th5 INTERNATIONALSYMPOSIUM
HYDROGEN & ENERGY
Hydrogen Production, Hydrogen Storage, Hydrogen Applications, Theory
and Modelling, Fuel Cells, Batteries, Synthetic Fuels, Functional Materialsthth

The 5 symposium “Hydrogen & Energy” follows the 4 symposium on 24. – 29. January 2010 inWildhaus with more than 80 participants. It serves as an information platform of the fundamental
science and technology and the frontiers of research on hydrogen and energy.
The symposium consists of invited keynote lectures reviewing the key elements of the hydrogen
cycle, i.e. the hydrogen production, hydrogen storage and hydrogen combustion and fuel cells.
Furthermore, contributions on the conversion of renewable energy in general and energy carriers
beside and beyond hydrogen are very welcome. The world leading experts present the current
research challenges and most important results in invited and contributing talks. Early stage andexperienced researchers present their newest results and the open questions on posters as well as
in a one slide presentation.
The conference will take place in the conference and wellness hotel Stoos in the beautiful small
village Stoos on 1'270 m above see level. The village is free of traffic on a alp above Schwyz incentral Switzerland.
The number of participants is limited to 80.

23. - 28. January 2011
Seminar- und Wellnesshotel Stoos
Ringstrasse 10
CH-6433 Stoos
Tel.: +41 (0)41 817 44 44
Fax.: +41 (0)41 817 44 45
info@hotel-stoos.ch
http://www.hotel-stoosth

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CONTENTS
Timetable
Abstracts
Sunday, 23. January 2011
I01: EKINS Paul: “Hydrogen Energy: Policy Responses to Economic and Social Challenges"
Monday, 24. January 2011
Morning
I02: DE JONGH Petra: “Impact of Nanoconfinement and Additives on the Hydrogen Sorption in
Boron Hydrides"
I03: LOHSTROH Wiebke: “Hydrogen Storage in Nanoscale Binary Hydrides"
O01: MARTELLI Pascal: “Iodine Stabilized HT Phase of LiBH4"
O02: BORGSCHULTE Andreas: “Building Blocks of the Pseudo-Ternary System LiBH4-LiNH2LiI"
O03: YAN Yigang: “Improved Hydrogen Storage Properties of LiBH4 by Addition of Nickel"
O04: BLANCHARD Didier: “Rotational and Translational Diffusion in Calcium Borohydride fromQENS and DFT Calculations"Monday, 24. January 2011
Afternoon
I04: KLASSEN Thomas: “Reactive Hydride Composites"
O05: CORNO Marta: “First Principles Prediction of Structural, Vibrational and Thermodynamic
Properties of Mixed Metal Hydrides and Fluorides"
O06: REMHOF Arndt: “The Role of Li2B12H12 in the sorption Cycle of LiBH4"
O07: ZÜTTEL Andreas: “Liquid Complex Hydrides"
O08: VOGT Ulrich: “Catalytic Combustion of Hydrogen on Platinum Coated Porous SiC
Ceramics "O09: LINDER Marc: “Gas-Solid Reactions for Heat Applications "O10: BIELMANN Michael: “Hydrogen for Off-Grid Power Systems"
Monday, 24. January 2011
Evening
P01: ATAMAS Alexander: “Monte Carlo Calculations of the Free Energy of SII and SH
Clathrates "P02: CYVIENE Jurgita: “Annealed GdC Thin Films Microstructure Evaluation"
P03: GORBAR Michal: “Characterization of Commercial Metal-Oxide Ceramic Diaphragms for
Hydrogen Production by Alkaline Electrolysis "P04: GRZECZKA Grzegorz: “Architecture of Air Independent Electric Supply System Based on
PEM Fuel Cell"
P05: KAZEMPOOR Pejman: “Dynamic Modeling and Simulation of Anode-Supported Planar
Solid Oxide Fuel Cell "P06: PHUNG Bac: “First-Principles Calculations of Hydrogen Diffusion into Palladium
Nanoparticles"
P07: MILANESE Chiara: “Investigation of the Hydrogen Sorption Properties of Nanocomposites
NaBH4-MgH2 Confined in Mesoporous SBA15”

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Tuesday, 25. January 2011
Morning
I05: ORIMO Shin-Ichi: “Complex Hydride Ionics"
O11: BERKE Heinz: “Conceptual Approach to new Metal-Organic Frameworks for Hydrogen
Storage"O12: LINDEMANN Inge: “New Double-Cation Borohydrides"
O13: MULLER Jiri: “Hydrogen Storage in Carbon Cones"
O14: WALTON Allan: “Hydrogen Processing / Recycling of Rare Earth Magnets"
O15: MILANESE Chiara: “Kinetic and Thermodynamic Investigations on pure and doped
NaBH4/MgH2 System.
O16: KHAMIS Ibrahim: “An IAEA Insight of Activities on Hydrogen Production"
Tuesday, 25. January 2011
Evening
P07: PONTIROLI Daniele: “Magnesium Fullerides for Hydrogen Storage (Hycarbo Workshop)"
P08: SHIM Jae-Hyeok: “Hydrogen Storage Properties of LiBH4-Based Reactive HydrideComposites"
P09: SZYMAK Piotr: “Control of Oxygen flow in Air Independent PEM Fuel Cell System"
P10: TORRES Alondra: “Hydrogen Storage in Structure II Clathrate Hydrates with Various
Promoters"
P11: WIEDENMANN Daniel: “Gas Separation Diaphragms for Alkaline Hydrogen Production:
Influence of Microstructure on Ion Conductivity and Gas Purities"
P12: ABAKEVICIENE Brigita: “Reduction Temperature Impact on NiO-YSZ Cermets
Microstructure"
Wednesday, 26. January 2011
Morning
I06: HASHIMOTO Koji: Methane Production Through Hydrogen from Renewable Energy"
I07: GEBALD Christoph: “CO2 Capture from Ambient Air"rd
O17: VON OLSHAUSEN Christian: “Sunfire – 3 generation fuels from CO2 and H2”.
O18: LAURENCZY Gabor: “Formic acid - The key compound in a viable hydrogen storage
system"O19: KATO Shunsuke: “Surface Oxidation of Hydrides”
O20: SHAO Huaiyu: “LiBH4 and Ti-Catalyzed Nanocrystalline MgH2 Composite for Hydrogen
Storage"Thursday, 27. January 2011
Morning
I08: CHORKENDORFF Ib: “New Catalyst for Hydrogen Evolution and Oxygen Reduction "I09: STOOTS Carl: “High Temperature Steam and Steam/CO2 Electrolysis Research andDevelopment at the INl"
O21: GUTTENTAG Miguel: “Hydrogen Production from Water"O22: MAN Isabela : “Competitive Chlorine and Oxygen Evolution from Sea Water at Rutile (110)
Surfaces, from First Principle Calculations"O23: RANJAN Chinmoy: “Oxygen Evolution Reaction on Single Crystalline Electrodes"
O24: STOJADINOVIC Jelena: “Electrochemical Investigation of Advanced Materials Used forDevelopment of Alkaline Electrolyzer’s Diaphgragms"
Thursday, 27. January 2011
Afternoon
I10: CAPUTO Riccarda: “No title”
O25: MAURON Philippe: “Hydrogen Adsorption in Advanced Carbon Materials"
O26: MAZZANI Marcello: “Hydrogen Interaction with Graphene Probed by µSR"
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Friday, 28. January 2011
Morning
I11: OTOMO Toshiya: “Neutron Total Diffraction for Structural Studies of Hydrogen Storage
Materials"
O27: ZHENG Qiang: “What Can We Learn From EXAFS for Hydrogen Storage Materials? "O28: PALMISANO Valerio: “Mg-Based Optical Hydrogen Sensors"
O29: CALLINI Elsa: “No title”
O30: MAISSEU André: “Nuclear Hydrogen Production - Basic Challenges"

SCIENCE OF HYDROGEN & ENERGY AWARD
List of Participants
Information
Notes

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Timetable

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Abstracts

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HYDROGEN ENERGY: Policy responses to economic
and social challenges
Paul Ekins
UCL Energy Institute, University College London, Central House, 14 Upper Woburn Place,
London WC1H 0NN, UK
Hydrogen as an energy vector has been subject to waves of enthusiasm as to its potential to resolvepressing concerns of climate change, energy security and local pollution resulting from the use of otherfuels. Sometimes this has obscured the very real technical, economic and social challenges that need tobe successfully addressed if this potential is to be realised in practice.

HydrogenTechnologies
Applications

andA range of more or less complex
technologies is involved in the production,
storage and distribution of hydrogen, and it
may be may put to a variety of end uses invehicles, as auxiliary power units or for
stationary power provision.

Hydrogen Economics and Policies,
and Social Implications
Very considerable technical innovation will be
required for hydrogen to break out fromcurrent niche applications into the mass
markets that could bring about its widespreaduse [1]. The innovation will need to improve
its performance economically and technically,
with a technological diffusion process likely totake place over decades through a transition
that transformed the current energy
infrastructure and end-use applications [2].
Hydrogen is emerging in different places inPaul Ekins

different ways, in each case as a result of
public policies, devised to achieve specificlocal and regional economic or environmental
objectives.
Current levels of public knowledge abouthydrogen are very low, and systematic public
engagement is required to ensure that thetechnologies win acceptance. The policies
required to bring about the widespreaddiffusion of hydrogen will need to range frombasic R&D through to demonstration projects
and public support for infrastructure provisionand diffusion of the key applications.

References[1]

Ekins, P. Ed. 2010 Hydrogen Energy:
Economic and Social Challenges, Earthscan,
London[2]

McDowall, W. & Eames, M. 2006 ‘Forecasts,
scenarios, visions, backcasts and roadmaps
to a hydrogen economy’, Energy Policy 34:
1236-1250

Born 24. 7. 1950 in Djakarta, Indonesia, before family moved back to UK. 1971 ElectricalEngineering Degree from Imperial College London. 1988 Masters in Economics from
Birkbeck College London 1996 PhD in Economics from Birkbeck College London 19962002 Senior Lecturer then Reader then Professor of Sustainable Development, Keele
University 2002-07 Head, Environment Group, Policy Studies Institute and Professor of
Sustainable Development, University of Westminster. 2002-08 Member of the UK Royal
Commission on Environmental Pollution 2008-09 Professor of Energy and Environment
Policy, King’s College London 2009-now Professor of Energy and Environment Policy,
UCL Energy Institute, University College London. Books include Economic Growth andEnvironmental Sustainability: the Prospects for Green Growth (Routledge, 2000). 1994
Global 500 Award ‘for outstanding environmental achievement’ from United Nations
Environment Programme

Corresponding author: Paul Ekins, email: p.ekins@ucl.ac.uk, Tel. (+44) (20) 3108 5990

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Impact of Nanoconfinement and Additives on the
Hydrogen Sorption in Boron Hydrides
Peter Ngene, Roy van den Berg, Petra de Jongh
Inorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht
University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands
Boronhydrides have a high hydrogen content, and hence are interesting hydrogen storage materials.
However, generally the kinetics for hydrogen desorption are sluggish, and (partial) reversibility can only beachieved at high temperatures. Confining the phases on a nanoscale, especially combined with certain
additives, has a large impact on the hydrogen desorption kinetics and reversibility.

Nanoconfined boronhydrides
Complex metal hydrides were loaded into
mesoporous carbon scaffolds by techniquessuch as melt infiltration and pore volume
impregnation. N2 physisorption allowed
assesment of the pore filling. As thenanoconfined hydrides typically lacked longrange crystallinity, analysis of the phaseevolution during cycling was based on solidstate NMR, EXAFS, EM, and HP-DSC. In
this contribution we discuss especiallynanoconfined LiBH4 and NaBH4.

2enhancement of reversibility. These results
will be related to the micr
ostructural development during cycling.

Hydrogen sorption - reversibility
Not only hydrogen sorption kinetics arechanged by nanoconfinement, but also
thermodynamical stability and decomposition
pathway. Another important aspect isreversibility, as illustrated in the Figure
showing the H2 uptake for LiBH4/carbon ato
320 C, 40 bar H2. Clearly nanoconfinement
improves the reversibility under mild
1
conditions . However, a small amount ofadditives leads to a significant additional

References[1]

A.F. Gross, J.J. Vajo, S.L. van Atta, G.L.
Olson, J. Phys. Chem. C 112 (2008), 5651.
[2]
P. Ngene, M. van Zwienen, P.E. deJongh, Chem. Comm. (2010): DOI: 10.1039/C0CC03218b.

