th

9 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory
and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materials
The 9th International Symposium “Hydrogen & Energy” serves as an information
platform of the fundamental science and the frontiers of research in Sciences
and Technology 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 elements of the hydrogen cycle, i.e. the hydrogen production, hydrogenstorage and hydrogen combustion and fuel cells. Furthermore, contributions on
the conversion 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 hotel Seeblick in Emmetten close toLucerne in Switzerland. Emmetten is very close to the "Rütli" the origin of
Switzerland (year 1291) and connected by ropeway to the skiing resort
Klewenalp.
The number of participants is limited to 120.

25. - 30. January 2015
Hotel SEEBLICK AG
Hugenstrasse 24,
CH-6376 Emmetten
Telefon: +41 41 624 41 41
e-mail: info@hotelseeblick.ch
http://www.hotelseeblick.ch

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ACKNOWLEDGEMENT

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CONTENTS
Timetable
Abstracts
SUNDAY afternoon

Chair: Andreas Züttel

17

17:10 - 18:00

I: Klaus LACKNER: Closing the Carbon Cycle with
Synthetic Fuels and Capture of Carbon Dioxide from
Ambient Air

17

MONDAY morning

Chair: Shin-Ichi ORIMO

18

09:00 - 09:20

I: Ronald GRIESSEN: H ABSORPTION IN PALLADIUMNANOCUBES

18

09:40 - 10:00

T:
Svetlana
SYRENOVA:
NanospectroscopyoftheThermodynamics in Individual
Nanocrystals with Different Size

Indirect
Plasmonic
HydrideFormation
Shape-Selected Pd

19

10:00 - 10:20

T: Petra E. DE JONGH: The Size Dependence of thehydrogen desorption and absorption for carbon-supported
MgH2 particles

20

10:20 - 10:40

T: Sveinn OLAFSSON: RYDBERG
HYDROGEN NEW PHYSICS

OF

21

11:10 - 11:30

T: Alex LAIKHTMAN: INTERCALATION OF PLASMAACTIVATED DEUTERIUM IN INORGANIC WS2-BASEDNANOPARTICLES

22

11:30 - 11:50

T: Yixiao FU: SYNTHESIS OF Mg@MgF2 CORE-SHELL
NANOPARTICLES TO STUDY ITS THERMODYNAMICS
DURING DE/HYDROGENATION

23

11:50 -12:10

T: Philippe MAURON:
intercalated fullerides

metal

24

12:10 - 12:30

T: Tayfur ÖZTÜRK: Carbon Coating Mg-Ni Nanoparticles
via Thermal Plasma

25

MONDAY afternoon

Chair: Michael HIRSCHER

26

14:00 - 14:20

I: Bernard DAM: A new class of photochromic materials.

26

T: Diogo M. F. DOS SANTOS: HYDROGEN EVOLUTION
AT NANOSTRUCTURED NI-CU FOAMS

27

09:20 - 09:40

MATTER

Coffee breakHydrogensorptionin

14:20 - 14:40
14:40 - 15:00

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9 Int. Symposium Hydrogen & Energy

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15:00 - 15:20

T: Nikola BILISKOV: Synthesis and characterisation of new
amidoboranes

28

15:20 - 15:40

T: Shumin HAN: Preparation and electrochemical
characteristics of single-phase La-Mg-Ni-based alloys withsuper-stacking structures29

16:10 - 16:30

T: Yijing WANG: NBN NANOPARTICLES AS ADDITIVEFOR THE HIGH DEHYDROGENATION PROPERTIES OF
LITHIUM ALANATE30

16:30 - 16:50

T: Gang WANG: THE PREPARATION OF MESOPOROUS
SILICA SUPPORTED COPPER BASED PHOTOACTIVE
NANOPARTICLES WITH TUNABLE SIZES

31

16:50 - 17:10

T: Nicholas STADIE: The Equilibrium Dehydrogenation
Pressure Of Magnesium Borohydride: Revisited32

17:10 - 17:30

T: Dieter PLATZEK: New concept for thermal management
in a hydrogen tank

33

MONDAY evening

POSTER Chair: Min ZHU

34

20:00 -P:
Georgia
CHARALAMBOPOULOU:THERMAL
COUPLING POTENTIAL OF SOFCs WITH METALHYDRIDE STORAGE TANKS

34

P:
Jasmina
GRBOVICNOVAKOVIC:DESOPRTION OF MgH2-TiO2 THIN FILMS

SITU

35

P: Md Amirul ISLAM: potential of algae for bio hydrogenproduction

37

P:
GiselaM.
ARZAC:HYDROGEN-OXYGENRECOMBINATION REACTION FOR TREATMENT Of
EXHAUST GASES FROM FUEL CELLS

38

P:
Aferdita
PRIFTAJVEVECKA:MECHANICALPROPERTIES OF NANOSTRUCTURED AL ALLOYSPRODUCED BY ECAP.

39

P: Hui WANG: Mg-In-Ni Ternary Alloys for Reversible
Hydrogen Storage: Structure and properties

40

P: Sathiskumar JOTHI:
aerospace materials

in41-21:30

P: Ales JÄGER: Preferential Sites for Hydride Formation in
Commercially Pure Titanium

42

TUESDAY morning

Chair: Ronald GRIESSEN

43

09:00 - 09:20

I: Min ZHU: LiBH4 destabilization system and its hydrogenstorage performance

43

Coffee break

09:20 - 09:40

HydrogenIN

Embrittlemnet

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09:40 - 10:00

T: Olena ZAVOROTYNSKA: IN-SITU RAMAN STUDY OF
H - D EXCHANGE IN γ-Mg(BH4)244

10:00 - 10:20

T: Zuleyha Ozlem KOCABAS ATAKL: Catalyzed Hydrogen
Sorption Mechanism in Alanates45

10:20 - 10:40

T: Stefano DELEDDA: Structural changes observed during
the reversible hydrogenation of Mg(BH4)2 with Ni-based
additives46

11:10 - 11:30

T: Baozhong LIU: IMPROVING THE HYDROGEN
STORAGE PERFORMACNES OF MAGNISIUM HYDIRDEBY ADDING CATALYSTS

47

11:30 - 11:50

T: Anna-Lisa CHAUDHARY: REACTIVE HYDRIDECOMPOSITE
SYSTEMSFOR
BOROHYDRIDEDESTABILISATION48

11:50 -12:10

T: Yigang YAN: Circumventing the formation of [B12H12]2species for reversible hydrogen Storage

49

12:10 - 12:30

T: Fadime HOSOGLU: Energy and CO2 at cement industry
for future

50

TUESDAY afternoon

Chair: Bernard DAM

51

14:00 - 14:20

I: Hubert GIRAULT: Redox flow batteries for on demandhydrogen production

51

14:40 - 15:00

T: Michael RANFT:ELECTROLYSISALKALINE

52

15:00 - 15:20

T: Mariana SPODARYK: Gas atomised hydrogen storage
alloys54

15:20 - 15:40

T: Ansuncion FERNANDEZ: INVESTIGATION OF A Pt
CONTAINING WASHCOAT ON SIC FOAM FOR
HYDROGEN COMBUSTION APPLICATIONS

55

16:10 - 16:30

T: Ansuncion FERNANDEZ: PREPARATION OF CO AND
CO-B SUPPORTED CATALYSTS BY MAGNETRONSPUTTERING: A STEP FORWARD IN UNDERSTANDING
THE ACTIVE PHASE AND DEACTIVATION PROCESSESIN SODIUM BOROHYDRIDE HYDROLYSIS

56

16:30 - 16:50

T: Domenico DE LUCA: A Matlab/Simulink design
procedure for Proton Exchange Membrane Fuel Cells.

57

16:50 - 17:10

T: Didier BLANCHARD: LIBH4: AN ELECTROLYTE FOR
ALL SOLID-STATE LI-ION BATTERIES

58

17:10 - 17:30

T: Marco HOLZER: AEROGELS FOR CO2 CAPTURE

59

Coffee break

14:20 - 14:40

HIGH

PRESSURE

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TUESDAY evening

POSTER Chair: Akihiro NAKANO

60

20:00 -

P: Shunsuke KATO: In Situ X-Ray Photoelectron
Spectroscopy Studies On Hydrogen Storage And Catalysis

60

P: Yali DU: Kinetics study on hydrolytic dehydrogenation ofalkaline sodium borohydride catalyzed by amorphous Momodified Co-B nanoparticles

61

P: Martin PANHOLZER: Catalytic effects of magnesium
grain boundaries on H2 dissociation

62

P: Klaus TAUBE: BOR4STORE - Development of an
integrated boron hydride based hydrogen tank - SOFC
system64

P: Meiqin ZENG: The Phase Transition and Hydrogen
Storage Properties of Mg-Ga Alloys

66

P: Marco HOLZER: AEROGELS FOR CO2 CAPTURE AND
H2 DRIVEN DESORPTION67

P: Bojana PASKAS MAMULA: Nature of bonding in
MgH2:TM doped systems

68

P: Andreas ZÜTTEL: FROM HYDROGEN TO SYNTHETICHYDROCARBONS

70-21:30

P: Marco CALIZZI: LOW TEMPERATURE CYCLING OF
MG-TI NANOPARTICLES FOR HYDROGEN STORAGE

71

WEDNESDAY morning

Chair: Hubert GIRAULT

72

09:00 - 09:20

I: Nigel BRANDON: Materials Engineering for Solid Oxide
Fuel Cells and Electrolysers

72

09:40 - 10:00

T: Christiaan BOELSMA: A New Class of Hydrogen
Sensing Materials

73

10:00 - 10:20

T: Torben R. JENSEN:HYDROGEN STORAGE

FOR

74

10:20 - 10:40

T: David MILSTEIN: Discovery of New Hydrogen Storage
Systems based on Organic Liquids75

11:10 - 11:30

T: Giovanni CINTI: RENEWABLE ELECTRICITY TO
METHANE: INTEGRATION OF HIGH TEMPERATURE
ELECTROLYZER AND METHANATION REACTOR

76

11:30 - 11:50

T: Günther DOLLINGER: 3D-HYDROGEN MICROSCOPY

77

11:50 -12:10

I: Thomas Justus SCHMIDT: Introduction to the Swiss
Competence Center for Energy Research (SCCER) Heat &Electricity Storage

79

09:20 - 09:40

NEW

MATERIALS

Coffee break

12:10 -12:30

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THURSDAY morning

Chair: Olaf JEDICKE

80

09:00 - 09:20

I: Olaf JEDICKE: Research Infrastructures for Researchand development of Hydrogen and Fuel Cell Technologies

80

T: Elsa CALLINI: Hydrogen Storage in the framework of
H2FC

82

T: Pietro MORETTO: TECHNOLOGY AND SAFETYISSUES RELATED TO REFUELING OF HYDROGEN
CARS

83

T: TBA:84

THURSDAY afternoon

Chair: Olaf JEDICKE85

14:00 - 14:20

T:
UlrichULMER:TOWARDSHARMONIZEDMEASUREMENTS OF INVESTIGATIONS OF SOLID
HYDROGEN STORAGE MATERIALS85

I: Vladimir MOLKOV: HYDROGEN SAFETY: THE STATEOF-THE-ART

86

09:20 - 09:40
09:40 - 10:00
10:00 - 10:20
Coffee break
10:50 - 11:10
11:10 - 11:30
11:30 - 11:50
11:50 -12:10
12:10 -12:30

14:20 - 14:40
14:40 - 15:00
15:00 - 15:20
15:20 - 15:40
Coffee break
16:10 - 16:30

Round Table Discussion: : Round Table Discussion

16:30 - 16:50
16:50 - 17:10
17:10 - 17:30

FRIDAY morning

Chair: Bjørn HAUBACK

89

09:00 - 09:20

I: Björn C HAUBACK: Structural studies of complex
hydrides89

I: Shin-ichi ORIMO: Cool Hydrides, Again !

90

T: Jjanmei HUANG: ZIRCONIUM BOROHYDRIDESYNTHESIS,OCTAAMMONIATE
Zr(BH4)4-8NH3:STRUCTURE
AND
DEHYDROGENATIONENHANCEMENT

91

09:20 - 09:40
09:40 - 10:00
10:00 - 10:20
10:20 - 10:40

Coffee break

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11:10 - 11:30
11:30 - 11:50
11:50 -12:10
12:10 -12:30

Emmetten, SWITZERLAND 2015

I: Akihiro NAKANO: EXPERIMENTAL STUDY OF A
METAL HYDRIDE TANK WITH DOUBLE COIL TYPEHEAT EXCHANGER BELOW 1.0 MPa (G) OPERATION92

I: Michael HIRSCHER: PORSPECTS FOR POROUS
MATERIALS IN HYDROGEN STORAGE AND GASSEPARATION93

SCIENCE OF HYDROGEN & ENERGY AWARD

95

List of Participants

117

Information

127

Notes

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Timetable

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CLOSING THE CARBON CYCLEWITH SNYTHETIC FUELS AND
CAPTURE OF CARBON DIOXIDEFROM AMBIENT AIR
Klaus S. Lackner
Arizona State University, Center for Negative Carbon
Emissions
The development of energy systems is pathdependent. Because these paths start in the past,current trajectories already constrain future scenarios.
The latest IPCC report suggests that the world has
waited too long, and that avoiding dangerous climate
conditions will require net negative carbon emissions
for a large part of the next fifty years. Reversing 100
ppm of past emissions would require the developmentof technologies to remove carbon dioxide from the air
and about 1500 Gt of CO2 storage capacity, which
exceeds the emissions of the 20th century. Assumingthat humanity succeeds in solving this existential
challenge, one may conclude that air capture
technology will be developed and carbon storage
capacity will be a scarce commodity, reserved forstoring carbon recovered long after it has been
emitted. This eliminates fossil carbon as a viable
source of energy. Carbon free energy sources
including solar and nuclear energy will therefore be ata premium.
It is here that air capture could have another importantrole. The transport and storage of energy can takeadvantage of carbon-based, synthetic fuels, as longas air capture technology can recover their carbon
emissions. Liquid, carbon-based fuels have theadvantage of a long history of use, they are also
genuinely attractive because they are easily handled,transported and stored. Advanced energy conversion

Emmetten, Switzerland 2015devices like fuel cells would extend the efficiency ofsynthetic liquid fuels even more. This leads toscenarios in which most energy resources would
initially produce electricity often without regard to
instant demand profiles, with excess power being
converted to liquid fuels. Electricity and synthetic
fuels would then be the main energy carriers, withadvanced electrochemical technologies converting
one into the other. CO2 produced in synthetic fuelconsumption is recovered by air capture and reused in
making fresh fuels.
For these scenarios to be relevant, air capture as wellas energy conversion must become economicallyaffordable. Today, it is the high cost of input electricity
that is most limiting in the development of such a
scenario. For air capture, the low concentration ofcarbon dioxide in air makes it is difficult to repurpose
existing industrial gas separation technologies.
However, novel technologies have the potential foraffordable implementations. Our own approach uses
humidity changes to allow sorption on a sorbent in thedry state and release of carbon dioxide in the wet
state. The process is fast, reversible and efficient interms of cost and energy. It is much simpler, andrequires far less material than a different air-capture
process, which based on a study by the American
Physical Society would cost $600 per ton of CO2 in a
first-of-a-kind implementation. Using cost reductions
experienced in windmills and solar panels as a guide,$600 per ton seems not very high for an initial cost.
Solar energy prices dropped 100 fold and wind energy
costs roughly 40 fold since the 1960s.
In summary, air capture, which will be driven by theneed to remove carbon from the atmosphere, can also
support the development of non-fossil energy
resources by connecting them to liquid synthetic fuels
which are the most efficient way of carrying large
amounts of energy on board of a car, a plane or aship.

Klaus S. Lackner, Klaus.Lackner@asu.edu, +1 (480) 727-2499
Director, Center for Negative Carbon Emissions
Professor, School of Sustainable Engineering and Built Environment, Fulton Schools of Engineering,
Arizona State University

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HYDROGEN ABSORPTION IN PALLADIUM NANOCUBES
R. Griessen1 and N. Strohfeldt2
1

Faculty of Sciences, Division of Physics and Astronomy, VU University, De Boelelaan 1081, 1081 HV Amsterdam, The
Netherlands
2
4th Physics Institute and Research Center SCoPE, University of Stuttgart, Pfaffenwaldring 57, 70569 Stuttgart,
Germany
Abstract: The recent experimental data on ab- and desorption of hydrogen in Pd nanocubes obtained by Darbhan et al[1], Baldi et al [2] and Guanggin Li et al [3] are well reproduced by a mean-field model that involves bulk and subsurface
sites, elastic coupling between outer shell and bulk, elastic and electronic effective H-H interaction and disorder. The
model can also be used for the interpretation of data on other nm sized particles.

Introduction
Several articles on the interaction of H with Pd
nanocubes and nanoparticles have recently been
published [1-4]. Each article provides detailed data on
specific aspects of H in nanoparticles and proposes ad
hoc mechanisms for their interpretation. In this work weshow that: i) on the basis of a scaling law the hysteresis
is consistent with a coherent interface model and ii) all
essential features of the literature data are quantitatively
reproduced by a mean field model.

The scaling law
Assuming that the upper spinodal pressure is equal to
the H absorption plateau, all the nanocube data collapse
together when plotted as a function of Tc /T, the ratio ofcritical temperature and measurement temperature. The
clear difference with Pd bulk data shows that incoherent
interfaces are not occurring during H loading.

The model
The basic assumption of the model is that H can beaccommodated at subsurface sites and inner sites. As
the enthalpy of solutions of the subsurface sites is morenegative than that of the inner sites, the surface H
concentration is larger than inside the nanoparticle. This
leads to H dependentinternal stresses and,
consequently, to H dependent enthalpies in addition to
the usual elastic and electronic effective H-H interaction
which are assumed to be the same as in bulk Pd. In
addition, the model takes also surface energy andclamping contributions to the enthalpy of hydride
formation.

Results
Agreement with the experimental data of Bardhan et al.

R. Griessen[1] and Baldi et al. [2] is obtained with an enthalpy ofsolution for subsurface sites of -20 kJ/molH, a shell
thickness of » 1 nm and a weak clamping effect. In
particular the p-c isotherms and critical temperatures ofensembles of Pd nanocubes [1], the size dependence ofthe plateau pressures of single nanocubes [2] and theincreased concentration range of the dilute D-phase are
well reproduced.
The data in [3] can only be reproduced if the surrounding
MOF extracts electrons from the underlying Pd andreduces the shell thickness to zero (i.e. there are no
subsurface sites).

Conclusions
The shape of the model p-c isotherms confirms that in
nanocubes H loading occurs coherently and unloading
partially incoherently. The huge difference between bare
Pd nanoparticles and HKUST-1 coated Pd in [3] isprobably due to kinetic effects. Our model provides also avaluable framework for the quantitative interpretation ofdata on the absorption of H in few nm particles for which
defects, disorder and surface tension effects are
essential [4-6].

References[1] Bardhan et al., Nature Materials 12 (2013) 905[2] Baldi et al., Nature Materials (2014)[3] Guangqin Li et al, Nature Materials13 (2014) 802[4] Wadell et al., Chemical Physics Letters 603 (2014)
75–81 and C. Langhammer, private communication.
[5] Sachs et al., Phys. Rev. B64 (2001) 075408[6] Salomons et al., Europhys. Lett. 5 (1988) 449

Ronald Griessen (1945) studied physics at the Eidgenössische Technische Hochschule in Zürich.
After his PhD at the same university he went to the McLennan Laboratory of the University ofToronto. In 1976 he joined the VU university in Amsterdam as head of the Condensed Matter
Physics department and worked on superconductivity, metal-hydrides and switchable mirrors. From2005 till 2010 he was Chairman of FOM (Fundamental Research of Matter) and Chairman of the
Physics Division of NWO (Netherlands Organisation for Scientific Research). He is since 2010 a
lecturer at the Amsterdam University College and presently guest professor at the University of
Stuttgart where he works on switchable plasmonic nanoantennas in the group of Harald Giessen.

Corresponding author: Griessen, r.p.griessen@vu.nl, Tel.0031 35 656 1451

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INDIRECT PLASMONIC NANOSPECTROSCOPY OF THE HYDRIDEFORMATION THERMODYNAMICS IN INDIVIDUAL SHAPE-SELECTED PD
NANOCRYSTALS WITH DIFFERENT SIZE
Svetlana Syrenova†, Tina A. Gschneidtner‡, Yuri A. Diaz Fernandez‡, Giammarco Nalin‡,
Dominika Świtlik§, Fredrik Westerlund‡, Tomasz J. Antosiewicz†§, Kasper Moth-Poulsen‡
and Christoph Langhammer††

Department of Applied Physics, Chalmers University of Technology, 412 96 Göteborg, Sweden
Department of Chemical and Biological Engineering, Chalmers University of Technology, 412 96 Göteborg, Sweden§
Centre of New Technologies, University of Warsaw, Banacha 2c, 02-097 Warsaw, Poland‡

Abstract We study hydride formation thermodynamics in individual Pd nanocrystals with different size (from 45 to 20 nm)
and shape (cube, rod and octahedron). Nanospectroscopic readout of the hydride formation process is achieved throughthe use of a plasmonic Au nanoantenna adjacent to the Pd particle of interest. These Au-Pd heterodimers are made by1electrostatic self-assembly of the consitituents .

Size and shape of functional nanoparticles determine not
only their physicochemical properties but also theirtechnological relevance in a wide range of applications
like, e.g., heterogeneous catalysis, where they may serve
to significantly increase reaction efficiency and selectivity.
Other examples are information and energy storage
technologies where phase transitions are of particularimportance, and where controlling particle size andshape offers unique prospects to manipulate and control
the latter. Experimental investigations of such effects are
traditionally conducted on nanoparticle ensembles andare thus plagued by inhomogeneous sample material
averaging effects. These can be entirely eliminated inindividual nanoparticle experiments. Here we present thefirst complete and comprehensive experimental study ofthe hydride formation thermodynamics in individual
single-crystalline Pd nanoparticles of different size andshape, using non-invasive plasmonic nanospectroscopy.
We find consistent size- and shape-independent
thermodynamics, in agreement with the classic
understanding of the first order phase transition for
hydride formation in metals. Our results provide thus ageneric experimental blueprint for in situ studies ofindividual nanoparticles that can provide unprecedented
insight into correlations between nanoparticle, size,
shape, and the targeted functionality.

ab

100 nmc

100 nmFigure 1. a, An artists view on the indirect plasmonicnanospectroscopy arrangement used to probe anindividual Pd nanocube by an attached spherical Au
plasmonic antenna. As H2 molecules (red) dissociate andare absorbed into the Pd cube, the process can bedetected by the plasmonic Au particle via its near field,
and read-off at the single particle level owing to its large
scattering cross-section at visible frequencies. b & c,
Side-view and top-view SEM images of an Au-Pd cube
and Au-Pd octahedron arrangements, respectively.

References[1] Gschneidtner, T. A.; Fernandez, Y. A. D.; Syrenova,
S.; Westerlund, F.; Langhammer, C.; Moth-Poulsen,
K. Langmuir 2014, 30, (11), 3041-3050

August 2012 – current: Ph.D. student at the school of Materials Science, Department of Applied
Physics, Chalmers University of Technology, Sweden
June 2012: M.Sc. in Nanoscience and Nanotechnology, Department of Applied Physics, Chalmers
University of Technology, Sweden
June 2008: B.Sc. in Nanotechnology, Department of Radio technology, electronics and physics,
NSTU Novosibirsk, Russia
Svetlana
Syrenova
Corresponding author: Svetlana Syrenova, syrenova@chalmers.se, +46 (0)31-772 3007.

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THE SIZE DEPENDENCE OF THE HYDROGEN DESORPTION AND
ABSORPTION FOR CARBON-SUPPORTED MGH2 PARTICLESY.S. Au1, Suwarno1, F. Cuevas2, C. Zlotea2, P.E. de Jongh1
1
2

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands
ICMPE/CNRS, UPEC UMR 7182, 2-8 rue Henri Dunant, Thiais, France

Abstract: Due to the natural abundance and high hydrogen content, magnesium hydride-based materials are widely
studied as potential hydrogen storage materials. It is known that decreasing the particle size allows faster kinetics, andbetter reversibility of the hydrogen sorption. However, it has not been clarified before which steps are exactly rate limiting
under given conditions. Based on series of measurements on carbon-supported MgH2 nanoparticles with well definedsizes (<20 nm as well as um sized) studied while applying different driving forces for hydrogenation, we discuss theorigin of the size-dependent kinetics.

Introduction
Nanostructured metal hydrides, for instance MgH2 based,
are of potential interest for solid state hydrogen storage,
but also for other applications such as rechargeable
batteries and hydrogenation catalysts. Our group was thefirst to report a strategy to prepare carbon supported
nanoparticles by simply mixing MgH2 with a porous
carbon support, and heating the mixture to above themelting point of magnesium [1]. It is known that particle
size can have a strong impact on hydrogen sorption
properties [2,3], but more detailed insight has beenhampered by the great challenge to prepare small andwell-defined light metal hydride particles. In thiscontribution we discuss recent progress in the
preparation of carbon-supported MgH2 nanoparticles withtunable particle sizes, and the size-dependenthydrogenation and dehydrogenation kinetics.

Results
We found vapor-phase transport (at temperatures(b)(c)
below the melting point of Mg) to be able to transport Mg
from larger crystallites to small nanoparticles being
formed inside the carbon support pores at higher
loadings than previously possible, and I will discusspossible origins of this counter-intuitive effect. Fast andreversible hydrogen sorption was maintained during
cycling of these supported particles material, showing theability of the carbon support to stabilize the small
nanoparticles. We were able to vary in a controlledmanner the MgH2 particle size between 6 and 20 nm byadjusting the support porosity, allowing us to measure
the size-dependent hydrogen absorption and desorption
rates, and attain information on the rate limiting factors as
a function of size and experimental conditions.

rdFigure: Size-dependent hydrogen sorption (3 cycle) ato
250 C and 18 bar H2 pressure
While for micrometers-sized particles indeed solidstate diffusion can be rate limiting, this is not the case forthe <20 nm particles. The difference in hydrogen kinetics
between nanometers and micrometers sized MgH2
particles were for the first time corroborated by intrinsic
hydrogen dynamics data obtained by solid state 1 H
NMR. [3]. For <20 nm particles both surface-limited
processes as well as nucleation barriers can play animportant role in limiting the sorption kinetics, dependingon the exact experimental conditions.
[1] P.E. de Jongh et al. Chem Mater. 19 (2007), 6052.
[2] P.E. de Jongh, C. Zlotea et al, MRS Bull,. 38 (2013),
488.
[3] C. Zlotea et al. Farad. Discuss. 151 (2011), 117.
[4] Y.S. Au, et al. Adv. Func. Mater. 24 (2014), 3604.

Petra de Jongh received a PhD in photoelectrochemistry in 1999, and after 5 years working at
Philips Research, joined Utrecht Utrecht University in 2004. She is currently chair of Inorganic
Nanomaterials at the Debye Institute for Nanomaterials Science, working on nanostructured
materials for applications in catalysis and energy storage and conversion.

Petra de Jongh
Corresponding author: Petra de Jongh, P.E.deJongh@uu.nl, +31 30 253 1747

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RYDBERG MATTER OF HYDROGEN, NEW PHYSICS
Sveinn Ólafsson
Science Institute University of Iceland Dunhaga 3 107 Reykjavík Iceland
Rydberg matter of H or D is a condensed phase of Rydberg H or D atoms forming clusters with large atomic distances2d=2.9aon . The Rydberg atoms can be formed inside a catalytic material such as Fe2O3:K. Rydberg matter can also be
described as frozen plasma state of plasma. The formed Rydberg matter has been shown to be able to transform to new
ultra dense state of matter HN(0) or DN(0) d=2.3pm where N stands for number of atoms in the ultra-dense cluster matter.
This new ultra dense state can be named Dirac matter since relativistic quantum theory is the only quantum theory that
can have stable quantum solutions for the hydrogen atom on this length or density scale. The ultra-dense DN(0) Diracmatter has been shown to under low energy Laser pulsing to induce D+D fusion [1,2,3]. In this talk the state of Rydberg
matter and ultra dense hydrogen is reviewed and some new experimental work is presented. A possible link for ultra
dense hydrogen being the underlying reason for the reported excess heat in cold fusion experiments for the last 25 years
will be discussed.

Rydberg Matter and ultra-dense hydrogen
Ultra dense hydrogen was reported by Leif Holmlid first
2008. Since then he has in number of 10 to 15 peer
reviewed publications he has reported on the propertiesof this exotic state of matter. His work has been largely
unnoticed due to the revolutionary character of his workand also since no one has tried for same reason to
replicate his work. The author presenting this contribution
has visited his lab and in a sense replicated small portionof his work using his own setup. In this talk a shortsummary will be given about his results. Experimental
setup is presented and interpretation of some data isgiven. Laser induced fusion [2-3] will also be describedand discussed. In the end experimental link to coldfusion
experiments in electrochemistry and gas phase will begiving by presenting simple Gamov based calculationthat indicate that ultra dense DN(0) d=2.3pm matter will
-5 -1
fuse with rate of 10 s . This can be converted to energy
production rate of 100kw per mole of DN(0).

Probing the formation of Rydberg matter
Properties of ultra dense Dirac matter has so far only
been studied by laser induced breakup, time of flight andradioactivity measurements. Here is a measurement
setup designed to interface electrically to the ultra-dense
phase in order to see dynamics of formation of suchphase as function of gas pressure and temperature. The
first conductivity measurements of ultra matter H and D
phases will be reported and discussed.

Sveinn Ólafsson

The Rydberg matter is condensed on top of surface ofultra thin Pt film grown on MgO.
References[1] Excitation levels in ultra-dense hydrogen p(−1)  and  d(−1)  clusters:  Structure  of  spin-based Rydberg
Matter. Leif Holmlid. International Journal of Mass
Spectrometry 352 (2013) 1–8[2] Laser-induced fusion in ultra-dense deuterium D( 1):
Optimizing MeV particle emission by carrier material
selection. Leif Holmlid. Nuclear Instruments andMethods in Physics Research B 296 (2013) 66–71[3] Electron, ion and neutral particle emission from laserinduced processes: nuclear fusion in ultra-dense
deuterium D(0) Leif Holmlid*, Johan Boman and
Sveinn Ólafsson To be Submitted des. 2014

Research on growth of thin films by sputtering and physics of hydrogen in metals. Growth of nanostructured materials with STM. Surface science work at MaxLab Laboratory Lund Sweden anddefects studies of semiconductors at ISOLDE lab CERN Switzerland: PhD 1995 Uppsala University
Sweden. Post Doc 1995-1998 IFM Linköping University Sweden. Senior research scientist 19982006. Research Professor since 2006 at Science Institute University of Iceland Teaching atUniversity of Iceland since 1998. Supervising 6 PhD students and a number of masters students.
Chairman of the Icelandic Physical Society 2008-2013. Co-chairing MH 2008 conference inReykjavik Iceland.

University of Iceland, emai: sveinol@hi.is

hompage: http://uni.hi.is/sveinol/

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INTERCALATION OF PLASMA-ACTIVATED DEUTERIUM IN INORGANIC
WS2-BASED NANOPARTICLESAlex Laikhtman1, Alla Zak1, Amnon Fruchtman1, Gennady Makrinich1, Marius Enachescu2,
and Meltem Sezen3
1

Sciences Department, Holon Institute of Technology (HIT), 52 Golomb St., Holon 5810201, Israel

2

Center for Surface Science and Nanotechnology, Politehnica University of Bucharest, Splaiul Independentei 313,
060042 Bucharest, Romania

3

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

The use of hydrogen in a distributed system requires an effective, safe, and stable storage solution. Nanostructured
materials such as inorganic nanotubes (INT) and inorganic fullerene-like (IF) nanoparticles are appealing because of
their extremely high surface area and layered structure, where potentially many sites can either chemi- or physisorbhydrogen. A newly developed technology enables the synthesis and production of pure IF and INT phases of WS2 incommercial quantities, beyond tens of kg. This is why we initiated a project to test WS 2 INT and IF as possible
candidates for hydrogen storage. These materials may allow hydrogen to be either chemi- or physisorbed inside theircrystalline structure, inside hollow core of fullerenes/nanotubes or in the open interstitial pore spaces between thenanoparticles  or  nanotubes,  on  the  surface  or  in  the  open  interstitial  pore  spaces  of  nanotubes’  powder  mesh.  Exposure  to high pressure molecular hydrogen at 77-720 K was found to have measurable but limited absorption rate - up to 0.36
wt.%. Whereas treatment of the WS2-INT and WS2-IF by hydrogen and deuterium activated by microwave (MW) or
radiofrequency (RF) plasma resulted in much higher value of absorbed hydrogen of ~ 0.5-1 wt.% so far. These results
could be attributed to more effective interaction of activated vs. molecular hydrogen with nanoparticles substrate surface
due to the strong either chemisorption of MW plasma activated hydrogen compared to weaker physisorption of molecularhydrogen, or to higher energy and momentum of the hydrogen molecules in the RF plasma. In addition, plasma
originated ions and electrons interact with the nanoparticles and then can produce new or modify existing defects andpores, and so contribute to hydrogen diffusion and its stability following exposure to ambient atmosphere.
To determine the chemical nature of so absorbed deuterium, micro-Raman measurements were performed. For the RF-1
plasma deuterated samples, a small peak centered at ~ 2970 cm was observed. This feature was previously attributed
to the D–D stretching mode, and, therefore, its appearance in our spectra proves that deuterium is present in the-1molecular form, as D2. To finally prove that the Raman feature measured at 2970 cm is indeed due to D2, both IF and
INT RF plasma deuterated samples were heated in vacuum to 450 ºC for 90 min. The intensity of the above Raman peakdecreased to nearly zero supporting our assumptions.
TEM investigation of the deuterated WS2 nanoparticles showed some increase of the interlayer distance as compared toreference materials along with notable changes in the defects distribution.
To investigate the possible effect of ions on both types of the target materials (IF and INT of WS2), they were exposed to+
FIB of Ga ions for different doses. Following ion bombardments, the samples were analyzed by SEM, EDS, and microRaman. The primary effect was in the drastic change of the near surface structure and morphology of the bombarded
region. From SEM images, melting or sublimation with subsequent recrystallization of the nanoparticles takes place. Thisis confirmed by micro-Raman measurements showing degradation of the crystalline perfection by decrease in theintensities of the characteristic peaks of WS2. However, no contamination, oxidation, or decomposition of the substratematerials was detected after FIB treatments. These results can explain why physisorbed hydrogen is stable at the room
temperature in the plasma-treated  IF  and  INT,  indicating  that  such  “melting”  could  happen  then  resulting  in  closing  some  of the pores through which hydrogen atoms diffuse inside these layered nanoparticles.

PhD in interaction of low energy electrons, photons and ions with diamond surfaces (Technion,
Israel), 2003.
Positions held:
2003-2004 Postdoctoral scientist, the Laboratory of Molecular Photophysics, Orsay (France)
2004-2007 Research Scientist, the lab. of materials for space environment, Soreq Nuclear ResearchCenter (Israel)Alex Laikhtman

From 2007: senior lecturer in physics and head of the Microscopy Labs, Holon Institute ofTechnology (HIT) (Israel)

Corresponding author: Alex Laikhtman, alexl@hit.ac.il, Tel. +97235026830

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SYNTHESIS OF MG@MGF 2 CORE-SHELL NANOPARTICLES TO STUDYITS THERMODYNAMICS DURING DE/HYDROGENATION
Y. X. Fu a,b, , H. Wang a,b, and M. Zhu a,baSchool of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, Chinab Key Laboratory of Advanced Energy Storage Materials of Guangdong Province

Abstract: This work aims to create adequate core-shell structure to study the effect of elastic constrain has onthermodynamics of de/hydrogenation. Mg@MgF 2 core-shell structure has been chosen and synthesized through surface
fluorination of Mg nanoparticle by triethylamine trihydrofluoride (Et3N-3HF). XRD result shows Mg residual after reactingwith excessive Et3N-3HF for 12hrs. SEM characterization shows MgF2 layer has a thickness of no more than 20nm.

Introduction
Theoretic calculation indicates that elastic constrain could
bring certain effect on the thermodynamics of Mg
de/hydrogenation [1,2]. However, there is little adequate
experimental data to support this theory. There aremainly two reasons for this shortage: 1). nano-sized Mg
is highly vulnerable to oxygen and water, making it
difficult to synthesize and create good connection withother constraining substances; 2). Well-connection
brought by alloying with other metal elements in vacuum
bring controversies about whether the effect shown on
thermodynamics is introduced by elastic constrain or theintermediate alloy compound [3].
Surface fluorination of Mg nanoparticle is able to form
Mg@MgF2 core-shell structure with a passive shell layerof none absorption of H 2 and well connection to the core,moreover, with less rigorous oxygen/water - freeenvironmental requirement and without the concerning of
total consumption of Mg core during formation progress.
This method is able to form a compact MgF 2 shell of no
more than 20nm, which could affiliate the investigation of
the effect elastic constrain has on thermodynamics.

Results
Mg nanoparticle is synthesized through following reactionin THF:XRD result shows coexistence of Mg and MgF2, after
fluorination in excessive Et3N-3HF for 12hrs. Broadpeaks of MgF2 indicate its nano-crystal structure.

Figure 1 XRD pattern of surface fluorinated Mg
nanoparticles in excessive Et3N-3HF.

References[1] A. Baldi et al., Phys. Rev. Lett, 2009, 102, 226102[2] Pasquini L et al., Int. J. Hydrogen Energy, 2014; 39(5):2115-23.
[3] C.J. Chung et al., Phys. Rev. Lett, 2012.108.106102

2K+MgCl 2→Mg+2KCl
Before fluorination, by-product KCl is majorly washedaway by D MF to minimize the formation of KMgF 3.
However, it greatly reduced the productivity of Mg
nanoparticles by forming Mg-DMF colloid, but on theother hand, it proves the as -synthesized Mg particle isvery small.

