of molecules on the surface of lowweight material. Graphene, with its excellent physical, chemical, and mechanical properties, displays promising features
for future attractive applications in the field of energy-storage but the binding energy of the hydrogen molecule is by far
too low for practical applications. The interaction can be however substantially increased if mediated by metallic atoms.
Here we present our success in decorating chemical synthesized graphene and ammonia-treated graphene with alkali
and transition metals, in particular Li, Ni and Ti, and their fully characterization.

Introduction
Chemically produced graphene compounds appear
particularly suitable for developing efficient gas storage2
systems, in virtue of its high porosity (up to 2630 m /g
specific surface), lightweight and robustness [1].
Unfortunately, hydrogen molecule interaction with the2bare sp carbon plane is too weak to be useful at ambientconditions (binding energy of 5 kJ/mol).
However, recent theoretical works indicated that it ispossible to bring this value in the range 20-40 kJ/mol,which represents the ideal binding energy for a reversible
storage system, by “decorating” graphene layers withmetal ions, in particular alkali, alkali-earth and transition
metal ions [2].

Results
Synthesis
Grams scale graphene was produced via thermal
exfoliation of graphite oxide (Staudenmeier/Brodie
method) in dynamical vacuum (figure 1).

In the case of ammonia-treated graphene, graphite oxide
was further heating in ammonia gas at 1023 K for 30 min.
Decoration with Li was obtained either by letting
graphene react with the metal in solution of NH3(l),CH3NH2, and CH3CH2NH2, or by impregnating graphenewith LiN3 and then by thermally decomposing the azide.
Decoration with transition metals was reached either
through metathesis reaction between Li-graphene andmetal chlorides (NiCl2, TiCl2), or by exploiting the thermal
decomposition of metallo-carbonyl clusters.
Characterization
The obtained metal decorated graphenes were fully
characterized with X-ray diffraction, Nuclear Magnetic
Resonance,
SQUID
Magnetometry,
NeutronSpectroscopy and Muon Spin Resonance.

References[1] Schlapbach, L.; Züttel, A. Nature 2001, 414, 353.
[2] Lee, H.; Ihm, J.; Cohen, M.; LLuie, S. Nano Lett.
2010, 10, 793.
Acknowledge
G. Vlachopoulou and M. Riccò acknowledge the SNFHycarbo project for the financial support.

Figure 1: Production of chemical “bulk” graphene.
thGeorgia
Vlachopoulou

Doct. Georgia Vlachopoulou was born in Athens (Greece) on February 17 1984. She obtained theChemistry Degree on 2006 from the University of Patras (Greece). She conducted her PhD in
Inorganic Chemistry. After receiving her PhD in 2009 she joined the group of Prof. A. Escuer at the
University of Barcellona (Spain), working on coordination chemistry of transition metals and theirmagnetic properties. After her experience in Spain, Doct. Vlachopoulou joined the group of Prof. S.
Enzo and Dr. G. Mulas at the University of Sassari (Italy) a research based on synthesis andcharacterization of complex metal hydride materials for hydrogen storage. She is currently amember of the group of Prof. M. Riccò at University of Parma (Italy) (SNF-HyCarbo Project). Her
research interest is focused on carbon nanostructures for the absorption of Hydrogen.

Corresponding author: Georgia Vlachopoulou, Georgia.vlachopoulou@fis.unipr.it

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HYDROGEN ABSORPTION IN METAL INTERCALATED FULLERENES
Philippe Mauron,1 Andreas Bliersbach,1 Arndt Remhof,1 Andreas Borgschulte,1 Andreas
Züttel,1 Denis Sheptyakov,2 Mattia Gaboardi,3 Fabio Giglio,3 Mauro Riccò,3
1
Empa. Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy, CH-8600 Dübendorf,
Switzerland
2

Paul Scherrer Institute, CH-5232 Villigen PSI, Switzerland

3

Dipartimento di Fisica, Università di Parma, Via G. Usberti 7/a, 43100 Parma, Italy

The hydrogen absorption of different metal (Na, Li, Ca, Mg) intercalated fullerenes (MxC60) was investigatedvolumetrically with a pcT system. Hydrogenation was done at pressures up to 200 bar and at temperatures up to 450°C.
Up to 4.5 mass% hydrogen can e.g. be absorbed in Li12C60. The samples were investigated by XRD, Raman- and IRspectroscopy and neutron powder diffraction.

Experimental
The MxC60 samples were synthesised by decomposing a
mixture of the metal azide and C60 pressed into a pellet at
temperatures between 380 and 450 °C or by reacting C60
with the metal dissolved in liquid ammonia andsubsequent distillation and annealing at 300 °C.
Hydrogenation/deuteration was performed at pressures
up to 200 bar at temperatures up to 450°C for several
hours. Dehydrogenation was done by applying atemperature ramp up to 400 °C at constant pressure of 1
bar hydrogen.

Results
Among the investigated metal fullerides the highesthydrogen absorption was reached in Li12C60 (4.5 mass%
H2). In Fig. 1 the deuterium absorption of Li12C60 up to atemperature of 225 °C at a pressure of 190 bar is shown.

5
200

4
3

150

2

100

1

Temperature [°C]

It has been shown that in Na10C60 up to 3.5 mass% ofhydrogen can be reversibly absorbed at a hydrogenpressure of 200 bar and a temperature of 200 °C [1].
During hydrogenation Na deintercalates and forms NaH
which decomposes during dehydrogenation and the Na
atoms reintercalate in the Na10-xC60. Infrared spectroscopy has shown the C-H stretching modes indicating thatthe hydrogen is covalently bonded to the C60.

XRD and neutron powder diffraction has shown thatduring the hydrogenation the metal hydride was formed
which decomposed again during dehydrogenation. The
C-H stretching modes also indicate the covalently
bonded hydrogen on the C60 forming C60H36-x.
Deuterium absorbed [mass% H2]

Introduction

50

0
0

10

20

30
40
Time [h]5060Fig. 1: Deuterium absorption in Li12C60 at a pressure of
190 bar up to 225°C (heating rate: 0.5 °C/min.)

References[1] Ph. Mauron, A. Remhof, A. Bliersbach, A.
Borgschulte, A. Züttel, D. Sheptyakov, M. Gaboardi,
M. Choucair, D. Pontiroli, M. Aramini, A. Goerreri, M.
Riccò, Int. J. Hydrogen Energ. 37 (2012) 14307.

1973 born 6. October in Fribourg, Switzerland.
1999 Diploma in experimental physics (solid state physics), University of Fribourg,
Switzerland.
2003 PhD at University of Fribourg, Switzerland.
2005 Postdoc at Vrije Universiteit Amsterdam, The Netherlands.
2007 Project leader at Empa. Swiss Federal Laboratories for Materials Science andTechnology, Dübendorf, Switzerland
Philippe Mauron
Corresponding author: philippe.mauron@empa.ch, Tel. +41 58 765 4099

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HYDROGENATION OF CO2 BY SUBSURFACE HYDROGEN
Jeffrey Gehrig, Andreas Borgschulte, Cedric Hugelshofer, Andreas Züttel
Empa Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
Starting from findings by Sabatier in 1902, it is known that CO2 can be reduced by H2 over a catalyst producing
eventually methane and water. If the hydrogen is produced from renewable energy sources by electrolysis and thecarbon dioxide is extracted from the atmosphere, the methane from such a process represents a CO2 neutral synthetic
fuel.

Sorption enhanced reaction
The reduction of CO2 by hydrogen eventually forminghydrocarbons depends on the interaction of CO2 and H2
with a catalyst surface, i.e. ad- and desorption ofhydrogen, CO2 and products [1]. A significant increase of
the process efficiency requires a novel concept tocatalyze the complex chemical reactions. In this talk, wewill utilize the link between surface and bulk to control
the surface reaction. This will be done either bycontrolling the educts’ side, or by controlling the products’side, both by using bulk sorption reactions (Sorption
enhanced reaction) [2].

The golden rule of catalysis (Sabatier principle) is
usually depicted by the volcano curve: an optimal catalyst
has intermediate binding energy to the adsorbent,
because an enhanced bonding strength increases theadsorption, but decreases the desorption reaction. Due tothe high mobility of hydrogen, it is most simple to control
the driving force of the Sabatier reaction by enhancing
the amount of chemisorbed hydrogen on the catalyst’s
surface. On this poster we will discuss the surface
reactions of CO2 on metal hydrides as measured by Xray photoelectron spectroscopy.

XPS
We investigated the reaction mechanisms by combining
temperature-programmed desorption (TPD) and X-ray
photoelectron spectroscopy (XPS). To feed the surface
with atomic hydrogen without being constrained by preadsorbed carbon species, we perform such experiments
on Ni-surfaces attached to NaAlH4 and Ni-membranes.
Hydrogen can diffuse through the membranes thus
allowing a higher H-coverage than possible by gas
adsorption in UHV [3].