Petra de Jongh received her PhD in photoelectrochemistry in 1999, andworked 5 years as a senior scien tist at Philips Research. She is now associate
professor at Utrecht University, where she (co)-supervises researchers working
on supported nanoparticles, especially for applications in catalysis and energy
storage and conversion.
P.E. de Jongh
Corresponding author: Petra de Jongh, email: P.E.deJongh@uu.nl, Tel. +31 30 2536766

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Hydrogen Storage in Nanoscale Binary Hydrides
Wiebke Lohstroh, Marcus Fehse, Arne Roth, Maximilian Fichtner
Institute of Nanotechnology, Karlsruhe Institute of Technology, P.O. Box 3640, 76021
Karlsruhe, Germany
Hydrogen storage properties of composites comprised of LiH, NaH and a carbon host material were
investigated. Compared to the pure alkali metal hydrides, decomposition temperatures are lowered in allcases and reversible hydrogen uptake was obtained around 300°C. NaH containing samples showed only
minor differences with porosity of the carbon host while different decomposition temperatures were foundfor LiH combined with graphite and activated carbon fibre, respectively.

The binary hydrides LiH, NaH have a highhydrogen capacity (12.6 and 4.2 wt%,
respectively) but they have also highthermodynamic
stability.
Thereleasetemperature for hydrogen is lowered whenthe materials are embedded in a carbon
matrix [1,2]. Similar composites with NaAlH4
or MgH2 exhibit also changes of thethermodynamic properties [3,4].

(with a molar ratio 1:1) mixtures with carbon
can be reversibly cycled at 300°C with similarhydrogen contents. For Li-C samples thehydrogen release temperatures are shifted tohigher temperatures and the formation of
Li2C2 is favoured.
For NaH containing samples the porosity of
the carbon appears to be of minor
importance while different decomposition
temperatures were found for LiH combined
either with graphite or activated carbon fibre.

LiH and NaH composites

References

Introduction

Composites of NaH and LiH with carbon(graphite and activated carbon fibre) havebeen investigated for the hydrogen storage
properties.
All samples showed a lowered hydrogen
release temperature compared to the purealkali metal hydrides. At 300°C, thereversible hydrogen capacity is 0.2 H atoms
per alkali metal atom. Likewise, LiH/NaH

[1]
[2]

[3]
[4]

Miyaoka H, Ichikawa T, Kojima Y.
Nanotechnology 20 204021 (2009).
Adelhelm P, de Jong KP, de Jongh PE.
Chemical communications 41, 6261-3(2009).
Lohstroh W, Roth A, Hahn H, Fichtner M.
ChemPhysChem. 11, 789-92 (2010).
Zhao-Karger Z, Hu J, Roth A, et al. Chemical
Communications DOI:10.1039/c0cc03072d(2010)

Born 13. 04. 1972 in Bad Nauheim, Germany. 1996 Diploma in Physics, GeorgAugust Universität Göttingen, Germany 1999 Dr. rer. nat. from the science faculty
Georg-August Universiät Göttingen, Germany 2000 Post doc at the Clarendon
Laboratory, Condensed Matter Physics, Oxford University 2003 Post Doc at the
Department of Physics and Astronomy, Condensed Matter Physics at the Vrije
Universiteit Amsterdam, The Netherlands 2005 Research Staff at the Insitute of
Nanotechnology, Karlsruhe Institute of Technology (then Karlsruhe Research CentreGmbH)
Wiebke Lohstroh
Corresponding author: Wiebke Lohstroh, email: mailto: wiebke.lohstroh@kit.edu, Tel. (+49) (7247) 826377

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Iodine Stabilized HT Phase of LiBH4
Pascal Martelli1,2, Arndt Remhof1, Ralf Ackermann3, Jan Peter Embs3,4,Andreas Züttel1,2
1

Empa Swiss Federal Laboratories for Materials Science and Technology, Hydrogen & Energy,
28600 Dübendorf, Switzerland, Physics Department, University of Fribourg, 1700 Fribourg,
3
Switzerland,Laboratory for Neutron Scattering, Paul Scherrer Institut, 5232 Villigen,
4
Switzerland, Saarland University, Physical Chemistry, 66041 Saarbruecken, Germany
LiBH4 is known to be a reliable candidate for hydrogen storage material but recently it has shown anotherinteresting property: it is a super ionic conductor at elevated T (>110°C). Mixed with LiI it shows a hightemperature (HT) phase behaviour at low temperature. Quasielastic neutron scattering measurement(QENS) is used in order to observe the rotational motion of the BH4 and therefore to confirm the HT phasestabilization.

Experimental

Stabilization of the HT phase

The measurements were carried out using
the time-of-flight neutron spectrometer
FOCUS located at the continuous spallation
source SINQ at the Paul Scherrer Institute in
Villigen, Switzerland.

Maekawa et al. [1] have discovered that
adding some halides (Cl, Br and I) permit tostabilize the HT phase at LT even at RT.
In order to better understand the diffusion
process of the mixture LiBH4-LiI, asystematic investigation has been made withQENS for several ratios (xLiBH4-LiI,
x=1,2,4).The dwell times of the rotations (psrange) vary with temperature (150-330K) andare fitted to the Arrhenius equation.
Jumps length and frequency occurring inside
the mixture has been determined as well as
the activation energy and a confirmation of
the stability of the HT phase below the RT.

References
Arrhenius behavior of the rotational motion of the
BH4-units in iodine stabilized LiBH4. The black line
is an extrapolation of the HT phase (Ea=68 meVand τ0 =75 fs) to lower temperatures [1].

[1] Remhof et al., Phys. Rev. B, 81 214304 (2010)[2] Maekawa et al., J. Am. Chem. Soc., 131,
894–895 (2009).

Born 12. 05. 1981 in Fribourg, Switzerland. 1998 language course in Germany. 2002
College in Math, Fribourg, Switzerland. 2007 University of Fribourg in physics and math.
2007 Diploma Thesis at "Hydrogen & Energy", EMPA Dübendorf, Switzerland.. Since2008 PhD student.

Pascal Martelli
Corresponding author: Pascal Martelli, email: pascal.martelli@empa.ch, Tel. (+41) (44) 823 4746

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Building blocks of the system LiBH4-LiNH2-LiI
Andreas Borgschulte,1 Andreas Züttel,1 Motoaki Matsuo,2 Shin-Ichi Orimo,2
1

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

2

Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan

The pseudo-ternary phase diagram LiBH4-LiNH2-LiI is investigated. The various phases may be formed via
the exchange of the neutral species NH3 competing with the exchange of ions. Depending on the
preparation method, NH3 may be included as an additional building block.

The phase diagram LiBH4-LiNH2-LiI
The pseudo-ternary phase diagram LiBH4LiNH2-LiI as sketched in the figure is aconcept
tosummarize
andpredict
compounds built from the three starting
compounds.

LiBH4

imides are known for releasing neutral
species, i.e. BHx respectively NH3. Ammonia,
in turn, forms stable compounds with LiI [3]and LiBH4 [4].
The latter reactions
proceeding via the exchange of a neutral
species compete with the exchange of ions.
Depending on the preparation method, NH3
may be included as an additional building
block.

Experiment
BH4-/NH2BH4-/I-

NH3
LiNH2
-

-

NH3/I /NH2

LiI

References[1]

However, this implies the existence andstability of the building blocks (pseudoanions) BH4 and NH2 . Upon mixing of
LiBH4-LiNH2, the pseudo-ions are exchanged
and form mixed compounds such as
Li4(BH4)(NH2)3 [1] and solid solutions
Li(BH4)1-xIx,[2] with ionic compounds such as+ Li I . However, the borohydrides as well as

A. Borgschulte

The existence and stability of the various
phases are investigated via gradient samples
probed by Raman spectroscopy andgravimetric thermo-desorption in combination
with infrared gas analysis.

[2]
[3]
[4]

see e.g. H. Wu et al. T. Chem. Mater. 2008,
20, 1245–1247.
A. Borgschulte, et al. Appl. Phys. Lett. 97,
031916 (2010).
H. Jacobs, et al. Z. Anorg. Allg. Chem. 2004,
630, 645648
E. A. Sullivan and S. Johnson, J. Phys.
Chem. 63, 233 (1959).

Born 1973 in Lippstadt, Germany. 1998/2002 diploma and PhD in physics fromTechnical University Braunschweig, Germany. 2002-2005: PostDoc at the VU
Amsterdam, The Netherlands, head Prof. R. Griessen, “Combinatorial Researchfor New Light Weight Complex Hydrides by Optical Spectroscopy.” 2005–2006:
Project co-ordinator of the hydrogen storage project FuncHy, GKSS ResearchCentre Geesthacht, Germany, head Prof. R. Bormann, “Kinetics and Stability ofmagnesium hydride.” Since 2006 Group leader in the Laboratory Hydrogen &Energy at Empa, Dübendorf, Switzerland.

Corresponding author: Andreas Borgschulte: andreas.borgschulte@empa.ch, Tel. (+41) (44) 823 4639

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Improved Hydrogen Storage Properties of LiBH4 byaddition of Nickel
Yigang Yan, Hai-Wen Li, Masaharu Menjo, Shin-ichi Orimo
Tohoku University, Institute for Material Research, Hydrogen Functional Materials Division,
Sendai 980-8577, Japan
LiBH4 starts to decompose over the melting point, and release 13.8 wt% of hydrogen according to LiBH4 →LiH + B + 3/2H2 [1]. To reduce the dehydriding temperature of LiBH4, an effective approach is to tailor theenthalpy change in dehydriding reaction by combination with metal or metal hydrides [2, 3]. By addition ofnanosized nickle, the dehydriding and rehydriding properties of LiBH4 were both significantly improved.

Combined LiBH4 system
The combined systems such as LiBH4-MgH2,
etc., show reduced enthalpy changes indehydriding reaction and improved reversiblehydrogen storage properties, due to theformation of metal borides (e.g. MgB2, etc.)
rather than elemental boron as thedehydriding product.

Adjustment of Reaction Pathway
The mixture of LiBH4 and 25 wt% Ni wasmechanically milled for 5 h. The hydrogenamount is referred to pure LiBH4.
Approximately 12.5 wt% of H2 was releasedin LiBH4 with and without Ni addition. The
dehydriding temperature was reduced byapproximately 90 K by addition of Ni.
The equilibrium pressure (Peq) of dehydriding
reaction increases from 0.35 to 1.2 MPa,
resulting in the reduction of enthalpy changes(∆H) from 76 to 68 kJ/mol H2. The reduced∆Hsuggeststhethermodynamic
improvement effect of Ni addition on thedehydriding reaction of LiBH4, according to

the reaction of LiBH4 + 4/3Ni → LiH +1/3Ni4B3 + 3/2H2.
The rehydriding amount of LiBH4 at 823 K
and 35 MPa H2 is increased from 4.3 to 10.8
wt% by addition of Ni, due to the rehydriding
reaction of LiH + Ni4B3 + 3/2H2 → LiBH4 +2Ni2B. Weaker B-B bonding in Ni4B3 thanthat in elemental boron (icosahedral B12units) facilitates the rehydriding reaction.
These results suggest that designing ofsystems similar to LiH/Ni4B3, in which boron
atoms could move fast between two borides(e.g. Ni4B3 and NiB2) during the reaction
process, is expected to bring about improved
reversible hydrogen storage properties.

References[1] S. Orimo, Y. Nakamori, J. R. Eliseo, A.
Züttel and C. M. Jensen, Chem. Rev. 107,
4111-4132 (2007)[2] J. J. Vajo, S. L. Skeith and F. Mertens, J.
Phys. Chem. B 109, 3719-3722 (2005)[3] M. Menjo, H.-W. Li, M. Matsuo, K. Ikeda
and S. Orimo, J. Ceram. Soc. Jpn. 117,457-460 (2009)

Born 14. 2. 1980 in Hubei Province, China. 2001 Bachelor in Chemical Engineering,
Chengdu, China. 2004 Master in Chemical Process Equipment from Sichuan University,
China. 2007 Ph.D in Material Science from Sichuan University. 2007 ~ 2008 senior
engineer in SAE Magnetics (H.K.) Ltd., China. 2008 Post doc Orimo Lab in Institute forMaterials Research (IMR), Tohoku University in Sendai, Japan. 2009 Japanese Society
for the Promotion of Science (JSPS) Post doc at IMR, Tohoku University. Research field:
Fundamental properties and hydrogen storage functions of metal borohydrides.
Yigang Yan
Corresponding author: Yigang Yan, email: mailto:yg-yan@imr.tohoku.ac.jp, Tel. (+81) (22) 215 2094

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Rotational and Translational Diffusion in Calcium Borohydridefrom QENS and DFT Calculations[1]D. Blanchard1, M. D. Riktor2, J. B. Maronsson1, H. S. Jacobsen1, J. Kehres1, D.
Sveinbjorsson1, E. Gil Bardají3, A. Léon3, F. Juranyi4, J. Wuttke5, B. C.
Hauback2, M. Fichtner3 and T. Vegge1.
1

AFM, Risø National Laboratory for Sustainable Energy, DTU, Roskilde, Denmark.
Physics Department, IFE, Kjeller, Norway.
3
Institute of Nanotechnology, KIT, Karlsruhe, Germany.
4
Laboratory for Neutron Scattering ETH Zurich, PSI, Villigen, Switzerland.
5
Forschungszentrum Jülich, JCNS at FRM II, Garching, Germany.
2

Metal borohydrides are of interest as hydrogen storage materials due to their high volumetric andgravimetric capacity. However, they are generally thermodynamically too stable, have slow absorption anddesorption kinetics and poor reversibility. Noting the lack of knowledge about their structural transition anddecomposition mechanisms we have investigated the hydrogen dynamics, using quasielastic neutron
scattering, in calcium borohydride, and observed rotational and translational diffusion events.