Yixiao Fu was born on 29 June 1990 in Jiangxi, China. 2011 Bachelor in Department of Materials,
South China University of Technology (SCUT), Guangzhou, China. Major in Metallic Materials
Science and Engineering. 2014 M.S degree at the Key Laboratory of Advanced Energy Storage
Materials of Guangdong Province, SCUT.
His research is focused on reversible hydrogen storage of Mg based core-shell structure andcompositing structure.
Yixiao Fu
Corresponding author: Min Zhu, E-mail: memzhu@scut.edu.cn, Tel.: +86-20-39380578.

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9 Int. Symposium Hydrogen & Energy

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HYDROGEN  SORPTION  IN  METAL  INTERCALATED  FULLERIDES
Philippe Mauron1, Mattia Gaboardi2, Arndt Remhof1, Mauro Riccó2, Andreas Züttel1,3
1

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

2

Dipartimento di Fisica e Scienze della Terra, Via G. P. Usberti 7/a, 43124 Parma, Italy

3

Ecole Polytechnique Fédérale de Lausanne (EPFL), Institut des Sciences et Ingénierie Chimiques, 1015 Lausanne,
Switzerland

Abstract For different hydrogenated metal intercalated fullerides (Na 10C60, Li12C60 and Li28C60) the activation energies forhydrogen desorption were determined by DSC. The decrease of activation energy as function of the extent of conversion
can be explained by an increasing charge transfer to the C 60H36+y cage during desorption. Na intercalation leads to asignificant thermodynamic destabilization for hydrogen desorption compared to pure hydrogenated C60.

Introduction
Metal intercalated fullerides represent a new class ofcompounds for reversible hydrogen storage, in which up
to 3.5 [1] (Na10C60) and 5.1 [2] (Li12C60) can be stored. By
intercalating alkali or alkali earth metals in to fullerene,
the so called fullerides are formed, where charges fromthe metal atoms are transferred to the fullerene cages.

(Li12C60Hx) and 250 °C (Li28C60Hx) compared to > 400°C
for pure C60H36.

Experimental
Lithium fullerides (Li12C60, Li28C60) were synthesized byball milling a stoichiometric mixture of pure C 60 with
granular lithium in an inert argon atmosphere for 15 min.
in a planetary ball mill. After the milling the sample washeated to 270 °C for 36h. Sodium fulleride (Na10C60) was
synthesized by mixing sodium azide (NaN3) with C60 andlong annealing at 450 °C. The samples were hydrogenated under the following conditions Na10C60: 225 °C /185 bar / 50 h, Li12C60: 350 °C / 180 bar / 50 h and
Li28C60: 350 °C / 170 bar.

Results
The activation energies for hydrogen desorption are thehighest for  low  α  and  decrease  for  increasing  α,  between  around 200-145 kJ/mol (see figure) and 245-175 kJ/mol
for the Na and Li compounds, respectively.
Dehydrogenation enthalpies of 52 (Na10C60), 66 (Li12C60)
and 69 kJ/mol H2 (Li28C60) were determined. These
values are lower compared to literature values fordesorption of pure C60H36 (74 kJ/mol H2). The onsets ofhydrogen desorption are 185 °C (Na10C60Hx), 260 °C

Activation energy as function of the extend of conversion for
Na10C60H36+y dehydrogenation.

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, Reversiblehydrogen absorption in sodium intercalated fullerenes. Int J
Hydrogen Energ 37 (2012) 14307.
[2] Ph. Mauron, M. Gaboardi, A. Remhof, A. Bliersbach, D.
Sheptyakov, M. Aramini, G. Vlahopoulou, F. Giglio, D.
Pontiroli, M. Riccò, A. Züttel, Hydrogen Sorption in Li12C60.
Phys Chem C 2013, 117, 22598-602.
[3] Ph. Mauron, M. Gaboardi, D. Pontiroli, A. Remhof, M. Riccò,A. Züttel, Hydrogen Desorption Kinetics in Metal Intercalated
Fullerides. accepted in Phys Chem C 2014.

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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CARBON  COATING  OF  Mg-Ni  NANOPARTICLES  VIA  THERMAL  PLASMA  Burak Aktekin and  Tayfur  Öztürk
Department of Metallurgical and Materials Engineering, Middle East Technical University, Ankara
There is a considerable interest in carbon coating of metal hydrides for energy storage purposes. This might result in
improved thermal conductivity of metal hydrides, an aspect which is of considerable interest in Mg based hydrogenstorage tanks. In batteries, such coatings might improve the electrical conductivity, thus obviating the need for the special
additives used for such purposes in the electrode make-up. In the current work, following a successful synthesis of Mg2Niand Mg nanoparticles using thermal plasma [1], we investigate whether in-situ encapsulation of such particles withcarbonaceous material would be possible with the same method.

Initial experiments were carried out with nickel. This has
yielded carbon encapsulated nanoparticles, where Ni
particles of average 56 nm in size was wrapped aroundby 3-9 graphitic layers, Fig.1(a). An important observation
was that the size of particles obtained in this way wassignificantly less than those obtained with direct
synthesis, i.e. without co-feeding of methane, implyingthat methane could be used as an agent of size
reduction.

(a)

A separate experiment was carried out in which thefeeding rate of Mg to that of methane varied over a wide
interval. It was noted that with the feeding rates ratio(mass) greater than CH4: Mg =1:7 was sufficient to makethe powders resistant to oxidation. When the feeding rateof methane was lower this ratio the powders burned
intensely when exposed to air.

(b)

(c)

Fig.1 a) Ni nanoparticles encapsulated by 5-8 graphitic layers, b) Mg particle wrapped around by graphitic layers
in a carbonecous matrix. c) Mg nanoparticles of 5-6 nm in size embedded in carbonaceous matrix
Attempts to wrap Mg particles in the same manner asthat of Ni given in Fig.1(a) was not as successful. It wastrue that occasionally some particles could be foundwhere Mg could be wrapped around by carbonaceous
material. But mostly the resulting material was in the formof carbonaceous matrix with embedded Mg particles.
This was particularly the case when the methane feeding
rate was high. Fig. 1(b) and (c) are examples of such
structures where Mg particles of 5-6 nm in size areembedded in a graphitic matrix.

Mg-C powders which was resistant to oxidation was
exposed up to 30 bar of hydrogen in a Sievert instrument.
Unfortunately the powders did not react with hydrogen
implying that the carbonaceous material wrapping the Mg
nanoparticles was impermeable to hydrogen also. To
improve the reactivity of powders they were milled for ashort duration. Powders in milled state did react withhydrogen.
[1] B  Aktekin,  G  Çakmak  and  T Öztürk, Induction thermal
plasma synthesis of Mg2Ni nanoparticles. Int. J of
Hydrogen Energy, 39, 2014,9859.

Prof. Tayfur Ozturk, Middle East Technical University, Ankara has obtained his degrees; B.Sc in
Istanbul Technical Univeristy and Ph.D from Cambridge University in 1978. His work concentrates
on the processing methods that would yield nanostructured materials. This covers solid stateprocessing; the classical milling as well as novel techniques such as direct synthesis of fine-particle
compounds via electroreduction of mixed oxides. Recent studies concentrate in gas-phase synthesis
covering thin films as well as nanopowders produced via thermal plasma.
Tayfur Ozturk
Corresponding author: Tayfur Ozturk, ozturk@metu.edu.tr, +90 312 210 5935.

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A NEW CLASS OF HYDROGEN SENSING MATERIALS
Bernard Dam, Yingying Luo, Nicky Law, Herman Schreuders
Department of Chemical Engineering - Materials for Energy Conversion and Storage,
Faculty of Applied Science, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands
Abstract –Recently a photochromic effect was discovered in YOyHx. Here we investigate the relation between the
excitation and the bandgap. We find that excitation over the band gap is essential for the effect to occur.

Photochromism
The phenomenon of photochromism – the reversible
change of colour on exposure to light – has been known
for a long time. Recently a very special photochromic
effect was discovered in YOyHx [1]. This ternary oxyhydride is unique, since it allows for a photochromic
effect induced by light in the visible part of the optical
spectrum. Moreover, the photochromic darkening iscolourless, resulting in a uniform darkening of the visible
transparency. The photo-induced changes of opticalproperties
areaccompaniedbypersistent
photoconductivity. The physics of both effects has not yet
been elucidated. The uniform darkening suggests anelectronic phase segregation of metallic areas in adielectric matrix, possibly induced by mobile vacancies.
This would open a new perspective on the design ofphotochromic materials.

The application
Since we can carefully tune the bandgap just beyond thevisible spectrum, this material allows us to design aphotochromic material, which is operative behind a glass
window. Photochromic sunglasses could then be used incars. More importantly, this development allows thedesign of photochromic window panes, where thephotochromic material is located at the inside of a double
glazing structure. For such practical applications, boththe contrast and the speed of the transition will need to
be improved.

The excitation
We are able to vary the bandgap between 2.3 and 3.1 eV
by modifying the reactive gas composition of the sputter
gas. We obtain the optical bandgap by extrapolating thesquare root of the optical absorption as a function thephoton energy to zero. We find a straight line, suggesting
an direct bandgap transition. After illumination with awhite light source, the absorption increases for photon
energies smaller than the bandgap only (fig.1).
Comparing the photochromic darkening of these films,
we find that the photochromic effect decreases for larger
band gaps. By using optical filters we established thatwhen the photon energy is too small to excite an electron
hole pair over the semiconductor gap, no photochromism
is observed.

References[1] T.Mongstad, Ch. Platzer-Bjorkman, Jan Petter
Maehlen, L. P.A. Mooij, Y.Pivak, B. Dam, E.S.
Marstein, B. C. Hauback, S. Zh. Karazhanov, A new
thin film photochromic material: Oxygen-containing
yttrium hydride, Solar Energy Materials & Solar Cells
95 (2011) 3596–3599

1982 – 1986:

PhD, Radboud University Nijmegen;1986 – 1992:

Philips Research Laboratories, Eindhoven.

1992 – 2009:

Condensed Matter Physics, VU University, Amsterdam

2009 – Present: Head of the Materials for Energy Conversion and Storage group, Delft
University of Technology.

B. DamCorresponding author: Bernard Dam, b.dam@tudelft.nl

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HYDROGEN  EVOLUTION  AT  NANOSTRUCTURED  NI-CU  FOAMS
D.M.F. Santos*, S. Eugénio, D.S.P. Cardoso, C.A.C. Sequeira, M.F. Montemor
Instituto Superior Técnico, Universidade de Lisboa, 1049-001 Lisboa, Portugal
Three-dimensional (3D) nanostructured nickel-copper (Ni-Cu) foams have been prepared by electrodeposition using a
dynamic hydrogen template. These 3D materials were tested as electrodes for the hydrogen evolution reaction (HER) in
8 M KOH solutions for possible application as cathodes for alkaline water electrolysis. Their stability and activity for HER
was evaluated by linear scan voltammetry (LSV) and main reaction parameters were calculated.

Introduction

Results

3D nanostructured metallic foams (NMFs) are structuresof interconnected pores with nanoramified walls formedof metallic particles, dendrites or other morphologies thatcombine good electric and thermal conductivity with ahigh surface area and low density. Electrodeposition
provides a one-step, low-cost method for the fabricationof NMFs by taking advantage of the dynamic template
formed by hydrogen bubbling that occurs simultaneously
to metal deposition [1,2]. In this way, self-supported
nanoramified foam structures with properly tailoredarchitectures can be designed, enhancing mass andcharge transfer processes. Application of 3D materials for
HER was previously reported to be advantageous.
Additionally, among low-cost, non-noble metals, Ni and
Ni-alloys have been extensively studied for HER [3]. This
work proposes the use of 3D Ni-Cu NMFs, formed byelectrodeposition procedures, as cathodes for the HER.

SEM analysis of the two Ni-Cu metallic foams revealed auniform morphology, with a 3D structure presenting
nearly-circular micrometric pores with non-compact walls
formed of dendrites. The foams 3D structure wasfavoured with increasing deposition time, due to increaseof foam thickness and mass. EDS showed no significant
differences on the foams chemical composition.

Experimental
Ni-Cu foams were prepared by electrodeposition on AISI
304 stainless steel from an electrolyte solution containing
the two ions, using a two-electrode cell connected to a
power source. Electrodeposition was carried out ingalvanostatic mode by applying a current density of 3 A
cm-2 for 90s (NiCu-90) or 180s (NiCu-180). Working
electrodes were of 1 cm2 geometric surface area.
Electrochemical measurements were performed using a
PAR 273A potentiostat controlled by PowerSuite
software. The experiments were carried out in a singlecompartment glass cell of 125 ml volume. 8 M KOH wasused as the electrolyte. Linear scan voltammetry (LSV)
was used to scan the Ni-Cu foams potential from theiropen circuit potential (OCP, ca. -1.1 V) until -1.4 V vs.
SCE at a potential scan rate of 0.5 mV s -1. Temperature
was ranged between 25 and 85 ºC.

D.M.F. Santos

sampleNiCu-90
NiCu-180

electrodeposition
conditions
j / A cm-2
t/s
3
90
3
180

chemical composition/ at. %
Ni
Cu
52.9
47.1
52.7
47.3

The analysis of the polarization curves enabled thedetermination of relevant kinetic parameters, namely
Tafel slopes, charge transfer coefficients, exchange
current densities, and activation energies allowing a
direct comparison of the performance of the foamelectrodes for HER.
The results suggest that these 3D electrodes can attainhigh HER efficiencies while using low metal amounts.
Their low cost, one-step fabrication method presents
several advantages over conventional procedures,making them an alternative to typical catalytic materials.

References[1] H.C. Shin, J. Dong, M. Liu, Adv. Mater. 15, 1610,
2003.
[2] S. Eugénio, T.M. Silva, M.J. Carmezim, R.G. Duarte,
M.F. Montemor, J. Appl. Electrochem. 44, 455, 2014.
[3] D.M.F.  Santos,  L.  Amaral,  B.  Šljukić,  D.  Macciò,  A.  
Saccone, C.A.C. Sequeira, J. Electrochem. Soc. 161,
F386, 2014.

Diogo M.F. Santos obtained his Ph.D. at University of Lisbon (Portugal) in 2009 in Chemical
Engineering for his studies on the borohydride oxidation reaction. He is currently a permanent
researcher of the Center of Physics and Engineering of Advanced Materials of University of Lisbon,
where his main research interests concern electrochemical energy conversion and storage, namely
for the development of low cost electrocatalysts for direct borohydride fuel cells or looking for novel
electrocatalysts for hydrogen production by alkaline water electrolysis. He has authored more than
60 journal papers and over 30 conference proceedings. He is currently the Assistant Director ofCiência & Tecnologia dos Materiais (Science & Technology of Materials) published by Elsevier.

Corresponding author: D.M.F. Santos, diogosantos@tecnico.ulisboa.pt, +351 218417765.

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SYNTHESIS  AND  CHARACTERISATION  OF  NEW  AMIDOBORANES  Nikola  Biliškova, Ivan Halasza, Elsa Callinib, Andreas Borgschulteb, Andreas ZüttelbaLaboratory   of   Solid   State   and   Complex   Compounds   Chemistry,   Ruđer   Bošković   Institute,   Bijenička c. 54, HR-10000
Zagreb, Croatiab
EMPA, Materials Science and Technology, Dept. Hydrogen and Energy, 8600 Dübendorf, Switzerland
A series of single- and bimetallic amidoboranes and their complexes with ammonia borane were prepared by ball millingfrom ammonia borane and corresponding metal hydrides. Products are characterised by means of IR spectroscopy andpowder XRD. Dehydrogenation was followed by DSC and variable temperature Raman spectroscopy. All of the preparedsystems dehydrogenate at considerably lower temperature with respect to ammonia borane.

Introduction

Results

Ammonia borane (NH3BH3, further in the text AB) is
extensively investigated due to its extremely high bothgravimetric and volumetric hydrogen density. However,serious drawbacks make it unfavourable system forpractical onboard hydrogen storage. Its reactivity islargely determined by intermolecular dihydrogen bonding+
interaction of N-HG ··· G H-B type, which operates in solid
AB. Thus, the flexibility of this interaction is of crucial
importance for fine tuning of properties of AB-based
systems. A very successful approach is its chemical+
modification by substitution of one HG of NH3 moiety byan electropositive element, such as alkaline or alkaline
earth metal, which gives rise to amidoboranes [1]. This
substitution causes a significant destabilisation of
dihydrogen bonding network, with assistance of
dehydrogenation via hydride transfer by intermediate MH
species. The changes in dehydrogenation mechanism,
as well as opportunity of tuning of thermodynamics [2]make them highly promising systems for hydrogenstorage. Additionally, complexation of amidoboranes withhydrogen bond donating species, such as NH3 [3] or AB[4] further promotes dehydrogenation.

Milling of the LiH with AB in all molar ratios gives rise tocorresponding   LiAB∙mAB products. As expected, IR
spectrum of the product obtained by reaction of 1:1
mixture is considerably simpler than those for 1:2 and 1:3
products.
On the other hand, all attempts to obtain NaAB by milling
1:1 mixture of NaH and AB were unsuccessful. The
obtained product immediately decompose during themilling process due to the increase of temperature in vial.
However, milling of the 1:2 ad 1:3 mixture of NaH and AB
readily gives NaAB∙mAB. Q(BH) region is complex, as in
the case of Li-containing counterparts. Complexation of
MAB considerably lower dehydrogenation temperatureswith respect to both AB and MABs.
Bimetallic amidoboranes Li2Mg(AB)4 and Na2Mg(AB)4
were successfully prepared. XRD of the product obtainedby milling of the 2:1:4 mixture of NaH, MgH2 and AB
corresponds to the one previously reported forNa2Mg(AB)4 [5]. Combined evidence from IR spectra and
XRD for prepared M2MgAB4 systems shows that thebonding in these systems is very similar, but they are notisostructural, as confirmed by structure of the Li2Mg(AB)4,
solved by Rietveld method. It revealed very similar
coordination of M and Mg atoms in both cases. DSC
indicates a rather extensive phase changes prior todehydrogenation in the case of Li2Mg(AB)4, which occurs
above 120 °C for both Li2Mg(AB)4 and Na2Mg(AB)4, as
evident from Raman spectra.

Here we report a series of novel complexes of lithium andsodium amidoborane with AB (MAB·mAB, where M = Li,
Na and m = 1, 2), as well as bimetallic amidoboranes of
M2MgAB4 composition.

Experimental
Samples were prepared by high energy ball milling (Spex
8000M) of stoichiometric mixtures of AB andcorresponding metal hydrides during 30 min in argon
atmosphere. Single-reflection ATR IR spectroscopy,
powder XRD were used for structural characterisation.
Dehydrogenation properties were investigated by DSC
and variable temperature Raman spectroscopy.

References[1] Y. S. Chua et al. Chem. Commun. 47 (2011) 51165129[2] Y. S. Chua et al. Chem. Mater. 24 (2012) 3574-3581[3] Y. S. Chua et al. Inorg. Chem. 51 (2012) 1599-1603[4] C. Wu et al. Chem. Mater. 22 (2010) 3-5[5] H. Wu et al. Chem. Commun. 47 (2011) 4102-4104

Born September 17, 1974 in Pula, Croatia.
1999 Masters degree of inorganic chemistry at Faculty of Sciences, University of Zagreb; thesis at
Faculty of Science in Zagreb.
2009 PhD degree  in  physical  chemistry  at  Ruđer  Bošković  Institute,  Zagreb;;  thesis  “”
2012 Research associate at the Laboratory of Solid State and Complex Compounds Chemistry,
Division  of  Materials  Chemistry,  Ruđer  Bošković  Institute,  Zagreb
2014 Visiting scientist at EMPA, Dept. Hydrogen and Energy, Dübendorf, Switzerland
Nikola  Biliškov
Corresponding author: Nikola  Biliškov, nbilis@irb.hr, Tel. +385 91 7209759

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Preparation and electrochemical characteristics of
single-phase La–Mg–Ni-based alloys with super-stacking structures
Shumin Han a,b, Yuan Li b, Yali Du b, Jingjing Liu baState Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004,PR
Chinab
College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China
Abstract: La–Mg–Ni-based hydrogen storage alloys are considered as a promising negative electrode candidate to[1]
replace traditional AB5-type alloys due to their large discharge capacity . The preparation of single-phase La–Mg–Nibased alloys is necessary for systematic investigation but this is full of difficulty and reports on the single-phase alloys
are rare. Our group explored the formation mechanism of the super-stacking phases and succeeded in preparing thesingle-phase AB3-, A2B7- and A5B19-type La–Mg–Ni-based alloys by step-wise sintering and long-time annealing method[2-4]. The phase conversions during hydrogen absorption/desorption and the relationship between the super-stacking
structures and the electrochemical properties were investigated. Moreover, the effects of the second phases appearing inthe single phase alloys were also studied.

AB3-type single phase La–Mg–Ni-basedalloy

LaNi5 and (La,Mg)2Ni7 phases during hydrogen
absorption/desorption jeopardized its cycle life.

The PuNi3-type single phase La0.69Mg0.31Ni3.05 alloy was
prepared by step-wise sintering LaMgNi4 and LaNi5
precursor powders. The alloy exhibited a maximum–1discharge capacity (Cmax) of 352 mAh g and a high rate–1dischargeability (HRD) of 36.6% at 1500 mA g . But its
thcapacity retention was as low as 66.1% at the 100 cycle
due to its unstable structure during hydrogen
absorption/deosrption cycles. Introducing Ce2Ni7-typephase into the single phase alloy could improve its
overall electrochemical properties and the optimal
electrode performance was obtained when the ratio of
PuNi3- to Ce2Ni7-type phase abundance was close to 1:1.

A5B19-type single phase La–Mg–Ni-basedalloy

A2B7-type single phase La–Mg–Ni-based
alloy
The Ce2Ni7-type single-phase La0.8Mg0.2Ni3.5 alloy was
prepared by long-time annealing, and it exhibited athcycling stability of 81% at the 100 charge/discharge
cycle, which was much higher than that of the AB3-typesingle phase alloy. It was found that the alloy structure
remained
unchanged
after
initialhydrogenabsorption/desorption cycles. But it decomposed into
amorphous La and Mg and nanocrystalline LaNi5 and Ni
phases after 20 cycles. Small amount of LaNi5 phaseappearing in the A2B7-type single phase alloy could
improve its HRD, but the discrete expansion between the

The La0.84Mg0.16Ni3.80 alloy with only Pr5Co19-type phase
was firstly prepared by our group by step-wise sintering
LaMgNi4 and LaNi5 precursor powders in a temperatureoorange of 600–980 C and then annealed at 900 C for 4
days. The alloy showed a relatively low discharge–1
capacity (338 mAh g ) but a promising high rate
dischargeability (HRD1500 = 51.5%). The introduction of
20 wt.% Ce2Ni7-type phase remarkably improved its
discharge capacity and cycling stability, and 20 wt.% of
LaNi5 phase appearing in the single phase Pr5Co19-type
alloy further developed its HRD.

References[1] Y.F. Liu, H.G. Pan, M.X. Gao, Q.D. Wang, J. Mater.
Chem. 21 (2011) 4743-4755.
[2] J.J. Liu, S.M. Han, Y. Li, J.L. Zhang, Y.M. Zhao, L.
Che, Int. J. Hydrogen Energy 38 (2013) 14903-14911.
[3] L. Zhang, S.M. Han, D. Han, Y. Li, X. Zhao, J.J. Liu, JPower Sources. 268 (2014) 575-583.
[4] J.L. Zhang, S.M. Han, Y. Li, J.J. Liu, S.Q. Yang, L.
Zhang, J. Wang, J Alloy Compd. 581 (2013) 693-698.

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials,
and rare earth chemistry.
In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogen storage
alloys, light weight hydrogen strorage materials, rare earth–Mg–Ni-based electrode materials andhydrogen generation catalysts.
Shumin Han
Corresponding author: Shumin Han, hanshm@ysu.edu.cn, +86-335-8074648.

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NBN  NANOPARTICLES  AS  ADDITIVE  
FOR  
THE  
DEHYDROGENATION  PROPERTIES  OF  LITHIUM  ALANATEHIGH  

Li Li,Yijing Wang*, Lifang Jiao, Huatang Yuan
Institute of New Energy Material Chemistry, Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Key Laboratory of Advanced Energy Materials Chemistry (MOE), Tianjin Key Lab of Metal and Molecule–based
Material Chemistry, Nankai University, Tianjin 300071, P.R. China
Abstract: The   effects   of   NbN   nanoparticles   synthesized   via   a   simple   ‘‘urea   glass’’   route   on   the   dehydrogenation  properties of LiAlH4 have been systematacially investigated. Surface configuration and dehydrogenation behaviors of the2   mol   %   NbN−doped   LiAlH4 (2%NbN–LiAlH4) system are also discussed. It is found that the 2%NbN–LiAlH4 sample
starts to decompose at about 95 °C and releases total 7.10 wt. % hydrogen, which is 55 °C lower than that of as–milled
LiAlH4. The isothermal dehydrogenation kinetics shows that the 2%NbN–LiAlH4 sample could release approximately 6.10
wt % hydrogen in 150 min at 130 °C, whereas as–received LiAlH4 only releases about 0.63 wt % hydrogen under same
conditions, revealing that enhancements arising  upon  adding  NbN  nanoparticles  are  almost  8−9  times  that  of  as−milled  -1
LiAlH4. The activation energy (Ea) is calculated to be 71.91 and 90.87 kJ mol for the first and second hydrogen
desorption of NbN–LiAlH4 sample, a 38% and 32% reduction relative to as–received LiAlH4, respectively. Detailed
modeling study presents that the first dehydrogenation step can be sufficiently interpreted with the nucleation and growth
in a one-dimensional model based on the first-order reaction. More interestingly, SEM image of dehydrogenated
8%NbN–LiAlH4 sample after HP–DSC under 5.5 MPa H2 shows that some nanorods appear.

Introduction
Safe and efficient hydrogen storage technology is one of
the key technical barriers to the development of a kind ofsuitable   on−board   hydrogen   storage   material. Amongcomplex metal hydrides, Lithium alanate (LiAlH4) is ofparticular interest. However, the practical application of
LiAlH4 is limited by relatively slow dehydrogenation rate
and poor reversibility. In order to overcome thesedrawbacks, an alternate approach to modifying thedehydrogenation kinetics of LiAlH4 is through altering thechemical bonding of LiAlH4 by adding additives. Here, wereport the synthesis o NbN nanoparticles. Their catalytic
effects on the kinetics and thermodynamics of LiAlH 4
have been investigated.

Results and conclusion
SEM and TEM demonstrate that the size of NbN
nanoparticle is approximate 10 nm. The prepared NbN is
a promising additive for as–received LiAlH4 that it
produces a significantly reduced dehydrogenation
temperature and dramatically enhanced dehydrogenation
kinetics. The onset desorption temperature of 2%NbN–

LiAlH4 sample is lowered to about 95 °C with little
decrease in dehydrogenation capacity. Isothermal
dehydrogenation results at 130 °C reveal thatapproximately 7.10 wt % is released at 130 °C. The Ea
values of NbN-LiAlH4 sample decrease to 71.91 and-190.87 kJ mol after doping NbN nanoparticles, resulting
in decline rates of 38 % and 32 %. From the above
analyses, it is reasonable to conclude that NbN
nanoparticles are an effective additive for significantly
enhancing the dehydrogenation properties of as-received
LiAlH4.

Acknowledgment
We are grateful to the MOST project (2012AA051901),
NSFC (51471089, 51171083), 111 project (B12015) andMOE (IRT-13R30).

References[1] Schlapbach L, Züttel A. Nature, 2001, 414:353-358.
[2] Eberle U, Felderhoff M, Schuth F. Angew. Chem. Int.
Ed., 2009, 48: 6608−6630.

Prof. Dr. Wang
Major research interests focus on：Synthesis and Characteristics of Hydrogen Storage Materials
and High-performance Electrode Materials.

Yijing Wang
Corresponding author:
Name: Yijing Wang, E-mail: wangyj@nankai.edu.cn, Tel.: +86-22-23503639.

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THE
PREPARATIONOF
COPPERBASEDPHOTOACTIVE
NANOPARTICLES SUPPORTED ON MESOPOROUS SILICA
1
G. Wang,
K. Bossers,1 R. van den Berg,1 K.P. de Jong,1 C. de Mello Donega,2 P.E. de
1
Jongh
1

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands

2Condensed Matter and Interfaces, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands

Abstract: Cu2O and CuxS attract much attention for the application in solar energy conversion and photocatalysis.
Although Cu2O is subject to photocorrosion, CuxS is relatively stable in aqueous solution under illumination. The stability
against growth of supported nanoparticles is influenced by their spatial distribution on support materials and particle size.
We aim to control the size and distribution of Cu2O and CuxS nanoparticles using a mesoporous silica support, andobtaining nanoscale Cu2O and CuxS by conversion of well-defined CuO nanoparticles. The size of the CuO nanoparticles
can be tuned by varying the pore diameter of the supporting silica and/or the loading. As a result Cu2O nanoparticles withsizes from 2 nm to 15 nm as well as supported CuxS nanoparticles were obtained.

Introduction
Cuprous oxide (Cu2O) is a p-type semiconductor with aband gap of 2.2 eV.[1] This makes it an interesting
candidate for applications in photocatalysis. However,Cu2O undergoes photodegradation in aqueous solutions
and its valance band edge is not low enough to provide
the necessary overpotential for efficient photocatalytic
oxygen evolution. Copper sulphides (CuxS) are p-typesemiconductors with unusual photocatalytic properties
that are relatively stable in aqueous solution. Little is
known on the effect of particle size, shape and facets on
photocatalytic activity and stability. Recent research inour group has led to great advances in the control oversize and location of Cu-based nanoparticles inmesoporous silica.[2] The aim of this research is toinvestigate how control over size and distribution of Cu 2O
and CuxS nanoparticles can be obtained and related
effects on the photocatalytic properties.

Methods and Results
Different strategies were explored to obtain Cu 2O:
reduction from CuO with CO or H2, oxidation from Cu
with limited supply of O2, liquid-phase oxidation andsulfidation. The gas phase reduction under CO was mostsuccessful to produce Cu2O because of the highreproducibility and the clear two-step reduction of CuO incontrast with under H2. Careful tuning of conditions
allows attaining pure and crystalline Cu2O nanopartucles.
XRD showed that 15 nm CuO nanoparticles werereduced completely to Cu2O within 4 min. The Cu2O

phase   was   subsequently   stable   while   holding   at   250   ˚C  for up to 60 min. The particle size was tuned from 2 to 15
nm by changing the pore size of supporting silica and theloading. UV-Vis results confirmed a relation between theparticle size band gap. (Fig.1a). CuS and Cu2S (Fig.1b)
nanoparticles were obtained by the sulfidation of CuO
nanoparticles with Thioacetamide and 1-dodecanethiol.
(a)

(b)

(b)

200 nm

Fig.1: (a) The relation between the particle size and band
gap of Cu2O nanoparticles. (b)TEM image of supported
Cu2S nanoparticles.

Conclusion
A controlled synthesis method of silica supported Cu 2O
and CuxS nanoparticles with variable particle size wasachieved which will be useful for the investigation of theparticle size effect of copper based semiconductors on
photocatalytic activity and stability.
[1] A.H. Jayatissa et al., Appl. Surf. Sci. 255 (2009) 9474
[2] P. Munnik et al., J. Phys. Chem. C 115 (2011) 14698

2012-Present PhD study in the group of Inorganic Chemistry and Catalysis at Utrecht University
under supervision of Prof. Petra de Jongh. Topic of the research is the supported catalysts for stablesolar fuels production. The research is financed by NRSC-Catalysis.
2009-2011   Master   degree   at   Uppsala   University,   Sweden.   Master   project   entitled   “Investigation   of  Cobalt Complexes as an Alternative Redox Couple in Dye-sensitized   Solar   Cells”   under   the  supervision of Dr. Gerrit Boschloo and Sandra Feldt.
Gang Wang

2004-2008 Bachelor degree at Dalian University of Technology, China.

Corresponding author: Gang Wang, g.wang@uu.nl, +31 646806615

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THE EQUILIBRIUM DEHYDROGENATION PRESSURE OF MAGNESIUM
BOROHYDRIDE: REVISITED
Nicholas Stadie, Elsa Callini, Andreas Borgschulte, and Andreas Züttel
Empa, Hydrogen & Energy Laboratory, Dübendorf, Switzerland
Abstract: Light metal borohydrides have been the subject of active investigation as potential hydrogen storage materials
for over a decade. Magnesium borohydride (Mg(BH4)2) boasts a very high content of hydrogen (14.9 wt%) and anintermediate temperature of dehydrogenation at ambient pressure (<600 K), typically measured in dynamic conditions.
The kinetics of the decomposition reactions of borohydrides are often slow, hindering the practical measurement of theirequilibrium properties. In this work, we reinvestigate the dehydrogenation reaction of Mg(BH4)2 by a novel technique thatprovides both kinetic and equilibrium information about the system under controlled pressure conditions. The results
indicate much higher plateau pressures of Mg(BH4)2 than previously measured (e.g. >10 MPa at 590 K).

Dehydrogenation Thermodynamics

Gamma-Phase Magnesium Borohydride

The release of hydrogen from complex hydrides duringdecomposition (dehydrogenation) follows a series of nontrivial steps compared to metal hydrides and reversibility
is often therefore a challenge.

Equilibrium flow isotherms were measured of γ-Mg(BH4)2,
a system in which it is crucially necessary to distinguishbetween mass loss due to H2 release and due toimpurities1,2. The experimental results set new bounds on
the pressures and temperatures at which decomposition
can partially occur.

Equilibrium Flow PCT: A New Method
Typical methods for measuring thermodynamic properties
of hydrides and hydrogen adsorption systems must be
cautiously applied in the long-time scales characteristic ofcomplex hydrides. Various novel strategies have beensuggested (e.g., the dynamic PCT method) and in manycases, true thermodynamic equilibrium cannot easily beachieved. Herein, we apply a new strategy, variedpressure TPD measurements, to generate a new type ofpressure-controlled “equilibrium flow” PCT isotherm.

References[1] Stadie et al., JACS, 136, 8181 (2014).
[2] Stadie et al., JoVE, (under review).

Nicholas Stadie

Nick was born in 1985 in Calgary, Alberta, Canada. He received a BS in chemistry from ArizonaState University in Tempe, Arizona, USA in 2007. He received a MS and PhD in materials science at
Caltech in Pasadena, California, USA with Prof. Brent Fultz and Dr. Channing Ahn, focusing on
synthesis and thermodynamic characterization of physisorptive materials for hydrogen storage. In
2013, he joined Empa as a postdoc, and is supported by the EU program Bor4Store, studying newtechniques for characterizing the decomposition pathways of light metal complex hydrides.

Corresponding author: Nicholas Stadie, nicholas.stadie@empa.ch, +41 58 765 4153

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NEW CONCEPT FOR THERMAL MANAGEMENT IN A HYDROGEN TANK
D. Platzek1, H. Platzek1, A. Bianchin2, E. Forlin2, M. Testi3, F. Alberti3, N. Laidani3, R.
Bartali3, L.Crema3, P. Matteazzi4, S. Ortega5, G. Noriega5, M. Bielewski6, J.C. Ruiz-Morales7
1 Panco GmbH, D - 56218 Muelheim-Kaerlich, email: info@panco.de, 2 Matres SCRL, I - 31100 Treviso, 3 Fondazione
Bruno Kessler, I - 38122 Trento, 4 MBN Nanomaterialia S.p.A., I - 31050 Vascon di Carbonera (TV), 5 Cidete Ing. S.L.,
ES - 08800 Vilanova I la Geltru, 6 JRC-IET, NL - 1755 ZG Petten 7 Universidad de la Laguna, ES - 38200 La Laguna
Abstract

Hydrogen storage is well known to be the major bottleneck for the use of H2 as energy carrier. Actually there
are few storage systems available for nice markets. The EDen project is addressing a technology able to store
energy in form of hydrogen in a solid state material. EDEN is proposing a high density, fully integrated material– tank – engineered system. This work presents a novel approach for the thermal management of a hydrogentank based on metal hydrides, working at temperatures around 350°C and thus compatible with SOFC.

Introduction

Thermal management

The development of solid state hydrogen storage
systems is a challenge for the whole specific sector. It isa real opportunity to apply promising materials in realtechnologies to grant a new energy storage solution. The
research on solid state materials has alreadydemonstrated high hydrogen storage capacity, but some
gaps are already a problem for the realization of a robust
technology and a real market product. Among thedifferent design and layouts, the system hereby
described has the objective to be managed in real-time,
specifically for distributed level applications, included ona specifically designed storage tank and interlinked to anenergy provision system able to match intermittent
energy sources with local energy demand (buildings,
small dwellings).
EDEN is proposing a high density, fully integrated
material – tank – engineered system, able to realize an
adaptable energy storage solution. Different suggestions
for the hydrogen tank design have been considered. The
aim was to develop a hydrogen storage tank and to
optimise the heat transfer, the heat exchange system, theheating system as well as the heat recovery system toincrease the total performance of the system. The H 2 isstored in Mg-based Hydrides, which are catalysed with
Nb2O5 and present a gravimetric capacity of 7 wt%. The
tank can store 600 g H2 and has a H2 density of about 40
g/l, the heat recovery rate for adsorption is more than
25%, the desorption rate 3 gH2/min. The adsorption anddesorption takes place at about 350°C, which has to be
managed with the tank.

A completely new concept for the heat transfer has beendeveloped and is currently being installed into the systemprototype: Heatpipes specially engineered for the use inhydrogen tanks should transport the heat either in theadsorption case to the ambient via thermoelectrics or in
the case of desorption of H2 the heatpipes should
transport the necessary heat to the storage material. The
heat distribution from the heatpipes to the storage
material has also been ensured. A control system andmeasurement of temperatures, pressure and gas flow is
considered. Simulations lead to parameters for theapplication and the design of the tank. The firstexperiments with the tank prototype have shown that theperformance criteria have been matched and even beat.