References[1] J. K. Nørskov, et al., Nature Chemistry 1, 37 (2009).
Fig.1: Sketch of the CO2 methanation via subsurface hydrogenfrom a metal hydride.

[2] B. T. Carvill, et al., AIChE J. 1996, 42, 2765.
[3] E. Vesselli, et al., J. Phys. Chem. Lett. 2010, 1, 402–
406.

Jeffrey Gehrig, born 1985 in Lucerne, Switzerland. He received his Bachelor in Physics ETH in 2010
and is doing his MSc at ETH, Zürich, Switzerland. He is conducting his master thesis in the
Hydrogen & Energy Laboratory at Empa, Dübendorf, Switzerland.

J. Gehrig
Corresponding author: Jeffrey Gehrig, Jeffrey.Gehrig@empa.ch, Tel. +41 58 765 61 68

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HYDROGEN ON GRAPHENE INVESTIGATED BY INELASTIC
NEUTRON SCATTERING
C. Cavallari1,2, S. Rols1, D. Pontiroli2, M. Aramini2, M. Gaboardi2, G. Vlachopoulou2, M. Mazzani2 and M. Riccò2
1 - Institut Laue Langevin, BP 156 38042 Grenoble, France
2 - Dipartimento di Fisica e Scienze della Terra, Università di Parma, 43124 Parma, Italy
Abstract: We report the first investigations, by inelastic neutron scattering, of defective graphene, chemically produced and differently treated in hydrogen atmosphere. The experimental vibrational Density ofStates (vDOS) of hydrogenated graphene evidences the presence of two different hydrogen populations,which can be attributed, respectively to hydrogen atoms saturating the edges and chemisorbed onto thegraphene plane.

Hydrogen storage and graphene
Graphene appears as a very promising basematerial for hydrogen storage applications[1]. Massive production of graphene, exploiting an efficient method for chemically exfoliating graphite planes through oxidationreduction processes [2], now opens practicalenergetic applications and, at the same time,
makes feasible experimental investigation
with techniques which are conventionallyreserved to bulk systems, such as neutron
scattering. In fact, thanks to the large hydrogen scattering cross section, neutron scattering is a perfect tool for studying hydrogenstorage materials [3].

Inelastic neutron scattering results
Chemically produced defective graphenesamples, differently treated in hydrogen atmosphere, were investigated by Inelastic
Neutron Scattering (INS) at the Institut Laue
Langevin (ILL), in Grenoble (France). Boththe hot neutron IN1-BeF spectrometer andthe Thermal Neutron TOF IN4 spectrometerdata were combined in order to investigate
the Vibrational Density of States (vDOS) in avery wide energy range (0-250meV). The
experimental DOS of as-prepared grapheneshows localized vibrational peaks, ascribedto C-H bending modes. This vibrational signature is not only noticeably enhanced when
compounds are treated in hydrogen flux at
1023K but additional features appear in thevibrational spectrum. This can be explainedby admitting the existence of two differenthydrogen populations: the first one located at
the edges and the second one, promoted byhydrogenation treatment, onto the graphene
plane. This hypothesis is supported by abinitio DFT calculations, performed using the
VASP code.

References[1] H. Lee, J. Ihm, M.L. Cohen, Belli, S., G. Louie,
Nano Lett., 10 (3), 793 (2010).
[2] S. Park and R. S. Ruoff, Nat. Nanotechnol., 4,
217 (2009).
[3] A. J. Ramirez-Cuesta, M. O. Jones, W. I. F.
David, Materials Today, 12, 11 (2009).

Chiara Cavallari graduated in Material Science at University of Parma (Italy) in 2011.
Starting in 2012, she is currently working in the TOF-HR group at the Institut Laue Langevin, in Grenoble (France), as PhD student. Her main research interests are carbon
nanomaterials for energy storage, neutron scattering and ab-initio calculations.
Chiara Cavallari
Corresponding author: Chiara Cavallari, email: Cavallari@ill.fr Tel. (+33) 476 207613

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GASOLINE PRODUCTION WITH NON-STOICHIOMETRICRECENT PROGRESS AND FUTURE WORKCERIA –

Alexander Bonk,1,2 Michal Gorbar,1 Aldo Steinfeld,3,4 Jeroen A. van Bokhoven,4 Andreas
Züttel,1 Ulrich F. Vogt,1,2
1

Department for Hydrogen and Energy, EMPA, CH-8600 Duebendorf

2

Department of Crystallography, University of Freiburg, D-79106 Freiburg i. Brsg.

3

Department of Mechanical and Process Engineering, ETH Zurich, CH-8092 Zurich

4

Solar Technology Laboratory, Paul Scherrer Institute, CH-5232 Villingen

Thermocatalytic production processes for fuels have been predicted and presented in the last years.[1,2] These
processes involve the synthesis of syngas, a H2/CO-mixture, in the first place and subsequently a catalytic conversion ofsyngas into any kind of fuel. Cerium dioxide as metal oxide catalyst has been tested for the production of H2/COmixtures. Reticulate porous ceramic (RPC) foams were produced by a replica method referred to as Schwartzwalder [3]method and tested in solar cavity-receiver directly exposed to concentrated solar radiation, at ETH Zürich.[1]Introduction
Amongst metal oxides, ceria has gained much attention
due to its high O2--conductivity and rapid oxygen release3+
starting from 900°C. Oxygen vacancies and Ce arecatalytically active sites for splitting H2O and CO2 to H2and CO, respectively. The efficiency of the system ishowever, limited by conduction and radiative heattransfer.[4] The presented work summarizes recent
developments and future work with a particular focus on
the RPC development for an improved performance.

Results & Discussion
RPC ceria foams were tested in a solar reactor atdifferent power inputs. The oxygen evolution from ceria
foams was measured. Upon removal of oxygen gas, CO2
was pumped into the reactor and reduced to CO. It was
found that the oxygen non-stoichiometry was fully
exploited for CO production.[4]In comparison to high surface ceria-foams, RPC felts
showed a much higher performance in terms of the total
amount of oxygen released and CO2 reduced.[4] This
was attributed firstly, to a higher mass loading of RPC in
the reactor compared to the felt and secondly, to deeper
penetration and thus more homogeneous absorption ofconcentrated solar radiation. Moreover, prepared ceria
RPCs exhibited great mechanical and catalytic stability
during long term measurements.

Alexander Bonk

Figure 1 Schematic of a two-step solar thermochemical cycle for H2O/CO splitting
based on metal oxide redox reactions

Future Work
Future investigations will focus on improvement of heattransfer and oxygen conductivity of the RPC by doping
and surface modification. Faster kinetics and optimized
optical thickness of the foam will greatly influence thesolar-to-fuel efficiency.

References[1] W.C. Chueh et al., Science, 2010, 330, 1797-1801[2] A. Steinfeld et al. Advances in Science andTechnology, 2010, 74, 303-312[3] Schwartzwalder et al. U.S. Pat. 3090094, 1963
[4] P. Furler et al., Energy Fuels, 2012, 26, 7051-7059

Born on 22nd of May 1987 in Erfurt, Germany. I studied Bachelor and Master of Science in Chemical
Engineering at Fachhochschule Münster, University of Applied Sciences, Germany, from 2007-2012.
Performed my bachelor thesis (2010) at the Monash University, Melbourne, Australia, on “Reactivityof dimeric Mg(I) complexes towards chalcogenes pnictogenes” and my master thesis (2012) at
EMPA, Dübendorf, Switzerland, on “Development of advanced membranes for alkaline waterelectrolysis”. Since Nov. 2012 PhD student at the University of Freiburg i. Brsg. and in thelaboratories of “Hydrogen & Energy” at Empa, Dübendorf. Doctoral research plan involves thedevelopment and characterization of ceria structures for the solar thermochemical production offuels from H2O and CO2.

Corresponding author: Alexander Bonk, alexander.bonk@empa.ch, +41-(0)-58 765 6519

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HYDROGEN ADSORPTION PROPERTIES OF METAL DECORATED
GRAPHENE
Andreas Bliersbach1*, Philippe Mauron1,
Mattia Gaboardi2 and Mauro Riccò2.

Arndt

Remhof1

andAndreasZüttel1,

1

Empa. Swiss Federal Laboratories for Materials Science and Technology, Division ‘‘Hydrogen and Energy’’,Überlandstrasse 129, 8600 Dübendorf, Switzerland

2

Dipartimento di Fisica, Università di Parma, Via G. Usberti 7/a, 43124 Parma, Italy

Abstract: Light weight carbon structures such as graphene are known to physically adsorb large quantities of hydrogen.
Hydrogen is bound to the carbon atoms via weak Van der Waals interaction, and it desorbs at temperatures above theboiling point of liquid nitrogen. Motivated by theoretical calculations we synthesize metal decorated graphenes andinvestigate them for their predicted high enthalpy of hydrogen adsorption.