In Ca(BH4)2 hydrogen dynamics canoriginate from long-range diffusion or
localized motions (rotations, librations andvibrations). In this study, the rotational anddiffusional dynamics of hydrogen were
investigatedbyquasielastic
neutronscattering (QENS) combined with Density
Functional Theory (DFT) calculations. QENS
experiments were performed with two
spectrometers:
SPHERES(Garching,
Germany), energy resolution: 0.65 µeV, and
MARS (PSI, Switzerland), energy resolution:
15 µeV. The DFT calculations were
performed using the Atomic Simulation
Environment package, the DACAPO plane
wave basis set implementation and the
Nudged Elastic Band method to calculate theenergy paths of the re-orientational changes.

Rotational re-orientation
Between 95-280K, two thermally activatedrotational motions were observed around the
2-fold (C2) and 3-fold (C3) axis of the BH4
units. At the lower temperatures, only the C3rotation was detected while at higher
temperatures a combination of the tworotations, with different characteristic times,

was observed. The DFT calculated energy
barriers were similar to the experimental
ones (EaC2= 0.15 eV and EaC3=0.11 eV).

Long-Range Diffusion
Long-range diffusion events, with an energy
barrier of EaD=0.12 eV and an effective jumplength of ~2.5 Å were observed at two
temperatures with SPHERES. H jumps
between two neighboring BH4’ , diffusion of
BH4 and BH3 groups were calculated anddiscarded due to their very high formationenergies and diffusion barriers. Interstitial H,
H2, and H2O diffusions were also calculated.
H2 interstitial diffusion gave results (0.09 eV,
2.1 Å) with the best agreement to theexperimental values nevertheless, H2Ointerstitial diffusion (~0.4 eV, <1.08 Å)
couldn’t be strictly discarded. H2 and/or H2O
interstitials might form during the synthesis of
the compound.

Reference[1]
D. Blanchard et al. J. Phys. Chem. C(2010), 114.

Corresponding author: Didier Blanchard, email: mailto:didier.blanchard@risoe.dk, Tel. (+47) 46 77 58 99

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Reactive Hydride Composites
Thomas Klassen, Ulrike Bösenberg, Claudio Pistidda, Christian Bonatto Minella,
Rapee Gosalawit, Ivan Saldan, Karina Suarez, Maik Peschke, Gagik
Barkhordarian, Rüdiger Bormann, Martin Dornheim
Institute of Materials Research, Helmholtz-Zentrum Geesthacht, Centre for Materials andCoastal Research, Geesthacht, Germany
Institute of Materials Technology, Helmut Schmidt University, University of the Federal Armed
Forces Hamburg, Germany
Reactive Hydride Composites (RHC) release or store hydrogen by redox reactions between at least two
hydrides. Upon desorption, components from both hydrides react exothermally, thus reducing the overall
reaction enthalpy. Up to 11 wt.% hydrogen may be stored reversibly at technically relevant temperatures.

Reactive Hydride Composites
Reactive
HydrideComposites
likecombinations of MgH2 with M(BH4)x (M being
Li, Na or Ca) show significantly reduced
values of reaction enthalpies as well as
improved ab- and desorption kinetics
compared to the pure borohydrides.

Reaction Kinetics
In spite of a significantly lowered reaction
enthalpy and thus high thermodynamic
driving force for desorption, hydrogen releasefrom LiBH4/MgH2-RHC still requires temperatures above 250°C.
In this presentation, an overview will be given
on reaction mechanisms, thermodynamic
properties and sorption behavior of
nanocrystalline
RHCs:
2LiBH4+MgH2,
2NaBH4+MgH2
andCa(BH4)2+MgH2.
Function and suitability of additives as

Thomas Klassen

potential catalysts on hydrogen ab- anddesorption will be discussed and recent
progress in optimizing reaction kinetics bynano-scaffolding will be presented.

System Integration
For application, suitable tank design isnecessary to exploit the properties of newly
developed hydrides. Key issues related toheat management and safety will be
discussed.

References
[1]
[2]
[3]

G. Barkhordarian et al., J. Alloys andCompounds 440 (2007) L18-L21
G. Barkhordarian et al. Journal of Physical
Chemistry C 112 (2008) 2743-2749
M. Dornheim, T. Klassen, Encyclopedia ofElectrochem. Power Sources (2009) 459472

Born 1965 in Schwelm, Germany. 1990 Diploma in Physics from Dortmund University,
Germany. 1990 Institute for Materials Research, GKSS-Research Centre Geesthacht
GmbH, Germany. 1993 Dr.-Ing. from Technical University Hamburg-Harburg,
Germany. 1994 Post doc Materials Research Lab, University of Illinois at UrbanaChampaign, USA. 1996 Head of the Department Powder and Nano Technology, GKSS
Research Centre Geesthacht, Germany. 1997 Young Scientist Prize of the German
Materials Society (DGM). 2005 Habilitation in Materials Science, Technical University
Hamburg-Harburg, Germany. 2005 Professor in Material Science, Head of the Instituteof Materials Technology, Helmut-Schmidt-University (HSU), University of the Federal
Armed Forces Hamburg, Germany. 2010 Director of the Institute of Materials
Research, joint Professorship between HSU and Helmholtz-Zentrum Geesthacht,
Centre for Materials and Coastal Research.

Corresponding author: Thomas Klassen, email: mailto:klassen@hzg.de, Tel. (+49) (4152) 87 2562

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First Principles Prediction of Structural, vibrational andthermodynamic properties of Mixed Metal Hydrides andFluorides
Marta Corno, Eugenio Pinatel, Piero Ugliengo, Marcello Baricco
Dipartimento di Chimica IFM, NIS Centre of Excellence and INSTM, University of Torino, Via P.
Giuria 7/9, 10125, Torino, Italy.
Anionic substitution in high capacity metal hydrides still represents a promising route in the synthesis of novel materials
for hydrogen storage applications. In the present work, fluoride anion was selected for the substitution and models of
several F-substituted simple hydrides were simulated using DFT calculations, emphasizing a number of potential pitfalls
encountered while modelling their thermodynamic properties.

Anionic substitution in hydrides
The aim of anionic substitution in highcapacity metal hydrides is to destabilize
thermodynamic properties of the too stablepure compounds by substituting some of the
H atoms with halogens. The nature of the
halogen plays an important role in the
resulting thermodynamic properties of themixed compound.

H/F substitution in simple hydrides
First of all, a complete characterization of
structural, vibrational and thermodynamic
properties of Li, Na, Mg, Ca and Al pure
hydride has been carried out in the DFT
scheme, using a Gaussian localized basis
set and the periodic ab initio CRYSTAL09
code [1].
Once chosen the reference methodology (areliable and feasible set of computationalparameters), calculations for the following
solid state reaction(1-x)MHn + xMFn → MHn(1-x)Fnx
were run and the mixed MHF compounds
were carefully analyzed in terms of theirproperties.

In the present contribution, the focus will bemainly on Li, Na and Ca cases, since it has
been recently demonstrated that for Al [2]and Mg no mixed structures resulted.
For these hydrides, promising results havebeen obtained, but relevant differences were
found in the thermodynamics depending on
the specific modelling approach. Considering
Ca(H,F) as a test case, for both the cubic
and orthorhombic phases, potential pitfalls
will be highlighted, to establish a sensible
choice of the computational strategy.

References
[1]

[2]

R. Dovesi, V.R. Saunders, C. Roetti, R.
Orlando, C.M. Zicovich-Wilson, F. Pascale,
B. Civalleri, K. Doll, N.M. Harrison, I.J. Bush,
P. D’Arco, M. Llunell, CRYSTAL09,
University of Torino, Torino 2009www.crystal.unito.it
J. E. Fonneløp, M. Corno, H. Grove, E.
Pinatel, M. H. Sørby, P. Ugliengo, M.
Baricco, B. C. Hauback, J. Alloy. Compd.,
2010, doi: 10.1016/ j.jallcom.2010.08.147

Born 25. 2. 1981 in Torino, Italy. 2004 Degree in Chemistry, Torino, Italy. 2004-2007 PhD
in Chemical Science at the University of Torino (Unito), Italy. 2007-2009 Post doc at the
Inorganic, Physics and Materials Chemistry Department in the University of Torino, in thegroup of Professor Piero Ugliengo, working on the simulation of biomaterials (National
Project PRIN06). 2009-now Post doc at the same Dep. in the same group working withProfessor Marcello Baricco on ab initio modeling of metal hydrides (European Project
FLYHY).

Marta Corno
Corresponding author: Marta Corno, email: mailto:marta.corno@unito.it, Tel. (+39) (011) 670 4597

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The Role of Li2B12H12 in the Sorption Cycle of LiBH4
Arndt Remhof1, Oliver Friedrichs1, Andreas Borgschulte1, Andreas Züttel1
Yigang Yan2, Hai-Wen Li2 Shin-ichi Orimo2, Sonjong Hwang3
1

Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2

Tohoku University, Institute for Material Research, Hydrogen Functional Materials Division,
Sendai 980-8577, Japan

3

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena,
California 91125 USA.

Li2B12H12 has been observed in the decomposition of LiBH4 as well as a product in the reaction of B2H6
with LiBH4, leading to a controversy whether Li2B12H12 is an intermediate or a by-product in the sorption
cycle of LiBH4.

Li2B12H12 as by productBy in situ X-ray diffraction (XRD) and nuclear
magnetic resonance (NMR) spectroscopy,
we show that Li2B12H12 is formed in the gassolid reaction of the sorption of B2H6 with
LiBH4 200 °C (See Fig.1) [1].

hypothesis that Li2B12H12 is a decomposition
by-product, resulting from the reaction ofB2H6 with residual LiBH4.

Li2B12H12 as intermediate
By choosing the suitable conditions (pH2, T),
the decomposition of LiBH4 can be forced toproceed via
LiBH4 → 5/6LiH+1/12Li2B12H12 +13/12H2.
The thermal decomposition of Li2B12H12 itself
leads to a further hydrogen release, so
Li2B12H12 also occurs as an intermediate in
the decomposition.
The role of Li2B12H12 obviously depends onthe conditions of decomposition
References

Fig. 1 Crystalline phase evolution during thereaction of LiBH4 with diborane at 200 °C
observed by in situ X-ray diffraction.

[1] O. Friedrichs et al, Chem Mater, 22 3265
(2010)[2] S. Kato, Phys. Chem. Chem. Phys. 12 10950(2010).
[3] Y. Yan et al, in preparation

B2H6 is also observed during thedecomposition of LiBH4 leading to theArndt Remhof

Born 1969 in Bochum, Germany. 1994. University Diploma, University of Kent at
Canterbury, UK. 1996 Master thesis at the institute Max von Laue - Paul Langevin (ILL)in Grenoble, France. 1999 Guest scientist at the Universidade Sao Francisco in Itatiba,
Sao Paulo, Brazil. 2000 PhD from the science faculty at the Ruhr-Universität Bochum.
2000-2002 PostDoc at the Faculty of Sciences, Vrije Universiteit in Amsterdam. 20022007 Research assistant at the Ruhr-Universität Bochum. From 2007 Group leader at
Empa in the Laboratory “Hydrogen and Energy.” 2010 Visiting Scientist at the Institutefor Materials Research, Tohoku University, Sendai, Japan

Corresponding author: Arndt Remhof, email: arndt.remhof@empa.ch, Tel. (+41) (44) 823 4369

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Liquid Complex Hydrides
Andreas Züttel, Shunsuke Kato, Oliver Friedrichs, Andreas Borgschulte
Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen& Energy, CH-8600 Dübendorf, Switzerland
Most known complex hydrides today are salt like solids and desorb the hydrogen only at elevatedtemperature. Liquid hydrides at room temperature in equilibrium with the hydrogen gas pressure of a few
bar are preferable in view of mobile applications. Al[BH4]3 exhibits a volumetric hydrogen density of 150
3
kg/m , melts at –60°C and spontaneously releases the hyd rogen even below room temperature.

Liquid ionic compounds
The melting temperature of an ioniccompound (salt) depends on the ratio of thediameter of the consisting ions. Partial
substitution of the ions allows to stabilize
phases and to change the melting
temperature of a given ionic compound.