Dieter Platzek

Acknowledgements
The research leading to these results has received
funding from the European Union’s Seventh Framework
Programme (FP7/2007-2013) for the Fuel Cells andHydrogen Joint Technology Initiative under grant
agreement nr. 303472.

References[1] A. Chaise, P. de Rango,Ph. Marty,D. Fruchart. (2010),
International journal of hydrogen energy, Vol. 35, pp.
6311-6322.
[2] M.Testi, F.Alberti, A.Bianchin, E.Forlin and L.Crema,
Proceedings of EFC2013 - Piero Lunghi Conference,
December 11-13, 2013, Rome, Italy

1966 born in Koblenz, Germany. 1994 Diploma (Master) at the University of Bonn. 1994-1997
Scientist at the Institute of Space Simulation of German Aerospace Centre DLR Cologne. 1997
Doctorate at the University of Bonn (Ph.D., „Dr. rer. nat.“), found evidence for a liquid ferromagnet.
1997 – 1999 Scientist at the Biomagnetic Centre of the University hospital Jena, Development ofactive shielding for magnetic fields. 1999 – 2000 Development engineer at the company LASOS
Lasertechnik Jena. development of a strong green diode laser including cooling technique. 2001 –2009 Scientist at the Institute of Materials Research of DLR development of thermoelectric material,measurement equipment. Since 2004 CEO of PANCO GmbH, Physics Technology Development
and Consulting development/manufacturing of measurement equipment as PSM, TEGeta etc.
Developments in the field of thermoelectrics and thermal management.

Corresponding author: Dieter Platzek, info@panco.de, +49 2630 964696
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THERMAL COUPLING POTENTIAL OF SOFCs WITH METAL HYDRIDE
STORAGE TANKS
A. Yiotis, M. Kainourgiakis, L. Kosmidis, G. Charambopoulou, Th. Steriotis, A. Stubos
National Center for Scientific Research “Demokritos”,  15310  Agia  Paraskevi,  Athens - Greece
Abstract - We study the thermal coupling potential between high temperature metal hydride (MH) tanks and a Solid
Oxide Fuel Cell (SOFC) aiming towards the design of an efficient integrated system, where the thermal power produced
during normal SOFC operation is redirected towards the MH tank in order to maintain H2 desorption without the use of
external heating sources.

BackgroundHydrogen storage in Metal Hydride (MH) tanks is an
exothermic process that produces significant excess
heat, in the range 40 - 80 kJ/mol for most materials
tested in the literature. Unless the produced heat is
efficiently removed from the tank, it results in increasingtank temperatures that eventually satisfy the activationenergy barrier for H2 desorption, thus leading toincomplete tank chargings. The design of efficient coolingsystems for MH tanks is thus a crucial factor for exploiting
the maximum theoretical storage capacity of the material.
Hydrogen desorption, on the other hand, is an
endothermic reaction that requires sufficient heat fluxes
to be provided to the MH bed in order to maintain thedesired desorption mass fluxes. In recent years, attempts
have been made to develop integrated, self-sustainable
MH/Fuel Cell systems, where the excess thermal power
produced from fuel cells under normal operating
conditions is redirected towards a MH tank to sustain H2
desorption. Most of these works have focused primarilyon the thermal coupling between low temperature MH
tanks and Polymer Electrolyte Membrane (PEM) fuelcells, where the cooling air flow stream from the fuel cellis used to heat the MH tank [1].

BackgroundIn this work, we study the thermal coupling potential
between high temperature MH tanks and a Solid Oxide
Fuel Cell (SOFC) aiming towards the design of an
efficient, self-sustainable integrated system [2]. Based on

Georgia
Charalambopoulou

principles of thermodynamics, we calculate the energybalance in the SOFC/MH system and derive analyticalexpressions for both the thermal power produced during
SOFC operation and the corresponding thermal power
required for H2 desorption, as a function of the operating
temperature, efficiency and fuel utilization ratio in theSOFC, and the MH enthalpy of desorption in the tank.
Based on these calculations, we propose an integrated
SOFC/MH design where heat is transferred primarily byradiation to the tank in order to maintain steady-state
desorption conditions. We develop a mathematical modelfor this particular design that accounts for heat/masstransfer and desorption kinetics in the tank, and solve forthe desorption dynamics of the system. Our results focus
primarily on tank operating conditions, such as pressure,temperature and H2 saturation profiles vs operation time.

Acknowledgments
This work is partially supported by the European Fuel
Cells and Hydrogen Joint Undertaking (http://www.fchju.eu) under collaborative project ”BOR4STORE”   (Grant  agreement no.: N 303428).

References[1] B.D. MacDonald, A.M. Rowe, Int. J. Hydrogen
Energy, 31 (2006) 1721-1731.
[2] A.G. Yiotis, M.E. Kainourgiakis, L.I. Kosmidis, G.C.
Charalambopoulou, A.K. Stubos, J. of Power
Sources, 269 (2014) 440-450.

Georgia is a Senior Researcher at the Environmental Research Laboratory of the National
Centre   for   Scientific   Research   “Demokritos”, located in Athens - Greece. She is a Chemical
Engineer and received her PhD in 2001 from the Chemical Engineering Department of the
National Technical University of Athens-Greece. Her research interests include the development
and characterization of porous materials, membranes (inorganic - polymeric) andnanocomposites for environmental & energy applications. Emphasis is on gas separations andstorage (specific interest in H2, CO2, CH4 etc.) for natural gas upgrade, oil & gas technologies
and hydrogen technologies.

Corresponding author: Georgia Charalambopoulou, E-mail: gchar@ipta.demokritos.gr, Tel.: +30 210 6503404

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IN SITU DESORPTION OF MgH2-TiO2 THIN FILMS
S.Milošević1, R.Vujasin1,   I.Milanović1, M.Lelis2,   D.Milčius2, R.Zostautiene3 J.R.Ares
Fernandez4,F.Leardini4, C. Sanchez4, J.Grbović  Novaković1
1

Vinča  Institute  of  Nuclear  Sciences,  University  of  Belgrade,  Laboratory for Material Sciences, Belgrade, Serbia
Center for Hydrogen Energy Technologies, Lithuanian Energy Institute, Kaunas, Lithuania
3
Department of Physics, Faculty of Mathematics and Natural Sciences, Kaunas University of Technology, Kaunas,
Lithuania
3
Dpto. de Física de Materiales M-04 Facultad de Ciencias Universidad Autónoma de Madrid
2

Desorption process of MgH2-TiO2 thin films obtained by RF sputtering were investigated by means of simultaneous
thermal desorption spectroscopy (TDS) and in situ optical microscopy. The random nucleation of spherical Mg nuclei isobserved in both samples, but the velocity of nuclei growing depends on thickness of the sample. Indeed thin sample
desorbs within 180s, while for thick sample 10 minutes is needed for complete desorption. Thick film exhibits lower Tonsetoofor desorption 389 C in comparison to 412 C for thin sample.

Introduction
Among various nanostructures used as potential material
for hydrogen storage, MgH2 thin films attract attention forvariety of reasons, such as easy way of synthesis andlow reactivity. Moreover, thin films offer the possibility to
study influence of microstructure and additives on
hydrides sorption properties in controlled way. The
activation energies for desorption varies and are causedby several issues [1]. Regarding the mechanism ofreaction, the desorption follows nucleation and growth
process, but in Pd-capped films an interface mechanism
is also proposed [2]. So, to clarify the mechanism ofreaction, in situ desorption from MgH2-TiO2 films coupledwith optical microscopy were studied.

desorption properties of thin films can be attributed
obviously to the shorter diffusion path for H atoms. The
random nucleation of spherical Mg nuclei is observed inboth samples (see Figure 1). The nucleation process inthin sample is very fast and can be attributed the fact that
nucleation and perhaps clustering of the Mg nuclei
occurs along some preferential directions determined by
the vacancies. All nuclei grow together with the same
velocity. On the other hand, in the thick sample there isformation of large and small nuclei alternately. There isno color variation prior to the desorption as it for pure
MgH2 film obtained by the same synthesis technique.
The change in color and halos are observed around theimpurities (holes) in thick sample but only after thecomplete desorption and could be a consequence offormation of intermetalics.

Experimental details
MgH2-TiO2 thin films were synthesized by RF
sputtering using Kurt J. Lesker 75 PVD apparatus onquartz substrate. Two different thickness of MgH2 layer
ranging were used (200 nm - S1 and 300 nm - S2) while
the thickness of TiO2 films was 10 nm for all films.
Deposition of TiO2 was done using pulsing DC current
supply for magnetron. MgH2 decomposition was studied
by means of simultaneous thermal desorption
spectroscopy (TDS) and in situ optical microscopy.
Optical microscope equipped with a hot stage able towork under inert atmosphere up to 873 K or under H2 up
to 573 K in transmitted or reflected mode enables video
acquisition and light intensity measurements during
sorption studies. Desorption were done in Ar flow of
1atm.
In-situ optical study [2] provides information on
hydride formation or decomposition kinetics andnucleation process.

Results and discussion
Regarding thinner film (S1), desorption starts atoo
412 C and ends at 427 C,while thick film (S2) desorbs
ofrom 389 to 434 C. For complete desorption in sample
S1, 180 seconds is needed, while for thick sample
desorption is finished in 10 minutes. The improved H2oa) S1 at 417 Cob) S2 at 415 C

Figure 1. Nucleation and growth process in MgH2-TiO2
thin films with different thickness a) S1 -200 nm and b)
S2 – 300 nm sample

References[1] J.R.  Ares,  F.  Leardini,  P.  Dıaz-Chao , I.J. Ferrer, J.F.
Fernandez ,C. Sanchez,Int J Hydrogen Energy 39(6);2014:2587–2596[2] M. Barawi, C. Granero,P.Diaz-Chao,C.V. Manzano,M.
Martin-Gonzalez,D. Jimenez-Rey,I.J.
Ferrer,J.F.Fernandez,C.Sanchez,J.R. Ares, Int J
Hydrogen Energy 39(18); 2014 :9865-9870

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x Born in Belgrade, Serbia 29.09.1973. Graduate degree in physical chemistry,1999,
Magisterium in physical chemistry, 2003, PhD in physical chemistry 2005. From 1999 sheworks in Vinca Institute of Nuclear Sciences in Laboratory of material sciences as principal
researcher. 2008 Post doc in ENEA CR Casaccia, President of Serbian Society for
Microscopy from 2010-2014. 2009 awarded from International Association of Hydrogen
Energy with IJHE outstanding Service Award. Leader of Hydrogen storage initiative Serbia.
Guest Editor: Novel Perspectives on Hydrogen Storage in Solid Media and International
Journal of Hydrogen Energy.

Jasmina Grbović Novaković
Corresponding author: Jasmina Grbovic Novakovic, email: jasnag@vinca.rs, Tel.+ 381 64 16 96 253

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POTENTIAL OF ALGAE FOR BIO HYDROGEN PRODUCTION
Mohamed AMIRUL ISLAM
Skolkovo Institute of Science & Technology, Energy Science & Technology, Moscow Region, Russia
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References

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MSc research student

Islam Md Amirul
Corresponding author: Mohamedd Amirul Islam , amirul.islam@skolkovotech.ru, Tel. +79854766037

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HYDROGEN-OXYGEN RECOMBINATION REACTION FOR TREATMENT
OF EXHAUST GASES FROM FUEL CELLS
G.M. Arzac*, D. Hufschmidt, A. Fernández
Instituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja. Seville. Spain.
Abstract
The study of H2/O2 recombination reaction is key in the development of hydrogen-based technologies. One application ofthis reaction is the elimination of H2 in the exhaust of fuel cells. In this work the reaction was studied in conditions which
simulate the exhaust gases from a fuel cell, namely 3% v/v H2/air mixture. 1% Pt/SiC and 1% Pt/TiO2 were tested as
catalysts. Both materials converted hydrogen into water efficiently at room temperature and reached a steady state aftera few minutes. TiO2 has demonstrated to be more efficient in terms of conversion probably due to metal-support
interactions. Further investigation will be conducted to explain this phenomenon.

H2-O2 recombination reaction or catalytic hydrogen
combustion (CHC, reaction 1) is receiving a lot of
attention in relation to the development of hydrogenbased technologies.[1] Reaction 1 is highly exothermic (286kJ.mol-1) and can be employed for safety and/or
heating purposes.
H2 + O2 ĺ H2O (1)It is known that the outlet gas from the fuel cell contains
certain amounts of unreacted hydrogen. For making theexhaust gases H2 free, it is essential to process theresidual gas in a simple manner. At this stage, CHC isneeded to convert hydrogen into water at room
temperature by using air as oxidant. [2]Pt is a well stablished catalyst for (1), and has thecapability to start up the reaction even at room
temperature. [3] For practical purposes, it is essential tohave the catalyst in a supported form which improvesdispersion, prevents aggregation and facilitates its use in
successive cycles.
In this paper we study the Pt-catalysed reaction using 3%v/v H2/ air mixtures simulating the conditions of theexhaust of a fuel cell. The catalysts were prepared byincipient impregnation of Pt on commercial TiO2 and SiC
supports and the results were compared. The kinetics ofthe reaction was monitored by measuring H2concentration by Gas Chromatography.
The 1%wt Pt/TiO2 catalyst was studied by Electron
Microscopy. The study reveals the formation of very small(less than 1nm) and disperse Pt nanoparticles asconfirmed by EDX (Energy Dispersive X-Ray Absorption).
Catalytic activity for the 1%wt Pt/TiO2 catalyst (12mg)-1
was measured for a 200ml.min H2/air mixture flow rate.
The reaction started at room temperature, and after a few
minutes, conversion and temperature achieved astationary state. Similar results were found in the second
cycle but with an increase in conversion (86 vs 92%) andaverage temperature (44 vs 46.5 ºC).
The activity for the 1%wt Pt/SiC catalyst was alsomeasured in the same conditions. TiO2 supported
catalyst shows improved activity respect to the SiC
supported one (86 vs 75%). According to previous report,
the differences could be attributed to the reducibility ofTi(IV) which generates lattice oxygen sites available for
the H2/O2 recombination. [4] However, further studies are
required for a full comprehension of this effect.

References[1] V.M. Shinde, G. Madras, Catalysis Today 198 (2012)
270-279.
[2] P. Despande, G. Madras, Appl. Catal. B Environ 100(2010) 481-490.
[3] M. Haruta, H. Sano, Int. J. Hydrogen Energy, 6 (1981)
601-608[4] P. Despande, G. Madras, Phys. Chem. Chem Phys,
13, (2011) 708-718.

I was born in Buenos Aires, Argentina. I studied Chemistry at the University of Buenos Aires (UBA).
As student and also as graduated, I worked for four years at the Organic Chemistry Department of
the UBA, synthesizing antitumorals. I was also teacher at the Inorganic Chemistry Department of thesame university during 7 years. I did my PhD at the University of Seville, Spain on hydrogen storage
through sodium borohydride hydrolysis reaction under the supervision of Dr. Asunción Fernández.
At present, my postdoctoral activity is still in relationship with hydrogen technologies and now
specially focused on catalytic hydrogen combustion.
Gisela Arzac*Corresponding author: Gisela M. Arzac, gisela@icmse.csic.es, +34954489552.

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MECHANICAL PROPERTIES OF NANOSTRUCTURED AL ALLOYSPRODUCED BY ECAP.
Aferdita Priftaj Vevecka
Polytechnic University of Tirana, Sheshi “ Nene Tereza”, N.4, Tirana, Albania.
Abstract
The novel multi-functional materials produced from the broad and multidisciplinary field that is nowadays called
nanotechnology, can be used for sustainable energy production, transformation and use. Magnesium, aluminium or Mg–
Al alloys in the form of bulk materials with nanograins, are envisaged as some of the potential optimal materials forhydrogen storage. During the last decades, fabrication of bulk nanostructured or ultrafine grained metals and alloys,
using severe plastic deformation (SPD) processing, has been evolving as a rapidly advancing direction of nanomaterials
science, aimed at developing materials with new mechanical and functional properties for advanced applications. Among
various SPD processes, Equal Channel Angular Pressing (ECAP), is the most well developed processing technique.
In the present work, the technologically interesting aluminium alloy AA6061 was selected for study. The strain ratesensitivity of AA6061 has been investigated in a conventional grain sized (CG) state and in two different ultrafine grained(UFG) conditions, processed by ECAP, for 2 and 6 passes at 100° C. Strain rate jump tests in compression were
performed at different temperatures, and the strain-rate sensitivity (SRS) exponent m was determined. It is shown thatboth UFG microstructures, exhibit a strongly increased strain-rate sensitivity (SRS) compared to CG state.

References[3] A.Veveçka, M. Cabibbo, T. G. Langdon, “Materials[1]M. J. Zehetbauer, H. P. Stüwe, A. Vorhauer, E.

Characterization”

Schafler, J. Kohout, Adv.Eng.Mater. 5 (2003) 330

Available online at www.sciencedirect .com

84

( 2 0 1 3 ) 1 2 6 – 1 3 3,[2]R. Z. Valiev, T.G. Langdon, Progress in Materials
Science 51 (2006) 881-981
Education: I have finished the faculty of Physics at the University of Tirana, Albania in 1970.
From 1970 to 1974 I have worked as assistant at the chair of ”General Physics” of the Faculty of
Natural Sciences, University of Tirana.
From 1974 to 1992 I have worked as lecturer in General Physics for students of the Engineering
Faculties, at the chair of ”Materials Science”, Faculty of Natural Sciences, University of Tirana.
Since 1992 I work as Lecturer in Physics at the Department of Physics, Polytechnic University ofTirana, Albania.
In 1982 I qualified for the Doctor’s Degree (PhD.) with the thesis: ” Study of structural changes ofaluminium and its alloys, during thermal and plastic treatments, by Transmission Electron
Microscopy (TEM)”.
In 1994 I received the title " Associate Professor" and in 1999, I received the title "Professor".
From March 1995 until April 2004, I was for 9 years, member of the editorial board
international premier academic journal “Materials Science and Engineering A”.

of theIn December 2008 I was elected Associate Academic member of the Albanian Academy of Science.
Name: Aferdita Priftaj - Vevecka
Address: Polytechnic University of Tirana
Department of Physics
Sheshi “Nene Tereza”, N.4, Tirana, Albania
Corresponding author: Aferdita Priftaj Vevecka, afvevecka@fimif.upt.al , + 355692107327

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MG-IN-NI TERNARY ALLOYS FOR REVERSIBLE HYDROGEN STORAGE:STRUCTURE AND PROPERTIES
Hui Wang1,2, Yanshan Lu1,2, Jiangwen Liu1,2, Liuzhang Ouyang1,2 and Min Zhu1,2
1School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, P. R. China
2

Guangdong Provincial Key Laboratory of Advanced Energy Storage Materials, Guangzhou, 510641, P. R. China

Abstract: A series of Mg-In-Ni alloys were prepared by sintering and ball-milling, and their structure and hydrogenstorage properties were investigated. It was found that two new Mg-In-Ni ternary phases were reversibly formed in thehydrogenation and dehydrogenation, which is responsible for the reduced decomposition reaction enthalpy of MgH2,
being 70.1 kJ/mol H2 for the Mg70In15Ni15 alloy. More importantly, the Ni addition could also improve the hydrogen
sorption kinetics of Mg. Therefore, the hydrogen desorption temperature of Mg-In-Ni alloys could be reduced down to
The results indicate that the Mg-In-Ni alloys

Introduction
Mg is considered to be a promising hydrogen storage
material with high gravimetric capacity and abundantresource. However, the over-high operating temperature
due to unfavorable thermodynamics of magnesium
hydride (MgH2) hinders its practical applications.
Composition and structure modification have been
proven to be effective in improving the hydrogen storage
properties of MgH2. For example, we found that Mg(In)and Mg(In,Al) solid solutions could be reversibly formed
as dehydriding from their hydrogenated products, andthat the desorption enthalpy was reduced [1,2]. In thiswork, we investigate the reversible phase transformationof Mg-In-Ni ternary alloys during de-/hydrogenation
cycles, and their de-/hydriding thermodynamic and kinetic
properties.

Experimental results
A series of Mg-In-Ni alloys were prepared from theelemental powders by sintering and subsequent ballmilling process. Figure 1 shows the composition range ofalloys to be explored, and their phase structure. The
crystal lattice of two new Mg-In-Ni ternary phases:
Mg70In15Ni15 and Mg50In25Ni25, has been determined by

3D reconstruction of transmission electron microscopy.
Further, the hydrogen storage properties of all Mg-In-Ni
alloys were compared, and the reaction mechanism ofseveral typical Mg-In-Ni alloys were investigated.

Figure 1 The composition and structure of as-prepared
ternary Mg-In-Ni alloys

References[1] H. C. Zhong, H. Wang, J. W. Liu, D. L. Sun, M. Zhu,
Scripta Mater. 65 (2011) 285.
[2] H. Wang, H. C. Zhong, M. Zhu, et al, Journal of
Physics Chemistry C, 118(2014)12087.

Hui Wang received his PhD in Materials Processing from South China University of Technology in
2003. He is currently A.P. Professor at the Key Laboratory of Advanced Energy Storage Materials of
Guangdong Province, South China University of Technology, Guangzhou, China. His researchinterest is focused on the Mg-base alloy for solid-state hydrogen storage, utilizing the strategies ofnanostructure, composite structure, alloying and catalyst doping to improve the hydrogen storage
properties of Mg.
Dr. Hui Wang
Corresponding author: A. Prof. Hui Min Zhu, memzhu@scut.edu.cn

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THE ROLE OF HYDROGEN IN WELDABILITY OF AEROSPACE MATERIALS*S. Jothi, T. N. Croft, S. G. R. Brown
College of Engineering, Swansea University, Singleton Park, Swansea SA2 8PP, UK*S.Jothi@swansea.ac.uk; jsathiskumar@gmail.com

Abstract:
Microstructures play a prominent role in aerospace components which are typically made ofhigh toughness, corrosion resistant and high strength structural polycrystalline metallic materials
such as nickel and nickel based super alloys. Nickel and nickel based super alloys are made up ofcomplex microstructures which are susceptible to delayed failure caused by absorption of hydrogenproduced during fabrication in manufacturing process such as electrodeposition and welding.
Several catastrophic failures have occurred in aerospace industries on nickel and nickel based superalloys due to hydrogen embrittlement (HE) and hydrogen stress cracking (HSC) near weld joints.
HE depends on many factors including hydrogen and impurities diffusion and segregation, heatsource during welding, weld residual stresses, microstructural morphology, defects and texture
morphological behaviour. Multiscale technique have been employed to investigate the influence of
these factors in hydrogen embrittlement both computationally and experimentally. The studies
provide insights on the influence of these factors and control it strategically to reduce thesusceptibility of materials to hydrogen embrittlement.

Corresponding author: Sathiskumar Jothi, s.jothi@swansea.ac.uk; jsathiskumar@gmail.com, Tel. 00447587876010

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Preferential Sites for Hydrides Formation in Commercially Pure
Titanium
Aleš Jäger, Walter Guy, Viera Gärtnerová, Karel Tesař
Laboratory of Nanostructures and Nanomaterials, Institute of Physics, Na Slovance 2, Prague 182 21, Czech Republic
Abstract: The aim of present study is to identify preferential sites for hydrides formation in commercially pure Titanium
grade 2. Ti with an initial H concentration of <0.015% was machined by electro discharge machining (EDM) to create asurface layer with an excess of H and subsequently annealed at 900° C to enables H diffusion into bulk . The heat
treatment resulted in an unusual duplex α and β microstructure with β phase decorating grain boundaries and triple
junction as well as lamellar β phase in grain interiors. High resolution transmission electron microscopy (HRTEM) andscanning transmission electron microscopy combined with electron energy loss spectroscopy (STEM-EELS) were mainly
used to correlate relations between hydride formation and crystal structure defects such as dislocations and interfaces. It
is shown that crystal structure defects serve as preferential sites for titanium hydrides creation and each type of crystal
defect prefer to be occupied by particular hydride.

Introduction

Outline of the Results

One of the most important impurities in titanium, which
also has potential for applications such as hydrogenstorage, is hydrogen. In access of hydrogen, there arethree major titanium hydride phases described inliterature, which may occur under certain conditions. Dueto the naturally high diffusivity of hydrogen, and its
relatively low solubility in titanium, gamma and delta
phase titanium hydrides can naturally occur even in CP
titanium [1]. Because of the importance and nearinevitability of hydrides in titanium, understanding themechanisms of hydride formation in titanium has been an
area of active research for 30 years or more. In spite ofthis effort, there is still incomplete knowledge about
defect - hydride relationship.

The microstructure after heat treatment consists of αphase grains and β phase mainly decorating grainboundaries. It was observed that the β phase appears in
two variations, the first along grain boundaries and triple
junctions, and the second as lamellar type lathes within
individual α phase grains. The heat treatment procedureused effectively stopped the α → β transition, which wasin progress when the sample was above the α transus of~887°C, and led to a duplex α+β microstructure, common
in some titanium alloys with β phase stabilizing elements[2]. Nanometer scaled features of the microstructure
were observed by TEM techniques. It is shown thatparticular titanium hydrides such as face centred
tetragonal titanium hydride and face centred cubic
titanium hydride are systematically formed around certain
crystal structure defects.

Experimental Part
An extruded rod of commercial purity titanium grade 2,
16mm in diameter, was machined into flat samples bywire EDM prior to heat treatment in an argon
atmosphere. The heat treatment was comprised of anincrease of 0.2°C/s up to a temperature of 900°C, w hich
was held for 1 hour, followed by cooling at a rate of 5°C/sback to room temperature. Transmission electron
microscopy (TEM) samples were cut into 3mm diameterdisks with a thickness of approximately 300 microns, andthen thinned by grinding to 50 or 100 microns before final
thinning by ion polishing or twin-jet electrolytic polishing,respectively. Two techniques of TEM sample preparation
were used in order to verify the minimal impact of sample
preparation procedures on hydride formation.

References[1] Banerjee, D., & Williams, J. C. (2013). Perspectives
on titanium science and technology. Acta Materialia,
61(3), 844–879. doi:10.1016/j.actamat.2012.10.043[2] Tesař, K., & Jäger, A. (2014). Electron backscatter
diffraction analysis of the crack development induced
by uniaxial tension in commercially pure titanium.
Materials Science and Engineering: A, 616, 155–160.
doi:10.1016/j.msea.2014.08.028

Aleš Jäger

1997 – 2002

Head of Group
Nanomaterials
and Interfaces

Faculty of Mathematics and Physics of Charles University in Prague
Master degree2002 – 2007

Faculty of Mathematics and Physics of Charles University in Prague
Ph.D. degree

Since 2007

Institute of Physics, Academy of Sciences, Postdoc position

Since 2011

Institute of Physics, Academy of Sciences, Group Leader

Corresponding author: Aleš Jäger, jager@fzu.cz, Tel. 00420 266 052 870

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LIBH4 DESTABILIZATION SYSTEM AND ITS HYDROGEN STORAGEPERFORMANCEMin Zhu1,2, Yijing Wang3
1. School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, P. R.
China.
2. Key Laboratory of Advanced Energy Storage Materials of Guangdong Province, Guangzhou 510640, P. R. China.
3. Institute of New Material Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Nankai
University, Tianjin 300071, P. R. China.
As a type of potential high-capacity hydrogenstorage material, LiBH4 has received intensive researchinterest over the last decade, for addressing its highthermodynamics, sluggish kinetics and irreversibility.
Herein, we demonstrate our latest effort on achieving areversible high hydrogen system with superior de-/rehydrogenation
properties,
through
introducing
nanosized NdH2+x, alkali metal hydroxides andnanostructured CoB with different morphologies into
LiBH4 by ball milling. The enhanced hydrogen storage
performace was realized and the mechanism was also
revealed.
A destabilized reversible reaction, 4LiBH4+NdH2↔
NdB4+4LiH+7H2Fehler! Eine Ziffer wurde erwartet.,
has been established [1]. The dehydrogenation kineticsof this reaction are fast, 6.0 wt.% hydrogen was
released within 1.5 h at 370 ºC. Significantly, we foundthat it is a nanosize-controlled reversible LiBH4-NdH2+x
system. The destabilization reaction could not proceedupondehydrogenation-rehydrogenation
cycling,because of significant growth of the NdH2+x particles.
However, the presence of NdH2+x continued to have apositive effect upon the dehydrogenation kinetics of
LiBH4. In a word, this novel finding is beneficial for
modifying the reversibility of the reactive hydridecomposite systems through nanosize-controlling.
To futher reduce the dehydrogenation temperature,alkali metal hydroxides were adopted to facilitatehydrogen through H+/H coupling mechanism [2]. The
main dehydrogenation temperature decreased to 207,
221, and 230 °C for LiBH4-LiOH, 2LiBH4-NaOH, and
2LiBH4-KOH, respectively. Further investigation in
LiBH4-xLiOH (x = 1, 1.36, 4) indicated thatdestabilization arose from different reaction pathways in
the composites, which depended on the LiBH4: LiOH
ratio. The dehydrogenation temperature increased from
207 to 250 °C, upon increasing the ratio of LiOH in
LiBH4-LiOH from 1 to 4. 4.1 and 6.5 wt.% of hydrogen
was liberated within 10 minutes by LiBH4-LiOH and

LiBH4-4LiOH, respectively. The latter exhibited fasterdehydrogenation kinetics. Unfortunately, LiBH4-alkali
metal hydroxide system was not reversible under therehydrogenation conditions of 400 ºC and 10 MPa
hydrogen pressure.
For achieving superior reversibility with enhanced
thermodynamic and kinetic behavior, nanostructured
CoB of different morphologies, being rod-like, flake-like,chain-like, waxberry-like and mulberry-like, wassynthesized by controlling chemical reduction process,and then doped into LiBH4 by ball milling [3]. The
catalytic activity of CoB is in the order of mulberry-like >waxberry-like > chain-like > flake-like > rod-like, whichis in accordance with their specific surface area fromhigh to low. This led to the different de-/rehydrogenation performance of CoB doped LiBH4 at 200°C and 350 °C. In contrast to other three CoBs,
mulberry-like and waxberry-like ones dramaticallyenhanced dehydrogenation of LiBH4 below 200 °C. 4.6
and 4.8 wt.% hydrogen was rapidly released from LiBH4
in 3 h respectively, and more than 2 wt.% hydrogen
was reversible for the later. For dehydrogenation at 350°C, mulberry-like CoB showed the best catalytic effectthan other CoBs, with which 10.4 wt.% hydrogen
liberated from LiBH4 within 1 h. Significantly, fullreversibility was achieved under 400 °C and 10 MPa
hydrogen pressure, and reversible 9.6 wt.%
dehydrogenation capacity was acquired at the fourth
cycle. To our knowledge, it is the first time to report thecatalytic effect of CoB through optimizing thenanostructureonthedehydrogenation
andrehydrogenation of LiBH4.

References[1] M. Zhu, et al. J. Phys. Chem. C, 2013, 117, 9566.
[2] M. Zhu, et al. RSC Advances, 2014, 4, 3082.
[3] M. Zhu, et al. Nano energy, 2014, 10, 235.

Corresponding author: Min Zhu, memzhu@scut.edu.cn, Tel. +86-20-87113924
Min Zhu is a professor in South China University of Technology. He received his Ph.D. from Dalian
University of Technology in 1988. His main research interest lies in the fields of advanced energy
storage materials, such as hydrogen storage materials, lithium ion battery materials, and electrodematerials for super-capacity. Zhu has published more than 200 journal articles.
Prof. Min Zhu

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9 Int. Symposium Hydrogen & Energy

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IN-SITU  RAMAN  STUDY  OF  H  →  D  EXCHANGE  IN  γ-MG(BH4)2O. Zavorotynska,1 G. Li,2 M.Matsuo,2 S. Deledda,1 S.I. Orimo,2 B.C. Hauback1
1

Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway

2

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

Abstract. Hydrogen-isotope exchange in γ-Mg(BH4)2 was studied by in-situ Raman spectroscopy. When γ-Mg(BH4)2 wasgradually heated in 0.3MPa D 2 atmosphere, the first evidence of isotope exchange appeared as already at 373 K, andbelow the temperature reported earlier for α-Mg(BH4)2. Gradual formation of BDH3, BD2H2, BD3H and BD4 anions wasfollowed at various temperatures until the formation of strongly fluorescent phase(s) at 498 K and above. Isothermal
steps allow us to follow the kinetics of isotopic exchange reaction.

Introduction
Isotope spectroscopy can provide useful insight intomolecular structure and bonding. Due to the large massdifference of H and D, vibrational spectra of themolecular groups containing the two isotopes are easily
distinguished and can be used to study the mechanismsofvariousintermolecular
processes.
Isotope
spectroscopy of complex hydrides, for example LiBH4
and Mg(BH4)2, have been used to investigate synthesis,
diffusion, decomposition and also thermodynamic
properties [1-3]. In this work in-situ isotope Raman
spectroscopy was applied to study the H-D exchange in
Mg(BH4)2 between300 and 543 K.

Methods and Results
Commercial γ-Mg(BH4)2 was used in this study. The
sample was soaked in 0.3MPa D2 at 300 K and gradually
heated at 5 K/min rate. Simultaneously Raman spectra
were recorded with a Nicolet Almega micro-Raman
spectroscope with 532 nm excitation wavelength. The
first evidence of H-D exchange appeared at 373 K as a-1
peak at 1717 cm and assigned to the B-D stretchingmode in BDH3. With increasing temperature, we wereable to record well-resolved peaks due to the B-D
stretchinginvarious

Olena
Zavorotynska

BH4-xDx ions. Isotope-exchange reactions were followed
isothermally at several steps, allowing us to study theisothermal reaction kinetics. The relative concentrationsof BH4-xDx ions were related to the integrated areas of thecorresponding symmetric B-D stretching. Experimental
data of the reaction rates at isothermal steps will becompared to various theoretical kinetic models.

Acknowledgements
This work was financed by the EU 7FP BOR4STORE
and the iTHEUS project funded by the ERA-NET
CONCERT-Japan
cooperative
program(http://www.concertjapan.eu/).

References[1] H. Hagemann, V. D'Anna, J.-P. Rapin, K. Yvon,
Deuterium-Hydrogen Exchange in Solid Mg(BH4)2, J.
Phys. Chem. C, 114 (2010) 10045-10047.
[2] A. Borgschulte, A. Jain, A.J. Ramirez-Cuesta, P.
Martelli, A. Remhof, O. Friedrichs, R. Gremaud, A. Züttel,
Mobility and dynamics in the complex hydrides LiAlH4and LiBH4, Faraday Discuss., 151 (2011) 213-230.
[3] R. Gremaud, A. Borgschulte, O. Friedrichs, A. Züttel,
Synthesis Mechanism of Alkali Borohydrides byHeterolytic Diborane Splitting, J. Phys. Chem. C, 115(2011) 2489-2496.

Dr. Olena Zavorotynska obtained her Specialist degree in Physics from Kyiv-Mohyla Academy in
Kyiv, Ukraine, in 2006. She continued her studies in the University of Turin, Italy, where she earned
her PhD degree in Materials Science in 2010 under the supervision of Prof. Giuseppe Spoto. During
her doctorate studies, she worked on hydrogen storage via adsorption in porous materials. The work
was   mainly   focused   on   characterization   of   the   materials’   surfaces   (zeolites,   MOFs,   polymers)   with  variable-temperature vibrational spectroscopy of probe molecules, and enhancement of theadsorption properties of these materials. In 2010-2012 she worked as the research assistant in
University of Turin, studying metal borohydrides for hydrogen storage applications. She continues
this research at present at the Institute for Energy Technology in Norway, where she works as post
doctorate fellow since 2012 in the group of Prof. Bjørn Hauback.

Corresponding author: O. Zavorotynska, olenaz@ife.no, +47 466 21 096

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9 Int. Symposium Hydrogen & Energy

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CATALYZED H SORPTION MECHANISM IN ALANATES
Zuleyha Özlem Kocabas Atakli a, Elsa Callini a, Shunsuke Kato a and Andreas Züttel a,b*
a EMPA, Swiss Federal Laboratories for Materials Research and Testing, CH-8600 Dübendorf, Switzerlandb Ecole polytechnique fédérale de Lausanne (EPFL), Institut des sciences et ingénierie chimiques, CH-1015 Lausanne,
Switzerland
Abstract: The hydrogen sorption pathways of alkali alanates were analyzed and a mechanism for the catalytic hydrogen
sorption was developed. Gibbs free energy values of each possible step were calculated based on experimental
determined thermodynamic data (enthalpies and entropies) of individual hydrides, MAlH4, M3AlH6, and MH. The values+
for the activation energies, based on the intermediates M , H , MH, and AlH3 were obtained. The mechanism of thecatalysis was unclear despite the large number of proposed models since the discovery of the catalytic activity of Ti in
NaAlH4 in 1996 by Boris Bogdanovic [1]. We present an atomistic model, where MAlH4 desorbs hydrogen through the+intermediates M , H , MH, and AlH3 to the hexahydride M3AlH6 and finally the elemental hydride MH. The catalyst acts as+
3a bridge to transfer the M and H from MAlH4 to the neighboring AlH4 forming AlH6 and finally isolated MH leaving
AlH3 behind which spontaneously desorbs hydrogen to Al and 1.5 H2. The proposed mechanism is symmetric in the
direction of the hydrogen sorption mechanism.

Introduction
Quite a number of possible mechanisms for the hydrogen
sorption in MAlH4 have been proposed [2]. However, allthese approaches suffer from the fact that Ti catalyzes
both hydrogen desorption steps as well as the adsorptionof hydrogen. We presented a completely symmetricmechanism where the function of the catalyst is welldefined. Firstly, we focused exclusively on understanding
the main intermediate steps in the dehydrogenation andrehydrogenation of MAlH4 and M3AlH6 (where M= Li, Na,
and K) based on thermodynamic considerations. With
this aim, Gibbs free energy values of each possible
compound were calculated from the experimental
thermodynamic properties of individual hydrides, MAlH4,
M3AlH6, and MH. Secondly, the activation barriers, with+
the intermediates M , H , MH, and AlH3, for the first andsecond step were obtained. Lastly, we presented an
atomistic model, where the catalyst acted as a bridge to
3transfer the M+ and H- from AlH4 to AlH6 and finally toform MH based on thermodynamic considerations.The
proposed mechanism was symmetric and the catalyst+
could be active on the intermediates M , H , MH, andAlH3 for the (de)hydrogenation.