Introduction

Experimental

Theoretical calculations predict that by decorating
graphene with metal atoms, molecular hydrogen can bindto the metal centers by means of Kubas interaction [1, 2,3].In this case a noticeably higher heat of adsorption forthe bound hydrogen and hence a higher desorption
temperature as compared to physisorbed hydrogen is
expected [4]. The Kubas interaction was discovered incomplex compounds with large ligands. Due to theirexceeding weight they are unattractive as hydrogenstorage materials. Molecular hydrogen bound to metal
decorated graphene is an ideal model system to study
the Kubas interaction in detail and promote theunderstanding of the underlying fundamental principles.
Furthermore it is a promising candidate for a cheap,
lightweight, moderate temperature hydrogen storage
material.

The resulting metal decorated graphene samples arethoroughly characterized by means of XRD, XPS, Raman
and IR spectroscopy and BET. Therewith we can monitor
the synthesizing process, get information on the chemicalcomposition (XPS, IR), the specific surface area (BET)and the structure (XRD, Raman).

Synthesis
Metal decorated graphene is synthesized by a two-step
approach. Initially graphite oxide, synthesized by the
Staudenmaier method [5], is thermally exfoliated in a
dynamic vacuum. During further thermal treatment undervacuum, oxygen and remaining traces of solvents aredesorbed, resulting in clean graphene sheets.
In the second step metal atoms are deposited throughthermal decomposition of metastable precursors
containing the metal atoms, such as Li-azide or Niacetylacetonate. The metastable precursors are
impregnated by means of THF.
2008-20092010-20112011
From 2012

The heat of adsorption and the gravimetric hydrogendensities, indicative of the strength and type of hydrogenbinding, are deduced from pressure composition
isotherms starting at cryogenic temperatures
The predicted Kubas interaction is not the only interaction
within the system. Hydrogen may form covalent bonds tothe metal or the carbon or it may be adsorbed due toelectrostatic interactions.
The experiments are intended to identify the origin of theattractive interaction and to clarify the role of the Kubas
interaction.

References[1] T. Yildirim et al., Phys. Rev. B, 72, 153403, 2005.
[2] H. Lee et al., Nano Letters, 10(3):793–798, 2010.
[3] Y. Liu et al., J. Phys.: Condens. Matter, 2(44):445301,
2010.
[4] G. J. Kubas et al., JACS, 106(2):451–452, 1984.
[5] L. Staudenmaier, Berichte der deutschen chemischen
Gesellschaft, 31, 1481-1487, 1898.

ERASMUS exchange student at Uppsala University.
Diploma in physics at the Rheinische Friedrich-Wilhelms University Bonn, Germany.
Master of Science at Uppsala University, Sweden in the group of Björgvin Hjörvarsson.
PhD student at EMPA, Switzerland in the group of Andreas Züttel.

Corresponding author: Bliersbach Andreas, andreas.bliersbach@empa.ch, 0041 / 58 / 765 48 62.

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HYDROGEN DYNAMICS IN NANOCONFINED LITHIUMBOROHYDRIDE
A. Remhof1, A. Züttel1, J. P. Embs2, Z. Łodziana3, A. J. Ramirez Cuesta4, P. Ngene5, P. de
Jongh51

Empa, Swiss Federal Institute for Materials Science and Technology, Hydrogen and Energy, Dübendorf, Switzerland
Laboratory for Neutron Scattering, ETHZ & PSI, Villigen, Switzerland
3
The Henryk Niewodniczański Institute of Nuclear Physics, Polish Academy of Sciences Kraków, Poland
4
ISIS Facility, Rutherford Appleton Laboratory, Didcot, United Kingdom
5Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Utrecht, The
Netherlands
2

Lithiumborohydride, LiBH4, attracts much attention as a promising material for hydrogen storage or as electrolyte inlithium-ion batteries. It contains 18.5 wt% hydrogen, and has a structural phase transition (orthorhombic→ hexagonal) at
383 K which is associated with a large increase in hydrogen and lithium solid-state mobility. Confining metal hydrides in a
nanoporous matrix is an encouraging strategy to enhance the hydrogen desorption kinetics and reversibility, andinfluence phase equilibria.

Introduction+

LiBH4 is an ionic crystal, consisting of (Li) cations and(BH4) anions [1]. LiBH4 melts at 550 K. It undergoes asolid-solid structural phase transition at 381 K; from an
orthorhombic low-temperature structure (Pnma) to ahexagonal high-temperature structure (P63mc). The
high-temperature phase is associated with dynamical
disorder, high Li+ translational mobility, rotational jumpsof the (BH4) anions in the terahertz range, and strong
lattice anharmonicities [2,3]. Within the low-temperaturephase the sharply defined structural phase transition at
381 K is preceded by a continuous increase in hydrogenand lithium mobility, which can be interpreted as asecond order mobility phase transition interrupted by afirst order structural phase transition [4, 5]
For LiBH4, nanoconfinement in a carbon scaffold leads toa strong improvement of the dehydrogenation andrehydrogenation kinetics as compared to the bulk [6].
We investigated the hydrogen dynamics in nanoconfined
LiBH4, prepared by melt infiltration into porous highsurface-area-graphite by means of quasielastic (QENS)
and inelastic (INS) neutron scattering.

Results
The confinement leads to a higher anion mobility and areduced activation energy of 8 kJ/mol at room
temperature as compared to 17.3 kJ/mol in bulk LiBH4. In
the nanoconfined phase the mobility resembles that of
the high-temperature bulk phase, no distinct phasetransition was detected. However, a substantial fractionof the hydrogen is immobile, leading to effectively
reduced anion dynamics as compared to the bulk hightemperature phase. We tentatively attribute these effects
to lattice distortions due to the finite pore size and tothermally induced stress leading to a loss in long rangeorder and an increase in dynamical disorder [7].
References:[1] Buchter, F.; Łodziana, Z.; Remhof, A.; Mauron, Ph.;Friedrichs, O.; Borgschulte, A.; Züttel, A.; Filinchuk,Y.; Palatinus, L. Phys. Rev. B 2011, 83, 064107.
[2] Buchter, F.; Łodziana, L.; Mauron, Ph.; Remhof, A.;
Friedrichs, O.; Borgschulte, A.; Züttel, A.;
Sheptyakov, D.; Strässle, T.; Ramirez-Cuesta, A. J.
Phys. Rev. B 2008, 78 094302.
[3] Remhof, A.; Łodziana, Z.; Martelli, P.; O. Friedrichs,
O.; Züttel, A.; Skripov, A. V.; Embs, J. P.; Strässle, T.
Phys. Rev. B 2010, 81, 214304.
[4] Hagemann, H.; Filinchuk, Y.; Chernyshov, D.; vanBeek, W. Phase Trans. 2009, 82, 344.
[5] Borgschulte, A.; Jain, A.; Ramirez-Cuesta, A. J.;
Martelli, P.; Remhof, A.; Friedrichs, O.; Gremaud R.;
Züttel, A. Faraday Discuss. 2011, 151, 213.
[6] Gross, A. F.; Vajo, J. J.; van Atta S. L.; Olson, G. L. J.
Phys. Chem. C 2008, 112, 5651.
[7] Remhof, A.; et al., submitted.

1994
University Diploma with distinction of the University of Kent at Canterbury, UK.
1995-1996 Master thesis at the Institute Max von Laue – Paul Langevin (ILL) in Grenoble, France.
1996-2000 PhD student at institute of solid state physics at the Ruhr-Universität Bochum, Germany.
1999
Guest scientist at the Universidade São Francisco in Itatiba, São Paulo, Brazil.
2000-2002 PostDoc at the Vrije Universiteit in Amsterdam, The Netherlands.
2002-2007 Scientist at the institute of solid state physics at the Ruhr-Universität Bochum.
From 2007 Group leader at Empa in the Laboratory “Hydrogen and Energy.”
2010
Guest scientist at the Tohoku University in Sendai, Japan
Arndt Remhof
Corresponding author: Arndt Remhof, arndt.remhof@empa.ch +41587654369

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SCIENCE OF
HYDROGEN &ENERGY AWARD
The “Science of Hydrogen & Energy” award is a prize, just similar to the Nobel
prize, for an extraordinary contribution to the sciences of hydrogen. The aim is
to award a prize to a distinct scientist for his scientific work of a life time.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2007

Prof. Dr. Ronald Griessen

Ronald Pierre Griessen, was born March 7, 1945 in Switzerland.
He received 1964 his Baccalauréat, from Gymnase français in
Bienne, Switzerland. From 1964 – 1969 he studied Physics andMathematics at the Swiss Federal Institute of Technology (ETH)in Zürich and finished with a Diploma-thesis on: "Magnetostrictionof type-II superconductors". From 1969 – 1973 he was PhD
student in the Low Temperature Physics Group of Prof.dr J.L.
Olsen at the ETH. PhD-thesis on: "Oscillatory Magnetostriction
and the stress dependence of the Fermi Surface of Al, In, Zn andMg". From 1974 – 1976 he was Research Associate at the
McLennan Physical Laboratory of the University of Toronto,
Canada where he worked on the electronic structure of spindensity-wave systems and quantum oscillations.In 1976 he wasvisiting scientist at the ETH, Zürich and from 1976 – 1980 seniorlecturer at the Vrije Universiteit in Amsterdam. Since 1980 he is
Full Professor in charge of the Department of Condensed Matter
Physics.