Stability
The complex hydride with a general formulax+of M [TH4 ]x (M = Li, Na, Mg, Ca…; T = Al, B,
N and x is the stoichiometry) releases H- toform MHx + x·TH3 [1]. The stability of the
AlH3 < BH3 < NH3, therefore, alanates
decompose into hydrogen and aluminum
while boranates tend to liberate besidehydrogen also B2H6 and the ammonium
spontaneously decomposes into NH3.
Therefore, the thermodynamics i.e. stability
and kinetics is calculated based on theintermediate products identified.
The stability of the TH4 is determined by the
localisation of the electron on the T-atom. As
a consequence the stability of the complex
hydride strongly depends on the electro-

negativity of the cation. However, thisapproach is only able to describe the stabilityof the forth hydrogen atom in the anion. The
stability of the neutral and “hypothetical” TH3
is also determining the equilibrium pressureof the complex hydride.
The empirical relationship between theenthalpy of formation and theelectronegativity of the cation is linear [2]. The
stability of the elemental hydride formed
upon hydrogen desorption is given by thePauling relation.
Therefore, the hydrogen desorption pressure
as well as the melting temperature can betaylored by specific substitution of the anion
and the cation in complex hydrides.

References
[1]

[2]

Y. Nakamori, K. Miwa, A. Ninomiya, H. Li, N.
Ohba, S.-I. Towata, A. Züttel, and Shin-ichi
Orimo, Physical Review B 74, 045126 (2006)
Shin-ichi Orimo, Yuko Nakamori, Jennifer R.
Eliseo, Andreas Züttel and Graig Jensen,« Complex Hydrides for Hydrogen Storage »,Chemical Reviews, October 2007, Volume
107, Number 10, 4111-4132

Born 22. 8. 1963 in Bern, Switzerland. 1985 Engineering Degree in Chemistry, Burgdorf,
Switzerland. Exchange student Dow Chemical in Terneuzen, Netherlands. 1990 Diploma
in Physics from the Unversity of Fribourg (UniFR), Switzerland. 1993 Dr. rer. nat. fromthe science faculty UniFR. 1994 Post doc AT&T Bell Labs in Murray Hill, New Jersey,
USA. 1996 Head of the Metalhydride Group at the UniFR. 1997 Lecturer at the Physics
Department UniFR. 2003 External professor at the Vrije Universiteit Amsterdam,
Netherlands. 2004 Habilitation in experimental physics at the science faculty UniFR.
President of the Swiss Hydrogen Association „HYDROPOLE“. 2006 Head of the section
Andreas Züttel “Hydrogen & Energy” at EMPA. Prof. tit. in the Physics department UniFR. 2009 Guest
Professor at IMR, Tohoku University in Sendai, Japan
Corresponding author: Andreas Züttel, email: mailto:andreas.zuettel@empa.ch, Tel. (+41) (44) 823 4038

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Catalytic Combustion of Hydrogen on Platinum Coated
Porous SiC Ceramics
U. F. Vogt, V. Siong, B. Fumey, M. Bielmann, A. Züttel
Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen& Energy, CH-8600 Dübendorf, Switzerland
A self igniting catalytic hydrogen diffusion burner, based on porous ceramics with a platinum catalytic
coating, has been developed for cooking and heating purposes in a novel autarky living unit. A very highpassive safety measure is reached through the strict separation of hydrogen and air, the gases are mixed
only on the catalytic coated SiC surface. Hazardous gases such as carbon monoxide, carbon dioxide,
nitrogen monoxide and nitrogen dioxide are no issue.

The project focus is to develop a novel typeof catalytic hydrogen burner. Highly porous
silicon carbon foams coated with platinum
are the basis of the development. Siliconcarbide ceramics show excellent hightemperature stability and thermal shock
resistance. Platinum assures catalyticoxidation of hydrogen even at low
surrounding
temperatures.
Forsafetyreasons, the premix of hydrogen and air isavoided. While hydrogen is fed from below,
defusing through the highly porous SiC foam,
air is supplied to the upper SiC foam surface.
Catalytic combustion thus mainly takes place
inside the porous SiC structure.

2000°C, catalytic combustion allows suchlow combustion temperatures. Due to thehigh safety standard and easy power
regulation, catalytic burners are favorable forsafe indoor cooking and heating applications.

.
Catalytic H2 combustion, IR image at 900°C

Principle of the catalytic burner

The combustion of hydrogen is free ofharmful gases such as carbon monoxide andcarbon dioxide and due to temperatures
below 1000°C, no nitrogen monoxide andnitrogen dioxide will arise. While a hydrogen
flame would burn at a temperature of ca.

H2 flow vs heating values, ASP and Lambda
value

1984 Diploma in Mineralogy, Univ. Freiburg, (D). 1984–1993 Krupp-Polysius (D),Degussa (D) and Alusuisse Neuhausen (CH). 1993 Dr. rer. nat. in Crystallography, Univ.
of Freiburg (D). Since 1993 at Empa, ceramic processing, SOFC, SOEC and membranedevelopment, catalytic hydrogen combustion. 1998 Diploma in Economics, ISZ/STV,
Zürich. Lecturer at the Univ. of Freiburg, D. Member of the American- & German
Ceramic Soc., Hydropole and the Association of Swiss Engineers of Economy.
U. Vogt
Corresponding author: Ulrich F. Vogt, email: mailto:ulrich.vogt@empa.ch, Tel. (+41) (44) 823 4160

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Gas-Solid Reactions for Heat Applications
Marc Linder, Inga Utz, Franziska Schaube, Margarethe Molenda, Antje Wörner
German Aerospace Center – DLR e.V., Institute of Technical Thermodynamics, Stuttgart
Pfaffenwaldring 38-40, 70569 Stuttgart, Germany
This paper gives an overview on current research projects at DLR concerning thermo-chemical heatstorage. Additionally, a new possible application of an open metal hydride system to generate cold byutilizing the hydrogen pressure difference available in hydrogen driven cars will be presented.

Background

Application for Hydrogen Cars

An efficient use of all available forms ofenergy is seen as one important path to asustainable and payable future energy
supply. In this context, efficient thermalenergy storage is one key-factor that allows
the utilization of e.g. intermittent solar
thermal energy or industrial waste heat.
Especially reversible gas-solid reactions arepromising candidates for future heat storage
systems as they offer high energy densities.

Up to now the cost for materials reacting withhydrogen are too high to be competitive withe.g. carbonates or hydroxides for thermalenergy storage. However, the fast reaction
kinetics of metal hydrides
at lowtemperatures together with the alreadyavailable compressed gas storage offers a
new application in future hydrogen driven
cars.

Operation Principle
The dissociation of a compound into twophases (gas, solid) by means of thermalenergy can be used as heat storage if the
products of the reaction are stored
separately. The heat is released again if thetwo reaction partners are brought together.
This principle is investigated at DLR for
different temperature levels, ranging fromaround 500 °C (hydroxides) [1] for solar
applications to lower temperatures (80 160°C) for industrial waste heat utilization(hydrates).
If the storage system is designed to operate
in a closed mode (e.g. carbonates andhydrides) a separated storage for thegaseous compound is necessary. This has tobe realized e.g. by mechanical compressionof the gas but offers at the same time thepossibility to transform heat as the reaction
temperature can by controlled by means of
the available pressure of the gaseous phase.

H2-Tank

Fuel Cell

Figure 1: Operation principle
The pressure difference between hydrogentank and fuel cell can be used to generate acontinuous cooling effect (sorption system),e.g. for onboard air-conditioning (Figure 1).
As the compression work for hydrogenstorage can be hereby partially re-utilized
onboard, the overall energy efficiency of the
car is increased. Additionally, conventional
climate-damaging refrigerants (HFC) can besubstituted.

References[1]

F. Schaube et al., Proceedings ofSolarPaces 2010, Perpignan, France (2010)

Corresponding author: Marc Linder, email: marc.linder@dlr.de, Tel. (+49) 711 6862 8034

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Hydrogen for Off-Grid Power Systems
Michael Bielmann, Ulrich Vogt, Andreas Züttel
Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div. Hydrogen& Energy, CH-8600 Dübendorf, Switzerland
Renewable off-grid power systems pose unique challenges for energy supply and management. The
inherent absence of a demand-balancing grid has to be replaced with storage capacity on site. Whilecurrently this function is mostly accomplished batteries, this approach offers severe draw backs. Hydrogenbased standalone power systems with on-site hydrogen generation offers opportunities to store large
amounts of energy, add flexibility to the system and offer the ability for seasonal storage – a function thatcannot be accomplished by batteries alone.

Challenges in renewable off-grid
power supply
In off-grid renewable energy supply systems,
demand and supply of energy is highly
fluctuating. In contrast to traditional
approaches, energy production by PV orWind are not under direct control. Therefore,
the balancing and matching of demand andsupply has to be an inherent functionality ofthe system itself. Traditionally, this function isserved by lead-acid batteries. Therefore, theamount of energy harvested is always aparameter of the available storage capacity,which is – depending on the situation –severely limited by volume and massconstraints. Especially PV pose a toughchallenge – the seasonal variation of
production cannot be serviced by battery
systems, making a large overdesign of the
PV system a necessity. The necessary large
capacities cannot be offered by batteries
which suffer from self-discharge and low
energy density.

Hydrogen for seasonal storage
Hydrogen offers the unique opportunity
energy densities unachievable by any battery
technology. Using excess energy to producehydrogen for seasonal storage on-site istherefore the perfect best of both worlds
approach, where batteries offer short term
storage and power capability while hydrogenthrough electrolysis, storage and fuel cells
add long term capabilities to the system. Thisapproach will be discussed in detail by thepratical example of SELF, a self-sufficientliving unit and technology platform developedby EMPA.

References[1]

M. Bielmann, U.F. Vogt, M. Zimmermann, A.
Züttel, Seasonal energy storage system
based on hydrogen for the self sufficientliving unit (SELF), submitted to Journal ofPower Sources (2010)

Born 2.7.1974 in Fribourg, Switzerland. 1999 Masters Diploma in Physics, University of
Fribourg, Switzerland, PhD Student at EMPA nanotech@surfaces, Thun, Switzerland
2005 Dr. rer. nat. from the University of Fribourg, Switzerland 2006 Post Doc at
Hydrogen and Energy Group, EMPA Materials Science and Technology, Dübendorf
Switzerland 2008 Scientific Project Leader, Demonstrations, Development andInstruments, Hydrogen and Energy Group, EMPA Materials Science and Technology,
Dübendorf, Switzerland
M. Bielmann
Corresponding author: M. Bielmann, email: mailto:michael.bielmann@empa.ch, Tel. (+41) (44) 823 4342

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Monte Carlo calculations of the free energy of SII and SH
clathrates
A. Atamas, S. W. de Leeuw
University of Leiden, Leiden Institute of Chemistry, Theoretical Chemistry Group, Leiden, The
Netherlands
Clathrate hydrates are crystalline molecularcompounds composed of a water host latticeand guest molecules. To stabilize thecompounds, the guest molecules called
promoters are entrapped into cavities of thehost water structure. Clathrate hydrates areof great technological interest for hydrogenstorage because of their capacity to store
gas at relatively high density and therefore
considered as prospective candidates forhydrogen storage materials [1]. Studies offree energies of gas hydrates are important
to explore stability, i.e. to find the mosteffective promoters, and to compute phase
diagrams. Recently developed self-referential(SR) method [2] for computing the freeenergy of crystals composed of rigid
nonlinear molecules is based only on theknowledge of intermolecular potential. In thiswork the SR technique was applied to
calculate free energy of sII and sH clathrates
with cavities occupied by hydrogenmolecules and different promoters.

References[1][2]

W.L. Mao and H. K. Mao, Proc. Natl. Acad.
Sci. 101, 708 (2004)
A. Atamas, M. V. Koudriachova, S. W. de
Leeuw, and M. B. Sweatman, Monte Carlocalculations of the free energy of ice-likestructures using the self-referential method,
Mol. Sim., 2010, submitted

Corresponding author: Simon W. de Leeuw, email: mailto:leeuwdes@chem.leidenuniv.nl, Tel. (+31) (0) 71
527 4437

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Annealed GdC Thin Films Microstructure Evaluation
Jurgita Čyvienė, Jolita Sakaliūnienė, Julius Dudonis, Brigita Abakevičienė
Department of Physics, Kaunas University of Technology, Studentu str. 50, LT-51368 Kaunas
Lithuania
Solid oxide fuel cells (SOFC) are considered a promising power generation technology. Gadolinia-doped
ceria (GDC) is an alternative electrolyte material which offering the possibility of lower temperature SOFC
operation (500°C ÷ 700°C). Magnetron sputtering is a well-developed, promising, flexible deposition
technique for preparing thin electrolytes of GDC. By this technique the layers are deposited from theatomic phase; for this reason deposited films do not need annealing at high temperatures.

Thin films formation
The method of nano-crystalline thin films
formation can greatly affect on thenanostructure and overall performance
properties of GDC. The quality of such thinfilms depends on structural peculiarities,
which are influenced by the technologicalparameters of formation methods [1, 2].