Result and Discussion
In order to tailor the thermodynamic stabilities, the(de)hydrogenation of LiAlH4, NaAlH4, and KAlH4 at 453 K

were systematically investigated by considering Gibbs
free energy of their starting materials, intermediates, andproducts. The Gibbs free energy diagrams wereconstructed according to the published experimental
thermodynamic parameters [3]. MAlH4 (where M= Li, Na,
and K) is known to release hydrogen in two distinct steps;
M3AlH6 and MH partially dehydrogenated phases appear
in the dehydrogenation process. In all cases, it was
obtained that two appearing intermediate phases at thefirst dehydrogenation step and one possible intermediate
for the second dehydrogenation step. It was shown that(de)hydrogenation happened in two-step processes+
including M , H , MH, and AlH3 phases. We proposed thatthe task of Ti as catalyzed in rehydrogenation reaction isfollowed same path with the dehydrogenation steps.

References[1] B. Bogdanovic, M Schwickardi J. Alloys Compd., 253254 (1997), pp. 1.
[2] A. Leon, O. Kircher, M. Fichtner, J. Rothe, D. Schild
J. Phys. Chem. B, 110 (2006), pp. 1192-1200.
[3] Z. Özlem Kocabas Atakli, Elsa Callini, Andreas
Züttel, J. Alloys and Compounds (2015),to be
published

Short CV
Züleyha   Özlem   Kocabas   Ataklı   received a doctorate from department of material science andengineering from Sabanci University in 2013 for her work on fabrication of porous and nanomaterials
as adsorbent materials for water treatment application. She is currently Postdoctoral Researcher at
Empa, Swiss Federal Laboratories for Materials Science and Technology. Her research interests arein the area of adsorption, synthesis of nanomaterials, surface properties of porous and nano materials,
carbonaceous material chemistry, heterogeneous catalysis, photocatalytic oxidation, and hydrogenstorage.
Corresponding Author: Andreas Züttel, andreas.zuettel@empa.ch, +41 21 693 97 34.

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9 Int. Symposium Hydrogen & Energy

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STRUCTURAL CHANGES OBSERVED DURING THE REVERSIBLE
HYDROGENATION OF Mg(BH4)2 WITH Ni-BASED ADDITIVES
I. Saldan1,2, S. Hino1, T. D. Humphries1, O. Zavorotynska1, M. Chong3, C.M. Jensen3, S.
Deledda1, B.C. Hauback1
1

Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway,

2

Department of Physical and Colloid Chemistry, Ivan Franko National University of L’viv, UA-79005 L’viv, Ukraine

3

Department of Chemistry, University of Hawaii, Honolulu, HI 96822, USA

Abstract 7KHGHFRPSRVLWLRQDQGUHK\GURJHQDWLRQRIȖ-Mg(BH4)2 ball milled together with 2 mol% of Ni-based additives –Ninano; NiCl2; NiF2; Ni3B – has been investigated during one hydrogen desorption-absorption cycle. Powders were
sampled after milling and hydrogen desorption-absorption in order to monitor the structural changes in the hydrogencontaining phases with PXD, XAS, NMR and IR spectroscopies. Hydrogen desorption results in the formation of a11reversible phase which was identified by B NMR as Mg(B3H8)2. However, IR could not confirm the presence of the B–
H–B bridged bonds, characteristic of Mg(B3H8)2Introduction
Magnesium borohydride, Mg(BH4)2, is one of the mostpromising hydrogen storage materials due to its
theoretical hydrogen capacity of 14.9 wt% [1]. However,its application is hindered by poor kinetics and lack ofreversibility. The development of additives that mightchange and speed up the H-sorption reaction pathway,
inhibiting the formation of stable higher polyboranes, iscurrently being extensively explored in order to improve
the kinetics and reversibility of H-sorption in Mg(BH4)2. In
the present work, four different Ni-based additives havebeen investigated as possible catalysts towards
reversible Mg(BH4)2 decomposition.

Experimental methods and resultsȖ-Mg(BH4)2 was ball milled together with 2 mol% ofdifferent Ni-based additives (Niadd): Ninano; NiCl2; NiF2;
Ni3B. Under the applied ball-milling conditions, no
PHFKDQRFKHPLFDO UHDFWLRQV EHWZHHQ Ȗ-Mg(BH4)2 andNiadd were observed. Hydrogen desorption carried out attemperatures 220-264 ºC resulted for all samples, inpartial decomposition of Mg(BH4)2 and formation of
amorphous phases, as seen by Powder X-ray Diffraction(PXD). PXD analysis after rehydrogenation attemperatures 210-262 ºC and at pressures between 100
and 155 bar revealed increasing IUDFWLRQVRIFU\VWDOOLQHȕMg(BH4)2, indicating a partial reversibility of the–composite powders. The highest amount of [BH4] is

StefanoDeleddaformed in the composite containing Ni3B. Analysis by Xray Absorption Spectroscopy (XAS) performed after ball
milling, after desorption and after absorption shows that
the Ni3B additive remains unaffected, whereas NiCl2 andNiF2 additives react with Mg(BH4)2 during the hydrogen
desorption-absorption, and forming compounds with alocal structure very similar to that of amorphous Ni3B.
Multinuclear NMR spectroscopy confirms the partial
reversibility of the system, as well as the formation of2–[B10H10] during hydrogen absorption. The presence of2–[BnHn] (n = 10; 12) was also detected by infrared (IR)
spectroscopy of the dehydrogenated and rehydrogenatedsamples. The IR measurements give no clear indicationthat ions containing B–H–B bridged hydrogen groups
were formed during the H-sorption cycle.

Acknowledgments
This work was supported by the Norwegian ResearchCouncil within the NANOMAT and FRIENERGI
programs, and by the European Fuel Cells and Hydrogen
Joint
Undertaking(http://www.fch-ju.eu)
undercollaborative project “BOR4STORE” (Grant agreement
no.: N° 303428).

References[1] Orimo, S.; Nakamori, Y.; Eliseo, J. R.; Züttel, A.;
Jensen, C. M. Chem. Rev. 2007, 107, 4111–4132

Dr. Stefano Deledda received his Master in Chemistry from the University of Sassari, Italy, and his
PhD in Chemistry from the Dresden Technical University, Germany. He has a 15-year-longexperience in the synthesis and characterization of metastable and nanocrystalline alloys andcompounds processed by non-equilibrium techniques. At IFE since 2005, his research activities
include the synthesis of complex hydrides, multicomponent alloys and composites by ball milling andtheir structural and thermodynamic characterization. He has authored and co-authored more than 40
publications. He is now project responsible for the construction of the new high-resolution neutron
powder diffractometer, work-package leader in an EU Project on hydrogen storage materials(BOR4STORE) and scientific contact for one on advanced magnetic materials (NANOPYME).

Corresponding author: Stefano Deledda, email: Stefano.deledda@ife.no, Tel.: +47 407 26 921

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IMPROVING THE HYDROGEN STORAGE PERFORMACNESMAGNISIUM HYDIRDE BY ADDING CATALYSTS

OF

Baozhong Liu1,2,*, Yanping Fan1, Yuan Li2, Shumin Han2
1 School of Material Science and Engineering, Henan Polytechnic University, Jiaozuo 454000, China
2 State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004,
China

Abstract: Adding the catalyst is an effective methods to improve hydrogen sorption performance of MgH2. Recently, we
studied the infulunce of the various catalysts, including MoS2, MoO2, Fe3S4, WS2, LaFeO3, MgTiO3 and 2D TiC MXene,on the hydrogen absorption/desorption kinetics of MgH2. The dehydrogenation temperature, hydriding/dehydriding rate
and the activation energy of the hydrogen desorption process are estimated, and the catalytic mechanism of thecatalysts has also been analyzed.

Background
Magnesium (Mg) is considered a promising candidate
material for reversible hydrogen storage owing to its highhydrogen storage capacity, outstanding reversibility andlow cost [1]. However, the hydrogen desorption
temperature of Mg hydride is usually very high due to thestrong affinity between magnesium and hydrogen.
Therefore, it becomes a critical issue to improvehydrogenation and dehydrogenation kinetics for thewidespread application of hydrogen storage materials
containing Mg. It is confirmed that adding various
catalysts is one of the effective methods to decrease thehydrogen sorption temperature and improve the rate of
hydrding/dehydriding.

Present work
(1) MoS2 has a superior catalytic effect over MoO2 on
improving the hydrogen kinetic properties of MgH2 [3].
The hydrogen desorption temperature decreased from662.10 K (pure MgH2) to 650.07 K (MgH2+20 wt.%MoO2)
and 640.34 K (MgH2+20 wt.%MoS2). According to the
Kissinger plot, the activation energy of the hydrogen
desorption process is estimated to be 101.34 kJ/mol of
MgH2 with MoO2 and 87.19 kJ/mol of that with MoS2,
indicating that the dehydriding process enhancement of
the hydriding/dehydriding kinetics of MgH2 is attributed tothe presence of MgS and Mo or MgO and Mo, whichcatalyze the hydrogen absorption/desorption behaviour of
MgH2. The comparisons between MoS2 and MoO2
suggest that S anion has superior properties than O
anion on catalyzing the hydriding/dehydriding kinetics.

(2) The synthesized Fe3S4 and WS2 were applied as thecatalyst to improve the hydrogen storage properties. The
dehydrogenation temperature of MgH2 by ball-milling with
Fe3S4 and WS2 were markedly reduced by 90 K and 60 K,
respectively. MgH2+20 wt.% Fe3S4 and MgH2+20 wt.%
WS2 could release 3.8 wt.% and 4.2 wt.% hydrogen
within 21 min at 623 K, respectively, while MgH2 was only
2.3 wt.%. These existed new Fe and MgS or W and MgSderived from the reaction between MgH2 and Fe3S4 or
WS2, and the synergetic effect of Fe or W and MgS was
responsible for the improvement of the hydrogen
performances.
(3) The synthesized LaFeO3 or MgTiO3 was applied as
the catalyst to improve the hydrogen storage properties,
The dehydrogenation temperature of MgH2 was reduces
by adding LaFeO3 and MgTiO3, and the hydrogen
sorption kinetics were improved. And the dehydriding
activation energy was also reduced by ball-milling with
LaFeO3 or MgTiO3.
(4) The hydrogen sorption performances of MgH2 were
improved by adding 2D TiC MXene prepared by
exfoliating the MAX phases.

References[1] Lu J, Choi YJ, Fang ZZ, et al. J. Am. Chem. Soc. 2009;
131: 15843-52.
[2] Bogdnovic B, Harwing TH, Spliethoff B. Int. J.
Hydrogen Energy 1993; 18: 575-89.
[3] Jia Y, Han SM, Zhang W, Zhao X, et al. Int J
Hydrogen Energy 2013, 38:2352-6.

Baozhong Liu was born on 18 September 1976 in Qinhuangdao city, China. 2000 Bachelor in
Department of Chemistry, Yanshan Univeristy, Qinhuangdao, China. 2007 Ph.D. in State Key
Laboratory of Rare Earth Resources Utilization, Changchun Institute of Applied Chemistry, CAS,
Changchun, China. 2009 Postdoctor in AIST, Japan. 2014 Professor in College of Materials Scienceand Engneering, Henan Polytechnic University, Jiaozuo, China, Research field: Hydrogen storage
materials, Hydrogen storage electrode alloys, nickel/metal hydride (Ni/MH) secondary battery
Baozhong Liu
Corresponding author: Baozhong Liu, email: bzliu@hpu.edu.cn, Tel. +86-391-3989859

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9 Int. Symposium Hydrogen & Energy

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REACTIVE HYDRIDE COMPOSITE SYSTEMS FOR BOROHYDRIDEDESTABILISATION
Anna-Lisa Chaudhary,1 Nils Bergemann,1 Guanqiao Li,2 Motoaki Matsuo,2 Chiara Milanese,3Shin-ichi Orimo,2 Claudio Pistidda,1 Thomas Klassen1 and Martin Dornheim1
1Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Geesthacht , Germany

2

WPI-Advanced Institute for Materials Research, Tohoku University, Sendai, Japan

3

Pavia H2 Lab, Department of Chemistry, Physical Chemistry Division, University of Pavia, Pavia, Italy

Abstract
Hydrogen as an energy carrier can be used in combination with renewable technologies as a complete clean,green energy source compared to current fossil fuel driven technologies. An effective hydrogen system requires
suitable hydrogen storage to enable the storage of excess energy produced by renewable energy to be used attimes when direct production from renewables is low. This then allows for continuous clean energy supply. One
such storage solution is the use of metal hydrides as they are able to store and release hydrogen by forming
and breaking chemical bonds. Complex hydrides are, especially, very promising as hydrogen-storage materials,
due to their high gravimetric and volumetric capacities. New combinations of complex metal borohydrides ballmilled with the transition metal complex hydrides, ScH2 or Mg2FeH6 are characterised and compared. Initially,
the Reactive Hydride Composite (RHC) systems of Li, Mg and Ca borohydrides are combined with ScH2 anddesorption properties studied using techniques such as in situ synchrotron X-ray analysis and coupled
differential scanning calorimetry with Sieverts apparatus. The effect of ScH2 on the borohydrides did have somedestabilization effect; however, reaction kinetic limitations did not allow the systems to achieve theoretical
thermodynamic equilibrium. Other RHC systems containing light metal borohydrides MBH4 (where M = Li, Na,
Mg, K or Ca) are milled with Mg2FeH6 and desorption properties characterised using thermal property analysis,
mass spectrometry and X-ray diffraction. It was found that these borohydrides combined with Mg2FeH6, at a
specific anionic ratio, underwent simultaneous desorption of the two hydrides, which resulted in a single eventof hydrogen release. These borohydrides-Mg2FeH6 systems also show cationic independence since, all five lightmetal borohydride mixtures desorbed hydrogen within a narrow temperature range centering around 300 qC.

Short CV for Anna-Lisa ChaudharyAnna-Lisa studied chemical engineering including a Master’s degree at the University of Queensland
in Brisbane, Australia. Whist studying her Master’s degree, she also spent 4 years living and working
as an English teacher in Kyoto Japan, occasionally visiting Tsukuba for some in situ X-ray diffraction
experiments. She was fortunate to be asked to work for Plantic Technologies Limited in Melbourne
after completing her studies. After some time, she then went on to complete a Ph.D. at Curtin
University in Perth. Currently, she is working as a research scientist at the Helmholz Zentrum
Geesthacht in Germany whilst travelling to Japan and Italy for collaborative research.

Corresponding author: Anna-Lisa Chaudhary, anna-lisa.chaudhary@hzg.de, +49 (0) 4152 87 2647

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9   Int.  Symposium  Hydrogen  &  Energy    Emmetten,  Switzerland  2015  CIRCUMVENTING   THE   FORMATION   OF   [B12H 12]2-­   SPECIES   FOR  REVERSIBLE  HYDROGEN  STORAGE  1Yigang  YAN,  1Arndt  Remhof,  2Daniel  Rentsch,  1Andreas  Züttel  1

Empa,  Hydrogen  &  Energy,  Dübendorf,  Switzerland  Empa,  Functional  Polymers,  Dübendorf,  Switzerland  2

There   is   a   common   belief   that   [B12H12]   compounds   (e.g.,   MgB 12H12)   form   as   intermediates   and   serve   as   boron   sinks  11preventing  the  re-­hydrogenation  for  metal  borohydrides  such  as  Mg(BH4)2  and  Ca(BH4)2.  In  this  study,  detailed   B  NMR  measurements   provide   evidences   that   [B 12H12]   compounds   can   be   avoided/circumvented   in   the   hydrogen   sorption  process  of  Mg(BH4)2  and  Ca(BH 4)2.  
  Introduction  Results  Metal   borohydrides   display   high   hydrogen   densities   and  thereby   offer   the   hope   to   overcome   the   challenges  associated  with  solid  hydrogen  storage.    

Figure   1   shows   B{ H}   NMR   spectra   of   DMSO-­d6  solutions   of   decomposed   Mg(BH4)2   and   the   reference  samples.  MgB12H12,  a  DMSO  soluble  compound,  was  not  observed   in   the   DMSO-­d6   solutions   of   all   decomposition  products  of  Mg(BH 4)2  from  265  to  400ºC.[2]  For  Ca(BH4) 2,  CaB12H12   was   also   not   observed   in   the   solid   residues   of  decomposition  under  vacuum.    

In   order   to   develop   a   reversible   storage   system   toward  the   practical   applications,   the   hydrogen   desorption  pathway   and   the   key   intermediates   involved   need   to   be  known.   Many   efforts   have   been   raised   to   identify   the  reaction  intermediates  during  the  decomposition  process.  
There  is  a  common  belief  that  [B12H12]  compounds   (e.g.,  MgB12H12)   form   as   intermediates   and   serve   as   boron  sinks   preventing   the   re-­hydrogenation   for   metal  [1]borohydrides   such   as   Mg(BH4) 2   and   Ca(BH4) 2.   
However,   it   is   still   lacking   of   firm   evidences   for   the  formation  of  MB 12H12  (M   =  Mg,  Ca)  and  their  roles  in   the  hydrogen  sorption  process  need  to  be  further  elucidated.  
11
Therefore,   we   carried   out   detailed  B   NMR  measurements   to   identify   the   intermediates   forming  during   the   desorption   processes   of   Mg(BH 4)2   and  Ca(BH4) 2.  

Experimental    

11

1

  

  
Solution-­state   B   NMR   spectra   were   recorded   on   a   5  11Figure   1.   B   NMR   spectra   of   DMSO-­d6    solutions   of   Mg(BH4 )2   mm   inverse   broadband   probe   at   298   K.   For   each  decomposed   at   265   to   400°C   under   dynamic   vacuum,   referred  measurement,   amounts   of   ≈   10   mg   solid   samples   and  to  Mg(BH4 )2  and  MgB12H12.  
about   5   mL   of   water   or   DMSO   were   weighed   into   tight  11References  vials   B   NMR   chemical   shifts   are   reported   in   parts   per  million   (ppm),   externally   referenced   to   a   1.0   M   B(OH)3  [1]  S.  J.  Hwang  et  al.,  J.  Phys.  Chem  C,  2008,  112,  3164.  
1
aqueous   solution   at   19.6   ppm,   and   H   NMR   chemical  [2]   Y.   Yan   et   al.,   Chem.   Comm.,   2015,   DOI:  shifts  are  referenced  to  the  resonances  of  water  (4.7  ppm)  10.1039/C4CC05266H  or  DMSO  (2.49  ppm).    
    2004-­07      PhD  student  at  Institute  of  materials  science  and  engineering,  Sichuan  University,  China.  
  2007-­08      Senior  engineer  at  SAE  Magnetics  (H.K.)  Ltd,  China.  
2008-­09      Postdoctoral  Fellowship  at  Institute  for  Materials  Research,  Tohoku  University,  Japan.    
2009-­11    JSPS  Postdoctoral  Fellowship  at  Institute  for  Materials  Research,  Tohoku  University,  Japan.    
2011-­12    Postdoctoral  Fellowship  at  Empa,  Switzerland.  
2012              Visiting  Scientist  in  Utrecht  University,  the  Netherlands.    
2012-­            Scientist  at  Empa,  Switzerland.  
11

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

  

  

    
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9 Int. Symposium Hydrogen & Energy

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ENERGY AND CO2 AT CEMENT INDUSTRY FOR FUTURE
Fadime HOSOGLU
Holcim Technology Ltd., Im Schachen, CH-5113 Holderbank AG, Switzerland
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FadimeHOSOGLU

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Dr. Fadime Hosoglu has finished school of Engineering in the Environmental engineering inuniversity of Mersin on 2008. During Engineering school have studied Polytechnic of Valencia on
2005. I have studied my Master at University Marne La Vallée in environmental department on 2009.
After my master, I have studied my PhD about: “Production of 1-propanol and 1-butanol from the
mixture methanol and ethanol over hydrotalcite catalyst” at university Science and Technology of
Lille 1 on 2012. From 2012 to 2014 I was Post. Doc. in the team of Prof. Andreas Züttel "Hydrogenand Energy" at Empa in Switzerland were I developed a new experimental setup for theinvestigation of CO2 reduction catalyst and I synthesised new catalysts. Since Sept. 2014 I'm a
project manager at Holcim Technology in Switzerland.

Corresponding author: Fadime HOSOGLU, fadime.hosoglu@holcim.com, Tel.

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Redox&flow&batteries&for&on&demand&hydrogen&production&
Véronique Amstutz, Heron Vrubel, Pekka Peljo, Hubert Girault
Laboratoire d’électrochimie physique et analytique, Ecole Polytechnique Féderale deLausanne
Graphical Abstract

Subtitle

Recently, we have shown that it waspossible to couple a vanadium redox flow
battery with two external circuits to carryout indirect and intermittent waterelectrolysis.
The gist of this approach is to store “junkelectricity” in a redox flow battery when its
prize from the grid or from renewablesources is low and to use this stored redox
energy to carry out indirect electrolysis.
Here, Vanadium(II) can be used to
produce hydrogen whilst Vanadium(V) canbe used to oxidise SO2 to generate
protons and sulfuric acid. Alternatively,
cerium can be used such that cerium IV
can oxidise water to oxygen.
To perform these reactions in external
reactors, it is important to use nanoparticle
catalysts.

We shall discuss here nanoparticles
supported on silica or other ceramics. Two
redox
half-reactions
take
on
the
nanoparticle, e.g. hydrogen evolution and
V(II) oxidation, and we shall discuss boththe thermodynamic and the kinetic
aspects.
More generally, we shall discuss strategies
to develop fuelling stations for tomorrow’s
cars.
References

Renewable& Hydrogen& Generation& from& a&
Dual;Circuit&Redox&Flow&Battery&
V.& Amstutz,& K.E.& Toghill,& F.& Powlesland,& H.&
Vrubel,&C.&Comninellis,&X.&Hu&and&H.H.&Girault&
Energy Env. Sci., 7 (2014) 2350-2358

Prof.&Hubert&Girault&&
Professor,(Laboratory(of(Physical(and(Analytical(
Electrochemistry,(EPFL(

(

&
&
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HIGH  PRESSURE  ALKALINE  ELECTROLYSIS

Michael Ranft1), Thomas
Jordan1), Andreas Class2)

1) Institute for Nuclear and Energy Technology, Karlsruhe Institute of Technology2) Areva Nuclear Professional School, Karlsruhe Institute of Technology
A hydrogen filling station stores hydrogen at a pressure of 450bar. Producing hydrogen at this pressure level with analkaline electrolyser would avoid the need of an external compressor. The approach leads to a less complex system withan increased overall efficiency. Additional a numerical tool reflecting H2 and O2 bubble behaviour at high pressure inpotassium hydroxide solution is developed and validated against appropriate experiments.

Motivation
The Karlsruhe Institute of Technology (KIT) operates afilling station which provides hydrogen for the two fuelcell-based buses that connects the different locations of
KIT. Currently an external supplier provides the requiredhydrogen   on   a   weekly   basis.   In   the   future   “green”  hydrogen shall be produced directly at KIT. Besides thepossible hydrogen sources VERENA [1] and bioliq [2] atCampus North of KIT, a high pressure alkaline
electrolyser is planned which uses the excessive electricenergy from the combined heat and power unit or fromsolar-panel installations within the Campus North.
Alkaline electrolysers are a well-known technology withhigh purity of produced H2 and good scalability. In
combination with our partner Instituto Tecnológico de
Buenos Aires (ITBA) from Argentina a high pressure
electrolysers is planned that provides H2 directly at apressure of about 450bar. The abstinence of acompressor prevents efficiency losses due to H2compression and yields to a higher reliability, due to lesscomplexity of the whole system.

Figure 1: Sketch of the high pressure experiments

Expected Results
At the end of the project a numerical tool exists whichreflects H2 and O2 bubble behaviour at high pressure
alkaline electrolysis. Construction rules are establishedbased on the simulation results for a better gas phasetransport inside the electrolyser and for optimizing thegas/electrolyte separation.

ApproachWith the aid of two-phase flow simulation and supported
experiments an optimized design of the electrolyser isdeveloped with enhanced gas phase transport from cellstack to gas-liquid separator and improved separation
process of H2 and O2 bubbles from the electrolyte The
simulation is based on solving an transport equation forgas mass fraction probability density function (pdf):
𝜕 𝜌𝑓𝜕 𝜌𝑆(𝑦)𝑓+ 𝛻 ∙ 𝜌𝒖𝑓 +𝜕𝑡𝜕𝑡= 𝛻 ∙ 𝐷   𝛻 𝜌𝑓

(1)+

1 𝜕 𝑦 − ⟨𝑌⟩
𝜌𝑓
2 𝜕𝑦
𝜏

Instead using a standard Lagrange approach this pdf isapproximated by a finite number of stochastic fields [3]. A
transport equation for each stochastic field is solved in
the Eulerian framework. This method avoids the EulerLagrange coupling. In addition a new model is developed
describing the bubble/bubble and bubble with freesurface interaction of both H2 and O2 bubbles inpotassium hydroxide solution at pressures up to 450bar.
Validation experiments are done investigating the bubble
production at the electrode surface at high pressure. In asecond series of experiments H2 bubbles are charged ina water column and their behaviour is analysed up to
background pressures of 450bar.

Figure 2: Sketch of the gas-liquid separator
The construction of the electrolyser is done incollaboration with ITBA. They are responsible for theelectrolyser with the gas separator and KIT for the safetyassessment and the integration of the whole system inthe existing hydrogen fuel station.

References[1] VERENA Pilot Plant,
http://www.ikft.kit.edu/english/138.php[2] bioliq Plant, http://www.bioliq.de/english/index.php[3] L. Valiño, Flow, Turbulence and Combustion 60(1998) 157-172.

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Michael Ranft finished his studies of Aerospace Engineering at the TU Dresden, Germany in 2012.
He participated in two semesters abroad at the Universidad del Valle de Atemajac (UNIVA) in
Guadalajara, Mexico and in a half year internship at Airbus in Bremen, Germany. In 2012 he wrote
his diploma thesis in collaboration with MTU Friedrichshafen, Germany at the Karlsruhe Institute ofTechnology (KIT) about the implementation of a new combustion model in the free C++ library
OpenFOAM. After a short period as scientific assistant Michael Ranft started his PhD work on highpressure alkaline electrolysis at KIT.
Michael Ranft
Corresponding author: Michael Ranft, michael.ranft@kit.edu, Tel. +49 721 608-24897

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GAS ATOMISED HYDROGEN STORAGE ALLOYSMariana Spodaryk1*, Larisa Shcherbakova1, Anatoliy Sameljuk1, Oleg Khyzhun1, Yurii
Solonin1, Philippe Mauron2, Arndt Remhof2, Andreas Züttel 2, 3
1

Institute for Problems of Materials Science, NAS of Ukraine, 3, Krzhyzhanovsky Str., 03680, Kyiv-142, Ukraine
Division ‘‘Hydrogen and Energy’’, EMPA Materials Science and Technology, 8600 Dübendorf, Switzerland
3
Ecole polytechnique fédérale de Lausanne (EPFL), Institut des sciences et ingénierie chimiques, CH-1015 Lausanne,
Switzerland
2

The phase composition, morphology, structure, and the surface state of gas atomised AB5 type hydrogen storage alloys
have been investigated. The influence of the production method and the alloy composition on the electrode propertiesare discussed in detail. We propose a mechanism for the capacity degradation of the gas atomised alloy electrodes.

Introduction
The alloy production method, defines the alloy microstructure, influences the electrochemical reaction
kinetics, storage capacity, and especially the cycle
stability of the metal hydride electrodes. High pressure
gas atomisation (HPGA) is a technology with a rapid
6
cooling rate of up to 10 K/s, which allows to produce
intermetallic alloy powders of spherical shape directly inthe µm size range. Large quantity of material can beproduced (up to 10 kg/h) and directly results in uniform,
well-defined particles, does not require the standard
timely grinding process of the AB5-type alloys for battery
electrodes Gas atomized alloy powders are sophisticatednon-equilibrium materials with unique properties for NiMH batteries, e.g. a surface with enhanced corrosion
resistance, leading to an increased cycle stability [1].
However, the electrochemical and hydrogen storage
properties of gas atomized materials are discussed
controversially from the viewpoint of application [1,2],
therefore, the results of a comprehensive study on four
representative gas atomized alloys are presented..

Results and Discussion
The phase composition, morphology, structure, and thesurface state of gas atomised AB5-type hydrogen storage
alloys, where Ni was partially substituted by Co and Al
and La by Mm have been investigated. All samples
exhibit the hexagonal CaCu5−type   structure.   The alloy
composition affected the morphology of the gas atomised
particles: Co-free alloys are spherical and Co-containing
alloys are irregularly shaped. The addition of Co

decreases the surface energy of the alloys, thus leading
to a less spherical shape [3,4]. The gas atomised alloy
electrodes show high electrochemical stability andhydrogen storage capacity. The activation, kinetics andhydrogen storage properties of gas atomised alloys
improve with increasing particle size, and thisimprovement is even more pronounced for Co-containing
alloys. Using impedance spectroscopy we found that thereaction resistance is determined by the surface
composition of the activated alloys. Co-free alloys
activate within a few cycles, show better high rate
discharge ability (4-17C) as compared to Co-containing
alloys, which exhibit the highest cycle stability due to thepassivation of the surface. We propose an alloy
electrodes degradation mechanism based on the
corrosion and decrepitation due to volume expansion [4].
According to it Co-containing alloy electrodes mostly
loose the cycle stability because of mechanicaldecrepitation, whereas the Co-free alloys mostly
degradate from selective dissolution of aluminum.

References[1] Yu.M. Solonin, V.V. Savin, S.M. Solonin et al., J.
Alloys Compd. 253–254 (1997) 594–597.
[2] K. Young, T. Ouchi, A. Banik et al., J. Alloys Compd.
509:10 (2011) 4896–4904.
[3] M. Spodaryk, L. Shcherbakova, A. Sameljuk et al., J.
Alloys Compd. 607 (2014) 32–38.
[4] M. Spodaryk, L. Shcherbakova, A. Sameljuk et al., J.
Alloys Compd. 621 (2015) 225–231.

Short CV of Mariana SPODARYKBorn 17th of October 1988 in Ivano-Frankivsk, Ukraine.
2011 Master Degree on Technical Electrochemistry in Kyiv National University of Technology and
Design, Ukraine
2011 - 2014 PhD student in the Institute for Problems of Materials Science, Ukraine National
Academy of Sciences in Kyiv, Ukraine
Mariana
Spodaryk

2013 - 2014 Guest Scientist at EMPA Materials Science & Technology, Switzerland

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

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INVESTIGATION OF A Pt CONTAINING WASHCOAT ON SIC FOAM FOR
HYDROGEN COMBUSTION APPLICATIONS
A. Fernándeza,b,*,G.M. Arzaca, U.F.Vogtb,c, F.Hosoglub, A.Borgschulteb, M.C. Jimeneza, O.
Montesa, A. ZüttelbaInstituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja. Seville.
bcSpain. EMPA, Dept. Energy, Environment & Mobility, Section Hydrogen & Energy, Dübendorf, Switzerland. Department
Crystallography, Institute of Earth and Environmental Science, Albert-Ludwigs-University of Freiburg, Germany
Abstract:
A commercial Pt based washcoat (Pt/SiC), was studied for the first time as catalyst for hydrogen combustion. Structuralcharacterization was performed using Electron Microscopy, X-Ray diffraction (XRD) and X-Ray Photoelectron
Spectroscopy (XPS). The reaction was monitored for the first time following water concentration by Fourier Transform
Infrared spectra (FTIR). The Pt/SiC catalyst has demonstrated to be active enough to start up the reaction very quickly
at room temperature and very small amounts of material were used to achieve the kinetic regime. The material has been
-1-1able to convert as much as 18.5Lhydrogen.min gPt in conditions of excess of catalyst. The activation energy obtained in-1
kinetic conditions was (35±1) kJ.mol .
________________________________________________________________________________________________
Catalytic hydrogen combustion (CHC, reaction (1)) is a
key reaction in the “hydrogen economy” which can be
employed as a means of heat production as well as forsafety purposes. [1,3]H2 + ½ O2 →  H2O

(1)
-1

Reaction (1) is highly exothermic (-286kJ.mol ) and canbe controlled using appropriate catalysts, in contrast to
flame combustion which produces NOx and presents
safety issues. Thinking of a practical application for (1),catalyst should be prepared in supported form, which
improves dispersion, prevents aggregation and facilitates
its use in successive cycles. For heating purposes,
silicon carbide should be the support of election. To ourknowledge, SiC has not been employed for CHC before.
In this work we used for the first time a commercial Pt
washcoat on highly porous SiC foams (Pt/SiC) as catalyst
for CHC for lean (1% v/v) H2/air mixtures. Kinetic studies
were conducted using a novel method which consists ofmeasuring water concentration by FTIR in the exhaustgas. This method is advantageous with respect to gas
chromatography because permits to monitor the reaction
second-to-second. The material was characterized by
XRD, XPS, Transmission Electron Microscopy (TEM) and
Scanning Electron Microscopy (SEM).
The catalyst is composed of 9-20 nm disperse Pt
nanoparticles decorating a mixture of SiC, Al2O3, SiO2
and small amounts of ceria. Pt particle size wasestimated using Scherrer´s formula (111) resulting in 17
nm. Pt/SiC has demonstrated to be active enough to

ASUNCIÓN FERNÁNDEZ

start up the reaction very quickly at room temperatureand very small amounts of material were used to achieve
the kinetic regime. The material has been able to convert-1-1
in conditions ofas much as 18.5Lhydrogen*min gPt
excess of catalyst. Pt/SiC was studied after use bymeans of XPS and no significant changes on Pt oxidation
states were found with respect to the fresh one.
Catalytic activity was studied in kinetic regime as afunction of temperature. The Arrhenius plot permitted to-1
obtain a (35±1) kJ.mol activation energy.

References[1] V.M. Shinde, et al Catalysis Today 198 (2012) 270279.
[2] A. M. Venezia, et al Surface and interface analysis,
19, (1992) 543-547[3] U. F. Vogt, B. Fumey, M. Bielmann, V. Siong, N.
Gallandat, A. Züttel, Catalytic Hydrogen Combustion
on Porous SiC Ceramics, European Fuel Cell Forum2011, 28 June -1 July 2011, Lucerne Switzerland,
Fuel Cell Applications II, chapter 15 – Session B07
pp. 45-54,

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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PREPARATION OF CO AND CO-B SUPPORTED CATALYSTS BY
MAGNETRON SPUTTERING: A STEP FORWARD IN UNDERSTANDING
THE ACTIVE PHASE AND DEACTIVATION PROCESSES IN SODIUM
BOROHYDRIDE HYDROLYSIS
V. Godinhoa, G.M. Arzacb, M. Paladinic, D. Hufschmidta, L.C. Gontarda, M.C. Jimeneza, A.
Fernándeza,*aInstituto de Ciencia de Materiales de Sevilla, CSIC-Univ. Sevilla. Américo Vespucio 49. Isla de la Cartuja.
Seville. Spain.
In this work we report on the preparation and characterization of Co and Co-B catalysts prepared by magnetron
sputtering supported on polymeric membranes for sodium borohydride hydrolysis. The preparation of both referencematerials with similar microstructure is an intrinsic capability of the sputtering technique and permits us to give new
insights into the study of the active phase and deactivation process, both being at present under intense discussion.

Over the last decade the hydrolysis of hydrogenstorage materials such as sodium borohydride (NaBH4,
SB) has been one of the most investigated approaches
for hydrogen generation. SB is stable in dry air andcombines lightweight with high hydrogen content (10.8
wt%).
NaBH4 + 2H2O      →      4H2 + NaBO2 (1)Tough spontaneous, SB hydrolysis (reaction 1)
needs catalysts to occur at appreciable rates. Co has
demonstrated to be a good choice because its
compromise between activity and cost. However, itsmajor drawback is related to stability: these materials
deactivate upon cycling.
Despite the great number of papers reporting Co
and Co-B based catalysts, the nature of the active phaseis still under intense discussion. Several compounds
0
have been proposed such as Co , CoxBy (cobalt borides),00
Co(BO2)2, (CoB)5H3, or mixtures of Co and B , etc. [1]The major difficulty in the elucidation of the active phaseis SB itself: its reducing and boron-donating capabilities
modify catalysts´ surface during the reaction. Most often
Co-B catalysts are prepared as ultrafine amorphous
powders by using a boron-containing reducing agent(usually SB). This permits to obtain Co in metallic statebecause the protective role of boron compounds forms
altogether a complex Co-B material. [2] The preparationof Co nanoparticles (without boron) of similar size andcrystallinity than the Co-B nanopowder is reallychallenging because, in absence of capping agent, theoxidation of cobalt would be inevitable.

ASUNCIÓN FERNÁNDEZ

We have recently reported the preparation of
supported Co metallic catalysts as thin films bymagnetron sputtering for sodium borohydride hydrolysis.
[3] Magnetron sputtering is a very versatile technique that
permitted us to deposit highly columnar coatings, withhigh surface area to be used as catalysts.
In this work we report on the preparation andcharacterization of Co and Co-B coatings prepared bymagnetron
sputtering
supportedonpolymericmembranes for sodium borohydride hydrolysis. Catalytic
activity of Co and Co-B films is investigated. Techniques
usually applied in the characterization of thin films will behere employed for the analysis of supported catalysts
before and after catalytic test.
Advanced Electron
Microscopy techniques will be also employed to fully
characterize samples from a chemical and structural
point of view. The preparation of Co and Co-B referencematerials with similar microstructure is an intrinsic
capability of the sputtering technique and permits us togive new insights into the study of the active phase anddeactivation process.