Ronald Griessen has investigated the thermodynamics of palladium films and theisotope effect on the electronic structure of hydrides. Furthermore, the effect ofanharmonicity and Debye-Waller factor on superconductivity of PdHx and PdDx havebeen studied by Ronald before he developed a semi-empirical model for the heat ofsolution of hydrogen in transition metals. He also studied the trapping energy forhydrogen on lattice defects as well as the heat of solution of disordered transition
metals. The volume expansion upon hydrogen absorption, the Gorsky-effect, thediffusion, electromigration and the hydrogen diffusion in magnetig fields are just a few
other subjects treated and described by Ronald Griessen. Then Ronald decided to test
the world of high pressure hydrogen and described the properties of hydrides formed atvery high pressure as well as the properties of hydrogen gas in a wide temperature andpressure range. During the intense investigation of superconductors and metal
hydrides under high hydrogen pressure in a diamond anvil cell, Ronald has discovered
the switchable optical properties of yttrium and lanthanum hydride films. This has thenstimulated Ronald to investigate thin films with optical methods and to develop new
methods for the combinatorial search of new hydride phases as well as for thedetermination of the thermodynamic parameters e.g. stability and kinetics of thehydrides. Furthermore, new applications for hydrides as hydrogen detectors and opticalfilters have been developed in his group.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2008
Louis Schlapbach, born March 4, 1944 in Belp Switzerland. He
graduated from the Swiss Federal Institute of Technology Zurich(ETHZ) in Experimental Physics and got his PhD in Solid State
Physics – Magnetism also at ETHZ. As a postdoc at a CNRS
laboratory in Paris, he studied hydrogen storage in intermetallic
compounds. Back at ETHZ, he developed the surface science
aspects of the hydrogen interaction with metals and alloys. From1988 till 2001, Louis Schlapbach was Full Professor for Physics
at the University of Fribourg. As such he built up a research teamof 20-25 people working on the topic „New Materials and theirSurfaces“ resulting in about 40 PhD, 200 scientific papers andsome patents. A strong collaboration with industry wasestablished. In spring 2001, he has been appointed CEO of
Empa, the materials science and technology institution of theProf. Dr. Louis Schlapbach ETH domain with 750 coworkers in Dübendorf, St. Gallen and
Thun.

Louis Schlapbach started his scientific work in 1970, 38 years ago, with theinvestigation of the Hall effect, electrical transport and magnetic susceptibility of liquid
rear earth elements like Cerium. 30 years ago in 1970 he was coauthor with Busch andWaldirich on a paper about the hydrides of La-Ni compounds. LaNi5 was subsequently
investigated in view of the structure, surface segregations, hydrogen occupation ofinterstitial sites and as electrode material.LaNi5 is still the base material for most of theelectrochemical applications of metal hydrides today. The work on LaNi5 wascomplemented by the research on FeTi. Louis Schlapbach realized the importance ofthe surface composition for the hydrogen sorption process and he was able to describe
the role of the surface-active species. Furthermore, he investigated the changes of thesurface composition of LaNi5 and FeTi in oxidizing atmospheres and he found theformation of metallic clusters as superparamagnetic particles acting as the active sites
in hydrogen dissociation and recombination. The investigation of the surface of metal
hydrides was further intensified by means of X-ray photoelectron spectroscopy. Louis
Schlapbach was the first scientist correctly describing the activation process of a metal
hydride and, furthermore, to model the chemical composition and states of theelements in a surface profile. He also succeeded to analyze the electronic structure ofraere earth elements and their hydrides by means of photoemission spectroscopy. In
1990 Louis Schlapbach edited the two books "Hydrogen in Intermetallic Compounds I& II" of the Springer Sereies. The books became a very important reference for all the
researchers active in the field of hydrides.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Dr. Gary Sandrock

Gary Sandrock received his master from the Institute ofTechnology, Cleveland in 1965 and his Ph.D. from the Western
Reserve University, Cleveland in 1971. He worked from 19621969 as a research metallurgist in the NASA Lewis ResearchCenter, Cleveland, Ohio. From 1971-1983 he was Section
Manager of Energy Systems at Inco Research and Development
Center, Suffern, NY. From 1983-1991 he was Vice President andDirector of Technology at Ergenics, Inc., Ringwood, NJ. From
1992-1993 Gary Sandrock was visiting professor at the Kogakuin
University, Hachioji, Tokyo, Japan where he developed a newchemical surface treatment and investigated the activation
characteristics of chemical treated AB5 alloys. Gary then became
the president of SunaTech, Inc., Ringwood, NJ, where hedeveloped reversible hydrogen storage systems. At the sametime Gary Operating Agent, International Energy Agency
Hydrogen Implementing agreement Tasks 12 & 17 (Hydrogen
Storage Materials) and worked as a consultant for the US DOE
via Sandia National Laboratories, Livermore, CA.

In 1995 Gary Sandrock started to creat and mainten Hydride Databases of
IEA(HIA)/DOE/SNL (http://hydpark.ca.sandia.gov) and he is author of several bookchapters and review papers e.g. “A panoramic overview of hydrogen storage alloys
from a gas reaction point of view”. His recent research concentrates on the catalysis of
the hydrogen desorption from alanates and most recently Gary investigated thehydrogen desorption behavior of AlH3 and explaned the mechanism of the kinetic
stabilisation of aluminumhydrid. Furthermore, he published a paper entitled“Accelerated thermal decomposition of AlH3 for hydrogen-fueled vehicles” where heshows the possible ways to change the activation barrier for the hydrogen desorption ina controlled way.
Gary Sandrock not only made significant achevements in understanding metal hydrides
he also built the bridge from sciences to application. Furthermore, his scientific review
papers and the hydride database are inestimably value for the hydride society.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2009

Prof. Dr. Jens Norskov

Jens Norskov was born on September 21 in 1952. He received
his Master dgree in physics and chemistry from the University of
Aarhus, Denmark in 1976 and his PhD in theoretical physics in
1979. During his PhD he published papers about the electronic
structure of H and He in metal vacancies and the contraction of
diatomic molecules upon chemisorption. Jens Norskov was a
Post Doc at IBM in Yorktown Heights, New York in 1979 and wasaffiliated with Nordita, (Nordic Institute for Theoretical Physics) in
Copenhagen before he became a member of the scientific staff ofHaldor Topsøe A/S, Lyngby in 1981. He continued theinvestigation of gas molecules at the surface of metals anddeveloped a picture of adsorption and desorption of hydrogenemerging from self-consistent model calculations. In 1992 he wasappointed as a professor of theoretical physics in the departmentof physics at the Technical University of Denmark, Lyngby andbecame the director of the Center for Atomic-scale Materials
Physics (CAMP), Department of Physics, Technical University ofDenmark, Lyngby.