MicrostructureFirstly Cex1Oy1 then Gdx2Oy2 multilayer
sandwich systems with 6 and 12 layers weremade by reactive magnetron sputtering inreactive O2/Ar gas mixtures. Increasing
number of the layers, taking in mind that a
Ceria must be 90 at.% and Gadolinia –about 10 at.%, were included to the general
thickness (~ 600 nm) of the films. These0
multilayer systems were annealed at 600 C
0
and 700 C temperature in air.
X-ray diffraction studies and SEM analysis of
GDC (Ce0,9Gd0,1O1,95) thin films were studied
there. The calculation of texture coefficients

showed the crystallized cubic fluorite
structure with orientation (111) of 6 and 12
layers at 600°C and 700°C annealed
temperatures. The highest value of texture
coefficient R = 0.901 was obtained for 12
layers system annealed at 700°C. The bestionic conductivity of this GDC structures
orientation is contemplated. It was found thatthe crystallite size of 12 layers GDC thin films
increased about 50% after annealing in
700°C temperature ( ∼12 nm) comparing with
600°C annealing temperature ( ∼8 nm).
From this work is shown that gadolinia-based
ceria thin films with applicable properties
could be formed using magnetron sputtering.

References[1] Jennifer L.M. Rupp, Anna Infortuna, Ludwig J.
Gauckler, J. Am. Ceram. Soc., 90/6, 1792–1797(2007).
[2]G. Laukaitis, D. Milcius, Solid State Ionics, 179,
66–71 (2008).

Born 12. 5. 1977 in Alytus, Lithuania. 1999 Bachelor Degree in Physical Science,
Kaunas, Lithuania. 2000 Traineeship - practice at Karlsruhe Scientific Research Centre,
Germany. 2001 Master Degree in Physical Science, Kaunas, Lithuania. 2002 Scientific
Associate of the Physical Science, Karlsruhe Germany. 2006 Doctor Degree in PhysicalScience, Kaunas University of Technology, Lithuania. 2007 Scientist, Lithuanian Energy
Institute. 2007 Senior Lecturer at Department of Physics, Kaunas, Lithuania. 2010
PostDoc position at Department of Physics, Kaunas University of Technology, Lithuania.
Jurgita Čyvienė
Corresponding author: Jurgita Čyvienė, email: jurgita.cyviene@ktu.lt , Tel. (+370) (37) 300346

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Characterization of Commercial Metal-Oxide Ceramic
Diaphragms for Hydrogen Production by Alkaline
Electrolysis
Michal Gorbar1, Ulrich Vogt1, Jelena Stojadinovic1, Daniel Wiedenmann1,2,
Valentina Zakaznova-Herzog1, Bernard Grobéty2, Andreas Züttel1,
1

Empa Materials Science & Technology, Dept. Energy, Environment and Mobility, Div.
Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
2
University of Fribourg, Department of Geosciences, Pérolles, 1700 Fribourg, Switzerland
Commercial metal-oxide ceramic diaphragms for hydrogen production by alkaline electrolysis were tested
in a lab-scale electrolyzer at ambient conditions for over-potential and gas purities. Additionally, thespecimens were characterized structurally by SEM (scanning electron microscope), XRD (X-ray
diffraction), and RS (Raman spectroscopy) and electrochemically by EIS (impedance spectroscopy). Shorttime corrosion tests at various concentration of KOH were performed.

Conventional alkaline electrolysers with zerogap cell geometry operate at 85°C, 32 bars
and use 25 wt% KOH as electrolyte.
Asbestos diaphragms, used as ionpermeable separator, prevent intermixing ofproduced H2 and O2 gases. Hydrogenproduce by this technology has a purity inrange of 99.98 - 99.99% [1]. Due to healthregulations but also low chemical stability attemperatures above 100°C, the replacementof ion-permeable asbestos diaphragms
essential.

impedance cells with current density of 200-2
mA.cm .
The characterization of the diaphragms
focusedonion-conductivity,
porosity,
structural and surface changes. The
chemical stability in KOH of 25 wt%, 30 wt%
and 50 wt%, respectively, at 85 °C wasdetermined by gravimetric analysis. The
density and porosity was determined byArchimedes
method.
Structure
characterization and its changes wereobtained by conventional scanning electron
microscopy, X-ray diffraction technique andRaman spectroscopy.

Experiments

References

Composite ceramics (CMCs), based on
Nextel 610 fibers as reinforcement andmixture of Al2O3/8-mol% Y2O3 doped ZrO2 as
matrix, were tested in lab electrolysis- and[1]

Introduction

IHT (Industrie Haute Technologie), Monthey,
Switzerland

Born 14. 11. 1982 in Levoca, Slovakia. 2001 - 2007, study of chemistry at the Comenius
University in Bratislava. In 2006 - 2007 Master Thesis "TiO2 surface modified ceramicfoams for catalytic applications" at Empa, Dept. of High Performance Ceramics. In 2007
graduated as Master of Science in inorganic chemistry. 2007 - 2008 employee of Empa,
at the Dept. of Internal Combustion Engines and High Performance Ceramics in
Dübendorf, Switzerland. 2008 - 2010, PhD student at University of Fribourg and in the
Laboratory "Hydrogen & Energy" at Empa, Dübendorf. Involved in the project "Newmembranes for alkaline electrolysers (NMAE2).
Michal Gorbar
Corresponding author: Michal Gorbar, email: michal.gorbar@empa.ch, Tel. (+41) (44) 823 4301

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Architecture of Air Independent Electric Supply System
Based on PEM Fuel Cell
Grzegorz Grzeczka, Piotr Szymak
Polish Naval Academy, Faculty of Mechanics and Electrical Engineering, Institute of ElectricalEngineering and Automatics, Smidowicza 69, 81-103 Gdynia, Poland
PEM fuel cell systems have to be supplied from hydrogen and oxygen sources. In most cases, oxygen isachieved from ambient atmosphere and hydrogen is stored in pressured tanks, metal hydrides storages or
chemically bounded in other chemical compounds. Unfortunately, in some cases e.g. during underwater
operation, oxygen is not accessible. Then, both hydrogen and oxygen have to be stored and fuel cellsystem has specific oxygen supply subsystem.

Introduction
An Air Independent Electric Supply System
AIESS based on PEM fuel cell was built in
Polish Naval Academy. The system can workin underwater conditions and is supplied byboth clean hydrogen and clean oxygen
stored in pressurized tanks [1].

Architecture of AIESS
AIESS was built in the Laboratory of Electric
Drives to demonstrate application of PEM
fuel cell technology in supplying underwater
platforms. The Air Independent Electric
Supply System consists of:1)
PEM fuel cell system with nominal
power 6 kW based on P8 stack from
Nedstack Company, Arnhem, Netherlands,
2) DC/DC converter stabilizing voltage atlevel 220 V, connected in parallel withsupercapacitors,
3) an electric load consisting of: an electricmotor, a lighting set and a heating,4) installations and pressured tanks ofoxygen, hydrogen and nitrogen.

The PEM fuel cell system is controlled by S7300 PLC. The controller is connected with atouch panel and PC through MPI protocol.
The touch panel performs Human MachineInterface, whereas PC visualizes operation
and registers parameters of the system.

Results
Based on achieved results of operation
AIESS [1], the PEM fuel cell system
responds on changes of an electric load(about 50 A) in short time (about 3 seconds)
with small over-regulation (about 2 V).

References
[1]

[2]

G. Grzeczka, P. Szymak, Grant Report on
Air Independent Electric Supply System
based on PEM Fuel Cell, Polish Naval
Academy, in Polish, Gdynia, Poland, 2010
G. Grzeczka, P. Szymak, System zasilania
wodoremogniwapaliwowego
PEMniezależnego od powietrza, ZN AMW, inpress,
2010

Born 21. 07. 1962 in Gdynia, Poland. 1989 Master of Science Degree in ElectricalEngineering, Polish Naval Academy, Gdynia, Poland. 1998 Doctor of Philosophy in
Mechanics and Mechanical Engineering, Polish Naval Academy, Gdynia, Poland.
1999 Secretary of Scientific Committee of Institute of Electrical Engineering andAutomatics, Gdynia, Poland. 2000 Assistant Professor at Polish Naval Academy,
Gdynia, Poland. 2010 Chairman of Military Commission for Power Engineering
Qualification, Poland.
Grzegorz Grzeczka
Corresponding author: Grzegorz Grzeczka, email: g.grzeczka@amw.gdynia.pl, Tel. (+48) (58) 626 2994

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Dynamic Modeling and Simulation of Anode-Supported
Planar Solid Oxide Fuel Cell
Pejman Kazempoor1,2, Viktor Dorer2
1

Tarbiat Modares University, Tehran, Iran

2

Empa Swiss Federal Laboratories for Material Testing and Research, Building Science andTechnology Laboratory, CH-8600 Dübendorf, Switzerland
To explore the dynamic characteristics of the SOFC system and to develop relevant control
strategies, a reduced-order dynamic cell model developed for planar solid oxide fuel cells,
based on existing and improved models. Appling two control strategies, the cell model is
implemented to analysis the dynamic behaviour of an anode-supported SOFC cell. The results
show that the relaxation time is strongly related to the thermal behaviour of the cell and theapplied control strategy.

Introduction
Dynamic studies and development of suitable
control strategies are key tasks for realisationof the SOFC systems. Therefore, the main
focus of the present research was developing
a computational model to explore thedynamic characteristics of the SOFC cell andto develop control strategies that can ensure
fast and safe transient operation.

MethodBased on the above goals, a reduced-order
dynamic cell mode developed for the planarsolid oxide fuel cell, based on existing andimproved models, comprising the mass,
momentum, energy and electrochemical
analysis as well as a kinetic model ofhydrocarbon reactions. The electrochemical
model includes a complete evaluation ofohmic, activation and diffusion losses. In
comparison to the most previous literaturemodels,dynamic
terms
have
been
implemented in both energy and massconservation equations. To verify the model,
it is compared with available experimental
and benchmark test data as well as someprevious numerical results, showing thecapacity of the model to accurately predict
the SOFC operating conditions. The cell
model is applied to analysis the dynamic
behaviour of an anode supported SOFC cellcaused by step load changes based on twocontrol strategies i.e. cell constant fuel flowrate and constant fuel utilization during theload variation. The effect of several
parameters e.g. interconnector materials,
load variation magnitude, has been
investigated.

Results
The results show that the relaxation time isstrongly related to the thermal behaviour ofthe cell as well as the applied control strategy
and cell material properties. However, it isalmost independent of the load variation
magnitude.

Born 27. 7. 1978 in Esfahan, Iran. 2001 B.Sc of Mechanical Engineering, Yazd, Iran.
2003 Msc. of Aerospace Engineering, Tarbiat Modares University, Tehran, Iran. 2008
Visiting Ph.D student in EMPA Swiss Federal Laboratories for Material Testing andResearch, Building Science and Technology Laboratory, Dübendorf, Switzerland. 2009
Ph.D in Mechanical Engineering majoring in Energy, Tarbiat Modares University,
Tehran, Iran.
Pejman Kazempoor
Corresponding author: Pejman Kazempoor, email: Pejman.kazempoor@hotmail.com, Tel. (+98) (912) 438 9239.

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First-Principles Calculations of Hydrogen Diffusion into
Palladium Nanoparticles
Phung Thi Viet Bac, Hiroshi Ogawa
Nanosystem Research Institute, National Institute of Advanced Industrial Science andTechnology (AIST), AIST Tsukuba Central 2, 1-1-1 Umezono, Tsukuba 305-8568, JAPANIn this research, density functional theory (DFT) calculations for the surface adsorption and subsurface
absorption of hydrogen on Palladium clusters are performed. We investigate the hydrogen-site specificeffects and how the hydrogen storage properties of Pd clusters change with the cluster size. The hydrogen
diffusion barriers are calculated for interstitial sites, from the surface to the subsurface of Pd clusters andcompared to those of bulk and Pd (111) surface systems, which can provide us an interpretation of thestability of the hydrogenated Pd clusters.

Hydrogen Storage by Palladium
Nanoparticles

Hydrogen
Diffusionicosahedral clusters

Pd is an archetypical hydrogen storage metaland stores hydrogen under ambientconditions. The hydrogen storage properties
of Pd nanoparticles vary depending on theparticle sizes and the stabilizers [1]. The
hydrogen solubility and equilibrium pressure
for the formation of palladium hydridedecrease with a decrease in the particle size.
Hydrogen is also known to adsorb strongly
on the surface of Pd clusters, thereby greatlychanging the structure of the clusters.

To examine the possibility of the diffusion ofa H atom from the surface into thesubsurface of Pd icosahedral clusters, weestimated the energy barriers for H migratingfrom the surface to the subsurface and themigration energy of H between the interstitialsites inside clusters. The energy profiles
along the H diffusion paths in Pd clusters arepresented. The results were compared tothose of (111) surface [2]. We suggest thatchemisorbed H occupies both surface andsubsurface sites of Pd clusters.

Computational Method
The density functional theory calculations
were performed using the VASP code with
PAW pseudopotentials to describe theelectron-ion interaction. The nudged elastic
band method was used to find the minimum
energy path and the corresponding energy
barriers for hydrogen diffusion process.