References[1]Demirci, U. B et al. Physical Chemistry Chemical
Physics 2014, 16 (15), 6872-6885.
[2]Arzac, G. M et al. Chemcatchem 2011, 3 (8), 13051313.
[3]Paladini, M. et al. Applied Catalysis B-Environmental
2014, 158, 400-409.

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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A MATLAB/SIMULINK® DESIGN PROCEDURE FOR PROTON EXCHANGE
MEMBRANE FUEL CELLS
Domenico De Luca, Petronilla Fragiacomo, Giuseppe De Lorenzo
University of Calabria, Department of Mechanical, Energy and Management Engineering, Rende (CS), Italy
Abstract The paper shows and examines a design procedure for performances estimation of Proton Exchange
Membrane Fuel Cells (PEMFCs), which are expressed through the analytical formulation of polarization curve, power®
output and inlet hydrogen flow rate. The procedure, which has been set up using a Matlab/Simulink model, is based on
the equations derived from the theory of electrochemistry and thermodynamics of PEMFCs. The analytical expressionsof performances can be used in order to evaluate the behaviour of a PEMFC in a power generating system.

Introduction
During the past few decades, PEMFCs have received anincreasing attention especially for use in transportation ininnovative powertrains as substitute of the Internal
Combustion Engine (ICE). [1]In this work, a design procedure has been developed
through a model, shown in Fig. 1, which allows thedefinition of the characteristics of PEMFCs, in terms ofvoltage, power and consumption using input data insideeach block.

exchange current density i0, limiting current density iL,transfer coefficient D, amplification constant D1, masstransport k and internal resistance r. The operating
variables are: operating temperature T, ambient
temperature Text, , operating pressure p, relative humidity
I, stoichiometric ratio at anode StH2 and at cathode StO2.
The cell specifications are: cell area Acell, number of cells
Ncells and membrane thickness tm.

Results
The results show the graphs in which voltage (V), power(W) and hydrogen consumption (g/s) are plotted overcurrent, as shown in Fig. 3.

®

Fig. 1 – Matlab/Simulink model for
performances calculations.
Then, the analytical expressions obtained are used as
look-up tables in the block diagram, shown in Fig. 2,
which contains the simulation of a PEMFC.

Fig. 3 – Results of design procedure.

Model validation
The model validation was done by the comparison
between the results of design procedure and thetechnical datasheet of main PEMFCs manufactures(Horizon, Ballard and Nuvera).

References
Fig. 2 – Block diagram for PEMFC simulation.

Input data
The most important input data used in the model can beclassified in empirical parameters, operating variables
and cell specifications. [2] The empirical parameters are:[1] X. Zhang, J. Guo, J. Chen:  “The  parametric  optimum  analysis   of   a   PEM   fuel   cell   and   its   load   matching”,  Energy, Vol. 35 (2010), pp. 5294-5299.
[2] M.G.   Santarelli,   M.F.Torchio,  P.   Cochis:   “Parameters  estimation of a PEM fuel cell polarization curve andanalysis of their behavior   with   temperature”,   Journalof Power Source, Vol. 159 (2006), pp. 824-835.

Born in 1979. He received a Master Degree in Mechanical Engineering in 2004 at the University ofCalabria. In 2004 he attended a fellowship project at ENEA, Research Center for Energy andEnvironment in Rome, about  “Development of Fuel Cell Use in Railway Field”. From 2005 to 2008
he worked in the R&D departments of private automotive companies in Turin. In 2008 he received a
specialization diploma for teaching at the Polytechnic of Turin and from 2009 to 2013 he worked ina high school as teacher of Mechanics. In 2013 he was visitor student at Hochschule Esslingen,Germany. He is currently developing a PhD program about “Innovative  design  of  hybrid  powertrain  Domenico De Luca
equipped  with  fuel  cells” with Prof. Petronilla Fragiacomo.
Corresponding author: Domenico De Luca, domenico.deluca@unical.it, Tel. +39 333 6575192

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LIBH4: AN ELECTROLYTE FOR ALL SOLID-STATE LI-ION BATTERIES
Didier Blanchard1, Dadi Sveinbjörnsson1, Suwarno2, Tejs Vegge1, and Petra E. de Jongh2
1

Department of Energy Conversion and Storage, Technical University of Denmark, Denmark2

Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, The Netherlands

Lithium borohydride, LiBH4, is potentially interesting as a solid state electrolyte for Li-ion batteries. It consists of a lattice+oof Li cations and BH4 anions and displays high lithium mobility, not at room temperature but above 110 C at which a+transition to a high temperature hexagonal structure occurs. This hexagonal and highly Li conducting phase can bestabilized at room temperature forming a solid solution with lithium halides, with a LiBH4-LiI solid solution yielding the+ohighest Li conduction. Another strategy to stabilize the high temperature polymorph below 110 C is to nano-confine
LiBH4 into mesoporous scaffold, leading to conductivities three orders of magnitude larger than for bulk LiBH4.

Lithium solid electrolytes: a Holy GrailFor quantum leap improvements of the Li-ion batteryenergy densities, safety and lifetimes, the use of solid
electrolytes is a must. Conventional Li-ion batteries
contain organic liquids or gels as electrolytes. These+electrolytes have high Li conductivities but are
flammable and allow lithium dendrite formation, causing
capacity fades and shortened lifetimes. Solid electrolytes
enable the assembly of all-solid-state cells with superior
thermal and mechanical stabilities. They allow the use oflithium metal as anode, which has a higher gravimetricenergy density than any electrodes used with liquid
electrolytes, and as dendrite formation is suppressed, thespace between the electrodes can be reduced.
Furthermore, high energy density sulphur cathodes canbe used, as solid electrolytes suppress the dissolution ofpolysulphides.

A new type solid electrolyte

electrolytes in all-solid-state cells, but the solid solution
electrochemical stability is reduced to 3 V compared to
5 V for the pure LiBH4. [3,4]We recently found [5] that confining the hydride inmesoporous silica scaffolds decreases the phasetransition temperature and brings the conductivity to-1values as high as 0.1 mS.cm at room temperature, thus
three orders of magnitude higher than for bulk LiBH4. The
system is stable over extended ranges of temperatureo(up to 140 C) and potentials (up to 6 V) which makes it
compatible with high voltage cathodes. The stability
against lithium metal as well as the use of this new typeof solid electrolyte in all-solid-state battery has beensuccessfully tested.
This discovery opens up new possibilities for the
production of efficient all-solid-state batteries.

References[1] H. Oguchi, et al., Appl. Phys. Lett. (2009), 94, 141912+

Lithium borohydride, LiBH4, exhibits a high ionic Li
conductivity in its high temperature polymorph (~1-1omS.cm at 120 C). This high temperature phase can bestabilized at room temperature by forming a solid solution
with Li-halides [1]. Using Density Functional Theory
calculations,
Quasi-Elastic
Neutron
Scattering
measurements[2]
andpositronannihilation
spectroscopy, we have studied in detail the mechanism+of the Li conduction in such solid-solutions. We haveshown that these solid solutions can be used as[2] J. S. G. Myrdal, et al., J. Phys. Chem. C (2013), 117,
9084.
[3] D. Sveinbjornsson, J. Electrochem. Soc. (2014), 161,
A1432.
[4] M. Matsuo et al., Adv. Energy Mater. (2011), 1, 161.
[5] D. Blanchard et al., Adv. Funct. Mater. (2014), DOI:
10.1002/adfm.201402538

D. Blanchard is, since 2013, Senior Researcher at the Technical University of Denmark, departmentof Energy Conversion and Storage (Group leader Tejs Vegge). He joined the group in 2008, as
postdoctoral researcher and then scientist. His research focuses on materials for energy storage:solid-electrolytes, metal hydride batteries, ammonia storage and hydrogen storage in complex
hydrides. He developed this later field of research while being postdoctoral researcher in Bjorn
Hauback’s group at the institute for Energy Technology, Norway. D. Blanchard received his Ph.D.
from the Université Joseph Fourier, Grenoble (France), after a curriculum in applied physics,
geophysics and chemistry of the atmosphere.
DidierBlanchard
Corresponding author: Didier Blanchard, dibl@dtu.dk, +45 46775899.

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9 Int. Symposium Hydrogen & Energy

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AEROGELS FOR CO2 CAPTURE
Marco HOLZER1,2, Shanyu ZHAO2, Matthias KÖBEL2, Wim J. MALFAIT2, AndreasZÜTTEL1,2
1) École Polytechnique Fédérale de Lausanne (EPFL), 2) EMPA Materials Science and Technology
Abstract
CO2 may be captured via ad- and desorption from a solid sorbent, often assisted by grafted amine groups . Aerogels
were synthesised with aminosilianes, designed to capture CO2 from 400 ppm in air. A novel silica aerogel absorbershows high CO2 absorption capacities combined with a high surface area, good mechanical strength and open pore
structure resulting in a high performance nanomaterial for CO2 capture.

C=

O

O

=C

=O

O=

O= C

O= C

Overview
Hydrocarbons played a crucial role in the development of
our society and are the most important energy vector formobility. Thus, our society requires synthetichydrocarbons for our future. Burning fossil fuels releases
gaseous products in the atmosphere. This causes a risein CO2 concentration, disturbing the fragile equilibrium of
our ecosystem. Hydrocarbons derived from atmospheric
CO2 are carbon neutral, can be synthesized upon
demand and have the energy density required to fly,contrary to H2.

CO2 capture
In April 2014, the northern hemisphere exceeded 400
ppm CO2 in the atmosphere [1]. In order to concentrate
CO2 from such a low concentration, work has the bedelivered:!"$/!"!

!!"# = !"#$

!"ℎ
$
!"#$
= 0.13!!! ↔ !! 9.10!
!"#!"!
!"#!"!
400!!"

O= C

=O

=O

=O

O= C

=O

Figure 2. Amine silanes, the building
blocks of aerogels absorbing CO2
This is the thermodynamic optimum, resulting in thecorresponding minimum cost assuming electricity isused. However, there is no technology operating evenclose to this value. The energy intensive step is thesorbent regeneration where vacuum and heat are applied
to remove CO2. Aerogels have unique properties, suchas very low density and high surface area. By using
amine silanes (Fig. 2), the basic groups are an intrinsic
material property resulting in high stability andmechanical strength.

References[1] World Meteorological Org., Press Release No. 991

2005 - 06 Exchange Program Milwaukee, USA

Marco Holzer

2011

Internship University Strathclyde, Glasgow, Scotland

2013

Master degree Chem. Bio. Eng. ETH Zürich

2014

Swiss Federal Laboratories, Dübendorf: Alkaline Electrolysis

2014 -PhD EPFL Sion LMER: H2 driven desorption of CO2 sorbents

Marco.Holzer@EPFL.ch, Marco.Holzer@EMPA.ch

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9 Int. Symposium Hydrogen & Energy

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IN SITU X-RAY PHOTOELECTRON SPECTROSCOPY STUDIES ON
HYDROGEN STORAGE AND CATALYSIS
Shunsuke KATO,1 Andreas ZÜTTEL1,2
1. Empa, Swiss Federal Laboratories for Materials Science and Technology, Switzerland
2. École Polytechnique Fédérale de Lausanne (EPFL), Switzerland
The aim is to develop X-ray photoelectron spectroscopy for in situ investigations relevant to a wide range of research
fields such as heterogeneous catalysis and energy storage. Near ambient pressure X-ray photoelectron spectroscopy
has become an emerging tool for determining electronic structure and depth resolved chemical composition for interfacial
reactions.

In Situ X-ray Photoelectron Spectroscopy(XPS)
Near ambient pressure XPS provides information about
the electronic structure of matter (gas, liquid, solid) under
defined conditions and bridges the pressure gap between
an ultra-high vacuum-based surface-science experimentand an experiment simulating realistic conditions at mbar
pressure, thus providing valuable information about
interfacial reactions, gas-solid, gas-liquid, and liquid-solid
reactions.

and the dependence of surface properties on pressure
can be analysed in situ with respect to elemental
composition, oxidation state, and chemical specificity. A
correlation between surface chemistry and surface
properties is determined by in situ XPS analysis.

Fig. 2 Surface analysis by ultrahigh vacuum (UHV) XPS
vs. ambient pressure XPS.

References

Fig. 1 Potential curves for activated chemisorption ofhydrogen on a metal surface covered with a surface layer
and exothermic solution in the bulk.
Therefore, this direct surface analysis has become an
immerging tool in a wide range of applications such asheterogeneous catalysis [1], environmental science [2],and electrochemistry. In heterogeneous catalysis, forexample, restructuring of the surface during reactions[1]

S. Kato, M. Ammann, T. Huthwelker, C. Paun, M.
Lampimäki, M.-T. Lee, M. Rothensteiner, J. A. van
3+
Bokhoven, Quantitative depth profiling of Ce in
Pt/CeO2 by in situ high-energy XPS in a hydrogen
atmosphere, Phys. Chem. Chem. Phys., 2015, inpress.

[2]

M.-T. Lee, M. A. Brown, S. Kato, A. Kleibert, A.
Türler, M. Ammann, Competition between organics
and bromide at the aqueous solution–air interface
as seen from ozone uptake kinetics and X-ray
photoelectron spectroscopy, J. Phys. Chem. A,
2015, in press.

2005 Master of Engineering from Tokai University, Japan. 2007 PhD student at the Laboratory for
Hydrogen & Energy, Empa, Swiss Federal Laboratories for Materials Science and Technology, andat the Department of Physics, the University of Fribourg, Switzerland. 2012 Dr. rer. nat. from the
University of Fribourg. The thesis: Surface properties of hydrides and reactions. 2012 Postdoc atLaboratory of Radio- and Environmental Chemistry, Paul Scherrer Institute, Switzerland. Since 2014
Postdoc at Empa, Swiss Federal Laboratories for Materials Science and Technology.
Shunsuke
KATO
Corresponding author: Shunsuke KATO, shunsuke.kato@empa.ch, Tel. +41 58 765 6086

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Kinetics study on hydrolytic dehydrogenation of alkaline sodium
borohydride catalyzed by amorphous Mo-modified Co-B nanoparticles
Yuan Li b, Dandan Ke b, Yali Du b, Shumin Han a,b,*abState Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, China
College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao 066004, PR China

Abstract: NaBH4 is a good candidate solid hydrogen carrier to supply pure hydrogen for portable application owing to its[1]
combined merits of high hydrogen storage gravimetric efficiency . Some non-noble metallic boride (M-B) or phosphide[2](M-P) show excellent activity in catalyzing hydrolysis of NaBH4 . Co-B is shown to be an effective catalyst in NaBH4[3]hydrolysis reaction, and some modification to Co-B compound has been reported . In our study, Molybdenum-modified
Co-B nanoparticles are obtained by the co-deposition chemical reduction method. The relationship between
microstructure, catalytic activity and kinetic performance for H2 generation by hydrolysis of alkaline NaBH4 is studied. The
synthesized nanoparticles are characterized by amorphous structure with smooth surface and homogeneous particle sizearound 30 nm. Mo promoter in the Co-Mo-B catalyst plays an important role for the high catalytic activity of NaBH4hydrolysis, in which the formed molybdenum oxides on the Co-B surface weaken the bond strength of the H-OH facilitating
the dissociation of water, and promote the whole hydrolysis reaction. As a result, Mo induced Co-B nanoparticles with the, whichoptimal Co/Mo molar ratio of 3:1 exhibit enhanced hydrogen generation rate as high as 4200
is about 2.5 times higher than that of the undoped Co-B catalyst. The promoting effect of Mo in the Co-Mo-B catalyst also
í1í1results in lower activation energy of 43.7 kJ mol as compared to 52.6 kJ mol of pure Co-B catalyst. Kinetic studies
reveal that, in low concentration, first-order reaction is observed with respect to NaBH4, indicating that surface adsorptionof BH4 is the rate-limiting step, whereas, at high concentration, hydrolysis reaction conforms to zero-order reaction owing
to that the hydrolysis rate depends on surface reaction of adsorbed molecules. This work represents a substantial
improvement in the synthesis of non-noble transition metal catalyst, opening the path for the application on catalytichydrogen generation of NaBH4.
Keyword: Mo-modified Co-B catalyst; Sodium borohydride hydrolysis; Hydrogen generation; Kinetics analysis

Fig. 1. TEM images of Co-B samples (a), Co-Mo-B(Co:Mo=3:1) samples (b) and the corresponding EDAX
spectrum of Co-Mo-B (Co:Mo=3:1) samples (c).

Fig. 2. Hydrogen generation volume of alkaline
NaBH4 hydrolysis in the presence of Co-B and
Co-Mo-B catalysts

Fig.3. Proposed mechanism for NaBH4 hydrolysis
catalyzed by Mo-modified Co-Bcatalyst.

References[1] H.B. Dai, Y. Liang, L.P. Ma, P. Wang, J. Phys. Chem. C, 112 (2008) 15886–15892.
[2] S. Carenco, D. Portehault, C. Boissière, N. Mézailles, C. Sanchez, Chemical Reviews, 113 (2013) 7981–8065.
[3] Y. Guo, Z. Dong, Z. Cui, X. Zhang, J. Ma, Int. J. Hydrogen Energy, 37 (2012) 1577–1583.

Shumin Han, Doctor, Professor, research field: hydrogen storage meaterials, electrode materials,
and rare earth chemistry.
In recent years, Professor Han and his group's work focuses mainly on Mg–based hydrogen storage
alloys, light weight hydrogen strorage materials, rare earth–Mg–Ni-based electrode materials andhydrogen generation catalysts.
Shumin Han
Corresponding author: Shumin Han, hanshm@ysu.edu.cn, +86-335-8074648.

619th Int. Symposium Hydrogen & Energy

Emmetten, Switzerland 2015

CATALYTIC EFFECTS OF MAGNESIUM GRAIN BOUNDARIES ON H2
DISSOCIATION
Martin Panholzer1, Markus Obermayer1, Iris Bergmair2 and Kurt Hingerl1
1Center for Surface and Nanoanalytics, Johannes Kepler University Linz

2

Profactor GmbH,Steyr-Gleink, Austria

Abstract: The influence of a Σ10(1124)/[1100] grain boundary in magnesium on the dissociation of the hydrogenmolecule has been investigated by ab initio calculations. It is found that the dissociation barrier is indeed lowered by
0.115eV, including zero point motion, compared to the clean surface. This results in a 25 fold increase in the transition
rate, at desorption temperature of 572K. Furthermore different diffusion paths of hydrogen in and out of the grainboundary plane are investigated.

Introduction
Magnesiumhydride is, due to its high volumetric andgravimetric hydrogen density, an attractive hydrogenstorage material. But there are two major drawbacks
which hinder this storage material from commercial
usage, i) the high desorption energy (resulting in adesorption temp. of 300°C) and ii) the poor kinetics.
Large progress has been made in the last few years in
improving the kinetics. The main improvements areachieved by addition of catalysts and nano structuring of
the materials. The latter is done either by high energy ball
milling (HEBM) which reduces the particle size to somenm, or by serve plastic deformation (SPD) which
increases the density of defects, i.e. grain boundaries(GB) and dislocations.
It has been found by Vegge [1] that dissociation of H2 isthe rate limiting step in ad- and desorption. From thatpoint of view it is clear that reduction of particle size
results in an increase of kinetics. On the other hand
Skripnyuk et al. [2] found that ECAP (equal channel
angular pressing, a method which falls in the class ofSPD) processed material shows similar kinetics
compared to the HEBM treated [3]. This is rather
surprising, since the particle size of the ECAP material,some microns, is huge compared to the HEBM powder.
Therefore naturally the question arises what exactly is
the effect of GB on the dissociation dynamics. In thispaper we investigate possible reaction paths andexamine a potential catalytic effect of GB’s.

we investigated a specific magnesium GB. We found thatfor the rather dense GB H2 diffusion is not possible, but
propose this possibility for less dense GB. This would
drastically increase the effective surface area and asconsequence the kinetics of the hydrogenation process.
Another effect of the GB on the dissociation rate occurs
for GB ending at the surface. A hydrogen molecule canenter the “GB surface layer” with a very low potential
barrier and reach the transition state.
Furthermore the GB will not be as dense as in the bulk
and will therefore have lower potential barriers for further
diffusion.
The results also show that the zero point motion has alarge effect on the energy barrier and the transition rates,
also through the pre factor. The contribution of the zero
point motion mainly contributes to the 25-fold rateincrease at desorption temperature of 572K.
We conclude that the results are a strong hint on acatalytic effect of GB either ending at surfaces or, forrather wide GB, even allowing H2 diffusion, which
drastically increases the effective surface. Further work isnecessary in order to determine which kind of GB or
dislocation has the strongest effect and to reduce
uncertainties due to the real path of the reaction.

References[1] Tejs Vegge. Phys. Rev. B, 70(3):035412, July 2004

Results and Conclusion[2] V.M. Skripnyuk, E. Rabkin, Y. Estrin, and R. Lapovok.
Int. J. Hydrogen Energy, 34(15):6320–6324, August
2009.

The aim of this presentation is to clarify the effects on
dissociation of H2 in a material with a high density ofdefects, as introduced by SPD methods. For that purpose[3] M. Krystian, M.J. Zehetbauer, H. Kropik, B. Mingler,and G. Krexner. J. Alloys Compd., 509:S449–S455,
June 2011.

629th Int. Symposium Hydrogen & Energy

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Date and Place of Birth: February 5, 1980, Linz
Marital status: Partner Martina, Children: Tobias, Olivia, Emma
Nationality: Austria

Employment and education:
2007-2010 Dissertation at Johannes Kepler University Linz (advisor E. Krotscheck). Title: Pair
excitations and exchange effects in the dynamics of strongly correlated Fermiuids
MartinPanholzer

26.8.2010 Promotion passed with distinction
9.-12.2010 Post doc at the Institute for Theoretical Physics, JKU Linz
2011-2013 Post doc at the Institute for electrical drives and power electronics, JKU Linz; ACCM
since 5.2013 Post doc at the Center for Surface and Nanoanalytics, JKU Linz; Project: H2desorb

Scientific interest:
Hydrogen storage in metalhydrides, photocatalysis (theoretical modeling)
Development of microscopic quantum many-body methods for strongly correlated systems

Selected Publications:
H. Godfrin, M. Meschke, H.J. Lauter, A. Sultan, H. M. Boehm, E. Krotscheck, and M. Panholzer.
Observation of a roton collective mode in a two-dimensional Fermi liquid. Nature, 483:576–579,
MAR 2012.
H. M. Boehm, R. Holler, E. Krotscheck, and M. Panholzer. Dynamic many-body theory: Dynamics ofstrongly correlated Fermi fluids. PHYSICAL REVIEW B, 82(22), DEC 6 2010.
M. Panholzer, H. M. Boehm, R. Holler, and E. Krotscheck. Exchange Effects and the Dynamics of
He-3. J. OF LOW TEMP. PHYS., 158(1-2,Sp. Iss. SI):135–140, JAN 2010.
Corresponding author: Martin Panholzer, martin.panholzer@jku.at, Tel. +4373224681478

639th Int. Symposium Hydrogen & Energy

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BOR4STORE – DEVELOPMENT OF A BORON HYDRIDE BASEDINTEGRATED SOFC – METAL HYDRIDE TANK SYSTEM
Klaus Taube1, José Bellosta von Colbe1, Giovanni Capurso1, Julian Jepsen1, Claudio
Pistidda1, Andreas Yiotis2, Michael Kainourgakis2, Athanassios Stubos2, Deniz Yigit3,
Henning Zoz3, Thomas Klassen1, Martin Dornheim1
1Helmholtz-Zentrum Geesthacht, Geesthacht, Germany; 2 National Centre for Scientific Research „Demokritos“, Athens,
Greece; 3 Zoz GmbH, Wenden, Germany

In the frame of the FCH JU project BOR4STORE – “Fast, reliable and cost effective boron hydride based high capacity
solid state hydrogen storage materials” (grant 303428), a metal hydride tank containing ca. 10 kg of a boron hydride
based storage material and storing ca. 1 kg of hydrogen shall be thermally integrated with a high temperature solid oxide
fuel cell (SOFC). Factors like required hydrogen flow for the SOFC at maximum power level, electric efficiency, fuelconsumption, reaction kinetics and engineering and safety requirements lead to a tank design, where the heat from the
SOFC exhaust gases is transferred via a heat exchanger system to the metal hydride tank. The complete system will be
set up in 2015 and tested for verification of the concept and stability of the hydrogen storage capacity during cycling.

Introduction
BOR4STORE (www.bor4store.eu) is a European projectwith the target of a) investigating various kinds of boron
hydride based hydrogen storage materials and b)
selecting the most suitable for a metal hydride tank to be
thermally integrated with a SOFC. Then, a prototype ofsuch an integrated system shall be constructed.

Selection of storage material
The selection of the special kind of boron hydride basedstorage material was based on the following
requirements:
x
x
x
x
x
x

hydrogen capacity t 8 wt.%, t 80 kg H2/m3hydrogen release temperature <450°C
Reaction enthalpy < 40 kJ/(mol H2)
loadable to full capacity in less than 1 hour
high stability of capacity over several tens ofloading and unloading cycles
potential for reaching competitive cost tocompressed hydrogen stores under mass
production conditions

In the broad range of boron based storage materials
investigated in BOR4STORE, so far only one material,
the Lithium based Reactive Hydride Composite 2LiBH4MgH2 (Li-RHC) exhibited the required combination ofproperties. Especially with respect of stability of capacity
most of the investigated materials failed, whereas the LiRHC exhibited stable properties over several tens ofcycles. From PcI measurements of Li-RHC, reactionstenthalpies of 75 kJ(mol H2) for the 1 desorption step
(MgH2 Æ Mg + H2) and of 52.6 kJ/(3mol H2) (2LiBH4 +Mg Æ 2LiH + MgB2 + 3H2) for the 2nd were obtained,
yielding an average of 32 kJ(mol H2). [1]Tank design
The BOR4STORE tank shall be used for supply of acommercial 1.3 kWelectric SOFC. With the electricalefficiency of nominally 40%, an average fuel consumptionof 80% of the input hydrogen flow, a required hydrogenflow at maximum power of 15 Nl/min and the known

reaction thermodynamics and kinetics of the Li-RHC, a
modular tank design was chosen, consisting of 10 - 20
tubes and containing ca. 500 - 1000g each of the storage
material.
The SOFC delivers an outgas flow of ca. 200 Nl/min at
ca. 900°C after an integrated afterburner, used to burn
any unreacted hydrogen and thus consisting of an
air/water vapour mixture. Model calculations, based on
preliminary considerations [2], showed, that this gas
stream delivers enough heat flow at a sufficiently hightemperature and homogeneity of the temperature
distribution via an inert gas based heat exchanger
system to the metal hydride tank for fulfilling therequirements for hydrogen supply of the SOFC.

OutlookDue to the expected high temperature of operation of theheat exchanger between SOFC and metal hydride tankof ca. 600 – 650°C, safety of the system against
accidental hydrogen release and ignition is of uppermost
importance in all design considerations.
Currently, the tank design is discussed with certification
bodies in order to fulfill requirements of European PED
and AD2000 directives. The final design and construction
is expected for early 2015, and testing of the whole
integrated system shall start in early summer 2015.

References[1] J. Jepsen, C. Milanese, A. Girella, G.A. Lozano,l J.
Puszkiel, B. Schiavo, J.M. Bellosta von Colbe, A.
Marini, S. Kabelac, T. Klassen, M. Dornheim;„Fundamental thermodynamic and kinetic propertiesof the Li-RHC system for hydrogen storage”,
submitted[2] A. G. Yiotis, M. E. Kainourgiakis, L. I. Kosmidis, G. C.
Charalambopoulou, A. K. Stubos, “Thermal coupling
potential of Solid Oxide Fuel Cells with metal hydridetanks: Thermodynamic and design considerations
towards integrated systems”, Journal of Power
Sources 269 (2014) 440 - 450649th Int. Symposium Hydrogen & Energy

Emmetten, Switzerland 2015

1979-1986: Study of physics at the University of Hamburg, 1987-1991: PhD Thesis at the Philips
Research Laboratory Hamburg, Dept. Thin Films, 1991-2000: Scientist at the Fraunhofer Institute for
Surface Technology and Thin Films, Braunschweig, 2000-2001: Head of Dept. Forming Technology
at IFU Institute for Forming Technology, Lüdenscheid, since 2002:Scientist at the Institute ofMaterial Science at Helmholtz-Zentrum Geesthacht Research Centre
Coordinator of the FCH JU Collaborative Project "BOR4STORE" (2012 – 2015, www.bor4store.eu/)
and of the Marie Curie ITN ECOSTORE (2013 – 2017, www.ecostore.eu)
Dr. Klaus Taube
Corresponding author: Dr. Klaus Taube, klaus.taube@hzg.de, Tel. +49 4152 87 25 41

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THE PHASE TRANSITION AND HYDROGEN STORAGE PROPERTIES OF
Mg-Ga ALLOYS
Daifeng Wua,b, Liuzhang Ouyanga,b,c, Meiqin Zeng a,b*, Hui Wanga,b, Jiangwen Liua,b, Min Zhua,baSchool of Materials Science and Engineering, Key Laboratory of Advanced Energy Storage Materials of Guangdong Province,
South China University of Technology, Guangzhou, 510641, PR Chinab

China-Australia Joint Laboratory for Energy & Environmental Materials, South China University of Technology, Guangzhou,
510641, PR Chinac

Key Laboratory of Fuel Cell Technology of Guangdong Province, South China University of Technology, Guangzhou, 510641, PR
China

The preparation of Mg-Ga alloys
To obtain Mg-Ga alloys, Mg and Mg5Ga2 were mixed atweight ratio 10:1, considering the solid solubility of Ga is
5wt. % at 573K, under Dielectric Barrier Discharge
Plasma (DBDP) assisted ball milling for 9 hours. Mg5Ga2
was prepared by vacuum induction melting in a magnesia
crucible under the protection of pure argon atmosphere.

Phase transition of Mg-Ga alloys duringhydrogenation and dehydrogenation
process
XRD patterns show that the as-melted and thedehydrogenation samples are mainly made up of Mg5Ga2
phase, with a few Mg2Ga phases. And the hydrogenation
sample is composed of MgH2 and Mg2Ga and Mg5Ga2
phases. These results show the hydrogenation anddehydrogenation process of Mg-Ga alloys is a reversible.

Thermodynamic properties of Mg-Ga alloys
PCI results show that the reversible hydrogen storage
capacity Mg-Ga alloys is 6.7wt%H2. With the increase of
temperature, dehydrogenation and hydrogen plateaupressures rise. Besides, the hysteresis betweenhydrogenation and dehydrogenation are pretty small.

Mg(Ga) + H2 ↔ Mg2Ga + MgH2

(1)

According to the van’t Hoff equation the enthalpy change(ΔH) of dehydrogenation reaction of Mg-Ga alloys arecalculated to be 76.9kJ/mol H2 , which are slightly lower
thanpure Mg measured at the same conditions(79.1kJ/mol H2). Also, DSC test shows that the only
dehydrogenation peak is located at 673K and around
10K lower than pure Mg. According to the above results,
the improved thermodynamics and related mechanism of
the present Mg-Ga alloys should be the same as thosefor the Mg(In) solid solution.

Dehydrogenation kinetics of Mg-Ga alloys
Mg-Ga hydrides thoroughly released 6.5 wt% H2 in 90
minutes at 598K. With the temperature rise, thethoroughly dehydrogenation time is reduced to 15
minutes and 10 minutes at 623K and 658K, respectively.
By fitting the dehydrogenation kinetic curves to JMAK
equation, the dehydrogenation activation energy of MgGa alloys was calculated to be 153kJ/mol, which is lower
than that of pure Mg.

References[1] L. Z. Ouyang, et al. J. Alloys Compd. 2014, 586,113

As there is a single plateau pressure duringhydrogenation and dehydrogenation process, it can be
confirmed that Mg(Ga) solid solution can be formed
during hydrogenation and dehydrogenation process at
relatively high temperature (above 573K) , and thereaction equation should be as follow :Ms Zeng is associate Professor in South China University of Technology. Her research interest liesin the fields of mechanical alloying, hydrogen storage materials, and hardmetals.

Meiqing ZENG
Corresponding author: Meiqing Zeng, memqzeng@scut.edu.cn, Tel. +86-20-87112762

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COMBINED CO2 AND H2 DRIVEN DESORPTION AND CO2 REDUCTION
Marco Holzer, Andreas Züttel
École polytechnique fédérale de Lausanne (EPFL), EMPA Materials Science and Technology
Abstract
Materials absorbing atmospheric CO2 are known and used in cyclic processes such as Temperature Vacuum Swing
Adsorption (TVSA). However, the energy intensive step is the regeneration of the sorbent producing pure CO2, which isthan in a latter step mixed with H2 to produce Hydrocarbons. The author proposes to directly produce a H2/CO2 mixture
by using H2 as a purge gas for sorbent regeneration. Alkaline electrolysis produces H2 at the temperature used in the
TVSA process and excess heat. The reactive mixture of H2/CO2 can be processed to many Hydrocarbons we need inour daily life such as Methanol, Dimethylether, Gasoline, Ethan and many more depending on the choice of the catalyst.

Sorbent
Amine modified aerogels absorb CO2 from atmosphericair. Many sorbent based on amine impregnated Silica
frameworks are known, however, Aerogels have uniqueproperties in regard of density and surface area, a key
feature in adsorption.

Desorption
Once the sorbent is loaded, CO2 has to be removed. Thismay be done by TVSA approached, where 50 mbar and85-95°C are applied to the sorbent. This is very energy
intensive since the sorbent is moist due to coabsorptionof water on the basic sorbent [1].

Hydrogen
The Hydrogen required to reduce CO2 can be producedby alkaline electrolysis, a green process requiring only
water and electricity. This process operates at 85°C andan efficiency of 80%. In order to regenerate an amine
sorbent, also a temperature of 85-95°C is required. The
author proposes a synergy between the two processes.
The desorption of CO2 from the sorbent can be enhancedwith moist H2 as a purge gas, producing directly the
mixture of CO2 and H2, ready for the reduction to thedesired hydrocarbon.

CO2 Reduction
With H2, CO2 can be reduced to many hydrocarbons oursociety needs. The key is the catalyst. One well-known

example is the Fischer Tropsch process, where an
Iron/Cobalt system produces a wide mixture, from C1 to
C20. Another established process is Methanol synthesis
where CuZnO/Al2O3 is used. In one step Methanol can bealtered to Dimethylether, a candidate for synthetic fuel.

References[1] C. Gebald, J. a Wurzbacher, A. Borgschulte, T.
Zimmermann, and A. Steinfeld, “Single-component
and binary CO2 and H2O adsorption of aminefunctionalized cellulose.,” Environ. Sci. Technol., vol.
48, no. 4, pp. 2497–504, Feb. 2014.
[2] M. Müller: "Dimethyl Ether“, Ullmann's Encyclopediaof Industrial Chemistry, Electronic Release, WileyVCH, Weinheim 2012.

2005 - 06 Exchange Program Milwaukee, USA

Marco Holzer

2011

Internship University Strathclyde, Glasgow, Scotland

2013

Master degree Chem. Bio. Eng. ETH Zürich

2014

Swiss Federal Laboratories, Dübendorf: Alkaline Electrolysis

2014 -PhD EPFL Sion LMER: H2 driven desorption of CO2 sorbents

Marco.Holzer@EPFL.ch, Marco.Holzer@EMPA.ch

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NATURE OF BONDING IN MgH2:TM DOPED SYSTEMS
B.Paskaš  Mamula, J.Grbović Novaković, B.Kuzmanović, N.Ivanović,N.Novaković
1

Vinča  Institute  of  Nuclear  Sciences,  University  of  Belgrade,  Laboratory  for  Nuclear and Plasma Physics, Belgrade,
SerbiaAb initio electronic structure calculations of the Mg 15TMH32 (TM –transition metal) systems for the entire 3d TM series
have been performed using full-potential (linearized) augmented plane waves method with addition of the local orbitals).
Details of bonding and the mechanism of the TM impurities influence on stability of MgH2 were investigated by means ofelectronic structure change after the TM impurities insertion into MgH2 and  using  the  “atoms  in  molecules”  (AIM)  Bader’s  charge density topology analysis. Obtained trends show that nature of TM-H bonding along the series change in a senseof directional bonding contribution rise, with maximum effect for late 3d metals Co and Ni. The effect of charge
redistribution is nevertheless local and it in general weakens Mg-H bonds and the surrounding MgH2 matrix.

Introduction
It is found that MgH2 sluggish kinetics can be
improved and rather high desorption temperaturesignificantly decreased by nanostructuring (mechanicalmilling, addition of transition metals, their oxides andintermetallics [1].
In our previous work [2], we have used the 2x2x2
supercell approach to investigate the influence of Ti and
Co dopants on MgH2 stability. It has been found thatthese dopants lower the overall stability of MgH2, and thatstronger bonding of TM and surrounding H atoms
weakens the rest of the structure, at least locally.
Here, we emphasize the importance of charge density
properties to get bonding nature details and mechanismsof observed MgH2 matrix destabilization. This wasachieved by means of "atoms in molecules" theory andpeculiarities of charge density in bonding critical points(bCP's).

Calculations details
All calculations have been performed using(L)APW+LO(lo) method. Supercell was constructed by
2x2x2 stacking of MgH2 rutile unit cell using its previously
optimized cell parameters and ionic coordinates. One Mg
atom was substituted with TM and relaxation of ioniccoordinates was again performed without further
optimization of supercell parameters. Every TM atom isoctahedrally coordinated with 6 H atoms at almost equal
distances. Systems were not treated in spin independent
manner. Obtained charge densities were used as input
for further Bader charge analysis.