Recent research of the group of Jens Norskov covers several of the most relevant
topics: 1) The development of theoretical methods e.g. “Scaling Properties of
Adsorption Energies for Hydrogen-Containing Molecules on Transition-Metal Surfaces”;
2) Theoretical surface science e.g. “Role of strain and ligand effects in the modificationof the electronic and chemical properties of bimetallic surfaces”; 3) Nanostructures andmaterials properties e.g. Atomic-scale imaging of carbon nanofiber growth”; 4)
Heterogeneous catalysis e.g. “Ammonia synthesis from first principles calculations”; 5)
Biomolecules e.g. “Biomimetic hydrogen evolution”; 6) Electrochemistry and fuel cells
e.g. “The origin of the overpotential for oxygen reduction at a fuel cell cathode”; 7)Hydrogen storage e.g. “Metal ammine complexes for hydrogen storage”
Jens Norskov is not only a creative and brilliant scientist, he also belongs to the few
scientist able to successfully combine theoretical approches with experimental
observations for the understanding of the basic phenomena. It is always a great
pleasure to listen to Jens Norskovs talks, which are exciting eye opening stories
combined with some great new stimulating ideas.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rüdiger Bormann was born September, 14 1952 in Germany. He
received 1977 his diploma in physics (Metalphysics), from the
University Göttingen and 1979 his Dr. rer. nat. from the University
Göttingen. From 1981 to 1982 he was visiting scientist in theDept. of Applied Physics at Stanford University, U.S.A. From1982 to 1988 he was Assistant Professor (Hochschulassistent) at
the University Göttingen where he received the Habilitation
University Göttingen, venia legendi in 1988. From 1989 to 1997
he was Professor of Metalphysics (GKSS Research Centre,
Geesthacht and Hamburg University of Technology) and from1996 to 2009 he was director of the Institute for Materials
Research, GKSS Research Centre, Geesthacht and since 2009
he is Professor of Applied Materials Physics and President of theProf. Dr. Rüdiger Bormann University of Bayreuth. Rüdiger Bormann died on 13. January
2013 in an accident in Cologne, Germany.

Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses,
metastable crystalline and amorphous alloys as well as the thermodynamics andkinetics of the amorphous phase formation by mechanical alloying. This was the basis
for the investigation of Mg and Mg-Ni hydrides and the thermodynamics of nanoscale
magnesim hydride. The discovery catalytic effect of metal oxides on the hydrogen
sorption kinetics of magnesium was a great step forward in the development ofhydrogen storage materials. Furthermore, very important was also the interpretation of
the role of the grain boundaries for the diffusion of hydrogen in the passivating hydride
phase formation. Recently the discovery of the so called reactive hydride composites
by the combination of two hydrides has opened a new field of materials design forhydrogen storage. Therefore, we aword Prof. Rüdiger Bormann with the Science ofHydrogen & Energy prize 2010.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Ivor Rex Harris was born August 31, 1939 in United Kingdom. In
1960 he rewceived his B.Sc. in Physical Metallurgy from the
University of Birmingham), 1964 his Ph.D and became a ICI
Research Fellow. From 1966 he was lecturer in the Departmentof Physical Metallurgy and1988he became a full Professor ofMaterials Science. From 1989 to 2002 he was Head of School,
Metallurgy and Materials and from 2004 to 2005 acting director of
the Institute for Energy Research and Policy. Since 2008
he is Honorary Professor of Materials Science of the School ofMetallurgy and Materials at the University of Birmingham.

Prof. Dr. Ivor Rex Harris

For around 40 years, Rex Harris was leader of the Applied Alloy Chemistry Group(AACG) in Metallurgy and Materials. During this time he maintained a long-standing
research interest in the fields of rare earth alloys, permanent magnets and hydrogen
purification and storage materials. He developed a close synergy between these fields
with the development and application of the Hydrogen Decrepitation (HD) process tothe manufacture of NdFeB magnets. The HD process resulted in up to a 25% saving in
production cost and is now used world-wide in the fabrication of NdFeB sinteredmagnets. These materials are playing a vital role in the production of energy efficientelectric drives, actuators and generators. The latest development within the group is
the use of the HD process in the recycling of 2/17 and NdFeB magnets. His researchalso made a very significant contribution to the development and understanding of theHydrogenation, Disproportionation, Desorption and Recombination (HDDR) process
which enabled coercive powder and hence bonded magnets to be formed from bulk
NdFeB alloys. He has published over 500 scientific papers and edited and co-edited anumber of books. During these years he has successfully supervised around 120
postgraduate students, many of whom are still working in applied materials science andoccupy senior positions in industry, government and academia throughout the world.
Since stepping down as group leader and head of school he has focused his activities
on the application of NdFeB magnets and hydrogen storage materials to practicaldemonstrators such as the Ross Barlow hybrid canal boat. This zero- carbon emission
craft is serving to highlight the huge potential of magnets and hydrogen in the drive
towards a sustainable transport system and he has given a large number of public
lectures on this subject with the aim of raising public awareness of the dual threats ofclimate change and resource depletion. He continues to be very active in this campaign
which he considers to be of paramount importance. Therefore, we award Prof. Rex
Harris with the Science of Hydrogen & Energy prize 2010.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rainer Kirchheim was born May 24, 1943 in Halle/Saale,
Germany. He studied Physics at the University of Stuttgart from
1966-1971 and received the diploma for the work
“Electrochemical studies of oxygen solid solutions in high melting
metals” at the Max-Planck-Institut für Metallforschung/Universityof Stuttgart. He received his Ph.D. for the thesis entitled “Thermoand electrotransport of oxygen and nitrogen in Va metals “ fromthe
UniversityofStuttgart,
Max-Planck-Institut
fürMetallforschung in 1973. In 1988 he received the Habilitation“Measurements and modelling of hydrogen solubility anddiffusivity in disordered metal lattices“ from the University of
Stuttgart, Faculty of Chemistry Metallurgy.
Since 1993 he is Full Professor (Gustav Tamman Chair)Prof. Dr. Rainer Kirchheim University of Göttingen Göttingen Germany and Director GeorgAugust-Universitaet Goettingen, Institut für Materialphysik
Göttingen Germany .

Prof. Rainer Kirchheim has investigated 30 years ago oxygen in metals, especiallydiffusion, thermo-transport and thermo-power of oxygen in transition metals and alloys.
In 1980 he started to study diffusion of hydrogen in dillute alloys of copper and niobiumin palladium. He developed an electrochemical method for the measurement of thehydrogen diffusion in palladium and palladium alloys and performed fundamental
studies on the diffusion mechanism of interstitial species. The interaction of hydrogenwith dislocations in palladium and the interpretation with a model based on the FermiDirac distribution are of great importance for the understanding of the interstitial site
occupation of hydrogen in alloys and amorphous metals.
For the enormous contributions on the hydrogen dynamics and thermodynamics inmetals as well as the hydrogen interaction with dislocations, grain bounderies andinterfaces we award Prof. Rainer Kirchheim with the Science of Hydrogen & Energy
prize 2010.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2011
Koji Hashimoto was born October 23, 1935 in Japan. He received
the M. Sc. In Chemistry from the Faculty of Science of the Tohoku
University, Sendai, Japan. In 1966 he received the Doctor degreein sciences from the Tohoku University and in the same year hebecame an associate professor in the Institute for Materials
Research (IMR) of the Tohoku University. From 1967 to 1969 he
was a Post Doctorate Fellow in the Division of Applied Chemistryof the National Research Council in Canada.
From 1987 to 1999 he was a Professor in the Institute forMaterials Research (IMR) of the Tohoku University and from 1999
to 2006 he was Professor at the Tohoku Institute of Technology.
Prof. Dr. Koji Hashimoto