Phung Bac

into

Pd

References[1]

M. Yamauchi, H. Hobayashi, H. Kitagawa,Chem. Phys. Chem., Vol. 10, 2566-2576(2009).
[2] R. A. Olsen, P. H. T. Philipsen, and E. J.
Baerends, G. J. Kroes, O. M. Lovvik, J.
Chem. Phys. 106 (22), 9286-9296 (1997).

Born 1980 in Vietnam. 2002 Bachelor Degree in Chemistry, Hanoi National University of
Education, Vietnam. 2004 Master Degree in Theoretical and Physical Chemistry, Hanoi
University of Science, Vietnam. 2006 Research student, Center For Interdisciplinary
Molecular Science (CIMS), National Chiao Tung University, Taiwan. 9.2009 Ph.D in
Computational Science, Kanazawa University, Japan. 3.2010 Postdoctoral Fellow, GP
project, Kanazawa University, Japan. 2010 Postdoctoral Fellow, Nanosystem ResearchInstitute, National Institute of Advanced Industrial Science and Technology (AIST),“Hydro Star” project funded by New Energy and Industrial Technology Development
Organization (NEDO), Japan.

Corresponding author: Phung Thi Viet Bac, e-mail: phung.bac@aist.go.jp, TEL: +81-29-861-34

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Investigation of the Hydrogen Sorption Properties of
Nanocomposites NaBH4-MgH2 Confined into
Mesoporous SBA15
1

1

2

3

3

3

C.Milanese , A.Girella , R.Campesi , S.Garroni , S.Doppiu , E.Napolitano , G.Mulas

3

1

CSGI, Dipartimento di Chimica Fisica "M. Rolla", Università degli Studi di Pavia, Pavia, Italy
JRC-IE, Petten, Netherlands
3
Dipartimento di Chimica, Università degli Studi di Sassari, Sassari, Italy
2

In the field of hydrogen storage materials, recent results underline improved sorption propertiesof nanosized powders with grain size lower than 20 nm with respect to the conventional bulk
materials. The reduction to nanometer scale and the control of grain size of hydride particles,
obtained through the confinement within nanoporous-scaffolds, appear to have beneficial
effects on the thermodynamic properties and kinetics of hydrogen release and uptake. Alongthis line in this work we focus on the hydrogen sorption properties of NaBH4-MgH2 systemembedded into Si-based mesoporous matrix, SBA15, by wet chemical or by melting
impergnation methods. Moreover, the pore network of the hosting material, controlling theparticle size of the active phases, could facilitate the interaction between the hydrides during theab-desorption process. Different hydride stoichiometries were investigated and different
additives were tested. Microstructural characterization of samples was performed by diffraction,
calorimetric and microscopic techniques, while the hydrogen ab-desorption properties werestudied by using gravimetric volumetric techniques as well as by thermal desorpion
spectroscopy analyses.

Chiara Milanese (born in 1974) graduated in Chemistry cum laude at the University ofPavia, Italy, in 1998 and she took her PhD in Chemical Sciences in 2002.
Subsequently, she obtained a post doc grant focused on the preparation andcharacterization of materials for energetics. Since 2008 she has been researcher at theFaculty of Pharmacy of the University of Pavia. Starting from the same year, she has
been the technical responsible of the Pavia H2 Lab. She is working on Mg – basedmaterials and MgH2 – borohydrides systems.
Chiara MilaneseCorresponding author: Chiara Milanese, e-mail: chiara.milanese@unipv.it, Tel. (+39) 0382 98767

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Complex Hydride Ionics
Motoaki Matsuo,1 Hiroyuki Oguchi,1 Yu Zhou,1 Shin-ichi Orimo1
Andreas Borgschulte,2 Andreas Züttel2
12

Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai, 980-8577, Japan
Empa, Lab. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

The new complex hydride, Li3(NH2)2I, with an unique crystal structure was synthesized, and then the ion
conductivity was experimentally studied.

Lithium Fast-Ion Conductivity in Li(BH4)
The ion conductivity of Li(BH4) increases by
three orders of magnitude at 390 K due to its
structural transition from the orthorhombic
low-temperature (LT-)phase to the hexagonal
1high-temperature (HT-)phase . From theapplication point of view, it is highly desirable
to enhance the conductivity of Li(BH4) at RT.

New Complex Hydride in
Li(NH2)–LiI: Conductivity?

The new complex hydride, Li3(NH2)2I, with an5unique crystal structure was synthesized .
The experimental result on its conductivity
will be explained in the presentation.

References[1]

Enhanced Conductivities in Li(BH4)–LiI
and Li(BH4)–Li(NH2)The enhanced conductivities in Li(BH4)–LiX
2,3
4(X = Cl, Br, and I) and Li(BH4)–Li(NH2)have been demonstrated. In Li(BH4)–LiI, theHT-phase of Li(BH4) can be stabilized below
390 K by forming solid solution phase with awide range of compositions; as a result, the−5conductivity (4 × 10 S/cm) becomes threeorders of magnitude higher than that of pure
−8
Li(BH4) (2 × 10 S/cm) at RT. In the case ofLi(BH4)–Li(NH2),
Li2(BH4)(NH2)and
Li4(BH4)(NH2)3 both with combinations of––[BH4] and [NH2] complex anions, show fast−4
ion conductivities of 1 × 10 S/cm at RT
because of new occupation sites available to+
Li ions. These experimental results suggestthat various fast-ion conductors may exist in
the Li(BH4)–Li(NH2)–LiI system.

Shin-ichi Orimo

Li(BH4)–

[2]

[3]

[4]

[5]

Matsuo, M.; Nakamori, Y.; Orimo, S.;
Maekawa, H.; Takamura, H. Appl. Phys.
Lett. 2007, 91, 224103.
(a) Matsuo, M.; Takamura, H.; Maekawa, H.;
Li, H. -W.; Orimo, S. Appl. Phys. Lett. 2009,
94, 084103. (b) Maekawa, H.; Matsuo, M.;
Takamura, H.; Ando, M.; Noda, Y.;
Karahashi, T.; Orimo, S. J. Am. Chem. Soc.
2009, 131, 894. (c) Oguchi, H.; Matsuo, M.;
Hummelshøj, J. S.; Vegge, T.; Nørskov, J.
K.; Sato, T.; Miura, Y.; Takamura, H.;
Maekawa, H.; Orimo, S. Appl. Phys. Lett.
2009, 94, 141912.
Borgschulte, A.; Gremaud, R.; Kato, S.;
Stadie, N.; Remhof, A.;Züttel, A.; Matsuo,
M.; Orimo, S. Appl. Phys. Lett., 2010, 97,
031916.
Matsuo, M.; Remhof, A.; Martelli, P.; Caputo,
R.; Ernst, M.; Miura, Y.; Sato, T.; Oguchi, H.;
Maekawa, H.; Takamura, H.; Borgschulte,A.; Züttel, A.; Orimo, S. J. Am. Chem. Soc.
2009, 131, 16389.
Matsuo, M.; Sato, T.; Miura, Y.; Oguchi, H.;
Zhou, Y.; Maekawa, H.; Takamura, H.;
Orimo, S. Chem. Mater. 2010, 22, 2702.

Born 11. 2. 1966 in Hiroshima, Japan. 1993-1995 JSPS Research Fellow, 1995
Ph.D. degree, 1995-2002 Research Associate, in/from Hiroshima University.
1998-1999 Guest Researcher in Max-Planck Institute for Metal Researchawarded Alexander von Humboldt Fellowship and MEXT Fellowships. 2002
Associate Professor, Institute for Materials Research (IMR), Tohoku University.
2010 Full-Professor, Head of the Section and Deputy of the Research Center“Integrated Materials Research Center for a Low-Carbon Society”.

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

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Conceptual Approach to New metal-organic Frameworks forhydrogen Storage
Samir Barman,a Hiroyasu Furukawa,b Olivier Blacque,a Koushik Venkatesan,aOmar Yaghi,b Heinz Berkeaab

University of Zurich, Institute of Inorganic Chemistry, CH-8057 Zurich, Switzerland. Center for
Reticular Chemistry, Department of Chemistry and Biochemistry, University of California-Los
Angeles, 607 Charles E. Young Drive East, Los Angeles, California 90095, USA.
Two Zn MOFs, MOF-645 and MOF-646, comprised of polarized 1,3-azulenedicarboxylate weresynthesized. The guest free MOF-646 showed strong MOF-H2 interactions (7.8 – 6.8 kJ mol−1), which
revealed the significant impact of internally polarized azulene backbone to stabilized H2 molecules in theframework.

Polarized binding of dihydrogen
In the last few decades an extensive
research focus have been devoted towards
finding a suitable Porous Coordination
Polymers(PCPs)
orMetal–Organic
Frameworks (MOFs) as an on-board[1]hydrogen storage system.
Based ontheoretical and experimental studies it has
become pertinent that the increase in thebinding energy of the materials up to 15-20
kJ/mol is the most crucial step towards
designing the ambient temperature storage[2]
systems.
Azulenes constitute dipolar aromatic systems
and we anticipated that these contained in a
MOF could contribute to build up of columbic
fields required for the polarization and[3]
polarized binding of H2. Therefore, we
strived to prepare MOFs namely MOF-646

Heinz Berke[Zn4O(link)3] (lcy net) and MOF-645[Zn5(OH)2(link)4] (bcu net) comprised ofpolarized angular 1,3-azulenedicarboxylate2+
and Zn . Indeed, the guest free MOF-646
demonstrates excellent volumetric H2 uptake-1of 20.9 g L at 77 K and 1 bar, and moreinterestingly the isosteric heat of adsorption-1-1
was as high as 7 kJ mol even at 13.3 mg g
[4]
of H2 loading. This reveals the significant
impact of internally polarized azulene
backbone to stabilize H2 molecules in theframework.

References[1] Ma, S.; Zhou, H.-C. Chem. Commun. 2010, 46, 44.
[2] Bhatia, S. K.; Myers, A. L. Langmuir, 2006, 22, 1688.
[3] Berke, H. ChemPhysChem, 2010, 11, 1837.
[4] Barman, S.; Furukawa, H.; Blacque, O.;
Venkatesan,K.; Yaghi, O.; Berke, H., Chem.
Commun. 2010, 46, 7981.

Born 05. 9. 1946 in Donndorf, Germany. 1974 PhD in Chemistry, University of Tübingen,Germany. 1981-1986 Assistant Professor. 1986-1988 C2-Professorship, University ofKonstanz. 1988 Full professor of Inorganic Chemistry, University of Zurich. 1991-2008
Director of the Institute of Inorganic Chemistry, University of Zurich. 1983-1987
Heisenberg Fellow of the Deutsche Forschungsgemeinschaft. 1983 Dozenten Award of
the Fonds der Chemischen Industrie, Germany. 2007 Honorary Professor, Fudan
University, Shanghai and Guangxi Normal University, Guilin, China. 2010 DistinguishedAward, Int. Union of Pure and Applied Chemistry, China.

Corresponding author: Heinz Berke, email: hberke@aci.uzh.ch, Tel. (+41) (44) 635 4680

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New Double-Cation Borohydrides
Inge Lindemann1, Roger Domènech Ferrer1, Lothar Dunsch1, Yaroslav
Filinchuk2, Hans Hagemann3, Radovan Černý3, Ludwig Schultz1 and Oliver
Gutfleisch1
1 IFW Dresden, P.O. Box 270016, D-01171 Dresden (Germany)
2
Swiss-Norwegian Beam Lines at ESRF, BP-220, 38043 Grenoble (France)
3
Departments of Physical Chemistry and Laboratory of Crystallography, University of Geneva,
30 quai Ernest-Ansermet, CH-1211 Geneva (Switzerland)
Conventional borohydrides are not meeting the thermodynamic requirements for hydrogen storage
materials used in mobile applications. It is the aim to adjust their stability by combining two different
cations forming novel double-cation borohydrides. Al-Li-borohydride (17.2 wt.% H2) and Al-Na-borohydride(14.6 wt.% H2) were synthesised by metathesis reaction during ball milling. Their decomposition occurs
around 70°C and 90°C, respectively. Decomposition p athways were analysed by means of in-situ Raman
spectroscopy.

Introduction
The stability of borohydrides is dependent on
the electronegativity of the cation [1]. In order
to meet stability requirements for hydrogenstorage materials two cations with very
different electronegativity are combined toform a double-cation borohydride withintermediate stability. NaBH4 is more stable
than LiBH4 therefore decomposition should
occur at higher temperature for Al-Naborohydride than for Al-Li-borohydride. Li etal. [2] did a similar milling of AlCl3 and LiBH4
which showed decomposition around 70°C.
We did further investigation on that andcompared it also with another system using
NaBH4.

Synthesis and Structure
The two double-cation borohydrides Al-Liborohydride and Al-Na-borohydride weresynthesized by metathesis reaction. Either
AlCl3 and LiBH4 or NaBH4 were ball milled for
5h in Ar atmosphere in different molar ratios.
Structural analysis was done by XRD and

Raman spectroscopy. Collected synchrotron
data was used for structure determination
backed up by DFT-calculation. Al-Li-borohydride showed a very different structure
than expected in the literature. It forms aprimitive cubic unit cell consisting of complex
3+
cations [Li4(BH4)] and anions [Al(BH4)4] .
Na-Al-borohydride contains only complex
anions and shows an orthorhombic structure.