Results and discussion
Ionic relaxation have confirmed that 3d TM's (with the
exception of Sc) tend to form shorter and stronger bonds
with their first coordination H atoms. The shortest bonds
are found for Fe and Co (~1.65 Å), while the longest (andof comparable length as Mg-H in pure MgH2 (~ 1.95 Å)
for Sc and Zn.
The distribution of so called bonding critical points(obtained from zero charge density gradient and specificsaddle point configuration conditions) and bonding paths
connecting two atomic sites gives us information about
the existence, strength and nature of atomic interactionsin the system. Beside expected Mg-H nearest neighbour(NN) bonds, charge density topology analysis of pure
MgH2 reveals existence of second neighbour (SN) longer
H-H bond with directional character and possible
contribution to and impact on overall stability of thissystem. Introduction of TM changes this picture. NN
bonding paths persist while SN H-H bonds are missing
in all TM doped systems. We conclude that the bonding
is more directional with significant redistribution ofavailable charge (TM are acting as electron donors)
towards NN TM-H direction. The rise of charge density
values in bonding critical points (Fig. 1a) goes in favourof such a conclusion.
Rise of covalent contribution of these bonds shouldbe accompanied with specific properties of charge
density laplacian. The value of this property is connectedto the ionic-covalency ratio in chemical bonding. The
results are given in fig 1b. The trend obtained does notfollow the trend in TM-H bond lengths and in-between
bCP's charge density values. The reason for this could
be spatial localization of 3d orbitals and specifics of
3 2 X
sp d -d (X-number of the remaining d electrons in the
3d-shell) hybridization.

a)b)

Figure 1. a) charge density and b) laplacian inbonding  CP’s  in  first  TM coordination. Both NN H2 andH4  bCP’s  are  presented,  along  with  SN  (b2)  and  third  nearest  (b3)  neighour  bCP’s.    

References[1] Bassetti A, Bonetti E, Pasquini L, Montone A, Grbovic
J, Vittori Antisari M. Eur Phys J B; 2005; 43:19-27[2] N.Novaković,   Lj.   Matović,   J.   Grbovic   Novaković,  I.Radisavljevic,  M.  Manasijevic,  B.Paskaš  Mamula,  N.  
Ivanović,  Int.J.Hyd.  Energy  35;;  2010; 598-608

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Born in Kraljevo, Serbia 23.10.1977. Graduate degree in physics 2005, Ph.D. candidate at Faculty ofPhysics, University of Belgrade since 2010. From 2010 works in Vinča Institute of Nuclear Sciencesin Laboratory for Nuclear and Plasma Physics as an research associate.

Bojana  Paskaš  Mamula
Corresponding author: Bojana Paskaš  Mamula, email: bpmamula@vinca.rs, Tel.+ 381 11 3408 610

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9 Int. Symposium Hydrogen & Energy

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FROM HYDROGEN TO SYNTHETIC HYDROCARBONS
Andreas ZÜTTEL1,2, Philippe MAURON1,2, Elsa CALLINI1,2, Shunsuke KATO1,2, Marco
HOLZER1,2, Jianmei HUANG1,2
1)

Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciences and Engineering (ISIC), École2)
polytechnique fédérale de Lausanne, EPFL Valais/Wallis, Switzerland,
EMPA Materials Science and Technology,
Dübendorf, Switzerland
Hydrogen is produced from water by means of electrolysis with renewable energy. CO2 is abundant in the atmosphere ata concentration of 400 ppm. The extraction of CO2 and reduction with hydrogen to hydrocarbons leads to synthetic andCO2 neutral fuels. Furthermore, the controlled reaction to a specific product like C10H22 would allow to store large
quantities of renewable energy in easy way based on established technology for diesel. Two major challanges have to be
overcome: 1) energy efficient extraction of CO2 from the atmosphere and concentration to pure CO2 at 1 bar, and todevelop new reaction pathways which allow to reduce CO2 to a specific product.

CO2 FROM THE ATMOSPHERE
The extraction of CO2 from the atmosphere (400 ppm =0.04%) to 1 bar pure CO2 requires the Gibbs freeenthalpy ΔG = 20 kJ/mol which corresponds to 0.126
kWh/kgCO2. However, with the today known adsorption
processes approximately 1.5 to 2 kWh/kgCO2 of heat arenecessary in order to concentrate CO2 [1]. Therefore,
new processes working close to the thermodynamic limit
have to be developed.

Thermodynamically the reduction of CO2 follows theestablished paths of the reversed water gas shift
reaction, Fisch-Tropsch synthesis or the Sabatier
reaction.

CO2 REDUCTION WITH HYDROGEN

Fig. 2. Free enthalpy of the CO2 reduction along theestablished reaction paths (red). The new controlled
reaction path (blue) will be investigated.

References
Fig. 1. Schematig representation of the various reduction
paths of CO2 on a surface with adsorbed H.
The reduction path of CO2 on a surface depends on thereaction conditions e.g. temperature, hydrogen partialpressure, and on the surface composition as well as the
local surface structure. CO2 is reduced to methane (CH4)on Ni and C-C coupling (C2H4) was only found on Cu [2].

AndreasZÜTTEL[1] http://www.climeworks.com/co2-capture-plants.html[2] Y. Hori, Modern Aspects of Electrochemistry 42,(2008), pp 89-189. Electrochemical CO2 Reduction on
Metal Electrodes.

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf,
Switzerland. 1990 Diploma in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr.
rer. nat. from the science faculty UniFR. 1994 Post doc "Amorphous hydrides and optical films" with
AT&T Bell Labs in Murray Hill, New Jersey, USA. 1997 Lecturer at the Physics Department UniFR.
2003 External professor at the Vrije Universiteit Amsterdam, Netherlands. 2004 Habilitation inexperimental physics at the science faculty UniFR. President of the Swiss Hydrogen Association„HYDROPOLE“. 2006 Head of the section “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics
department UniFR. 2009 Guest Professor at IMR, Tohoku University in Sendai, Japan. 2012 Visiting
Professor at Delft Technical University, The Netherlands. 2014 Full Prof. in Physical Chemistry andhead of the Laboratory of Materials for Renewable Energy (LMER), Institute of Chemical Sciencesand Engineering (ISIC), École polytechnique fédérale de Lausanne, EPFL Valais/Wallis, Switzerland

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

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9th Int. Symposium Hydrogen & Energy

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LOW TEMPERATURE CYCLING OF MG-TI NANOPARTICLES FOR
HYDROGEN STORAGE
Marco Calizzia, Luca PasquiniaaDepartment of Physics and Astronomy - University of Bologna, viale Berti-Pichat 6/2, 40127 Bologna, Italy

In the field of solid state hydrogen storage magnesium is an element of great interest because of the desirable propertiesof its hydride (MgH2): it is abundant, cheap and light. The two big obstacles that are yet to be overcome are the highworking temperatures and the slow sorption kinetics of the bulk system. In this work we show how the Mg/MgH2 system
can be improved to have better storage properties combinig the addition of a catalyst with the production of
nanoparticles.

Synthesis and characterisation

Hydrogen storage properties

The samples were syntesised evaporating Mg with thetechnique of the Inert Gas Condensation (IGC), aphysical deposition technique, resulting formed bynanoparticles (NPs). Nanostructuring the systemincreases the surface to volume ratio and reduces H
diffusion paths enhancing material's sorption kinetics.
Together with Mg is evaporated another element, titanium(Ti), which is known to be a good catalyst [1-3] and has
the best combination of price and weight among thetransition metals. The NPs are collected on a liquid
nitrogen-cooled rotating cylinder and then in situ
transferred to a secondary chamber where they arehydrogenated at 150°C under 133 mbar of H pressure for
2h. Characterisation is performed with x-ray diffraction(XRD), scanning electron microscope (SEM) and energy
dispersive spectroscopy (EDS) analyses. From SEM and
XRD, NPs turn out to be in the 10-20 nm size range. Mg
and Ti are immiscible with each other, but in these NPs isobserved a metastable substitutional hcp alloy in themetallic phase before hydrogenation. The samples are
succesfully hydrogenated after the mild in situ treatment.

Reaction kinetics and pressure-composition isotherms
are measured with a homemade Sievert apparatus. In
this work we focused on the low-temperature range, thatmeans for Mg-based systems below 300°C, in order tolimit the coarsening and degradation of thenanostructure. For these samples the enthalpy of hydride
formation is unaltered, compared with that of bulk Mg, but
the kinetics are faster by orders of magnitude: these MgTi NPs at 225°C already absorb hydrogen within 200 s at
1,3 bar and desorb in 400 s starting from vacuum.

References[1] A. J. Du et al. J. Phys. Chem. B 109 (2005)[2] S. X. Tao et al., Phys. Rev. B 79 (2009)[3] Cuevas, Korablov, Latroche, PCCP 14 (2012)

Born 10/10/1989 in Bologna.
2011 – Bachelor degree in Physics at University of Bologna, Italy;
2013 – Master degree in Physics at University of Bologna, Italy with thesis “The nanostructured MgTi system for solid state hydrogen storage” in collaboration with ICMPE-CNRS in Paris, France with
Dr. F. Cuevas;
since January 2014: PhD student in Physics at University of Bologna, Italy with Dr. L. Pasquini.
Marco Calizzi
Corresponding author: Marco Calizzi, marco.calizzi@unibo.it, +39 051 2095133
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MATERIALS ENGINEERING FOR SOLID OXIDE FUEL CELLS AND
ELECTROLYSERS
Nigel Brandon
Imperial College London
The paper will present work within the authors group on the use of 3D imaging and analysis, and Raman spectroscopy,
to understand the properties and behaviour of porous electrodes for use in solid oxide fuel cells and electrolysers. A
brief overview of technology status in the UK in these areas will also be presented.

Introduction

Raman spectroscopy

There is increasing interest in both high temperature solidoxide fuel cells for the production of heat and power, andin the use of high temperature electrolysers for the
production of hydrogen from steam, and/or the reductionof carbon dioxide to carbon monoxide.
Whilstencouraging progress continues to be made, there
remain challenges regarding the long term durability ofelectrodes for both applications. Work in the authorsgroup is seeking to understanding and mitigate theseissues through the application of advanced 3D imaging
and analysis of electrode microstructure, to inform adesign led approach to the fabrication of optimum
electrode structures, and the application of Raman
spectroscopy to understand carbon formation during CO2
electrolysis, and fuel cell operation on hydrocarbon fuels.

Raman spectroscopy is particularly sensitive to thepresence of carbon on electrode surfaces.
Anelectrochemical cell has been developed that allows suchmeasurements to be made under SOC operating
conditions. Both ex-situ and in-situ measurements havebeen used to explore the formation of carbon during theelectrolysis of carbon dioxide to carbon monoxide, andthe addition of ceria at the electrode-electrolyte has beenshown to inhibit carbon formation [3].

3D imaging and analysis
Recent advances in experimental methods allows us toimage, quantify and model the properties of the porouscomposite electrodes used in Solid Oxide Cells (SOCs)[1]. An example from a recent paper is presented below[2], showing the reconstructed image of a porous Nidoped ceria electrode (sample shown has a size ofaround 2x2x4 µm), fabricated from a ceria ceramic
scaffold impregnated with nickel particles, where thescaffold is shown in grey and the nickel particles ingreen.

References[1] Tariq F, Kishimoto M, Yufit V, Cui G, Somalu M,
Brandon NP, 2014, 3D imaging and quantification ofinterfaces in SOFC anodes, JOURNAL OF THE
EUROPEAN CERAMIC SOCIETY, Vol: 34, Pages:
3755-3761.
[2] Kishimoto M, Lomberg M, Ruiz-Trejo E, Brandon NP,
2014, Enhanced triple-phase boundary density ininfiltrated electrodes for solid oxide fuel cells
demonstrated by high-resolution tomography,
JOURNAL OF POWER SOURCES, Vol: 266, Pages:
291-295.
[3] Duboviks V, Maher RC, Kishimoto M, Cohen LF,
Brandon NP, Offer GJ, 2014, A Raman spectroscopic
study of the carbon deposition mechanism on Ni/CGO
electrodes during CO/CO2 electrolysis, PHYSICALCHEMISTRY CHEMICAL PHYSICS, Vol: 16, Pages:
13063-13068.

Prof Nigel Brandon (NPB) OBE FREng is Director of the Sustainable Gas Institute at Imperial
College London. He is an electrochemical engineer whose research interests lie in electrochemical
devices for energy applications, with over 150 peer reviewed papers and 12 patents in the field. He
is Director of the Hydrogen and Fuel Cell SUPERGEN Hub and Co-Director of the Energy Storage
SUPERGEN Hub. He was awarded the RAE Silver Medal in 2007, the Baker Medal in 2011 for his
work on microgeneration, the ASME Francis Bacon Medal in 2014, and co-founded the fuel cellcompany Ceres Power in 2001 based on his research.
Corresponding author: Prof Nigel Brandon OBE FREng, n.brandon@imperial.ac.uk, Tel. +44 20 7594 5704

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A NEW CLASS OF HYDROGEN SENSING MATERIALS
C. Boelsma1, R. J. Westerwaal1, and B. Dam1
1

Department of Chemical Engineering - Materials for Energy Conversion and Storage,
Faculty of Applied Science, Delft University of Technology,
Julianalaan 136, 2628 BL Delft, The Netherlands
Abstract – We recently discovered a new class of optical hydrogen sensing materials. We demonstrate this by the caseof hafnium hydride, which shows a well-defined relation between the optical response and the applied hydrogenpressures over a very large pressure range (> 7 orders of magnitude. We do not observe any signs of hysteresis, whileobserving a high degree of stability upon cycling. Remarkably, the optical contrast decreases with increasing hydrogencontent.

Optical Fiber Sensors
In a sustainable economy with hydrogen as a majorenergy carrier, a sensitive hydrogen sensor is
indispensable. We focus on optical fiber sensors, which
are ideal for continuous sensing hydrogen in small
spaces and/or in atmospheres that can form explosive
mixtures.
In literature usually two classes of optical hydrogensensing materials are reported. The first class consists of
Pd-based compounds. These compounds show fast andreversible kinetics and are very stable, but the opticalcontrast is rather low with a small detectable range of3
5partial hydrogen pressure (10 – 10 ppm) [1,2]. The
second class consists of Mg-based compounds where
the optical contrast is superior compared to Pd-based
compounds, but the detection range spans also only two
13
orders of magnitude (10 – 10 ppm) [3]. Furthermore,
Mg-based compounds exhibit a large hysteresis, limiting
the possibility to monitor fluctuations in hydrogenconcentration.

are a 10 000 to 1 000 000 times more sensitive than Mgbased and Pd-based compounds, respectively. The
sensors show a high stability upon cycling (the sensors
can be reactivated after 6 months in air without the use ofa protective layer) with good kinetics (response time is in
the range of seconds to minutes at elevatedtemperatures, depending on the pressure change), while
we found no signs of hysteresis.

Optical Contrast
Although electronic and structural properties as functionof the hydrogen content are different for the group IV andgroup V elements, their sensing behavior is the same.
They all show a significant decrease in optical contrast
with increasing hydrogen content. This is remarkable, as
other optical sensing materials (e.g., Mg-based and Pdbased compounds) all show an increase in opticalcontrast with increasing hydrogen content. Here we
discuss the origin of this effect.

References[1] R.J. Westerwaal et al., International Journal of
Hydrogen Energy, 38 (2013).

A New Class
Here we introduce a new class of hydrogen sensing
materials. This class consists of a group IV (Ti, Zr, Hf)and group V (V, Nb, Ta) elements of the periodic table.
We demonstrate their behavior by means of HfHx, whichshows a well-defined relation between optical response
and the pressures over a very large range of at least 7orders of magnitude. First results show that we are able
to detect hydrogen at partial pressures as low as a few
ppb up to a hundred ppm. This means that these sensors[2] R.J. Westerwaal et al., Sensors and Actuators B, 165(2012).
[3] M. Slaman et al., Sensors and Actuators B, 123(2007).

2004 – 2008:

Bachelor Physics and Astronomy, VU University Amsterdam;

2008 – 2011:

Master Physics, Specialization Advanced Matter and Energy Physics;

2011 – Present: Ph.D. in Chemical Engineering, Materials for Energy Conversion and Storage, Delft
University of Technology.

C. Boelsma
Corresponding author: Christiaan Boelsma, c.boelsma@tudelft.nl, 0031-15 27 83891

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Emmetten, Switzerland 2015

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, which can facilitate efficient utilization of
unevenly distributed renewable energy. Here we report an overview of our recent results within new materials forhydrogen storage: (i) synthesis of novel metal borohydrides and studies of their properties, (ii) tailoring materials
properties by formation of eutectic melting systems, and (iii) in situ powder X-ray diffraction for studies of hydrogen
release and uptake reactions. We conclude that the chemistry of hydrides is very divers, towards multi-functional
materials, including ion-conductors for batteries, methanisation of carbondioxide etc.

Metal borohydrides

Multi-functionality

Hydrogen has the highest gravimetric energy density of
all known substances and is attractive for future storageof renewable energy [1]. We have recently developed
new synthesis strategies combining mechano-chemicaland solvent based methods for synthesis of new
hydrides. The metal borohydrides MM’BH4, typicallycontain an alkali metal, M, and a di- or tri-positive cation,M’.  Apparently, the structural complexity increase with theincreasing size of the alkali metal and also the tendency
to form mixed borohydride-halide compounds and ternary
chlorides [1-4]. A fascinating structural chemistry is
discovered within metal borohydrides, e.g. interpenetrated   ‘MOF-like’   networks   or  zeolite-type structures withup   to   30%   ‘empty’   space   in   the   porous   structures   of  JMg(BH4)2, M = Mg or Mn, which additionally canphysisorp molecular hydrogen, e.g. JMg(BH4)2~2H2, Um= ~20 wt% H2 [5,6]. Another polymorph has extremely
dense packing of hydrogen, GMg(BH4)2, UV = 147 g H2/L.
Recently, we stabilized NH4BH4 with extreme hydrogendensity, 24.5 wt% H2, as NH4Ca(BH4)3 (15.7 wt% H2) withhigher decomposition temperature, Tdec = 97 qC [7].

A series of 30 new complex hydride perovskite-typematerials and new synthesis protocols involving rareearth
elements
wasrecentlypresented[7].
Photophysical, electronic and hydrogen storage
properties was discovered along with trends in structural
behaviour. In this view, homopolar hydridic di-hydrogencontacts arise as a potential tool to tailor crystal
symmetries, hence merging concepts of molecularchemistry with ceramic-like host lattices. Furthermore,anion-mixing provides a link to the known ABX3 halides.

Ion conductors for batteries
Recently, a series of new fast Li-ion conductors,
LiM(BH4)3Cl, M = La, Ce, Gd, Pr or Nd, which
simultaneously store significant amounts of hydrogen
was discovered. The conductivity is due to unoccupied
cation position around the large cubane like composite
anions [8]. Closo-boranes containing large anions of2
2
B12H12  or B10H10  are of increasing interest and may
provide ion conductors.

Some metal hydrides are found to react with carbon
dioxide and provide a new approach for direct
metahanisation of CO2. In this talk, we will also illustratethat in situ powder X-ray diffraction is a unique, sensitiveand informative technique for probing gas-solid reactions.

References[1] M. B. Ley, et al, Mater. Today, 2014, 17, 122. [2]Rude, et al, Physica Status Solidi 2011, 208 1754. [3] L.
Jepsen, et al, Mater. Today, 2014, 17, 129. [4] J. Huot, etal. Prog. Mater. Sci. 2013, 58, 30. [5] E. Roedern, et al,
J. Phys. Chem. C, 2014, 118, 23567. [6] Filinchuk, et al,
Angew. Chem. Int. Ed. 2011, 50, 11162. [7] P.
Schouwink, Nature Comm. 2014, DOI: 10.1038/
ncomms6706. [8] Ley et al. Chem. Mater. 2012, 24,
1654.

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) and Research 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, a Carlsberg
research stipend (2005) form the Carlsberg Foundation and a doctor of science degree from the faculty ofscience and technology at Aarhus University. His research interests are focused on synthesis, structural,
physical and chemical properties of new inorganic materials and utilisation of synchrotron X-ray radiation formaterials characterization.
Corresponding author: Torben R. Jensen, trj@chem.au.dk, +45 87155939 (mobile: +45 2272 1486).

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9 Int. Symposium Hydrogen & Energy

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DISCOVERY OF NEW HYDROGEN STORAGE SYSTEMS BASED ON
ORGANIC LIQUIDSDavid Milstein
Department of Organic Chemistry, The Weizmann Institute of Science, Rehovot 76100, Israel

The ability to store and transport H2 within a liquid carrier at standard temperatures and pressures provides many
advantages over current H2 storage methods. However, although potentially significantly more cost efficient than highpressure or cryogenic tanks, the development of efficient liquid-organic hydrogen carrier systems (LOHCs) remains
challenging.
We have developed new catalytic reactions of organic compounds capable of efficiently releasing hydrogen gas(“acceptorless dehydrogenation”) [1], such as dehydrogenative coupling of alcohols to form esters and H2 [2],dehydrogenative coupling of alcohols and amines to form amides and H2 [3], and oxidation of alcohols to carboxylic acids
using water as oxidant, with liberation of H2 [4]. We have also developed the reverse hydrogenation reactions under very
mild pressure and temperatures reactions. These reactions now provide a foundation for novel hydrogen storage
systems. We will describe novel LOHC systems based on new catalysts using inexpensive organic hydrogen carriers
capable of high hydrogen storage capacity. The performance of these systems will be compared with those of reported
LOHC systems.

References[1] C. Gunanathan, D. Milstein. Applications ofacceptorlessdehydrogenation
andrelatedtransformationsinchemical
synthesis.
Science, 2013, 341, 1229712 (review)[3] C. Gunanathan, Y. Ben-David and D. Milstein. Direct
Synthesis of Amides from Alcohols and Amines with
Liberation of H2. Science, 2007, 317, 790-792

David Milstein[2] C. Gunanathan, D. Milstein, Metal-Ligand Cooperation
by Aromatization-Dearomatization: A New Paradigm in
Bond Activation and “Green” Catalysis, Accts. Chem.
Res. 2011, 44, 588-602[4] E.Balaraman, E. Khaskin, G. Leitus, D. Milstein,
Catalytic transformation of alcohols to carboxylic acidsalts and H2 using water as the oxygen atom source.
Nature Chemistry, 2013, 5. 122-125

David Milstein is the Israel Matz Professor of Chemistry and the Director of the Kimmel Center ofMolecular Design at the Weizmann Institute of Science in Israel. He received his Ph.D. degree at the
Hebrew University in 1976 and performed postdoctoral research at Colorado State University, where
together with his advisor, John Stille, he discovered the Stille Reaction. In 1979 he joined DuPont
Company’s CR&D department and in 1986 he moved to the Weizmann Institute, where he headed
the Department of Organic Chemistry in 1996-2005. His research interests include fundamentalorganometallic chemistry, particularly the activation of strong bonds, and the design and applicationsof environmentally benign processes and sustainable energy related processes catalyzed bytransition metal complexes. Awards include: the Kolthoff Prize (2002); the Israel Chemical Society
Prize (2006); the ACS National Award in Organometallic Chemistry (2007); the RSC Sir Geoffrey
Wilkinson Award (2010); the Humboldt Senior Award (2011); and the Israel Prize (2012, Israel’s
highest honor). He was also awarded several lectureships and visiting professorships, and heserves on several Editorial Boards. He is a member of the Israel National Academy of Sciences andHumanities, and the German National Academy of Sciences-Leopoldina.

Corresponding author: David Milstein, david.milstein@weizmann.ac.il Tel. +972-89342599

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RENEWABLE ELECTRICITY TO METHANE: INTEGRATION OF HIGHTEMPERATURE ELECTROLYZER AND METHANATION REACTOR
Arianna Baldinelli, Linda Barelli, Gianni Bidini, Giovanni Cinti*
Affiliation : Department of Engineering, University of Perugia
Abstract : The increased production of energy from renewable sources has recently introduced critical issues, such as
grid congestion and perturbation. Because of the unpredictable, intermittent and fluctuating character of these sources,
such as sun and wind, the integration of energy storage in the energy system at both local and systemic level is required.
This to mitigate grid interconnection issues due to RES plants and to increment their exploitation avoiding curtailments.
To this end, chemical storage is one of the most promising direction, due to high energy density and the possibility oflong term storage application, particularly at local and small grid level [1].
This study presents the concept of a high temperature solid oxide electrolyzer (SOE) integrated with a methanation
reactor (MR). Operating the SOE in co-electrolysis mode [2], the electricity is converted into hydrogen and CO which arethen transformed into methane. The main advantage of this solution is that methane can be distributed by means of awidespread existing net, avoiding the need of a hydrogen storage. At the same time CO2 from an external local source
can be turned back into fuel, realizing CO2 separation and reuse. As a consequence, the infrastructure costs are strongly
less than the ones that a hydrogen-based system would have to face. Starting from the experimental activity, a SOEmodel was developed. Then, the complete system was designed and overall performances were evaluated.

Experimental
A 4 cells SOE was operated in co-eletrcolysis mode to
get experimental data and develop the model. Operative
temperature was kept at 750°C while inlet composition
was varied, in particular H2O/CO2 ratio was changed
keeping a 10% content of H2 in the inlet flow. Total flow
was kept constant at 190 Nl/h. For each composition a2polarization curve was performed up to 0.5 A/cm . Outlet
gas composition was measured during polarization.

Model
Based on experimental data the model of the stack wasdeveloped in Aspen Plus. The electrodes were modelledconsidering electrochemical equilibrium while voltage
was calculated starting from experimental data. A gibbs
reactor was added to the model after the electrochemical
equilibrium. This latter permits to reach gas composition
equilibrium in accordance to gas analysis. Once enthalpy
due at operative reactant utilization was calculated thepolarization curves were used to calculate active area atthermoneutral conditions. Also methanation reactor wasmodelled using available data in literature considering all
occurring reactions. Heat balance of the system was

Giovanni Cinti

obtained integrating the two units and balance of plantcomponents. CO2 and electricity are fed to the system byexternal sources. Efficiency was calculated as the ratio
between total input energy and produced chemicalenergy stored into methane.

System study
The model design was tested in different operative
conditions varying temperature, pressure and gas mix.;
For each condition the integrated system efficiency, as
defined above, was determined. Temperature decreasestrongly effect system efficiency and, in several
conditions, methanation occurs directly inside the stack.
On the other hand, temperature reduction increases
losses into SOE unit; consequently the optimize
operation point was individuated increasing active area.

References[1][2]

H. Chen, T.N. Cong, W. Yang, C. Tan, Y. Li, Y.
Ding, Prog. Nat. Sci. 19 (2009) 291.
C. Graves, S.D. Ebbesen, M. Mogensen, Solid
State Ionics 192 (2011) 398.

Researcher at FCLab of Department of Engineering. Member of research units within projects
developed by University of Perugia in the fuel cell area. Competences in the microCHP fuel cellbased system design and test. Specifically, the latter relates to experimental test on SOFC and
SOEC. SOFC studies focus mainly on effect of innovative fuels (syngas, ammonia, biogas) in termsof efficiency and system integration issues. Contaminant effect is part of these studies with particularattention to H2S and TAR as contaminant of biogas and syngas respectively. Due to the high interestin energy storage, research activity was extended to hydrogen production and, in particular, to hightemperature electrolyzes both in electrolysis and in co-electrolysis, analyzing through experimental
investigation the impact of temperature equilibrium on thermal and energy balance.

Corresponding author: Giovanni Cinti, giovanni.cinti@unipg.ti, +390755853991.

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3D-HYDROGEN MICROSCOPY
G. Dollinger1, M. Moser1, P. Reichart1, S. Wagner², A. Pundt²
1) Universität der Bundeswehr München, LRT2, 85579 Neubiberg, Germany2) Universität Göttingen, Institut für Materialphysik, 37077 Göttingen, Germany
Proton-proton scattering at the Munich microprobe SNAKE gives the unique possibility for sensitive 3D hydrogenmicroscopy [1]. It is especially well suited to investigate microdistributions of hydrogen in any material that interacts withor contains hydrogen. We have shown detection limits as low as 0.08 at-ppm and a submicrometer resolution. A main
advantage of the method is that standardless quantification is possible without any matrix effects. Thus, in terms oflateral resolution, sensitivity and quantification it is the method of choice for hydrogen microscopy in any kind of material.
We show results of 3D-hydrogen microscopy on niobium, tungsten and diamond in order to demonstrate the potential ofthis method for applications in hydrogen storage and fuel cell materials.

Description of 3D-hydrogen microscopemeasuring the sum energy of the coincidently detected

The method of 3D-hydrogen microscopy relies on the use

proton pair. fig. 1of 20 MeV protons that are delivered at the Munich 14
MV tandem accelerator. The proton beam is focused to a
submicrometer sized beam spot by means of the
microprobe SNAKE (Superconducting Nanoscope forApplied nuclear (Kern-) physics Experiments). Protons of
the beam may be elastically scattered from hydrogenatoms in the sample, thus creating two protons that are
emitted on the back side of the sample – if it is thinnerthan about 100 µm - and detected in coincidence (fig. 1).
By scanning the beam across the sample a twodimensional image of the hydrogen distribution is
obtained that quantitatively shows the lateral hydrogen
distribution in the sample. The depth of origin of each of
the detected hydrogen atoms is analyzed in addition by

Applications
The first prove of sub-0.1 at ppm sensitivity and sub-µm
resolution was obtained when analyzing hydrogen at
grain boundaries in chemical vapor deposition (CVD)grown diamond [2] using 3D-hydrogen microscopy.
Regarding hydrogen storage applications, we obtainedlaterally resolved measurements of inhomogeneoushydrogen distributions in niobium thin films when thesolution limit for hydrogen of 0.13 H/Nb in the clamped Dniobium is passed and islands of E-niobium show up thatare detached from their silicon substrate [3]. Fig. 2 shows
an optical micrograph (left) and the correspondinghydrogen distribution in one of the films (right). Thus we
were

able

for

the

first

time

to

demonstrate

inhomogeneous hydrogen loading due to the microscopic
evolution of phase changes in the material duringhydrogen loading. fig. 2

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Referencs[2] P. Reichart, et al., Science 306 (2004) 1537.

[1] P. Reichart, et al., Nucl. Instr. and Meth. B197 (2002),
pp. 134-149.

[3] S. Wagner et al, Int. J. Hydr. Energy 38 (2013) 13822.

Prof. Dr. rer. nat. GÜNTHER DOLLINGER* August 02, 1960 in Kempten, Germany
Universität der Bundeswehr München
Fakultät für Luft- und Raumfahrttechnik
Institut für Angewandte Physik und Messtechnik, LRT 2
Werner-Heisenbergweg 39
D-85577 Neubiberg, Germany
Phone: +49 89 6004 3505
Fax: +49 89 6004 3295
E-mail: Guenther.Dollinger@unibw.de
http://www.unibw.de/lrt2/
EDUCATION
Jun. 1998

Habilitation in Experimental Physics, TU München

Feb. 1990

Ph.D. in Physics, TU München

Dec. 1985

Staatsexamen Lehramt für Gymnasien

1980-1985

Studies of Physics and Mathematics, TU München

ACADEMIC CAREER
Since 2004

Professor (head of institute) for Applied Physics and Metrology,
Faculty for Aerospace Sciences, Universität der Bundeswehr
München

2001-2004

Permanent Staff and Lecturer, Physics Department, TU München

2000-2001

Senior Researcher at National Accelerator Center (nowiThemba Labs)
Somer Set West, South Africa

1988-2000

Member of Staff, Physics Department, TU München

1986-1988

Research Scholar, Physics Department, TU München

RESEARCH FOCUS
Experimental Physics/Materials Science/Metrology/Radiobiology. Ion-matter interaction, Positronmatter interaction, Ion microscopy: development and application in materials science andradiobiology. Positron microscopy: development and application in materials science
HONORS
Prize for most excellent PhD in Physics, TU München, 1990

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THE SWISS COMPETENCE CENTER FOR ENERGY RESEARCH:
HEAT AND ELECTRICTY STORAGE
Thomas J. Schmidt
Electrochemistry Laboratory, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland
The establishment of eight Swiss Competence Centers for Energy Research (SCCER) within the so-called Action Plan
Coordinated Energy Research is part of the Swiss Energy Strategy 2050. Besides other topics – Energy Supply, Grids,
Efficiency in Mobility, industrial process and buildings, Biomass, and Economy, Environment, Law, Behavior – theSCCER Heat & Electricity Storage plays a key role. In this contribution, this SCCER is introduced with its contents, goals
and current achievements.

Introduction
The future of the Swiss energy supply, after the nuclear
energy phase out, will heavily rely on intermittent
renewable energies such as solar or wind. To guarantee
the continuous (temporal and regional), reliable, andcost-efficient supply of power, heat, and fuels derived
from these energy sources, it is critical to develop thescience and technology of electricity storage comprisingadvanced rechargeable batteries and synthetic fuels(hydrogen, hydrocarbons), respectively. In the heatstorage domain short-term and seasonal heat storage
solutions also call for new developments.
The establishment of the Swiss Competence Centers forEnergy Research (SCCER) is a key-element to realize
the Swiss Energy Strategy 2050. It addresses the interuniversity coordination of energy research across
Switzerland. For the period of 2013 to 2016, a total of
CHF 72 million has been spoken to the set-up SCCER inseven predefined action areas including energy storage.
The implementation of the SCCER is supervised by theCommission for Technology and Innovation (CTI).

The SCCER Heat & Electricity Storage
Within the framework of these seven SCCER, the
SCCER on Heat and Electricity Storage is dedicated toactive research on different related topics organized infive work packges.

Her the focus is on Li- and Na-type batteries in terms ofenergy density, cost and the high explorative area of
beyond Li-ion technologies.
Thermal Energy Storage
with a focus on buildings and processes by exploring
advanced adiabatic compressed air storage (AA-CAES),
pumped heat electric storage (PHES) and hightemperature process heat.
Hydrogen Generation and Storage
by exploring emerging technologies in the field including
redox flow batteries, radically lower cost catalysts, andhigh energy density liquid storage routes.
Development
reductionofadvancedcatalysts

for

CO2

Within this work package, the reduction of CO2 bycatalytic and electrocatalytic (co-electolysis) means isstudied aiming at high efficiencies selectivities forsyngas/hydro-carbons production
Technology Interaction of Storage Systems
explores the storage technology in a wider context tomake the SCCER more powerful. Questions oftechnology interaction is part of the research, covering awide range of aspects from socio-economical aspects tosystem integration and modeling

Advanced Battery and Battery Materials
In February 2011, Thomas J. Schmidt became Chair of Electrochemistry at ETH Zurich, combinedwith the appointment as Head of the Electrochemistry Laboratory at Paul Scherrer Institute in
Villigen, Switzerland. Since 2014 Prof. Schmidt is Director of the Swiss Competence Center for
Energy Research (SCCER) Heat & Electricity Storage. After graduating from University of Ulm,
Germany (2000), he spent time as Post-Doc at Lawrence Berkeley National Laboratory (2001) andPaul Scherrer Institut (2002), before he continued his career in industries at BASF Fuel Cell GmbH,
where he led the R&D activities as Director R&D. He received the Charles W. Tobias Young
Investigator Award from the Electrochemical Society in 2010. He was awarded the Otto-Monsted
Visiting Professorship at the Technical University of Denmark (Lyngby) in 2013.
T. J. Schmidt
Corresponding author: T.J. Schmidt, thomasjustus.schmidt@psi.ch, Tel. +41-56-310-5765

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RESEARCH INFRASTRUCTURES FOR RESEARCH AND DEVELOPMENTOF HYDROGEN AND FUEL CELL TECHNOLOGIESOlaf Jedicke
Karlsruher Institute of Technology; Hermann-von-Helmholtz Platz 1; 76344 Eggenstein-Leopoldshafen; GERMANY

Abstract
Successful research and development base especially on the availability of modern laboratories, technical research
installations and in some specific cases, also on big research facilities, such as neutron sources or synchrotron radiation
dedicated to material investigation. Nowadays, this does apply for nearly all kind of scientific work. “Hydrogentechnology” covers very different aspects of essential research and development and thus requires sophisticatedexperimental installations and research facilities, to proceed effectual, to generate new and novel results. However, whatsounds reasonable often lacks success while general instructions do not exist how to determine experimental
installations and/or research facilities to solve or investigate more detailed problems in research and development or to
examine scientific ideas. The Integrating European Infrastructure was created 2011 to resolve this problem. Even more,
the integrating infrastructure likes to support research and development regarding hydrogen and fuel cell technologies
towards the European strategy of sustainable, competitive and secure energy.

H2FC European Infrastructure
H2FC European Infrastructure project was formed 2011
to integrate the European research and development
community around rare and/or unique infrastructureelements that will facilitate and significantly enhance theresearch and development of hydrogen and fuel cell
technology in a broad scope. The project is coordinatedby Karlsruher Institute of Technology (KIT) and combines
19 European’s research centers and universities. The
total project budget of € 10.147.583,60 is dedicated tosupport external research and development by offering
free access to technical research installations, to modify
and improve existing research installations according thenecessities and to team and strengthen the up to now
separated communities (e.g. fuel cell-, safety- andhydrogen technology communities).

H2FC Major Targets
Major targets of H2FC European Infrastructure based
upon identified needs of the different communities withinfuel cells and hydrogen technology:
1.
2.
3.

Transnational Access to research installations
and infrastructures
Joint research on improvements and further
development of research infrastructures
Teaming of the different communities bycompiling and exchange of general and specificknowledgeThree main pillars govern the project work, networking
activities, joint research activities and transnational
access activities, further subdivided in 23 work packages,
whereat each work package has its own objectives[fig.1.0]

Fig. 1.0 Structure of H2FC European Infrastructure
project

H2FC Objectives (Joint Research)
The total budget of € 10.147.583 H2FC European
Infrastructure forebodes the importance of the specifictheme and challenges associated. Main challenge of the
project is to originate a coordinated and integrated
alliance based on complementary, state-of-the-art, oreven beyond state-of-the-art unique infrastructures, toserve the necessities of the scientific hydrogen and fuelcells community and to facilitate world class research.
The key research topics identified are described by thework package headings and focus basically on the
integration, enhancement and improvement of existing
technical research infrastructures:
1.
2.

Facility improvements for investigation of basic
hydrogen properties and material behaviour
Facility improvements for investigation ofcomponents and systems of the hydrogenenergy chain

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9 Int. Symposium Hydrogen & Energy
3.