Prof. emeritus Koji Hashimoto has published over 520 papers in scientific journals in
addition to review articles and book chapters. He has worked on corrosion-resistantalloys, electrolysis, especially he pioneered the electrolysis of seawater. He tailored thecatalysts for carbon dioxide methanation, in particular, he has built a prototype plant for
global CO2 recycling in 1995 on the roof top of the Institute for Materials Research,
Tohoku University. The plant consists of power generation by photovoltaic cells,
hydrogen production by seawater electrolysis and methane formation by the reaction ofcarbon dioxide with hydrogen, carbon dioxide recovery at an energy consuming district,and transportation of carbon dioxide. The plant uses tailored key materials with highperformance and durability, that is, cathodes for hydrogen production, anodes for only
oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for
rapid and selective production of methane by the reaction of carbon dioxide withhydrogen. The performance of the plant has substantiated that global CO2 recycling
can supply abundant energy generated from solar energy on deserts in the form of
methane and can really prevent global warming induced by carbon dioxide emissions.
In 2003, he has built a pilot plant of global CO2 recycling at Tohoku Institute ofTechnology which is the minimum unit of industrial scale for seawater electrolysis andcarbon dioxide methanation.
He is in the Editorial Board of "Corrosion Science", a Member of NACE International,
the Electrochemical Society and the International Society of Electrochemistry. Memberof Japan Society of Corrosion Engineering, the Japan Institute of Metals, the Surface
Finishing Society of Japan, the Iron and Steel Institute of Japan, the Electrochemical
Society of Japan, the Society of Chemical Engineers, Japan, the Chemical Society ofJapan, and other scientific societies in Japan.
He received many awards among those also The Electrochemical Society Fellow
Award in 1997 in recognition of contribution to the advancement of science andtechnology, for leadership in electrochemical and solid state science and technology
and for active participation in the affairs of the Electrochemical Society, Inc.
We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogenand the use of hydrogen for the reduction of CO2 with the Science of Hydrogen &Energy prize 2011.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2012
Mogens Mogenson is research professor in the fuel cells andsolid state chemistry division, Risø National Laboratory for
Sustainable Energy, Technical University of Denmark (DTU).
He has spent 37 years in electrochemistry. He received his
MSc in 1973 and PhD in 1976 from the Department ofMetallurgy, DTU. After a postdoctoral period at the
Department of Chemistry A, DTU, and a short period in thebattery industry (Hellesens A/S), he was employed at Risø
National Laboratory in 1980. He was manager for numerous
projects and programs (mainly within R&D of practicalelectrochemical cells such as solid oxide fuel cells) and now
the Strategic Electrochemistry Research Center (SERC). He
has coauthored more than 250 scientific papers and reports,and has 16 patents/patent applications.
Prof. Dr. Mogens MOGENSON
Prof. Mogens Mogensen from the Risø National Laboratory for sustainable Energy made anenormous contribution in the development for electrochemical systems like SOFCs (High
Temperature Solid Oxide Fuel cells), SOEC (Solid Oxide Electrolyser Cells) as well as oxygen
separation membranes over the last 20 years. His topics in this field include the material
development for electrodes, electrolytes as well as interconnects, coatings and sealing’s.
Mogens is known for his broad knowledge and understanding of the total systems andespecially the deep knowledge of the thermodynamics and electrochemical behavior of thecells.
The driving force behind his research activities are the principle understanding of the aging
mechanisms in SOEC and SOFC systems, the electrochemical behavior, but also thedevelopment of new materials for better performance and competitive prices. In the field ofadvanced materials he was very active and successful in the development of catalytic metaloxides with fluorite and perovskite related structures. These compounds are extremely flexible
with respect to substitution of host cations and non-stoichiometry. By this purpose he has done“material engineering” by tailoring the basic materials properties for aspects like high electronic
and ionic conductivity, matching thermal expansion coefficient, stability in hydrogen and/or
oxygen atmosphere, etc. The development of novel materials was leading to the “world record”
in power density for electrochemical cells, accompanied by a low aging- and degradation rate(>1%/1000h) and an outstanding mechanical strength and flexibility. Mogensen was also very
active in cells and stack development with high electrical efficiency and fuel flexibility including
natural gas, biogas, diesel, LPG, methanol, DME and ethanol.
Recently his topic and interest are the synthetic fuels derived from water and CO2. This isinteresting as the produced syngas (H2 + CO) can react to form methane, which is a moresuitable energy carrier. In this process, the catalytic process is taking place inside the cell, so
the reaction heat can be utilized.
We award Prof. Mogens Mogenson for his outstanding work on the electrochemistry ofelectrolysers and fuel cells with the Science of Hydrogen & Energy prize 2012.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2013
Graduated Nagoya University with Msc applied physics and
Bsc in physics..
Joined Toyota Motor Corporation in 1981, then working as
engineer in production engines and advanced engine
systems. Later working as Toyota Engine representative at
Toyota Europe in Brussels. Involved for first hybrid (Prius)development as manager for emission and fuel economy. In
later years working as a planner for world hybrid deployment.
From 2004 fuel cell development manager.
Currently project general manager at R&D management
division and Energy Affairs department.

Mr. Katsuhiko HIROSE

Katsuhiko HIROSE has a very important role in the development of hydrogen formobility by building the bridge between industry (Toyota) and academia as well as thebridge between Asia and Europe.
He initiate the hydrogen's economical value assessments. Hydrogen fuel is valuable forthe economy as well as for the environment. The value-chain analysis of Fuel Cellvehicles and Hydrogen Energy analysis identifies the big economical value of the useof hydrogen as a fuel. This analysis has re-ignited many activities on hydrogen all over
the world
He also initiated the H2Mobility activities and brought many OEM and stakeholder into
these activities. Resulting in the German H2mobility report. A portfolio of power-trains
for Europe: a fact-based analysis, which stimulated the hydrogen activities world wide
again.
The large number of key-note speeches in both engineering conference and academic
conference stand for his continuous efforts as an interpreter between the industries andacademic scientists.
He is responsable for the world leading research in hydrogen storage by means ofhybrid tank systems, i.e. the combination of pressurized hydrogen gas and metal
hydrides, which leads to a hydrogen storage with greater gravimetric and volumetrichydrogen density as compared to the individual system. Furthermore, he also
developed a Cryo-adsortion tank system.
We award Mr. Katsuhiko HIROSE for his outstanding work on the implementation ofhydrogen for mobility and for linking the key people worldwide together with the
Science of Hydrogen & Energy prize 2013.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2013
Hans Geerlings studied experimental physics in Amsterdam,
where he received his PhD degree in 1987. In that year hemoved to Shell, where he worked in research on a number of
topics including synthesis gas conversion, hydrogen storage
and CO2 capture and storage. In 2007 he was appointed asa part time professor at the Delft University of Technology.
His current research interests are in the area of ‘Solar Fuelsynthesis’ and ‘Mineralization of CO2’.

Prof. Dr. Hans GEERLINGS
Hans Geerlings has worked on complex hydrides, i.e. alanates, especially on the synthesis andthe characterization of MgAlH4 and CaAlH4, before he focused on the CO2 capture andmineralization. Recently, he published a paper in Environmental Science entitled “Efficient
Production of Solar Fuel Using Existing Large Scale Production Technologies” in which theefficient production of solar fuels today using existing technologies is described. The feasibilityof liquid hydrocarbon fuels production from CO2 and water with efficiencies approaching 10%
from solar energy is demonstrated, this is about an order of magnitude higher than alternativetechnologies currently under development. The reduction of CO2 with hydrogen for the
production of synthetic fuels is a new challenging research branch with an enormous potential
for the future energy economy.
We award Prof. Hans Geerlings for his outstanding work on the hydrogen production andstorage as well as his effort to open new fields in a world leading oil producing company with
the Science of Hydrogen & Energy prize 2013.

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013BEST POSTER AWARD 2011
Ms. Alondra TORRES TRUEBA“Hydrogen Storage in Structure II
Clathrate Hydrates with Various
Promoters”
Department of Process & Energy,
Delft University of Technology,
Delft, Netherlands
M.Sc. Alondra Torres earned herbachelor degree from Universidad
Autonoma del Estado de Mexicoand her master degree (cum laude)from Universidad Iberoamericana in
Mexico City. Currently Alondra
Torres is appointed as a Ph.D.
student at Delft University ofTechnology in the Netherlands.
During her studies Alondra Torres
has been involved in several
projects including; heavy metals
removal from waste water withorganic material and the formationof polymeric membranes withforgassupercritical
CO2
separation. Her current Ph.D.
project involves the study of thepotential of clathrate hydrates forhydrogen storage.

Hydrogen Storage in Structure II Clathrate Hydrates with Various Promoters
Hydrogen (H2) is a promising alternative to fossil fuels, because it offers a solution for threemain global challenges: (i) reduction of greenhouse gas emissions, (ii) fulfilment of energy
requirements and (iii) reduction of local air pollution. However, due to the difficulty in finding aneffective storage medium, the application of H2, for instance in the automotive sector, iscurrently limited. Clathrate hydrates, have been regarded as a favorable alternative for H2
storage. Their profitability, safety, fast and high reversibility and efficient production make themmore suitable for this application than other H2 storage materials.

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013BEST POSTER AWARD 2012
Mr. Andreas BLIERSBACH“How to Watch Hydrogen Diffuse in
any Absorbing Material”
Department of Physics andAstronomy, Materials Physics
Division, Uppsala University,
Sweden.
Born 1986 in Cologne, Germany.
2011 Diploma in physics at the
RheinischeFriedrich-Wilhelms
University Bonn, Germany. 2008 –2009 studies and research, as
exchange student, at Uppsala
University, Sweden. 2010 – 2011
research on hydrogen diffusion innano sized materials by direct
imaging at Uppsala University,
Sweden. Since December 2011
PhD student at EMPA, Dübendorf,
Switzerland and involved in smart
carbon based hydrogen storage
materials.

“HOW TO WATCH HYDROGEN DIFFUSE IN ANY ABSORBING MATERIAL”
The kinetics of interstitial hydrogen are of great interest and importance for many technologies.
In particular nano-sized materials motivate fascinating applications and scientific questions.
Even though diffusion is one of the most studied phenomena the complex combination ofquantum effects and dynamic interplay with the displacement of host atoms [1,4] is still only
partially understood. We present a method to quantify chemical diffusion of hydrogen in nanosized materials. The changes in the absorptance of a vanadium single crystal thin-film, inducedby hydrogen, are observed visually and in real-time as a function of position. Concentration
profiles and their evolution in time, during chemical diffusion, can be measured down to ahydrogen content corresponding to just a few effective monolayers, randomly distributed within
VHx.