References[1]

Y. Nakamori, K. Miwa, A. Ninomiya, H. Li, N.
Ohba, S.-I. Towata, A. Züttel, and Shin-ichi
Orimo, Physical Review B 74, 045126 (2006)[2] H.-W. Li, S. Orimo, Y. Nakamori, K. Miwa, N.
Ohba, S. Towata, A. Züttel, J. Alloys Compd.
446–447, 315–318 (2007)[3] I. Lindemann, R. Domènech Ferrer, L.
Dunsch, Y. Filinchuk, R. Černý, H.
Hagemann, V. D'Anna, L.M. Lawson;Daku,
L. Schultz, O. Gutfleisch, Chem. Eur. J. 16,
8707-8712 (2010)
Authors are grateful to the European Union andthe Free State of Saxony (ECEMP
13853/2379).

Born 8.4.1984 in Cottbus, Germany 2003-2009 Studies in Materials Science at the
University of Technology in Dresden, Germany (Diploma 2009) 2006 Exchange
student at Advanced Nanotechnology Ltd. in Perth, Australia Since 2009 PhD student
in the group of Oliver Gutfleisch at IFW Dresden, Germany

Inge Lindemann
Corresponding author: Inge Lindemann, email: I.Lindemann@ifw-dresden.de, Tel. (+49) (351) 4659 337

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Hydrogen Storage in Carbon Cones
Jiri Muller, Henning Heiberg-Andersen and Arne T. Skjeltorp
Institute for Energy Technology, NO-2007 Kjeller, Norway
Large scale production of conical carbon nanostructures (so-called carbon cones) [1] that are
fundamentally different from the other nanocarbon materials, such as buckyballs and nanotubes, canbe made using the so-called Kvaerner Carbon Black & Hydrogen Process [2]. This involves pyrolysis
of hydrocarbons using a torch plasma process. The carbon cones that occur appear in five distinctly
different forms. Earlier reports indicated that these structures exhibit unusually high H2 uptake andrelease at room temperature not known in other forms of carbon [3]. Here we report about the recent
progress of the experimental research and theoretical modelling of these cluster particles withemphasis on H2 storage.
References:[1] Helgesen et al, Mater.Res.Soc.Symp.Proc. Vol. 1057, 2008 Materials Research Society.
[2] Kvaerner ASA, patent No. PCT/NO98/00093 for production and micro domain particles by use ofplasma process.
[3] Norwegian patent No. 307986 (2000), US patent no.6,290, 753 (2001), EPO Patent No. 1051539(2004), Hydrogen storage in carbon materials

Corresponding author: Jiri Muller, email: jiri@ife.no

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Hydrogen Processing / recycling of rare earth magnets
Allan Walton, Miha Zakotnik, Ivor Rex Harris, Andy Williams
Metallurgy and Materials, University of Birmingham, Edgbaston, Birmingham, B15 2TT
Rare earth magnets such as NdFeB are strategically important materials for many clean technologies. The
Chinese completely dominate the rare earth market supplying around 97% of the world’s rare earth metals.
This is causing considerable concern in the EU, US and Japan. The house of representatives in
Washington recently approved a bill authorising research to address the supply of rare earths, saying theminerals were critical to energy, military and manufacturing technologies [1]. The Magnetic Materials
Group at the University of Birmingham has been investigating the use of hydrogen to reprocess / recycle
NdFeB magnets. This work outlines the case for recycling rare earth magnets and gives an overview of theresearch activities which have been carried out to date.

Introduction
China produces approximately 97% of theworld’s rare earth elements including
neodymium and dysprosium. Rare earth
mining/refining
processes
areenvironmentally damaging as these activities
are energy intensive and develop waste
products such as fluorine, radioactive
thorium, sulphuric acid, hydrofluoric acid anddust. Nd and Dy are used in rare earthmagnets which are strategically important fora huge number of modern day applications
including for example motors in electricalvehicles, generators in wind turbines andsmall electronic devices such as mobile
phones and hard disk drives. Chinesedemand for Nd is expected to outstrip its own
production in the next few years and they
have already begun restricting exports to therest of the world [2]. In the last twelve months
Nd prices have risen from ~20$/kg to~100$/kg. Given the strategic importance of
these elements, the market dominance ofChina and the environmental damage
caused by mining these materials, there is avery strong argument for recycling existing
scrap NdFeB magnets.

Allan Walton

Hydrogen is already employed commerciallyto produce NdFeB magnets by breaking up
cast NdFeB into a powder (HD process) [3].
Hydrogen is initially absorbed by the Nd richgrain boundary phase (at RT andatmospheric pressure) with an associatedvolume expansion. This results in thematerial breaking into a powder, which caneasily be jet milled and then pressed to
produce sintered NdFeB magnets. In thiswork, the HD process has been employed to
re-process and recycle existing sintered
NdFeB magnets into a powder which can beused to produce new magnets [4].

References –
[1]
[2]

[3]

[4]

th

New York Times article Oct 4 2010.
C.Hurst. Report by the US Institute for the
Analysis of Global Energy Security, March2010 – China’s Rare Earth Elements
Industry.
P.J.McGuiness, I.R.Harris, E.Rozendaal,
J.Ormerod, M.Ward, J.Mat.Sci. 21, (1986) p
4107.
M.Zakotnik, I.R.Harris, A.J.Williams. J.Alloys
and Comp. 469 (2009) p 314.

Born 06.04.1976 in Middlesbrough, UK. 1994 - 1997 Degree - BEng in Materials
Science, University of Birmingham. 1997 - 2001 PhD on coatings for NdFeB magnets,
University of Birmingham. 2001 - 2009 Post Doc - Hydrogen Storage Materials andHydrogen Purification Membranes, Hydrogen Materials Group, University of Birmingham.
2009 – Senior Science City Research Fellow, Energy Theme – University of Birmingham
and University of Warwick.

Corresponding author: Allan Walton, email: a.walton@bham.ac.uk Tel. (+44) 121 414 3960

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KINETIC AND THERMODYNAMIC INVESTIGATIONS ON PUREAND DOPED NaBH4 – MgH2 SYSTEM.
Chiara Milanesea, Alessandro Girellaa, Sebastiano Garronib, Gabriele Mulasc,
Maria Dolors Barób, Amedeo MariniaabPavia H2 Lab, CSGI & Dept. of Physical Chemistry, University of Pavia, Italy; Dept. de Fisica,c
Universitat Autonoma de Barcelona, Spain; Dept. of Chemistry, University of Sassari, Italy.
In this work, NaBH4 – MgH2 mixtures with 2:1 and 1:2 molar ratio have been deeply investigated bythermal programmed desorption (TPD) runs and coupled manometric – calorimetric analyses in order todescribe the Mg/MgH2 effect on the kinetics and thermodynamic of NaBH4 desorption. A mechanistic
hypothesis on this complex process has been drawn and the dissociation enthalpy of the compound in thebinary systems has been obtained. Moreover, the catalyzing/destabilizing effect of different additives(fluorides, chlorides, hydroxides, fluoroborates) has been studied. The best results have been obtained for
MgF2 concerning the 2:1 stoichiometry.

Introduction
The NaBH4 – MgH2 system has gained
attention in the last few years as possiblehydrogen storage system thanks to its hightheoretical gravimetric capacity (10.7 wt%),
low cost (less than 1 € for each kg) and thehigher stability of NaBH4 with respect to theother borohydrides. The challenges are tofind good catalyzing/destabilizing agents inorder to make the decomposition of NaBH4
contemporary to that of MgH2 and to achieve
fully reversibility for the system.

Experimental
NaBH4 + MgH2 binary mixtures with 1:2 and2:1 molar stoichiometry and ternary mixtures
added with 0.05 mol of dopants (fluorides,
chlorides, hydroxides, fluoroborates) weremilled under Ar for 20 h by a planetary mill ina stainless steel vial with a 10:1 balls topowders ratio. TPD and coupled manometric– calorimetric measurements up to 600 °C @0.1 bar H2, combined with ex – situ X-ray
powder diffraction analysis, allowed to obtain

Chiara Milanesedetails on the kinetics and thermodynamics
of the different decomposition steps.

Results
For all the mixtures, MgH2 dehydrogenation
takes place at temperatures much lower than
NaBH4 decomposition (the differences being
up to 140 °C). For the 2:1 composition, thislast process takes place in the wide range
between 450 °C and 550 °C, where themelting temperature of NaBH4 (505 °C) is
comprised. A melting/decomposition mechanism, driven by MgB2 formation, is
proposed, with the decomposition enthalpy of
NaBH4 (90 kJ/mol H2) decreased of about 18
kJ/mol H2 with respect to the pure compound. For the 1:2 stoichiometry NaBH4
decom-position ends at about 490 °C, so
involving only solid phases, and it appears
thermo-dynamically less favourable. Amongthe tested dopants, for the 2:1 stoichiometry,
MgF2 appears effective in both reducing thetemperature lag between the decompositionof the hydrides and improving the sorption
thermodynamics and kinetics.

Chiara Milanese (born in 1974) graduated in Chemistry cum laude at the University ofPavia, Italy, in 1998 and she took her PhD in Chemical Sciences in 2002.
Subsequently, she obtained a post doc grant focused on the preparation andcharacterization of materials for energetics. Since 2008 she has been researcher at theFaculty of Pharmacy of the University of Pavia. Starting from the same year, she has
been the technical responsible of the Pavia H2 Lab. She is working on Mg – basedmaterials and MgH2 – borohydrides systems.

Corresponding author: Chiara Milanese, e-mail: chiara.milanese@unipv.it, Tel. (+39) 0382 987670.

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An IAEA Insight of Activities on Hydrogen Production
Ibrahim KhamisInternational Atomic Energy Agency (IAEA), Vienna International Center, P. O. Box 100,
Vienna, Austria
Current energy demand keeps increasing worldwide especially in China and India. This demand has been
met so far primarily by burning fossil fuel. As hydrogen is being considered as the replacement of fossil
fuel, the viability of hydrogen economy is becoming more feasible. The use of nuclear energy forcommercial hydrogen production is predicted to play a major role in future. The potential of hydrogenproduction using nuclear energy has lead the IAEA to carry out an active programme on the nuclearhydrogen production. The programme includes meetings for information exchange on status of nuclearhydrogen production, future challenges to nuclear hydrogen production with emphasis on safety ofcoupling, future aspects of hydrogen economy, and very recently the development of the hydrogen
economic evaluation software HEEP for nuclear hydrogen production.
In addition to presenting a summary of the IAEA activities on nuclear hydrogen production and somedetails of the IAEA HEEP software which is developed mainly for the evaluation of the economic
assessment of the hydrogen economy, the paper will highlight some insights from recent activities
covering major conclusions presented by participants from some Member States which are very active on
nuclear hydrogen production

Ibrahim Khamis

Born 20. 8. 1956, Syria. 1979 B.Sc. in Mechanical Engineering, Aleppo, Syria. 1986
M.Sc. in Nuclear Engineering, and 1988 Ph.D. in nuclear engineering from the
University of Arizona, Tucson, Arizona, USA. Since 2006, he is the Project Manager of
non electric applications of nuclear energy at the Nuclear Power Technology
Development Section, Division of Nuclear Power, International Atomic Energy Agency(IAEA). His duties involve nuclear desalination, hydrogen production, district heating
and other industrial applications of nuclear energy.
Served as consultant and member in several National and International committees on
Reactor technology and water desalination. An author and coauthor of more than 70
research publications and conference presentations. His main interest is reactor
physics, design and simulation, and non electric applications of nuclear energy.

Corresponding author: I. Khamis, email: mailto:i.khamis@iaea.org, Tel. (+43) (11) 2600 22822.

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Magnesium fullerides for hydrogen storage
Daniele Pontiroli, Marcello Mazzani, Mauro Riccò
Dipartimento di Fisica, Università degli Studi di Parma, Via G. Usberti 7/a, 43124 Parma, Italy
Abstract: The successful intercalation of magnesium in the lattice of C60 obtained by different preparation
procedures opens to the possibility of employing these new materials for the storage of hydrogen. The H2
molecule interaction with both charged C60 and magnesium ions can fall into the useful energy range toachieve a reversible H2 storage at room temperature.

Hydrogen in fullerenes
Many recent theoretical works indicate theclass of metal doped fullerene compounds asvery promising for hydrogen storage [1]: on
the one hand, the calculated binding energy
of hydrogen on a curved graphene plane
should be enhanced by increasing its
curvature; on the other hand, DFT
calculations predict a further relevant
increase if fullerenes are in a charged state.
2+2+Moreover, the metal ion (i.e. Ca and Mg )could play an important role in optimising thehydrogen binding energy to the 20-40 KJ/mol
useful value, either by a charge-induced
polarisation, or even by a partial hybridisationof the hydrogen molecular orbitals (Kubas
interaction [2]). However, a systematic studyof these systems is still missing, especially
due to the difficulties inherent the preparationof these materials.