4.

Emmetten, Switzerland 2015

Methods, protocols and benchmarking on fire
resistance, solid storage materials, fuel cell
degradation and fuel quality
Development of a cyber-laboratory and central
database to practice simulation and modellingon fuel cells and hydrogen safety aspects

H2FC Objectives (Networking)
The networking activities
communities in concerns of:
1.
2.

3.

4.

are

headingthePerformance &Durability

R&D

Relevant education and training actions
Foresight, knowledge and innovation onhydrogen technologies and especially toinvestigate existing scientific bottlenecks but
also to inform and discuss with national andinternational authorities about necessities anddemands
Dissemination and public relations to inform
communities and strengthen collaboration andtransfer of knowledge to generate impact inindustrial aspects
Long term perspectives to develop and install
instruments for sustaining communication andcollaboration

H2FC Objectives (Transnational Access)Main support to European’s hydrogen and fuel cellcommunities will be given through the transnational
access activities, by offering very different technical andexperimental facilities to external users. Approximately
52 different technical installations are offered by the
consortium free of charge to the fuel cell and hydrogen
communities to support scientific ideas, technical

Olaf Jedicke

development and generation of knowledge [fig.2.0].
Access activities are divided into 7 calls and announced
each separately; no exclusion of submitted proposals is
effected by. Access activities in the special concern “freeof charge” ends with the project in October 2015.
Solid
Solid Storage
Storage Materials
Materials
HYSORB,
HYSORB, SOLTEF
SOLTEFFCFC Performance
Performance
H2QF,
H2QF, ETC,
ETC, FCLab
FCLab

H2
H2 Permeation
Permeation
GASTEFGASTEFFCFC Durability
Durability
DurSOFC,
DurSOFC, FCTESTFCTEST

Embrittlement,
Embrittlement, Life
Life time
time analysis
analysis
PretHy,PretHy, HyCy
HyCy
Basic
Basic Material
Material Investigations
Investigations
SINQ,
SINQ, IFEIFE Neutron
Neutron Beam
Beam
H2 Production

StorageTransport

Fuel Cells

Other H2 Application

H2
H2 Sensors
Sensors
SenTeF,
SenTeF, Sens
Sens
Flow
Flow andand Mixing
MixingHySac,HySac, HiPres,
HiPres, TunEn,
TunEn, TTS
TTS
Ignition
Ignition andand Combustion
Combustion
HySac,HySac, HyKa
HyKa (PROFLAM),(PROFLAM), ExCell
ExCellHazards, Risks &SafetyFig.2.0 Experimental and technical portfolio of H2FC
European Infrastructure

Acknowledgement
H2FC European Infrastructure is funded by European
Commission under FP7 framework und Capacities,
project no. 284522
http://www.h2fc.eu
http://ec.europa.eu/research/infrastructures/pdf/h2fc_dec
12.pdfPhysicist and Mathematician; studies elementary particle physics and mathematics at University ofKarlsruhe, scientist at Fraunhofer Community (Institute for Chemical Technology, Pfinztal) science
1992 to developed digital, optical high speed measurement techniques to investigate practically fast
dynamic deformation behavior of polymeric materials. Modeling of polymeric material behavior.
Parallel investigation and application of sub- and super critical water conditions, 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 Ministryof Education and Science (BMBF), to develop and arrange national research- and investigation
programs. Teaching Fluid Dynamics at the University of Cooperative Education since 1994, Higher
Mathematics and Numeric since 2000. Olaf Jedicke started working with EU Framework programsrd
already in the 3 FP, act as project coordinator of BIONIRS, co-coordinator of e.g. HySafe, NanoHy,
ScinTax, RELATE, EUMINAfab and is coordinator of the European infrastructure projects H2FC
European Infrastructure. Since 2011 senior scientist at Institute of Nuclear- and EnergyTechnologies, “Hydrogen Safety Group” in 2011.

Olaf Jedicke; olaf.jedicke@kit.edu; Phone +49 (0) 721 6082 5274

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HYDROGEN STORAGE IN THE FRAMEWORK OF H2FC
E. Callini1, A.Borgschulte1, A. Züttel1,2
1

Empa, Ueberlandstrasse 129, 8600 Duebendorf, Switzerland.

2

EPFL, SB, ISIC, 1015 Lausanne, Switzerland.

Abstract: H2FC European Infrastructure Project is intended to integrate European Infrastructure and support science anddevelopment of Hydrogen and Fuel Cell Technologies towards European Strategy for Sustainable Competitive andSecure Energy. The Project addresses 4 different aspects of hydrogen related research: Storage, Production, End-use /Systems and Safety. This contribution will focus on the state of the art of Hydrogen Storage and how this topic is tackled
in the framework of H2FC project.

Hydrogen Storage – State of the Art
There are 3 different ways to store hydrogen [1], as
illustrated in Figure 1: liquefied [2], as compressed gas[3] and in solid [4] or liquid hydrogen containing species.
The latter category can moreover been differentiatedweather the hydrogen is physisorbed or chemisorbed into
the compounds. For all these different systems thiscontribution will summarize the state of the art, present
the current technology and underline the challenges tostill be addressed.

[2]http://www.lindegas.com/internet.global.lindegas.global/en/images/LT
01_2011_GB17_19666.pdf[3] GreenPower project,meeting, 2011.

Nano-Tera

plenary

annual[4] E. Callini, et al., APL 94, 221905 (2009).
[5] www.h2fc.eu

Hydrogen Storage – H2FC
In the framework of the H2FC project [5], most of theresearch efforts have been focused on storing hydrogenin solid or liquid hydrides. Several Trans National Actions
have been involved in this topic and Empa is one of thehost centres for synthesis and characterization ofhydrogen containing materials. An overview of the
projects and scientific highlights will be presented toillustrate the work and the collaboration within the H2FC
platform.

References[1] A. Züttel, A. Borgschulte, L. Schlapbach, (eds.)
Hydrogen as a Future Energy Carrier, Wiley-VCH,
Heidelberg 2008

Figure 1: Different ways of storing hydrogen. Top as
compressed gas [3], bottom as metal hydride [4],right liquefied [2].

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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TECHNOLOGY AND SAFETY ISSUES RELATED TO REFUELING OF
HYDROGEN CARS
Pietro MORETTO
DG Joint Research Platform, Petten, The Netherlands
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TOWARDS HARMONIZED MEASUREMENTS OF INVESTIGATIONS OF
SOLID HYDROGEN STORAGE MATERIALS
a

a

b

b

c

c

Ulrich Ulmer , Maximilian Fichtner , Pietro Moretto , Marek Bieliewski , Christoph Frommen , Magnus H. Sorby , Georgia
d
d
e
e
f
f
Charalambopoulou , Thanos Stubos , Phillipe Mauron , Andreas Borgschulte , Vasile Iosub , Olivier Gillia
a Karlsruhe Institute of Technology, Institute of Nanotechnology, P.O. Box 3640, D-76021 Karlsruhe, Germanyb Institute for Energy and Transport, European Commission DG-JRC, P.O. Box 2, 1755 ZG, Petten, The Netherlands
c Institute for Energy Technology, P.O. Box 40, 2027 Kjeller, Norway
d National Center for Scientific Research Demokritos, P.O. Box 60037, 15310 Athens, Greecee Division of Hydrogen and Energy, Department of Mobility, Energy and Environment, EMPA, Swiss Federal
Laboratories for Materials Testing and Research, 8600 Dübendorf, Switzerland
f CEA Grenoble, DRT/LITEN/DTH, 17 rue de Martyrs, 38054 Grenoble, France

Abstract: The progress in the development of methods and protocols for a harmonization of the investigation of solidstate hydrogen storage materials in the framework of the H2FC European infrastructure project is presented.
For the implementation of a hydrogen economy, safe andefficient storage of hydrogen is one of the key issues.
Large amounts of hydrogen can only be stored whenbound to a carrier material. That can be an organic liquid,a physisorption material at cryogenic temperatures, or ametal hydride. Such materials must be qualified before
they can be used in an application relevant technicalenvironment. Thus it is necessary to develop harmonised
characterization methods which are targeted atapplication relevant parameters.
The accurate and reliable assessment of the H2 storage
performance of candidate solid stores remains a criticaland controversial issue, severely plaguing solid storage
research by incorrectly measured and overestimatedcapacity values mainly due to the complexity of theexperimental parameters involved. These problems need
to be identified and methods need to be tested tocircumvent these problems.
The partners performed a literature review on existingdata of most relevant solid storage materials. A criticalanalysis of these results allowed the identification oflacks and controversial issues. Smart, in-situ sorption
methodologies were developed with a special attention tointerfaces and sample environments/cells were designed
to couple gas sorption concepts and rigs with calorimetry,mass spectrometry, spectroscopy or XRD/neutron
scattering.
To validate the new characterization platform an interlaboratory comparison on MgH2 is currently performed
with participation of laboratories (H2FC internal andexternal) around the world. The emphasis is put on
calorimetric measurements.
For efficient safety assessment of H storage materials
and systems it is necessary to develop a procedure
where the safety characteristics of a new H storage
material can be assessed at an early stage, with typicalamounts of material and in a way that is alsotransferrable to real storage devices.
In this respect, a method which correlates microstructuraland chemical changes in a material with a slowdown ofabsorption/desorption rates and decreased cycling
capacity has been developed at KIT. These efforts havebeen complemented by the improvement at JRC of acycling test device capable of thousands ofhydrogenation cycles. Regarding the system design, theCOMEDHY installation at CEA that allows themeasurement of hydride materials swelling and shrinking
when absorbing and desorbing hydrogen between 20 °C
and 200 °C under 0-200 bar, had its resolution increased
to obtain accurate and quantitative information of theswelling phenomenon under controlled loading withrespect to the hydride container.
It is expected that the development of these partly uniqueexperimental and modelling capabilities coupled withharmonized round robin approaches will have asignificant impact on the deployment of solid hydrogenstorage materials.

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HYDROGEN SAFETY: THE STATE-OF-THE-ART
Vladimir Molkov
Hydrogen Safety Engineering and Research Centre, University of Ulster, Newtownabbey, BT37 0QB, UK
Abstract. The state-of-the-art and future tasks in hydrogen safety engineering are presented. Calculation of deterministic
separation distances for unignited and ignited releases using the similarity law and the universal flame length correlations
is demonstrated. Spontaneous ignition of hydrogen during the sudden release of hydrogen is discussed. The effect of arelease diameter on delayed ignition overpressure is demonstrated. The increase of local overpressure when usingbarriers is described. Unique for hydrogen so-called the pressure peaking phenomenon is explained. Calculation ofparameters of the hydrogen ventilation system is explained. New correlations for venting of hydrogen-air deflagrations for
mixtures occupying the whole enclosure and only its part are presented. Peculiarities of well-ventilated and underventilated fires are discussed in detail. Some important knowledge gaps and technological bottlenecks are identified.

Introduction
Hydrogen Safety Engineering is defined as theapplication of scientific and engineering principles to theprotection of life, property and the environment from theadverse effects of accidents involving hydrogen [1]. The
state-of-the-art in hydrogen safety engineering ispresented along with some future tasks.

51.7 mm, laminar and turbulent flows, sub-sonic, sonic,
and super-sonic velocities of release.

Deterministic separation distances
Concentration decay in expanded and under-expanded
jets is described by the similarity law validated against awide range of experiments at pressure up to 400 bar, andrelease diameters 0.25-25 mm (Fig. 1). Hazard example
include an intake of flammable mixture into the nearbybuilding ventilation system that can cause an explosion,
etc.

Figure 2. The universal flame length correlation.
There are three separation distances for jet fires.
oSeparation distance 1: 2xLF is the “death” limit (300 C, 20os); Separation distance 2: 3xLF is the pain limit (115 C, 5min); Separation distance 3: 3.5xLF is the “no harm” limito(70 C).
Figure 1. The similarity law for hydrogen concentration
decay in momentum-dominated expanded and underexpanded jets.
The universal flame length correlation allows calculationof flame length for all regimes of hydrogen fires (Fig. 2). It
gives dependence of the dimensionlised by release
diameter flame length LF/D as a function of the product of
two ratios: a ratio of density of hydrogen in the nozzle(can be calculated by means of Cyber-Laboratory,
www.h2fc.eu) to density of surrounding air, and a ratio ofhydrogen velocity in the nozzle to the speed of sound ofhydrogen in the nozzle. The correlation is validated in therange of pressure 0.1-90 MPa, release diameters 0.4-

“Unexpected” conclusion: all three separation distances
for hydrogen jet fire are longer than distance to the lower
flammability limit (LFL) of 4% of hydrogen in air [1].

Selected issues of hydrogen safety
The LES model of spontaneous ignition of hydrogen by“diffusion mechanism” during the sudden release into a
T-shaped channel reproduced experimental results. The
model is based on the eddy dissipation concept andincludes reduced chemistry of hydrogen oxidation in air.
Experimental study of HSL demonstrated that
overpressure during delayed ignition of hydrogen jetstrongly depends on release diameter. At storage
pressure 20 MPa the overpressure of delayed
deflagration of the jet was 16.5 kPa for 9.5 mm diameter

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9 Int. Symposium Hydrogen & Energy
release pipe and there was no overpressure at all for 1.5
mm diameter. The conclusion is to reduce the piping
diameter (in case of full bore rupture) as low asreasonably practical for technological purposes.

Emmetten, Switzerland 2015
New vent sizing correlation for layers of flammablehydrogen-air mixtures is developed and validated for the
first time (Fig. 5).

Introduction of a barrier reduces the separation distancebased on the flame length. However, the overpressureoincreases from 16.5 kPa to 42 kPa for 90 barrier and too
57 kPa for 60 barrier posing potentially higher harm topeople nearby.
The pressure peaking phenomenon has been recently
released phenomenon characteristic for hydrogen. Figure
3 demonstrates overpressure dynamics in the SAE
3garage of size 4.5x2.6x2.6 m (volume 30.4 m ) with a“brick” vent (sizes 25x5 cm, i.e. area of 0.0125 m2).
Release from thermally activated pressure relief device(TPRD) installed at vehicle’s onboard storage is with amass flow rate 390 g/s (350 bar, TPRD diameter D=5.08mm). It can be concluded from Fig. 3 that such garage
will be demolished in 1-2 s.

Figure 5. Vent sizing correlation for layers of hydrogen-air
mixture in enclosures.
General rules for indoor fire regimes in an enclosure with
one vent are derived by numerical study: there is wellventilated fire for small leak rates; then there is atransition to under-ventilated fire with an external flame
for moderate release rates; then under-ventilated fire with
self-extinction is observed for higher flow rates; andfinally again under-ventilated fire with external flame
takes place with very high flow rates. Figure 6 shows
dynamics of external fire (left) and self-extinction regime(right).

Figure 3. Pressure peaking phenomenon for four gases
in SAE garage with a vent of one brick size.
The study within the HyIndoor project has shown that
passive ventilation equation should be used instead offormer natural ventilation equations. The difference
between the two methods is described by a function f(X).
Underestimation by natural ventilation equations is x2
times for lean hydrogen-air mixtures, and overestimation
is x2 times for rich mixtures.

Figure 6. Two regimes of under-ventilated fire: external
flame (left) and self-extinction (right).

Some gaps and bottlenecks in safety
The main objective of hydrogen safety is life safety.
Innovative safety strategies and engineering solutions yet
to be developed to make hydrogen and fuel cell systems
and infrastructure even inherently safer.

Figure 4. Passive ventilation (solid line) against naturalventilation.

Comparatively large deterministic separation distancesfrom unignited release, jet fire, blast wave and fireballduring high pressure vessel rupture have to be reduced.
It can be achieved by a coupled action of reducing therelease (piping, TPRD) diameter and increasing fire
resistance rating of the storage tank.

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9 Int. Symposium Hydrogen & Energy
A promising system of multi-level thermal protection of
on-board storage tank with the use of Intumescent paintand external protective low pressure vessel is shown in
Fig. 7. It is expected that fire resistance rating for theprotected tank can reach 1-2 hours instead of current 612 minutes.

Vladimir Molkov

Emmetten, Switzerland 2015
Figure 7. A system of thermal protection of high pressurestorage tank.

References[1] V. Molkov, Fundamentals of Hydrogen Safety
Engineering (free download eBook,
http://bookboon.com, available since October 2012)

Prof Vladimir Molkov is a physicist graduated from Moscow Institute of Physics and Technology(MIPT). He received PhD degree in Chemical Physics, including Physics of Combustion and
Explosion from MIPT, and DSc degree in Fire and Explosion Safety from All-Russian ResearchInstitute for Fire Protection (VNIIPO). Before joining the University of Ulster (UU) as Professor of Fire
Safety Science in 1999, he worked at VNIIPO as a Head of Department. In 1997-1998 he carried out
joint research with Prof Toshisuke Hirano at the University of Tokyo (UT) as a Fellow of JapaneseSociety for Promotion of Science, and in 2012 visited UT as an advisor of their explosion research
programme. Since 2004 he is specialising in hydrogen safety with thrust on modeling and numericalsimulations. Research interests include but not limited to under-expanded jet releases anddispersion outdoors and indoors, ventilation of unscheduled hydrogen releases, spontaneous
ignition of hydrogen during sudden releases to oxidizer, well- under-ventilated hydrogen fires,
including self-extinction and re-ignition phenomena, modeling and simulations of large-scale
deflagrations and detonations, thermal protection of on-board storage, blast waves and fireballs fromhigh-pressure hydrogen storage tank rupture, mitigation techniques, including deterministic
separation distances, etc. In 2008 he has established and directs the Hydrogen Safety Engineeringand Research Centre (HySAFER) at the University of Ulster, one of key providers of hydrogensafety research and education globally. He has coordinated and participated in major European and
UK projects relevant to hydrogen safety. Since 2012 he is a Visiting Professor at Karlsruhe Instituteof Technology, HECTOR School of Engineering and Management (Germany). Since 2013 he is UK
expert in ISO TC/197 “Hydrogen technologies”.

Corresponding author: Vladimir Molkov, v.molkov@ulster.ac.uk, +447790026451

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STRUCTURAL  STUDIES  OF  COMPLEX  HYDRIDES
Bjørn C. Hauback, Stefano Deledda, Christoph Frommen, Magnus H. Sørby
Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller, Norway
Neutron diffraction is the main method to determine hydrogen/deuterium positions in metal hydrides. For complicatedstructural features the combination of X-ray (including synchrotron radiation) and neutron diffraction is needed to obtain acomplete description of the crystal structures. The rare-earth borohydrides show a big structural diversity, with anion
substitution, polymorphism, different coordination numbers and multiple oxidation states of the rare-earth. Selected
detailed crystal structure studies and in-situ sorption experiments will be described.

Introduction
Detailed knowledge about the positions of the atoms is ofmajor importance both for development of new metal
hydrides and for understanding of their properties.
Neutron diffraction is a unique tool for studies of metal
hydrides since it is the only method to determine thepositions of the hydrogen/deuterium atoms in the crystal
structures. For structural studies the use of deuterium is
crucial due to the challenge with incoherent scatteringwith normal hydrogen. Furthermore for studies of boron11
based compounds, borohydrides, the B isotope has tobe used because of the strong absorption of neutrons in10normal boron (mainly B). The weak interaction ofneutrons with most elements results in determination ofreal bulk properties and easy use of complex sample
environments. Examples of structural studies of novel
aluminium and boron-based complex hydrides will bepresented.

Experimental
The boron-based samples are prepared using ball milling
techniques by mixing LiBH4 and the corresponding rareearth chlorides in different ratios. For neutron diffraction
11
double labelled Li BD4 is used as the starting material.
Most of our powder neutron diffraction (PND)
experiments are performed with the high-resolution
powder diffractometer PUS at the JEEP II reactor at IFE.
For studies of complex structures and samples
containing different phases, the combination of PND and
X-ray diffraction is needed. For very complicatedstructural features and in-situ experiments, the use ofsynchrotron radiation powder X-ray diffraction (SR-PXD)
is important. The SR-PXD experiments are performed at
the Swiss-Norwegian Beamlines (SNBL) at the ESRF in
France. IR, Raman and NMR methods are used in orderto characterize the non-crystalline components in thesamples. TG-DSC, TPD combination with mass
spectrometry and Sieverts apparatus are used for thecharacterization of the hydrogen storage properties.

Results
Selected detailed crystal structure studies and in-situ
desorption and absorption diffraction experiments will be
described. The presentation will address some of ourrecent studies on complex hydrides. By in-situ highpressure NMR and combination of in-situ SR-PXD and
PND the hydrogenation of NaAlH4 have been studied indetails [1]. We have performed a systematic investigationof the rare-earth borohydrides, and the big structural
diversity will be discussed [2]. In these compounds there
are
anion
substitution,polymorphism,
different
coordination numbers and multiple oxidation states of therare-earth. The combination of neutron and synchrotron
radiation X-ray scattering is in particular important andwill be emphasized.

Acknowledgements
Financial support from The Research Council of Norway,
EU 7FP projects FLYHY, BOR4STORE, H2FC and ERANET CONCERT-Japan We acknowledge the skilful
assistance from the staff of SNBL at ESRF.

References[1] T. Humphries, D. Birkmere, B.C. Hauback, G.S.
McGrady, C.M. Jensen, Phys. Chem. Chem. Phys.
(2013) 15, 6179-6181; T. Humphries, J.W.
Makepeace, S. Hino, W.I.F. David, B.C. Hauback, J.
Mater. Chem. A (2014) 2, 16594-16600[2] J.E. Olsen, C. Frommen, T.R: Jensen, M.D. Riktor,
M.H. Sørby, B.C. Hauback, RSC Advances (2014) 4,
1570-1582;

Bjørn C. Hauback is Department Head of the Physics Department at Institute for Energy Technology
and adjunct professor of Physics at the University of Oslo. He has a PhD in physics from NorwegianInstitute of Technology from 1989. His main interests are structure-property relationships ofhydrogen storage materials and neutron diffraction. He is a member of Norwegian Academy ofTechnological Sciences and led the Task 22 on hydrogen storage materials of the IEA Hydrogen
Implementation Agreement in 2006-2012. He will be co-chair of the Gordon Research Conference
Hydrogen-Metal Systems in July 2015.
B.C. Hauback
Corresponding author: Bjørn C. Hauback, bjorn.hauback@ife.no, tel: +47 97 40 88 44.

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Cool Hydrides, Again !
Shin-ichi ORIMO1,2
1
2

WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
Institute for Materials Research, Tohoku University, Sendai 980-8577, JapanThe significance of the research on materials containing hydrogen has increased rapidly and extensively due to theconsideration of hydrogen as a future energy source/carrier. Accumulation of knowledge of hydrogen behavior in metallic,inorganic, and polymer-like materials is vital in order to develop hydrogen production, storage, and transportation
technologies. Besides the practical aspects, fundamental studies of hydrogen in materials are indispensable tounderstand the intrinsic properties of the materials, and in many cases, to modify/improve their properties. In thispresentation, some selected research topics and trends currently underway in Japan will be discussed (partially“reviewed” according to the presentation in MH2014).
- Commercialization of fuel cell vehicles planned in thenext year (recently announced “December 15, 2014”),and on-going improvements of related infrastructures andlegal systems.

?
http://toyota.jp/sp/fcv/catalog/performance.html- Focused research on liquid-state hydrides (ammonia
and methylcyclohexane (MCH), etc.) as hydrogen/energy
carriers.
MCH

3H2

C6H11CH3“Evolution” of Fe-based Complex Hydrides- Multiplicity of complex hydrides, including all-solid-statebattery device studies and applications.

+ TolueneC H CH
6

5

3

Li- Research progress in solid-state hydrides, especiallyusing advanced neutron and synchrotron beamtechniques, combined with high-pressure technique.
- Recent studies on iron-hydrogen systems in bothmaterials science (hydrogen embrittlement/storage) andearth science.

H

B- New phenomena observed in hydrogen-dope materials;
superconductivity and electronic properties.

Shin-ichi ORIMO received his Ph.D. in materials science/physics from Hiroshima University in
1995. He was a JSPS research fellow (1993-1995), a research associate in Hiroshima University(1995-2002), and a guest researcher of Max-Planck Institute for Metal Research awarded byAlexander von Humboldt Fellowship and MEXT Fellowship (1998-1999); and is a professor of
WPI-AIMR / IMR, and the Head of Integrated Materials Research Center for a Low-Carbon
Society, Tohoku University. His research interests are fundamentals and energy-related
applications of hydrides. He was awarded “The Prize for Science and Technology (Research
Category), The Commendation for Science and Technology by the Minister, MEXT (2012)”.
Shin-ichi ORIMO

http://www.hydrogen.imr.tohoku.ac.jp/

Corresponding author: Shin-ichi ORIMO, Email: orimo@imr.tohoku.ac.jp, Tel. (+81)22-215-2093.

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NH3BH3  MODIFIED  Zr(BH4)4· 8NH3  DEHYDROGENATION  PROPERTIES  WITH  

ENHANCED  Jianmei Huanga*, Xuebin Yub, Liuzhang Ouyanga, Min Zhuaa

School of Materials Science and Engineering and Key Laboratory of Advanced Energy Storage Materials of Guangdong
Province, South China University of Technology, Guangzhou 510641, Chinab

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

A new complex system, Zr(BH4)4·8NH3-nNH3BH3 (n = 2, 3, 4, 5), was prepared via ball milling of Zr(BH4)4·8NH3 andNH3BH3 (AB). The combination of two compounds effectively reduced the ammonia release and the dehydrogenation
temperature when compared to the individual compounds. In the optimal composition, Zr(BH4)4·8NH3-4AB, the hydrogenpurity was improved to 96.1 mol.% and 7.0 wt.% of hydrogen was released at 100 qC. These remarkable improvements
are attributed to the interaction between AB and the NH3 group in Zr(BH4)4·8NH3, which enables a more active
δ+ -δ
interaction of H ··· H. These advanced dehydrogenation properties suggest that Zr(BH 4)4·8NH3-4AB is a promising
candidate for potential hydrogen storage applications.

Introduction
Zr(BH4)4·8NH3 shows the highest coordination number of
NH3 groups among all the known metal borohydrideammoniates. It could fast release hydrogen close toambient conditions. Hence, Zr(BH4)4·8NH3 is considered
as a promising chemical hydrogen storage materials.
However, 16.3 mol.% of ammonia is released during thedehydrogenation process of Zr(BH4)4·8NH3, which
reduces the hydrogen purity and amount. Herein,ammonia borane was applied to inhibit the release of[1]ammonia.

Synthesis and Dehydrogenation
The combination system of Zr(BH4)4·8NH3 and NH3BH3
was prepared through ball milling. When compared toZr(BH4)4·8NH3 and pure AB, these composites show amutual dehydrogenation improvement in terms of
reduced toxic by-product gas release, decreasedhydrogen evolution temperature, and enhanced
dehydrogenation kinetics. As shown in Fig.1, thehydrogen purity in the gaseous products is improved withincreasing the amount of AB, and reaches a maximum of
96.1 mol.% for Zr(BH4)4·8NH3-4AB. This composite also
shows a reduced dehydrogenation temperature from 130
qC to 85 qC and releases 7.0 wt.% of hydrogen within 45
min at 100 qC.

Fig.1 Summary of hydrogen release capacity, purity andtemperature.

Mechanism
11

From the FTIR and
B NMR results, thedehydrogenation of Zr(BH4)4·8NH3-4AB occurs throughthe interaction between AB and the NH3 groups inZr(BH4)4·8NH3, resulting in a decrease in thecoordination number of NH3 on the Zr cations. The gas
impurities released from AB as well as Zr(BH4)4·8NH3
were simultaneously reduced. An amorphous B-N based
polymer was found to be the final product.

Reference[1] J. M. Huang et al, J. Mater. Chem. A., accepted.

Born 1987 in Guangxi, China. Jianmei Huang is a PhD student of Materials Processing at South
China University of Technology. Her current research interests are focused on novel borohydridebased hydrogen storage materials.
2009.9-present: A student for continuous Master and PhD study, School of Materials Science andEngineering, South China University of Technology
2013.4-2014.6: Guest PHD student, Department of Materials Science, Fudan University
Jianmei Huang

2014.7-present:Guest PHD student, Empa-Swiss Federal Laboratories for Materials Science andTechnology

Corresponding author: Jianmei Huang, email: hjm052027@163.com, Tel.: +41 768143314

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EXPERIMENTAL   STUDY   OF   A   METAL   HYDRIDE   TANK   WITH   DOUBLE  COIL  TYPE  HEAT  EXCHANGER  BELOW  1.0  MPa  (G)  OPERATION
Akihiro Nakano a,*, Hiroshi Itoa, Satya Shekhar Bhogillaa, Theodore Motykab, Claudio
Corgnaleb, Scott Greenwayc, Bjørn C. Haubackda

National Institute of Advanced Industrial Science and Technology (AIST)
Savannah River National Laboratory (SRNL)c
Greenway Energy LLCdInstitute for Energy Technology (IFE)b

A metal hydride tank, which is operated below 1.0 MPa (Gauge), has been developed with the aim of recovering thereaction heat of metal hydride for the Totalized Hydrogen Energy Utilization System application. The hydrogen mass
flow data from hydrogen production by renewable energy (solar power) and the fuel cell operation, which were obtainedat SRNL, were used for the testing at AIST and the reaction heat recovery rates were evaluated.

Introduction
A metal hydride tank has been developed for the
Totalized Hydrogen Energy Utilization System (THEUS)
1application . The metal hydride tank, which had the same
geometrical configuration set at SRNL, was fabricate witha different composition of the metal hydride alloy for
operation below 1.0 MPa (G). By using the mass flow
controller, the data for the hydrogen production fromrenewable energy and the fuel cell at SRNL werereproduced at AIST. The absorption and desorption tests
were carried out and the reaction heat recovery rates ofthe metal hydride tank were investigated in this study.

Experimental set-up
A double coil type heat exchanger was installed in themetal hydride tank for recovering the reaction heat of themetal hydride. 50kg of MmNi5 (AB5) metal hydride alloy
was placed in the tank. The hydrogen was provided fromhydrogen cylinders. The hydrogen flow rate wascontrolled by a mass flow controller (MFC) and apersonal computer. When the experimental simulations
were carried out, the mass flow data obtained from SRNL
were read into the personal computer and the hydrogenflow rate was reproduced by the MFC.

Experimental results and comments
Fig. 1 presents the experimental results for absorption.
The circulation water temperature was set at 32 °C. Fig.
1a shows the reproduced hydrogen flow rate. 6451 NL ofhydrogen was absorbed in this case. Fig. 1b shows the
P-C isotherm. The maximum pressure was 0.974 MPa.
The hydrogen was fully charged in the metal hydride tank.
Fig. 1c shows the temperature in the tank, and the inlet

Akihiro Nakano

and outlet temperatures of the circulation water.
Temperature drops are presented in Fig. 1c, when thehydrogen flow rate was diminished. It is also noted from
Figs. 1b and 1c that the temperature is more sensitive tothe hydrogen flow rate as compared with the pressure.
The metal hydride reaction heat recovery rate was 83 %.
On the other hand, the fuel cell at SRNL was capable ofproducing 5 kW net of DC power. Since the hydrogen
supply capability of the metal hydride tank was small,small electric loads were selected in the experiments at
SRNL. In case of the experimental simulation using thehydrogen flow rate data with the load of 0.5 kW, thereaction heat recovery rate was 86 %. The details of theexperimental results will be reported in the symposium.

Fig.1 Experimental simulation results. (a) Reproduced hydrogenflow rate. (b) P-C isotherm. (c) The temperatures in eachposition in the tank and the inlet and the outlet temperatures of
the circulation water.

References[1] Masuda M, Kato A, et.al. Energy efficiency evaluationof totalized hydrogen energy utilization system forcommercial buildings. Proc. of 17th world hydrogenenergy conference 2008; Paper No.260, CD-ROM.

1993: Doctor of Philosophy in Engineering of University of Tsukuba.
1994-1996: NASA Jet Propulsion Laboratory (JPL) (Guest Researcher)
1996-2000: Mechanical Engineering Laboratory (MEL)
2001: National Institute of Advanced Industrial Science and Technology (AIST).
(2011)
Savannah River National Laboratory (Guest Researcher)& University of South Carolina (Visiting Professor)(2012-13) Energy Tech. Research Institute (ETRI), Integrated Hydrogen System Group Leader.
(2014- ) ETRI, Hydrogen Energy Technology Group Leader.

Corresponding author: Akihiro Nakano, email a.nakano@aist.go.jp, Tel. +81-29-861-7250

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Emmetten, Switzerland 2015

PORSPECTS FOR POROUS MATERIALS IN HYDROGEN STORAGE ANDGAS SEPARATION
Michael Hirscher
Max Planck Institute for Intelligent Systems, Stuttgart, Germany
In the past 10 years the number of known porous structures is basically exploded, since new types of porous frameworkmaterials, e.g., MOFs, ZIFs, COFs etc., have been synthesized. These novel materials possess extremely high specificsurface areas combined with a well-defined uniform pore size distribution. The presentation will give an overview on the
progress and the limitations of hydrogen storage via physisorption. Furthermore, possible applications in gas separationand especially for hydrogen isotope separation will be discussed.

Porous Materials
For a long time the field of porous materials was
dominated on the one side by activated carbons,possessing an amorphous-like structure and high surface
areas, and on the other side by zeolites, which are
crystalline with well-defined pores, however, limited in
specific surface area below 1000m2/g. The field has
tremendously grown, when porous coordination polymers
or framework materials could be prepared with a stable
and robust structure after removal of solvent molecules,
exhibiting ultra-high porosity and large specific surface
areas [1]. Different classes of these novel highly porous,
crystalline structures, e.g., metal-organic frameworks(MOFs), zeolitic imidazolate frameworks (ZIFs) orcovalent organic frameworks (COFs), have been
extensively studied for applications in gas storage.
Frameworks with small pores and/or even smaller
apertures can be designed enabling sieving effects forgas separation. Recently, quantum sieving in nanoporeswith a diameter near the kinetic extension of thehydrogen molecule was proposed as one promisingpossibility for separating D2/H2 isotope efficiently andeffectively [2].

Hydrogen Storage
For the maximum hydrogen uptake at high pressure and77 K an almost linear correlation with the specific surface
area is found for many different nanoporous frameworkmaterials [3]. Furthermore, frameworks possessing
smaller pores show typically a higher heat of adsorption.
Both, maximum hydrogen storage capacity and heat ofadsorption have to be considered to optimize thematerials for their potential application [4]. Furthermore,

M. Hirscher

the enhancement of the storage capacity at room
temperature by metal doping will be critically assessed.
In general the enhancement is very small and below any
technological relevance [5].

H2/D2 Isotope Separation
In microporous materials hydrogen isotopes can beseparated by two principles: i) confinement in small poresi.e. “Kinetic Quantum Sieving” [2,6] ii) strong adsorption
sites i.e. “Chemical Affinity Quantum Sieving” [7]. For
different framework materials, experimental results will bepresented for the selectivity directly measured by thermal
desorption spectroscopy after exposure to isotope
mixtures of H2 and D2. Both sieving mechanisms will be
discussed regarding possible technical applications.

References[1] G. Férey, Chem. Soc. Rev., 37 (2008) 191; S.
Kitagawa et al., Angew. Chem. Int. Ed., 43 (2004)
2334; O.M. Yaghi et al., Nature, 423 (2003) 705;
X.C. Huang, Y.Y. Lin, J.P. Zhang, X.M. Chen, Angew.
Chem. Int. Ed., 45 (2006) 1557.
[2] J.J.M. Beenakker et al., Chem. Phys. Lett., 232(1995) 379.
[3] M. Hirscher, Angew. Chem. Int. Ed. 50 (2011) 581.
[4] M. Hirscher, M. Schlichtenmayer, J. Mater. Chem.,
22 (2012) 10134.
[5] C. Zlotea et al., J. Am. Chem. Soc., 132, (2010) 2991;
S.B. Kalidindi et al., Chem. Eur. J., 18 (2012) 10848.
[6] J. Teufel et al., Adv. Mater. 2013, 25, 635.
[7] H. Oh et al., ACS Nano, 2014, 1, 761.

Michael Hirscher is group leader at the Max Planck Institute for Intelligent Systems, Stuttgart,
Germany. He studied physics at the University of Stuttgart, Germany and at the Oregon State
University, Corvallis, USA, receiving a Master’s degree, a Diploma, and Ph.D. degree in 1982, 1984,
and 1987, respectively. For his achievements he was awarded the Otto Hahn Medal of the Max
Planck Society in 1988. Prior to taking his position in Stuttgart, he spent a post-doctoral fellowship at
the University of Pennsylvania, Philadelphia, USA. He published over 100 papers and edited
recently the “Handbook of Hydrogen Storage”. Since 2013 he is Operating Agent of Task 32“Hydrogen-based Energy Storage” in the Hydrogen Implementation Agreement of the IEA. His
current research interests focus on nanoporous materials for gas storage and separation.