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PARTICIPANTS

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Name

Address

Phone / Fax / emailp

Mr. Matteo ARAMINI

University of Parma
Department of Physics
Via Usberti 7
IT-43100 Parma

Tel: +390521906067
email: matteo.aramini@fis.unipr.it

Dr. Feray BAKAN

Sabancý University
Nanotechnology Research&Application
CenterTuzla
TR-34956 Istanbul

Tel: +90 216 483 9000-2417
Fax: + 90 216 483 9550
email: feraybakan@sabanciuniv.edu

103

Mr. Thomas BIBIENNE

Hydrogen Research Instituteemail: thomas.bibienne@ugtr.ca

111

des Forges 3351
CA-G9A 5H7 Trois-Rivières
Mr. Andreas BLIERSBACH

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: 0041 58 765 48 62
email: andreas.bliersbach@empa.ch

129

Mr. Alexander BONK

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: alexander.bonk@empa.ch

127

Prof. Yvonne BRANDTANDERSSON

Uppsala University
Dept of Chemistry - Ångström
Laboratory
Box 538
SE-75121 Uppsala

Tel: 46706598147
email:
yvonne.andersson@kemi.uu.se

Mr. Urs CABALZAR

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: urscabalzar@bluewin.ch

Dr. Elsa CALLINI

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4933
email: elsa.callini@empa.ch

19

Dr. Chiara CAVALLARI

Institut Laue Langevin
TOF-HR
6 Rue Jules Horowitz
FR-38042 Grenoble

Tel: +33 47620 7613
Fax: + 33 47648 3906
email: cavallari@ill.fr

125

Dr. Peter CENDULA

ZHAW
ICP
Wildbachstr. 21
CH-8406 Winterthur

email: cend@zhaw.ch

PROCEEDINGS

148

7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / emailpProf. Bernard DAM

Delft University of Technology
Chemical Engineering
Julianalaan 136
NL-2628BL Delftemail: b.dam@tudelft.nl

87

Prof. Petra DE JONGH

Utrecht University
Inorganic Chemistry and Catalysis
Universiteitsweg 99
NL-3584 CG Utrecht

Tel: +31 6 22736345
Fax: +31 30 2511027
email: P.E.deJongh@uu.nl

51

Mr. Moreno DE RESPINIS

Delft University of Technology

email: m.derespinis@tudelft.nl

109

Julianalaan 136
NL-2628 BL Delft

Mr. Andrea DE SIMONE

AlstomOpen Innovation
Brown-Boveri Strasse 7
CH-5400 Badenemail:
andrea.desimone@power.alstom.com

Dr. Martin DORNHEIM

Helmholtz-Zentrum Geesthacht
Nanotechnologie
Max-Planck-Straße 1
DE-21502 Geesthacht

email: martin.dornheim@hzg.de35

Dr. Maria ESCUDEROESCRIBANOTechnical University of Denmark
Physics
Fysikvej
DK-2800 Kongens Lyngby

email: maria.escudero@fysik.dtu.dk

65

Prof. Dr. AsunciónFERNÁNDEZ

CSIC
Institute of Materials Science of SevilleAvda. Americo Vespucio 49
ES-41092 SevilleTel: +34-95448951
Fax: +34-954460665
email: asuncion@icmse.csic.es

107

Dr. Maximilian FICHTNER

KITInstitute of Nanotechnology
P.O. Box 3640
DE-76021 Karlsruhe

email: m.fichtner@kit.edu

Mr. Mattia GABOARDI

Università di Parma
Physics
Viale G.P. Usberti n.7/A
IT-43124 Parma

Tel: +39 0521 906067
email:
mattiagianandrea.gaboardi@fis.unipr.
it55

Prof. Hans GEERLINGSTU Delft

Tel: +31655123169
email: j.j.c.geerlings@tudelft.nl

49

Julianalaan 136
NL-2628 BL Delft

PROCEEDINGS

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / emailp

Mr. Jeffrey GEHRIG

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: jeffrey.gehrig@empa.ch

Ms. Corinne GIANOLA

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: 41587654692
Fax: 41587654692
email: corinne.gianola@empa.ch

Dr. Olivier GILLIA

CEA/LITEN
DTBH/LTH
17 rue des Martyrs
FR-38054 GRENOBLE Cedex 09

Tel: 00 33 4 76 38 78 62 07
email: olivier.gillia@cea.fr

Prof. Hubert GIRAULT

Ecole Polytechnique Fédérale deLausanne
Laboratoire d'Electrochimie Physique etAnalytique
SB/ISIC/lepa/Station 6
CH-1015 LausanneTel: +41.21.693.3145
email: hubert.girault@epfl.ch

Mr. Michal GORBAR

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: 4301
email: michal.gorbar@empa.com

115

Prof. Dr. Ronald
GRIESSEN

VU university/Amsterdam University
College
Physics
Emmaweg 29 B
NL-1241 LG Kortenhoef

Tel: 0031-35-6561451
Fax: 0031-20-598-7991
email: r.p.griessen@vu.nl

33

Mr. Ulrik GRØNBJERG
VEJ-HANSENTechnical University of Denmark
Department of Physics
Fysikvej 307
DK-2800 Kgs. Lyngby

email: ulrik.groenbjerg@fysik.dtu.dk

75

Mr. John Bøgild HANSEN

Haldor Topsøe A/S
Company Management
Nymøllevej 55
DK-2800 Lyngby

email: jbh@topsoe.dk

79

Prof. Bjorn C HAUBACKInstitute for Energy Technology

email: bjorn.hauback@ife.no

123

43

P.O. Box 40
NO-2027 Kjeller
Dr. Valentina HERZOGPROCEEDINGS

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: valentina.herzog@empa.ch150

7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / emailp

Mr. Katsuhiko HIROSE

Toyota Motor Corporation
R&D management
1,Toyota-cho,Toyota
JP-471-8572 Aichi

Tel: +81-565-72-5448
email:
hirose@katsuhiko.tec.toyota.co.jp

15Prof. Björgvin
HJÖRVARSSON

Uppsala University
Department of physics and astronomy
Box 516SE-75120 Uppsalaemail:
bjorgvin.hjorvarsson@physics.uu.se

105

Dr. Reto HOLZNER

Econimo-Drive AG

Tel: +41 7966717
email: reto.holzner@econimodrive.com

Gewerbestrasse 11
CH-6330 Cham
Dr. Fadime HOSOGLU

EMPAHydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41587654692
Fax: +41587654022
email: corinne.gianola@empa.ch

69

Dr. Jianjiang HU

Karlsruhe Institute of Technology
Institute of Nanotechnology
Herrmann-von-Helmholz Platz 1
DE-76344 Eggenstein-Leopoldshafen

Tel: +49 721 60828915
email: jianjiang.hu@kit.edu

21

Mr. Dirk HUFSCHMIDT

CSIC/University of Sevilla
Institute for Material Sciences of Seville
Américo Vespucio 49
ES-41092 SevillaTel: +34 954489527
Fax: +34 954460665
email: dirk@icmse.csic.es

67

Mr. Olaf JEDICKE

Karlsruher Institut für Technologie
Institut für Kern- und Energietechnik
Hermann-von-Helmholtz-Platz 1
DE-76344 Eggenstein Leopoldshafen

Tel: +49(0)721 6082 5274
email: olaf.jedicke@kit.edu

47

Prof. Dr. Craig JENSEN

University of Hawaii
Department of Chemistry2545 McCarthy Mall
US-96822 Honolulu

email: jensen@hawaii.edu

17

Dr. Torben R. JENSEN

Aarhus University
iNANO, Chemistry Department
Langelandsgade 140
DK-8000 Aarhus

Tel: +45 2272 1486
email: trj@chem.au.dk

37

Dr. Georgios
KALANTZOPOULOS

Institute for Energy Technology (IFE)
Physics
P.O. Box 40
NO-2027 Kjeller

Tel: +47 6380-6181
email: georgiosk@ife.no23

PROCEEDINGS

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / emailpProf. Gábor LAURENCZY

EPFL
SB ISICBCH 2405
CH-1015 LausanneTel: +4121.693.9858
Fax: +4121.693.9780
email: gabor.laurenczy@epfl.ch73

Ms. Inge LINDEMANNIFW Dresden
Dept. 21Helmholtzstr. 20
DE-01069 Dresden

email: I.Lindemann@ifw-dresden.de53

Dr. Marc LINDER

German Aerospace Center (DLR)
Institute of Technical Thermodynamics
Pfaffenwaldring 38-40
DE-70569 Stuttgart

email: marc.linder@dlr.de

99

Dr. Philippe MAURON

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: philippe.mauron@empa.ch

121

Prof. Amelia MONTONE

ENEA

Tel: +390630484762
Fax: +390630483176
email: amelia.montone@enea.it

93

via anguillarese 301
IT-123 Rome

Mr. Lennard MOOIJ

Delft University of Technology
Department of Chemical Engineering
Julianalaan 136
NL-2628BL Delft