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

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

Prof. Dr. Rainer Kirchheim

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)
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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SCIENCE OF HYDROGEN & ENERGY AWARD 2014
Qidong WANG is a professor of Department of Materials
Science and Engineering, Zhejiang University. He was bornin 1921, and obtained his BSc degree in 1943 from Zhejiang
University of China, MSc degree in 1948 from Stanford
University and PhD in 1951 in the University of Iowa of USA,
majoring in the heat power of mechanical engineering. He
returned China in January of 1951 to teach and do research
in Zhejiang University until he retired in 2011. His main
research work focuses on hydrogen storage materials andtheir actual applications. Besides the researching tasks andteaching, he has also done many administrative and social
services.
Prof. Dr. Qidong WANG
Prof. Qidong WANG from the Department of Materials Science and Engineering of Zhejiang
University was involved in the fields of mechanical engineering, metallurgical engineering andfunctional materials in his 60 years’ research career. He has made many outstanding
contributions in the topics such as process intensification of melting procedure in cupola,
precision casting of high speed steel cutting tools and developments of new hydrogen storage
materials and systems. In particular, he is well known as a pioneer in the development andapplications of hydrogen storage alloys in China. He has done a lot of excellent work in the
research fields of rare earth based hydrogen storage materials and new metal-hydride systems.
His research interests also focus on the purification and transportation of hydrogen as well as
Ni-MH batteries.
Since 1978 he devoted himself into the research on hydrogen storage alloys and compounds
and their applications for storing and transporting hydrogen and the use of hydrogen as
supplementary fuel for internal combustion engines. He firstly used lanthanum-rich mischmetal,
which has almost the same hydrogen storage capability but the cost of the alloy lowers by one
third, to replace the pure lanthanum. Moreover he firstly employed mechanical milling method toprepare mischmetal cathode materials for hydrogen storage batteries, which hereafter were
widely accepted by peers. He has contributed with his coworkers more than 500 scientificpapers and reports and he has 18 patents and more than 20 awards on his contributions inscientific researches, teaching and social contributions. So far, his scientific papers have been
cited more than 5000 times and his H-index reached as high as 33. Even though at anadvanced age, he is still concerning on the development of hydrogen economy. His endurance
and diligence are the merits we scientific workers should learn from.
We award Prof. Qidong WANG for his outstanding work on hydrogen storage materials andtheir applications with the Science of Hydrogen & Energy prize 2014.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2014

Prof. Dr. Andreas ZÜTTEL

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering
Degree in Chemistry, Burgdorf, Switzerland. 1990 Diploma in
Physics from the Unversity of Fribourg (UniFR), Switzerland.
1993 Dr. rer. nat. from the science faculty UniFR. 1994 SNF
Post doc with AT&T Bell Labs in Murray Hill, New Jersey,
USA. 1997 Lecturer at the Physics Department UniFR. 2003
External professor at the Vrije Universiteit Amsterdam,
Netherlands. 2004 Habilitation in experimental physics at thescience faculty UniFR. President of the Swiss Hydrogen
Association „HYDROPOLE“. 2006 Head of the section“Hydrogen & Energy” at EMPA. Prof. tit. in the Physics
department UniFR. 2009 Guest Professor at IMR, Tohoku
University in Sendai, Japan. 2012 Visiting Professor at Delft
Technical University, The Netherlands

Andreas Züttel has worked on metal hydride electrodes and developed new overstoichiometric
AB2 Laves-phase alloys wher the B atoms partially occupy A-sites. He developed amathematical model for the capacity of a metal hydride electrode. With the discovery of carbon
nanotubes and first reports about the great hydrogen storage capacity of single wall carbon
nanotubes he started to investigated the interaction of hydrogen with nanostructures by meansof electrochemical sorption measurements and described the relationship between thehydrogen density and the materials surface area of nanostructures. Furthermore, the size
dependent hydrogen sorption properties of monodisperse Palladium clusters as small as 55
atoms were investigated electrochemically and modeled by A. Züttel. He intitiated the researchon borohydrides for hydrogen storage 10 years ago and published together with S.I. Orimo
important papers on the properties of borohydrides e.g. a model for the stability and thehydrogen sorption mechanism. Recently his activities have expanded to the reduction of CO2
with hydrogen for the production of synthetic hydrocarbons as fuels. This is the basis to closethe materials cycle for hydrocarbons as energy carriers.
We award Prof. Andreas Züttel for his outstanding work in the science on the interaction ofhydrogen with solids e.g. intermetallic compounds, nanostructures and complex hydrides with
the Science of Hydrogen & Energy prize 2014.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2015

Prof. Dr. Bernard DAM

After the Thorbecke Scholengemeenschap Arnhem
Gymnasium Beta (1969 – 1975) Bernard Dam studied
chemistry at the Radboud Universiteit Nijmegen (1975 –
1982) where he graduated (cum laude) in EPR-spectroscopy
and solid state chemistry, with a minor in philosophy ofscience. His PhD in physical chemistry he received from theRadboud Universiteit Nijmegen (1982 – 1986) for the thesis:"Growth and morphology of classical and superspace
crystals". He joined Philips Research Laboratories (NatLab)
where he worked on the growth and properties of metallic,superconducting and complex oxide thin films by various
vapor deposition techniques (Sputter Deposition, Pulsed
Laser Deposition and Molecular Beam epitaxy) from April
1986 – May 1992. He became Associate Professor at thevrije universiteit amsterdam, with the main areas of research:HTc-superconductivity,
switchable
mirrors,hydrogenstorage, hydrogen sensing. He is co-founder of the Bachelor
program 'Science, Business and Innovation' researcher (May
1992 – January 2009). Since January 2009 he is full
professor in chemistry at Delft University of Technology,
Department of Chemical Engineering, Head of the section'Materials for Energy Conversion and Storage', Scientificdirector Sustainable Energy Technologies-3TU, Chair of theexam committee of the applied science faculty

Bernard Dam's goal is to develop new materials for sustainable energy applications. He want's
to contribute to scientific breakthroughs and see his research transformed into commercial
products. His field is functional thin film materials science: find relations between growth,(defect) structure and physical properties in relation to their application. At present he aims forapplications based on metal hydrides, such as hydrogen sensors, hydrogen storage, hydrogenmembranes and chemochromic windows. In addition, he investigate the mechanism of photoelectrochemical water splitting. The direct conversion of sunlight into fuel has the advantage
that, as compared to electricity, such fuels can be more easily stored.
We award Prof. Bernard Dam for his outstanding work in the science of hydrogen in thin films
witch lead to the "hydrogenography" as a new experimental method for the investigation of thehydrogen diffusion in solids as well as the screening of hydries and the development of a new
type of hydrogen detector with the Science of Hydrogen & Energy prize 2015.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2015
1993-1995 JSPS (Japanese Society for the Promotion of
Sciences) Research Fellow. 1995 Ph. D., Fac. Integrated
Arts and Sci., Hiroshima University, 1995 - 2002 Research
Associate, Hiroshima University. 1998 - 1999 Guest
Researcher, Max-Planck Institute for Metal Research, asAlexander von Humboldt Foundation and Japanese Ministryof Education Fellows. 2002 Associate Professor, Institute forMaterials Research (IMR), Tohoku University. 2009
Professor, Institute for Materials Research (IMR), Head of
Hydrogen Functional Materials Division, Tohoku University

Prof. Dr. Shin-Ichi ORIMO
Shin-Ichi Orimo's early work was on composite hydrides based on Mg where he synthesised
new materials by mechanical alloying and characterized their hydrogen sorption properties. His
fundamental achievements on Mg based composits and nanomaterials e.g. grain boundary
diffusion, amorphisation and kinetics of the hydrogen sorption process is of great importants for
Mg based hydrogen storage materials. From the year 2000 on he investigated the hydrigen
interaction with nanostructured graphite and crabon materials and combined carbon with metal
nanoparticles. In 2003 the paper entitled "Material properties of MBH4 (M = Li, Na, and K)"
which presented the beginning of the worldwide intense research on complex borohydrides.
Many essential contributions for the understanding of the structure, the reaction mechanism andthe hydrogen sorption kinetics came from Orimo's group. Especially to mention the relationshipof the hydrogen desorption temperature and the cation electronegativity. Very early Orimo'sgroup also worked on the combination of complex hydrides and amides. Recently, the hightemperature phase of LiBH4 was stabilized by a partial substitution of the [BH4] with the iodinions leading to a very high ionic conductivity at ambient temperature.
We award Prof. Shin-Ichi Orimo for his outstanding work in the science of hydrides, thediscovery of new hydride systems and tunable properties of hydrides with the Science ofHydrogen & Energy prize 2015.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2015
Michael Hirscher is group leader “Hydrogen storage” at the
Max Planck Institute for Intelligent Systems, Stuttgart,
Germany. He studied physics at University of Stuttgart,
Germany and Oregon State University, Corvallis, USA. For
his achievements during his PhD he was awarded the Otto
Hahn Medal of the Max Planck Society in 1988. Prior to
taking his position in Stuttgart, he spent a post-doctoral
fellowship at the University of Pennsylvania, Philadelphia,
USA. Recently, he edited the “Handbook of Hydrogen
Storage” and is operating agent of IEA-HIA Task 32“Hydrogen-based energy storage” since 2013. His current
research interests focus on nanoporous and nanoscalematerials for gas storage and separation.
Dr.Michael HIRSCHER
Michael Hirscher investigated the hydrogen adsorption in carbon nanostructures from the
beginning of there discovery and especially after the publication of Michael Heben (Heben, M.
J.; Dillon, A. C., “Room-temperature hydrogen storage in nanotubes” Science 2000, 287,
(5453), 593-593.) which turned out to be a missinterpretation of the measurements. M. Hirscher
carefully investigated the surface site occupation of the carbon nanostructures and theinteraction energy. His present studies focus on novel nanoporous framework materials, e.g.,
metal-organic frameworks (MOFs), with high specific surface area and microporosity, which canbe applied for cryo-adsorption tanks.

Furthermore, these crystalline, nanoporous framework materials are investigated for their ability
to separate isotopes of light gases, e.g., hydrogen-deuterium mix--tures, by quantum sieving.
We award Dr. Michael Hirscher for his outstanding work in the science of the interaction ofhydrogen with porous nanostructures, the investigation and description of the quantity ofhydrogen as well as the adsorption energy of the Van-der-Waals interaction of hydrogen withvarious nanoporous materials with the Science of Hydrogen & Energy prize 2015.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2015
Head of Physics Department, Institute for Energy
Technology (IFE), 2011- Scientific responsible Energy
Storage, IFE, 2009- Principal Scientist New Materials, IFE,
2007- Adjunct Professor of Physics, University of Oslo (UiO),
2000- Deputy Head of Physics Department, IFE, 20012011 Principal Research Scientist, Physics Department, IFE,
1993-2007. Postdoctoral Associate, NTH, 1988-1991; IFE,
1991-1993. Fellow, NTH and Research Council of Norway(RCN), 1983-1988. Dr. ing. (PhD) Norwegian Institute ofTechnology (NTH), Trondheim, Norway 1988. Siv. ing.
(Master degree) NTH, Trondheim, Norway 1981.
Prof. Dr. Bjørn HAUBACK
Bjørn Hauback has made enormous contributions to the structure determination of intermetallic
hydrides and complex hydrides, i.e. deuterides. Furthermore, he is an expert in the charge andmagnetic ordering of intercalated compounds as well as oxydes. Hs group was the first
determining the structure of the LiAlD4 and NaAlD4 in the years 2002 and 2003 and heinvestigated the hydrogen desorption reaction of alanates and borohydrides in great detail bysynchrotron and neutron diffraction.
Bjørn Hauback was Operating Agent for IEA Hydrogen Implementation Agreement Task 22 "Fundamental and Applied Hydrogen Storage Materials Development" from 2006. Within thistask an enormous progress on the investigation and understanding of complex hydrides wasachieved.
We award Prof. Bjørn Hauback for his outstanding work in the structur determination of hydrides
and the host materials as well as the complicated structures of substituted complex hydrides
and composite hydrides with the Science of Hydrogen & Energy prize 2015.

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BEST 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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BEST 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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BEST POSTER AWARD 2013
Mr. Moreno DE RESPINIS“Optimization of Anneal Procedure in Metal Oxides: Case
Study of Nanostructured Tungsten Processed via Low-Energy
Helium-Ions”
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
Moreno de Respinis received his bachelor degree in physics at
the University of Milan in 2008, and earned his master degree
in sustainable energy with study line hydrogen and fuel cells at
the Technical University of Denmark (DTU) in 2011. He
concluded his master with a fellowship at the Lawrence
Berkeley National Laboratory with Dr. Heinz M. Frei’s group, in
which he performed mechanistic studies of water photooxidation by visible-light driven Co3O4 catalyst. He is currently
a Ph.D. student at Delft University of Technology where he isresearching on photoanodes for solar water splitting.

“Optimization of Anneal Procedure in Metal Oxides: Case Study of Nanostructured
Tungsten Processed via Low-Energy Helium-Ions”
One challenge in developing highly efficient nanostructured photoelectrodes is to control theirmorphology, crystal phase and stoichiometry. We present a novel physical processing route thatuses high-flux of low-energy helium- ion 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 temperature andcan be tuned between 30 nm and 1 µm. Our research shows that a two-step anneal procedureis optimal to oxidize surface nanostructures into crystalline WO3, preserving the bulk as metallic
W for good electrical contact. As a result, IPCE of 20% is obtained, resulting in an AM1.522
photocurrent of 0.75 mA/cm at 1.23 VRHE (compared to 0.15 mA/cm after standard thermaloxidative anneal). The excellent control over feature size offers an exciting new processing
route to nanostructure materials for e.g. solar water splitting.

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BEST POSTER AWARD 2014
Mr. Yixiao FU"Study on the hydrogenexchange behavior in themetal hydride-LiBH4
composite"
School of Materials Scienceand Engineering, South China
University of Technology, Key
Laboratory of Advanced
Energy Storage Materials of
Guangdong Province, P. R.
China
Born 1990 in Jiangxi, China.
2011 Bachelor in Metallic
Materials Science andEngineering in Department ofMaterials, South China
University of Technology(SCUT), Guangzhou, China.
He is currently a M.S
candidate at SCUT. Focusedon LiBH4-MgH2 system andMagnesium core-shellstructure.

"Study on the hydrogen exchange behavior in the metal hydride-LiBH4 composite"
Hydrogen-exchange effect discovered in hydride composite gives an angle to study the nonreaction interaction between components and to study detailed desorption mechanism.
Although obvious phenomena had been observed to prove the existence of this effect, the detailmechanism has not been proposed. Our research presents a desorption model relating to H
exchange and proves that interface between two hydrides and mobile H atoms from bothhydrides are crucial for the exchange to happen. Desorption gas specie in LiBH4-VD2 systemdrastically changed after melting of LiBH4 and only then showed obvious H-D exchange
phenomena, in LiBH4-MgD2 system inhibition of desorption of MgD2 by 4MPa H2 nearlyannihilate B-D signal in FTIR indicating nearly no D atoms was found in LiBH4.

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PARTICIPANTS

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9 Int. Symposium Hydrogen & Energy

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Name

Address

email, tel.

Gisela ARZAC (Dr)Instituto de Ciencia de Materiales deSevillaAv. Américo Vespucio 49, Isla Cartuja
SevilleSpainemail: gisela@icmse.csic.es
Tel.: +34954489552
mobil:

Nikola BILISKOV (Dr.)

Rudjer Boskovic Institute
Bijenicka c. 54
10000 Zagreb
Croatia

email: nbilis@irb.hr
Tel.: +38514561084Â¸
mobil: +385917209759

Didier BLANCHARD (Dr.)

DTU
Frederiksborgvej 399
Roskilde
Denmark

email: dibl@dtu.dk
Tel.: +45 46775899
mobil: +45 50394893

Christiaan BOELSMA(Mr.)

TU Delft
Granaat 8
1703BC Heerhugowaard
Netherlands

email: c.boelsma@tudelft.nl
Tel.:
mobil:

Nigel BRANDON (Prof.,
Director)

Imperial College London, Sustainable
Gas Institute11 Princes Gardens
LondonUnited Kingdom

email:
n.brandon@imperial.ac.uk
Tel.: +442075945704
mobil:

Elsa CALLINI (Dr.)

EMPA Materials Science & Technology
Ueberlandstrasse 129
8600 Dübendorf
Switzerland

email: elsa.callini@empa.ch
Tel.:mobil:

Georgia
CHARALAMBOPOULOU(Dr.)

National Center for Scientific Research"Demokritos"
Patriarchou Gregoriou & Neapoleos
15310 Agia Paraskevi Attikis
Greeceemail: gchar@ipta.demokritos.gr
Tel.: +30 210 6503404
mobil: +30 6977 201516

Anna-Lisa CHAUDHARY(Dr)

Helmholtz Zentrum Geesthacht
Max-Planck Strasse
Geesthacht
Germany

email: annalisa.chaudhary@hzg.de
Tel.: +4916093473360
mobil: +4916093473360

Giovanni CINTI (Dr)University of Perugia
via Duranti 69
6125 Perugia
Italyemail: giovanni.cinti@unipg.it
Tel.: +390755853991
mobil: +393406141983

Bernard DAM (Prof. Dr.)TU Delft
julianalaan 136
2595 GE Delft
Netherlands

email: b.dam@tudelft.nl
Tel.:
mobil:

Petra DE JONGH (Prof.)

Debye Institute for Nanomaterials
Science, Utrecht University
Universiteitsweg 993584 CG/Utrecht
Netherlands

email: P.E.deJongh@uu.nl
Tel.:mobil:

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9 Int. Symposium Hydrogen & Energy

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Name

Address

email, tel.

Domenico DE LUCA (M.
ENG.)

UNIVERSITY OF CALABRIAPONTE BUCCI 44/C 5TH FLOOR
87036 Calabria
Italyemail:
domenico.deluca@unical.it
Tel.: +39.0984.494942
mobil: +39.333.6575192

Stefano DELEDDA (Dr.)

Institute for Energy Technology
P.O. Box 40
2027 Kjeller
Norwayemail: stefano.deledda@ife.no
Tel.: +47 407 26 921
mobil:

Günther DOLLINGER(Prof. Dr.)

Universität der Bundeswehr München
Werner Heisenberg Weg 39
D-85577 Neubiberg
Germany

email:
guenther.dollinger@unibw.de
Tel.: +49 89 6004 3505
mobil:

Yali DU (Ms.)

Yanshan University
438 Hebei Street
066004/Qinhuangdao
China

email: hanshm@ysu.edu.cn
Tel.: +86-335-8074648
mobil:

Adrian EPPRECHT (Mr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Dübendorf
Switzerland

email:
adrian.epprecht@empa.ch
Tel.:mobil: +41 79 253 1668

Asuncion FERNÀNDEZ
(Dr.)

Instituto de Ciencia de Materiales deSevillaAv. Américo Vespucio 49, Isla Cartuja
SevilleSpainemail: asuncion@icmse.csic.es
Tel.: +34954489531
mobil:

Yixiao FU (Mr.)

South China University of Technology
PanYu district
GuanzhouChinaemail: scut.fuyixiao@gmail.com
Tel.:mobil: +86 13068708656

Viera GÄRTNEROVÀ
(Ph.D.)

Institute of Physics
Na Slovance 1999/2
182 21 Prague 8
Czech Republic

email: gartner@fzu.cz
Tel.: +420 266 052 870
mobil:

Hans GEERLINGS (Prof.
Dr.)

Shell / TU Delft
Grasweg 311031 HW Amsterdam
Netherlands

email:
hans.geerlings@shell.com
Tel.: +31206302393
mobil: +31655123169

Hubert GIRAULT(Professor)

EPFL (Ecole Polytechnique Fédérale
de Lausanne)
SB-ISIC-LEPA Station 61015 LAUSANNE
Switzerland

email: hubert.girault@epfl.ch
Tel.: +41216933145
mobil: +41 79 560 2164

Jasmina GRBOVICNOVAKOVIC (Dr.)

Vinca Institute of Nuclear Sciences
M.Petrovica Alasa 12-14
11000 Belgrade
Serbia and Montenegro

email: jasnag@vinca.rs
Tel.: +381 11 3408 662
mobil: + 381 64 16 96253

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Name

Address

email, tel.

Ronald GRIESSEN (Prof.
Dr.)

VU university
Emmaweg 29 B
1241 LG Kortenhoef
Netherlands

email: r.p.griessen@vu.nl
Tel.: +31-35-6561451
mobil: +31 62033 6322

Shumin HAN (Prof.)

Yanshan University
438 Hebei Street
066004/Qinhuangdao
China

email: hanshm@ysu.edu.cn
Tel.: +86-335-8074648
mobil:

Bjørn C. HAUBACK(Professor)

Institute for Energy Technology
P.O. Box 40
Kjeller
Norwayemail: bjorn.hauback@ife.no
Tel.: +47 9740 8844
mobil:

Michael HIRSCHER (Dr.)

Max-Planck-Institut für Intelligente
SystemeHeisenbergstr. 370569 Stuttgart
Germany

email: hirscher@is.mpg.deTel.:mobil:

Marco HOLZER (Mr.)

EPFL & EMPAÜberlandstrasse 129
8600 Dübendorf
Switzerland

email: marco.holzer@empa.ch
Tel.: +41 79 763 37 93
mobil: 0

Fadime HOSOGLU (Dr.)

Holcim Ltd.
Schaffhauserstrasse 272
8007 Zurich
Switzerland

email:
fadime.hosoglu@holcim.com
Tel.: +41 79 961 5364
mobil: +41 79 961 5364

Jianmei HUANG (PHD
student)

EMPA & South China University ofTechnology
Ueberlandstrasse 129
8600 Duebendorf
Switzerland

email: jianmei.huang@empa.ch
Tel.:mobil: +41 76 814 3314

Md Amirul ISLAM (Mr.)

Skoltech - www.skoltech.ru
Novaya 100, Skolkovo
143025 Moscow Region
Russian Federation

email:
amirul.islam@skolkovotech.ru
Tel.:mobil:

Aleå¡ JAGER (PhD.)

Institute of Physics
Na Slovance 1999/2
182 21 Prague 8
Czech Republic

email: jager@fzu.cz
Tel.: +420 266 052 870
mobil:

Olaf JEDICKE (Dr.)

Karlsruher Institute for Technology
Hermann-von-Helmholtz-Platz 176344 Eggenstein-Leopoldshafen
Germany

email: olaf.jedicke@kit.edu
Tel.: +49 721 6082 5274
mobil: +49 173 697 0210

Torben R. JENSEN(Assoc. Prof. D.Sc.)

iNANO and Department of Chemistry,
Aarhus University
Langelandgade 140
8000 Aarhus
Denmark

email: trj@chem.au.dk
Tel.:mobil:

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Name

Address

email, tel.

Sathiskumar JOTHI ()Swansea University
singleton park
Swansea
United Kingdom

email: s.jothi@swansea.ac.uk
Tel.: +447587876010
mobil: +44 758 787 6010

Xin JU (Prof.)

Department of Physics, University of
Science and Technology Beijing
30 Xueyuan Road, Haidian District
Beijing 100083
China

email: jux@ustb.edu.cn
Tel.: +86-10-62333921
mobil: +86 1358520 9127

Shunsuke KATO (Dr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Dübendorf
Switzerland

email: shunsuke.kato@empa.ch
Tel.: +41 58 765 6086
mobil: +41 79 949 34 63

Zuleyha Ozlem
KOCABAS ATAKLA (Dr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Dübendorf
Switzerland

email:
oezlem.kocabas@empa.ch
Tel.:mobil:

Christian KRELL (Dr.)

Fronius International GmbH
Günter-Fronius-Strasse 14600 Wels
Austria

email:
woegerbauer.silvia@fronius.com
Tel.: +43 664 602415786
mobil:

Klaus LACKNER (Prof.,
Director)

Arizona State University, Center for
Negative Carbon Emissions
660 South College Avenue, PO Box
87300585287-3005, Tempe, AZ
United States

email: klaus.lackner@asu.edu
Tel.: +1 (480) 727 2499
mobil:

Alexander LAIKHTMAN(Dr.)

Holon Institute of Technology (HIT)
52 Golomb St.
5810201
Israelemail: alexl@hit.ac.il
Tel.:mobil:

Yuan LI (Dr.)

Yanshan University
438 Hebei Street
066004/Qinhuangdao
China

email: liyuan@ysu.edu.cn
Tel.:mobil:

Baozhong LIU (Dr.)

School of Material Science andEngineering, Henan Polytechnic
University
2001 Century Avenue,
JiaozuoChinaemail: b_z_liu@163.com
Tel.: +86 391-3986901
mobil: +86 391 3989859

Philippe MAURON (Dr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Dübendorf
Switzerland

email:
philippe.mauron@empa.ch
Tel.:mobil:

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Emmetten, SWITZERLAND 2015

Name

Address

email, tel.

David MILSTEIN (Prof.)

Weizmann Institute of Science
1 Herzl St
Rehovot
Israelemail:
david.milstein@weizmann.ac.il
Tel.: +972 8934 2599
mobil: +972 8934 2599

Vladimir MOLKOV(Professor)

Ulster University
Shore Road
Newtownabbey
United Kingdom

email: v.molkov@ulster.ac.uk
Tel.: +44 2890 368731
mobil: +44 7790 026451

Jiri MULLER (Dr.)

IFE

email: jiri@ife.noTel.:mobil:

2027 Kjeller
NorwayAkihiro NAKANO (Ph.D.)

AIST
Tsukuba East 1-2-1 namiki305-8564/TsukubaJapanemail: a.nakano@aist.go.jp
Tel.: +81-29-861-7250
mobil: +81-80-4327-6564

Sveinn OLAFSSON(Research Professor)

Science Institute University of Iceland
Dunhaga 3
Reykjavík
Icelandemail: sveinol@hi.is
Tel.: +354 525 4693
mobil: +354 525 4693

Shin-Ichi ORIMO(Professor)

WPI-AIMR / Institute for Materials
Research, Tohoku University
2-1-1 Katahira, Aoba-ku
Sendai, 980-8577
Japan

email: orimo@imr.tohoku.ac.jp
Tel.: +81-22-215-2093
mobil:

Tayfur OZTURK (Prof.)

Middle East Technical University
Dumlupinar Bulvari No 106800 Ankara
Turkeyemail: ozturk@metu.edu.tr
Tel.: +90 312 210 5935
mobil: +90 532 4566352

Martin PANHOLZER (Dr.)

Johannes Kepler University Linz
Altenberger Str. 69
4040/Linz
Austria

email: martin.panholzer@jku.at
Tel.: +43 7322468 1478
mobil:

Bojana PASKASMAMULA (M.Sc.)

Vinca Institute of Nuclear Sciences,
University of Belgrade
PO Box 522
11001 Belgrade
Serbia and Montenegro

email: bpmamula@vinca.rs
Tel.: +381 11 340 8610
mobil:

Dieter PLATZEK (Dr. rer.nat.)

Panco GmbH
Kaerlicher Str. 756218 Muelheim-Kaerlich
Germany

email: info@panco.deTel.:mobil:

Aferdita PRIFTAJVEVECKA (Professor)

Polytechnic University of Tirana
Sheshi "Nene Tereza", N.4
10023 Tirana
Albania

email: afvevecka@fimif.upt.al
Tel.: +355 42 222 7914
mobil: +355 69 210 7327

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Name

Address

email, tel.

Michael RANFT (Dipl.Ing.)

Karlsruhe Institute of Technology
Hermann-von-Helmholtz-Platz 176344 Eggenstein-Leopoldshafen
Germany

email: michael.ranft@kit.edu
Tel.: +49 721 608 24897
mobil:

Diogo SANTOS (Dr.)

Instituto Superior Tecnico
Pavilhao de Minas, Piso 4, Av. Rovisco
Pais
1049-001 Lisboa
Portugalemail:
diogosantos@tecnico.ulisboa.pt
Tel.:mobil:

Thomas Justus
SCHMIDT (Prof. Dr. )Paul Scherrer Institut
OLGA/1135232 Villigen PSI
Switzerland

email:
thomasjustus.schmidt@psi.ch
Tel.: +41 56 310 57 65
mobil:

Ulrich SCHMIDTCHEN(Dr.)

BAM Fed. Inst. for Mat. Res. andTesting
Unter den Eichen 87
12205 Berlin
Germany

email:
ulrich.schmidtchen@bam.deTel.: +49 30 8104 4402
mobil: +49 173 621 1533

Sok Gun SONG (Mr.)

National industrialization company
P.O. Box 26707 Riyadh 11496
RiyadhSaudi Arabia

email: rakesong@hotmail.com
Tel.:mobil: +966 540 304 279

Mariana SPODARYK(Ms.)

Institute for Problems of Materials
Science
Verhovynna str.85, ap.48
03176 Kyiv
Ukraineemail: poshtamary@ukr.net
Tel.:mobil: +380 68541 7935

Nicholas STADIE (Dr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Dübendorf
Switzerland

email: nicholas.stadie@empa.ch
Tel.: +41 58 765 4153
mobil:

Svetlana SYRENOVA(Ms.)

Chalmers University of Technology
Department of Applied Physics, Divisonof Chemical Physics
41296, Göteborg
Swedenemail: syrenova@chalmers.se
Tel.: +46 31772 3007
mobil: +46 76344 2249

Osman TAHA (Sinor
Radiation Physicist )Hamad Medical Corporation
Qatar - Doda PO 3050
974
Qatar

email: otaha@hmc.org.qa
Tel.:mobil:

Klaus TAUBE (Dr.)

Helmholtz-Zentrum Geesthacht
Max-Planck-Strasse 1
Geesthacht
Germany

email: klaus.taube@hzg.de
Tel.: +49 4152 87 25 41
mobil: +49 175 59 16 984

Ulrich ULMER (Dr.)

Karlsruhe Institute of Technology
Hermann-von-Helmholtz-Platz 176344 Eggenstein-Leopoldshafen
Germany

email: ulrich.ulmer@kit.edu
Tel.:mobil:

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Name

Address

email, tel.

Izumi UMEGAKI (Dr.)

Toyota Central R&D Labs., Inc
41-1, Yokomichi, Nagakute
Aichi
Japan

email:
umegaki@mosk.tytlabs.co.jp
Tel.: +81-561-71-8111
mobil:

Gang WANG ()Utrecht University
Universiteitsweg 993584 CG Utrecht
Netherlands

email: g.wang@uu.nl
Tel.:mobil: +31 64680 6615

Hui WANG (Dr.)

South China University of Technology

email: mehwang@scut.edu.cn
Tel.:mobil:

510640 Guangzhou
China
Yijing WANG ()Institute of New Energy Material
Chemistry
94 Weijin Road
Nankai District, Tianjin
30071, P.R.China

email: wangyj@nankai.edu.cn
Tel.:mobil:

Yigang YAN (Dr.)

EMPA Materials Science & TechnologyÜberlandstrasse 129
8600 Duebendorf
Switzerland

email: yigang.yan@empa.ch
Tel.:mobil:

Olena ZAVOROTYNSKA(Dr)

Institute for Energy Technology

email: olenaz@ife.no
Tel.: +4746621096
mobil:

P.O. Box 40
NO-2027 Norway
Meiqin ZENG ()South China University of Technology
510640 Guangzhou
China

Min ZHU (Prof. Dr.)South China University of Technology
510640 Guangzhou
China

Andreas ZÜTTEL (Prof.
Dr.)EPFL & EMPAÜberlandstr. 129
8600 Zürich
Switzerland

email: mezengmq@scut.edu.cn
Tel.:mobil:
email: memzhu@scut.edu.cn
Tel.:mobil:
email: andreas.zuettel@epfl.chTel.:mobil: +41 79 484 2553

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Information

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

Map of the region Emmetten

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Travel to Emmetten from Zürich airport:
Please go to the ticket counter in the airport and ask for a ticket to Emmetten (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 Flughafen

So 25. 1. 15 dep

13:47 4

Luzernarr

14:49 6

Luzerndep

15:10 13

Stans

arr

15:23 1

Stans

dep

15:51

Emmetten Post

arr.

16:24

IR 2653

Direction: Luzern

IR 2976

Direction: Engelberg

Bus 311

Direction: Seelisberg

Duration: 2:37; runs daily
http://www.sbb.ch/en/home.html

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EMERGENCY TELEPHONE NUMBERS
countrycode
for
Switzerland +41...
POLICE

117

FIRE FIGHTERS

118

AMBULANCE144

RESCUE HELICOPTER (REGA)

1414

Adrian EPPRECHT
Administration / Organizer

079 253 1668

Andreas ZÜTTEL
Organizer

079 484 2553

Hotel SEEBLICK AG
Hugenstrasse 24
CH-6376 Emmetten
email: info@hotelseeblick.ch
URL: http://www.hotelseeblick.ch

041 624 41 41

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CLIMATE
Average air temperature in Emmetten in °C

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SOCIAL EVENTS
Rütli
Bus to Beckenried, Ship to the "Tellplatte" andshort walk to "Rütli". Gided tour withinformation about the cradle of Switzerland.

SkiingFree skiing, skipass will be provided(depending on the snow condition)

Sledging
Free sledging(depending on the snow condition)

Snowwalk
Guided tour
(depending on the snow condition)

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HISTORY OF SWITZERLAND
From the beginnings to the present.
Much of the territory covered by present-day Switzerland is mountainous. For thisreason, the Alpine passes have played a significant role in the development of thecountry, as have the powers that sought to control these important communication andtrade routes.
The inaccessible mountains with their particular living conditions provided the area withprotection and a great deal of freedom because they made it difficult for foreign powers
to enforce their control in the longer term. This enabled the population to develop its own
traditions and forms of government. This situation also favoured the neutrality that has
been in force since 1515 and which has also served the neighboring countries byforming a safety zone between the European states. The state of Switzerland as we know
it today only assumed its current form in 1848. Prior to this time there was no real Swisshistory as such; rather, it was the history of the various territories that gradually
coalesced up until 1848 in order to form modern-day Switzerland.
From thebeginnings to the
RomansThe oldest traces of human existence are about 150,000 years old, while the oldest
flint tools that have been found are about 100,000 years old. The territory of thepresent-day Switzerland developed in a similar way to that of the rest of Europe.

Under Roman
influence, 58 BC

In 58 BC, the Mittelland-based Helvetians tried to avoid the Germanic incursion
from the west and migrate to the south of France. But Caesar sent them back andsettled them as a "buffer people".

Switzerland after
the Romans

After the departure of the Romans, the Alemanni gradually colonised Switzerlandfrom the north. Western Switzerland was ruled by the Burgundians, while the Alpine
regions were dominated by local Gallo-Roman rulers.

The rise of
Christianity, 6th
century

Initially brought to Switzerland by the Romans, Christianity only really started tospread in the 6th century when the wandering monks from Ireland began
establishing monasteries.

Under German rule

Supported by noble families, non-aristocratic landowners, abbots and bishops, theGerman Emperor Conrad II ruled over large parts of western and central Europe –and united the Swiss territories in 1032.

Switzerland in thelate Middle Ages

1291 is traditionally regarded as being the founding year of the Confederation – thiswas when three rural valley communities banded together in order to be better
prepared for attacks from the outside.
In the 14th and 15 centuries there developed a loose federation with rural and urban
members. By the end of the 15th century it was strong enough to affect the balanceof power in Europe. Various wars were fought in which the Confederates displayedcourage and ingenuity, and they gained a reputation as a formidable opponent incombat. The Confederation was enlarged in various ways with some areas joining
voluntarily and as equal members while others were more or less forced. The
members of the Confederation mainly administered the affairs of their own regions
but representatives of each area also met regularly to discuss issues of common
interest.

Rise of the Swiss
Confederation

The desire for freedom on the part of rebellious miners in their ancestral country
prompted the Habsburgs to enforce their claims to power by the force of arms. In
the process they suffered heavy losses - while the Confederates grew increasingly
confident.

Dissension and the
Burgundian Wars

The relationships between the Confederates and other parts of what is now
Switzerland were very diverse. At the instigation of Bern and of the French king, theConfederates went to war against the Burgundian duke, Charles the Bold, who

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suffered a crushing defeat in three battles.
Independence andthe end of
expansion

Following the success of the Swabian wars the interest of those in central
Switzerland now turned towards the south. The Confederates’ dreams of having
great power finally came to an end with their crushing defeat at Marignano.

Reformation andthe 17th century

The 16th century in Western Europe was dominated by the Reformation, amovement which divided western Christianity into two camps. Although the riots anddestruction were fought on a religious level, this reflected, above all, the desire forsocial change and the social tensions that existed primarily between town andcountry. The 17th century saw three further landmarks in the development ofmodern-day Switzerland. All came as a result of the 30 Years' War (1618-48). Whilelarge parts of Europe were involved in this war, the Confederation remained neutral.
An important consequence of the Thirty Years' War was Swiss independence fromthe Holy Roman Empire, which was formally recognised by the Treaty ofWestphalia.

Two Reformers:
Zwingli and Calvin

The 16th century was marked by reformations, counter-reformations and religious
wars - and also by renewal within the Catholic Church.

Political structure in
the 17th century

The rights and freedoms within the Confederation varied greatly depending on thelocation. There were rural cantons, city cantons, cities dominated by aristocrats,
common lordships ruled by bailiffs as well as subject territories.

Thirty Years’ War
and independence

The Confederation was able to keep out of the Thirty Years’ War – had it been
involved, it would have led to the collapse of the Confederation due to confessional
differences.

Peasant revolts andreligious peace

Whereas a currency devaluation led to a peasant uprising, it was the confessional
divide that sparked the Villmergen Wars that led to the restoration of a balanced
religious peace and an end to Catholic hegemony.

18th and 19th
century

In 1798, French troops invaded Switzerland and proclaimed a centralised state.
Later, the old cantonal system was restored - albeit in a more centralised form. In
1798, French troops invaded Switzerland and created the centralised Helvetic
Republic. For the first time in its history, Switzerland was forced to abandon its
neutrality and to provide troops for France. After the Sonderbund War, thefoundations for the modern Switzerland were finally laid down with the adoption of
the Constitution of 1848. It brought about a more centralised form of government
and a single economic area, which put an end to the cantonal rivalries and enabled
economic development. Despite this progress, the 19th century was a difficult time
for many people in Switzerland. Poverty, hunger and poor job prospects led to awave of emigration, including to North and South America.

20th century

The 20th century was generally marked by a series of striking developments in thepolitical, economic and social arenas. Domestically there was a shift towards a
multi-party system. While at the beginning of the century one party occupied all the
positions in the government (Federal Council), there were four parties represented
there at the end of the century. Agrarian Switzerland developed into an industrial
state with the result that there were more immigrants than emigrants and thestandard of living rose significantly. Working conditions and social security steadily
improved and there was greater access to a more extensive range of consumer
goods. The development of the export sector changed the country’s relationshipwith Europe and the rest of the world. Although Switzerland remained politicallyneutral – it did not actively participate in either of the two World Wars – neutrality
remained the subject of intense debate.

Ref.: http://www.myswitzerland.com/

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KLEWENALP Region

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NOTES

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