Tel: +31(0)15 27 83 891
email: l.p.a.mooij@tudelft.nl

89

Mr. Romain MOURY

CNRSInstitut Européen de Membranes
300, Avenue du Professeur Emile
Jeanbrau.
FR-34095 Montpellier

email: romain.moury@univ-montp2.fr

71

Dr. Jiri MULLER

IFE

Tel: +47 63 80 61 85
email: jiri@ife.noBox 40NO-2027 Kjeller
Dr. Angeloclaudio NALE

Utrecht University
Department of Chemistry
Universiteitsweg 99
NL-3584 CG Utrecht

Tel: +31622736392
email: ac.nale@uu.nl

59

Prof. Maria OLEA

Teesside University
School of Science and Engineering
Borough Road
GB-TS1 3BA MiddlesbroughTel: + 44 1642 34 2447
Fax: + 44 1642 34 2401
email: m.olea@tees.ac.uk

85

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / emailpProf. Dr. Liuzhang
OUYANGSouth China University of Technology
Dept. of Materials Science&Technology
TIANHE ZONE, WUSHAN STREET
CN-510640 GUANGZHOU

Tel: 00862087114253
Fax: 00862087111317
email: meouyang@scut.edu.cn

95

Mr. Dinesh PALATTYKOONATHAN
AUGUSTINE

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: 058 765 4327
Fax: 058 765 4022
email: dinesh.augustine@empa.ch

Dr. Giulio PARCIANELLO

EMPAHydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41587654746
email: giulio.parcianello@empa.ch

Prof. Dr. Luca PASQUINIUniversity of Bologna
Dept. Physics and Astronomy
Berti-Pichat 6/2
IT-40127 Bologna

Tel: +39 051 2095149
email: luca.pasquini@unibo.it

Prof. Dr. Bruce
PATTERSONPaul Scherrer Institute
SwissFELOVGA 418
CH-5232 Villigen

Tel: 056 310 4524
email: bruce.patterson@psi.ch

Dr. Andreas PEDERSEN

University of Iceland
Science InstituteDunhaga 3
IS-101 Reykjavik

Tel: 3548688177
email: andreas@hi.is101

Dr. Daniele PONTIROLI

University of Parma
Physics Department
Via G. Usberti, 7/aIT-43124 Parma

Tel: +390521905231
Fax: +390521905223
email: daniele.pontiroli@fis.unipr.it

77

Mr. Edoardo PUOZZOEMPAHydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: Edoardo.Puozzo@empa.ch

Mr. Julian RANDALL

Euresearchemail: julian.randall@euresearch.ch

29

Effingerstrasse 19
CH-3001 Bern
Mr. Hardy RAUCHFUSSPROCEEDINGSALSTOM (Schweiz) AG
TIFT
Brown-Boveri Strasse 7
CH-5401 Badenemail:
hardy.rauchfuss@power.alstom.com

153

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / email

Dr. Arndt REMHOF

Empa
Hydrogen & EnergyÜberlandstrasse 128
CH-8600 Dübendorf

Tel: 058 765 4369
Fax: 058 765 4022
email: arndt.remhof@empa.ch

25,
131

Prof. Dr. Mauro RICCO'

Università di Parma
Dipartimento di Fisica e Scienze della
Terra
Via G. Usberti 7/a
IT-43124 Parma

Tel: +390521905217
Fax: +390521905223
email: Mauro.Ricco@fis.unipr.it

117

Dr. Jan ROSSMEISLTechnical University of Denmark
Physics
Fysikvej
DK-2800 Kongens Lyngby

email: jross@fysik.dtu.dk

63

email: samuele.sanna@unipv.it

91

Mr. Samuele SANNA

Physics Department
Via Bassi 6
IT-I-27100 Pavia

pProf. Dr. Jürgen
SCHUMACHER

Zurich University of Applied Sciences
Institute of Computational Physics
Wildbachstrasse 21
CH-8401 Winterthur

Tel: +41 (0)58 934 6989
email: schm@zhaw.ch

83

Dr. Meltem SEZEN

Sabanci University Nanotechnology
Research and App
SUNUM
Orhanli, Tuzla
TR-34956 Istanbul

Tel: 905053730817
Fax: +902164839885
email:
meltemsezen@sabanciuniv.edu

39

Ms. Mariana SPODARYKInstitute for Problems in Materials
Science
Structural chemistry of solid bodyKrzhizhanovsky str., 3
UA-3680 Kyiv

Tel: (+38) (068) 5417935
email: poshtamary@ukr.net

113

Dr. Nicholas STADIE

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: nstadie@caltech.edu

41

Dr. Petra SZILAGYIDelft University of Technology
Materials for Energy Conversion andStorage
Julianalaan 136
NL-2628 BL Delftemail: P.A.Szilagyi@tudelft.nl

57

Prof. Dr. Jeroen VAN
BOKHOVEN

ETHZ
Chemistry and Bioengineering
Wolfgang-Paulistr. 10
CH-8093 Zürich

email:
jeroen.vanbokhoven@chem.ethz.ch

61

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Name

Address

Phone / Fax / email

Dr. Georgia
VLACHOPOULOU

University of Parma
Department of Physics and Earth
Sciences
Via G. Uberti 7/A
IT-43100 Parma

Tel: 0039-3926043566
email:
georgia.vlachopoulou@fis.unipr.it

119

Dr. Ulrich VOGT

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 5876 4160
Fax: +41 5876 4022
email: ulrich.vogt@empa.ch

81

Prof. Dr. Chaoling WU

Sichuan University
School of Materials and Engineering
24#, South section 1, Yihuan Road
CN-610065 Chengdu

Tel: 0086013981807020
Fax: 008602885466916
email: wuchaoling@scu.edu.cn

97Prof. Fangming XIAO

Guangdong General Research Instituteof Industrialhydrogen alloy
363 ChangXing lu
CN-510650 Guangzhou

Tel: 0086-2037238406
Fax: 0086-20-37238523
email: xfmworld@163.com

31

Dr. Yigang YAN

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: 058 765 4082
Fax: 0580765 4022
email: yigang.yan@empa.ch

27

Mr. Dominik
ZIMMERMANN

Empa
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email:
Dominik.Zimmermann@empa.ch

Prof. Dr. Andreas ZÜTTEL

EMPA Materials Science & Technology
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

Tel: +41 58 765 4038
Fax: +41 58 765 4022
email: andreas.zuettel@empa.ch

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Information

PROCEEDINGS

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Map from Zürich (upper left corner) to Stoos (center bottom)

Map of the region Schwyz-Stoos

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

Travel to Stoos from Zürich airport:
Please go to the ticket counter in the airport and ask for a ticket to Stoos (roundtrip). Pleasealso ask the person at the counter to print you the timetable for your connection e.g.:

Station/Stop

Date

Time

Platform Travel with Comments

Zürich FlughafenMo,
21.01.13

dep 13:47 4

Zürich HB

arr 13:59 5

Zürich HB

dep 14:09 4

Schwyzarr 15:00 2

SchwyzIR 2343

InterRegio

IR 2275

InterRegiowalk

2 min., Y

Bus 1

Low-floor bus
Direction: Muotathal,
Höllochwalk

2 min., Y

FUN 18Funicular

Schwyz, Bahnhof
Schwyz, Bahnhof

dep 15:06

Schwyz, Stoosbahnarr 15:24

Schwyz, Stoosbahn
Schwyz Stoosbahn(Talstation)
Schwyz Stoosbahn(Talstation)

dep 15:40

Stoos

arr 15:48

Duration: 2:01; runs daily, not 8. Apr until 8. May 2013, 18. until 29. Nov 2013
http://www.sbb.ch/en/home.html

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

EMERGENCY TELEPHONE NUMBERS
country code for Switzerland +41...
POLICE

117

FIRE FIGHTERS

118

AMBULANCE144

RESCUE HELICOPTER

1414

Corinne Gianola
Andreas Züttel
Hotel Stoos, Reception

079 124 0183
079 484 2553
041 817 4444

Seminar- und Wellnesshotel Stoos (AG Sporthotel Stoos)Ringstrasse 10
CH-6433 Stoos
info@hotel-stoos.ch
http://www.hotel-stoos.ch

PROCEEDINGS

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Stoos, Switzerland 2013

STOOS Region

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

TIMETABLE

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7th Hydrogen & Energy Symposium

Stoos, Switzerland 2013

NOTES

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