MgxC60 compounds
In this work we focus on magnesium
intercalated fullerenes. On the one hand, thesmallest alkali-earth atoms are expected to
donate two electrons each to the C60
molecule and stabilise a charge transfer salt
thus preventing the formation of Mg clusters.

2+

On the other hand, the Mg valence orbitals
could mix with the bonding and anti-bonding
H2 orbitals, thus modifying the H-H bondlength. This interaction (Kubas interaction)
was shown to be attractive and in the proper
energy range for applications for the storageof hydrogen. We managed to prepare various
Mg fullerides with different composition andstructure. Their synthesis was achieved
either through solid state reactions (alsousing metallorganic precursors) or insolution. Measurements of H2 absorption
efficiency are now in progress.

References
[1]

[2]

M. Yoon, S. Yang, C. Hicke, E. Wang, D.
Geohegan and Z. Zhang, “Calcium as theSuperior Coating Metal in Functionalizationof Carbon Fullerenes for High-Capacity
Hydrogen Storage”, Physic Review Letters,
2008, Volume 100, 206806.
G. J. Kubas, “Metal–dihydrogen and σ-bondcoordination: the consummate extension of
the Dewar–Chatt–Duncanson model for
metal–olefin π bonding”, Journal of
Organometallic Chemistry, 2001, Volume635, 37-68.

Corresponding author: Daniele Pontiroli, email: mailto:daniele.pontiroli@fis.unipr.it, Tel. (+39) 0521 905786

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Hydrogen Storage Properties of LiBH4-based Reactive HydrideComposits
Jae-Hyeok Shim, Jae-Hag Lim, Young-Su Lee, Young Whan Cho
Materials/Devices Division, Korea Institute of Science and Technolofy, Seoul 136-791, Republicof Korea
Among complex metal hydrides, lithium borohydride (LiBH4) has recently received great attention as asolid-state hydrogen storage material owing to its high gravimetric hydrogen storage density. LiBH4 isknown to decompose into LiH and B, releasing 13.9 wt% hydrogen. In this talk, hydrogen storage
properties of LiBH4-based reactive hydride composites are presented.

Dehydrogenation behavior of 6LiBH4 + CaH2
+ composite has been investigated. The
composite starts dehydrogenation before themelting of LiBH4 and releases 9.1 wt%
ohydrogen up to 400 C. The equilibrium
dehydrogenation temperature under 1 bar ofohydrogen is estimated to be 309 C with areaction enthalpy change of 56.5 kJ/mol H2,
which is consistent with thermodynamic
calculation. Rehydrogenation behavior of thecomposite has been studied between 350oo
and 500 C after dehydrogenation at 450 C.
The
composite
exhibitsthebestorehydrogenation feature at 450 C in terms of
the overall rehydrogenation rate and theamount of absorbed hydrogen. It is foundthat about 9 wt% hydrogen is absorbed ato
450
C for 12 hours. Up to 10
dehydrogenation-hydrogenation cycles havebeen carried out for the composite. It isdemonstrated that 6LiBH4 + CaH2 with 15
wt% NbF5 maintains a reversible hydrogenostorage capacity of about 6 wt% at 450 C
after a slight degradation between the 1st
and 5th cycles.

Hydrogenbackpressure
remarkably
promotes the formation of metal boride
during the dehydrogenation of 4LiBH4 + YH3,
6LiBH4 + CeH2 and 6LiBH4 + CaH2
composites, which seems to be a general
phenomenon in LiBH4-based reactive hydridecomposites
thatenablesmutualdestabilization between LiBH4 and metal
hydride. The formation of metal boride plays
a crucial role in the reversible hydrogenstorage properties of these composites. The
dependenceofthedehydrogenation
behavior on hydrogen back pressure might
be associated with the microstructural
evolution of the dehydrogenation products
formed by a solid-liquid reaction.

References[1]

J.-H. Lim, J.-H. Shim, Y.-S. Lee, Y.W. Cho,
J. Lee, Scr. Mater. 59, 1251 (2008).
[2] J.-H. Shim, J.-H. Lim, S. Rather, Y.-S. Lee, D.
Reed, Y. Kim, D. Book, Y.W. Cho, J. Phys. Chem.
Lett. 1, 59 (2010).
[3] J.-H. Lim, J.-H. Shim, Y.-S. Lee, J.-Y. Suh,
Y.W. Cho, J. Lee, Int. J. Hydrogen Energy 35,
6578 (2010).

Born 18. 3. 1971 in Seoul, Republic of Korea. 1994 Bachelor degree in MetallurgicalEngineering from Seoul National University. 1996 Master degree in MetallurgicalEngineering from Seoul National University. 2000 Doctoral degree in MetallurgicalEngineering from Seoul National University. 2001 Research Scientist, Korea Institute of
Science and Technology, Seoul, Republic Korea. 2003 Post-doctoral Research
Associate at University of California, Berkeley, USA
J.-H. Shim
Corresponding author: Jae-Hyeok Shim, email: jhshim@kist.re.kr, Tel. (+82) 2 958 6760

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CONTROL OF OXYGEN FLOW IN AIR INDEPENDENT PEM
FUEL CELL SYSTEM
Piotr Szymak, Grzegorz Grzeczka
Polish Naval Academy, Faculty of Mechanics and Electrical Engineering, Institute of ElectricalEngineering and Automatics, Smidowicza 69, 81-103 Gdynia, Poland
More often, hydrogen fuel cells are used to supply different devices and vehicles both for civilian andmilitary applications. One of the more popular hydrogen fuel cells are low-temperature PEM (Proton
Exchange Membrane). In the case of using them in conditions without access to air e.g. underwaterconditions, it is necessary to deliver to a fuel cell both hydrogen and oxygen.

Introduction
An Air Independent Electric Supply System
AIESS based on PEM fuel cell was built in
the Polish Naval Academy. The system canwork in conditions without access to air e.g.
under the surface of sea. The fuel cell is
supplied by both clean hydrogen and clean
oxygen stored in pressurized tanks. The
whole air independent system is described in[1].

Structure of oxygen supply
subsystem
Opened-loop structure of oxygen supply
subsystem was used in AIESS. This type ofsubsystems releases an excess of oxygen toan ambient environment. The excess can be
consumed by a crew e.g on a board of asubmarine. In this case, it is necessary tocontrol a flow of an oxygen very carefully andprecisely.
The oxygen supply subsystem consists ofseveral elements, carrying out proper flowrate and humidification of an oxygen. The
main device is a flow controller. The

Piotr Szymak

Bronkhorst F-201 flow controller was used asa main element of oxygen supply subsystem.

Results
The results of a control of an oxygen flow
were presented in detail in [1][2]. Good
response of the system on changes of anelectric load was achieved by means of
Bronkhorst flow controller with implemented
PID controller. Moreover, a safe level ofoxygen excess was registered. Maximal
registered value of the oxygen excess (1,5
NL/min) corresponds to quantity of oxygen
consumed by 4-5 people (the crew has 20
and more people).

References
[1]

[2]

G. Grzeczka, P. Szymak, Grant Report on
Air Independent Electric Supply System
based on PEM Fuel Cell, Polish Naval
Academy, in Polish, Gdynia, Poland, 2010
P. Szymak, G. Grzeczka Sterowanie
przepływem tlenu w zasilaniu ogniwa
paliwowego
PEMniezależnego
od
powietrza, ZN AMW, in press, 2010

Born 25. 10. 1975 in Gdynia, Poland. 1999 Master of Science Degree in Electronics
and Telecommunication, Military University of Technology, Warsaw, Poland. 2004
Doctor of Philosophy in Mechanics and Mechanical Engineering, Polish Naval
Academy, Gdynia, Poland. 2004 2005 Secretary of Scientific Committee of Institute ofElectrical Engineering and Automatics, Gdynia, Poland. 2006 Secretary of MilitaryCommission for Power Engineering Qualification, Poland. 2006 Assistant Professor at
Polish Naval Academy, Gdynia, Poland.

Corresponding author: Piotr Szymak, email: p.szymak@amw.gdynia.pl, Tel. (+48) (58) 626 2881

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Hydrogen Storage in Structure II Clathrate Hydrates with
Various Promoters
Alondra Torres Trueba,1 Laura J. Rovetto,1 Louw. J. Florusse,1 Maaike C.
Kroon,1 Cor J. Peters1,2
1

Department of Process & Energy, Delft University of Technology, Delft, Netherlands
Chemical Engineering Program, Petroleum Institute, Abu Dhabi, United Arab Emirates

2

Hydrogen (H2) is a promising alternative to fossil fuels, because it offers a solution for three main 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 an effective storage medium, theapplication of H2, for instance in the automotive sector, is currently limited. Clathrate hydrates, have been
regarded as a favourable alternative for H2 storage. Their profitability, safety, fast and high reversibility andefficient production make them more suitable for this application than other H2 storage materials.

Clathrate hydrates are a class of crystalline
inclusion
compounds,
where
water
molecules form cavities that can hostsuitable guest molecules. The guest
molecules are typically gases or volatileorganic compounds, which fill the cages
and stabilize the hydrate structure.
Depending on the size and properties of theguest molecules, clathrate hydrates may
occur in three different crystal structures: (i)structure I (sI), (ii) structure II (sII), and (iii)
structure H (sH). H2 clathrate hydrates,
exhibit a structure II (sII) configuration,
where 136 water molecules form sixteen
small cavities and eight larger ones. Suchmaterial exhibits a storage capacity of 5.0
wt % of H2 at extremely high pressures, i.e.
in excess of 200 MPa. The addition of asecond type of guest molecule, a so-called“promoter”, reduces the formation pressure
two orders of magnitude, by means of

Cor Peters

forming mixed sII H2 + organic clathrate
hydrates. However, the addition of apromoter significantly reduces the H2
storage capacity (close to 1.1 wt%). In
order to be considered practical, clathrate
hydrates should have sufficiently high H2storage capacity (> 5 wt%) at relatively mild
temperature and pressure conditions.
Motivated by this, five new promoters formixed sII H2 clathrate hydrates werestudied. These promoters are known toform sII clathrate hydrates with water. The
incorporation of these potential promoters
into the sII H2 clathrate hydrates decreases
the necessary storage pressure. The
results from this study may also elucidate
the relation between the properties of thepromoter molecules and the mixed H2clathrate
hydratesstability.

Dr.ir. Cor J. Peters earned his bachelor (cum laude), master (cum laude), and Ph.D.
degrees from Delft University of Technology in the Netherlands. Dr. Peters is an expert
in the areas of thermodynamics, phase equilibria, ionic liquids, hydrogen storage, gas
hydrates and CO2-sequestration. For the period 2002-2006 he was appointed as avisiting professor at the Center of Excellence of Tohoku University, Sendai, Japan. Dr.
Peters has worldwide extensive collaborations. His current collaborations comprise
Stanford and Vanderbilt University, University of Maryland, Colorado School of Mines, allof them in the USA. In addition, he has strong ties with the Center of Excellence at
Tohoku University (Japan), the Universidad Nacional del Sur (Argentina), University of
Nottingham (UK) and the University of Valladolid (Spain). He is Distinguished Professorof Chemical Engineering at the Petroleum Institute in Abu Dhabi, United Arab Emirates.

Corresponding author: Cor Peters, email: cpeters@pi.ac.ae Office: +971 2 607 5492

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Gas Separation Diaphragms for Alkaline Hydrogen Production: Influenceof Microstructure on Ion Conductivity and Gas Purities
Daniel Wiedenmann1,2, Lorenz Holzer2, Jelena Stojadinovic2, Michal Gobar2, Ulrich
Vogt2, Valentina Zakaznova-Herzog2, Andreas Züttel2, Bernard Grobéty1
1

University of Fribourg, Department of Geosciences, Pérolles, 1700 Fribourg, Switzerland
Empa Materials Science & Technology, 8600 Dübendorf, Switzerland

2

High purity of hydrogen produced by high-pressure alkaline electrolysis is ensured by a porous and ion
conductive diaphragm separating anode and cathode of an electrolysis cell. In order to keep the cell
resistance low, the ionic conductivity of the porous diaphragm is crucial. Thereby, the conductivity isrelated to the pore structure. In this study we characterize the pore structure of different diaphragms bymeans of multi scale tomography and establish a link to the electrochemical cell performance.

Introduction
Until today, flexible asbestos tissues areused in alkaline electrolysis, as they show
good ion conductivity and easily can beinstalled between the electrodes without
being damaged. Due to recent healthregulations, asbestos based diaphragms areprohibited in new electrolysers. For thedevelopment of alternative material concepts,
a thorough understanding of the link between
microstructure and cell performance isfundamental.

Experimental

with low voltage FIB-nanotomography [1] andsynchrotron-microtomography resolves thepore structure of the asbestos reference
diaphragms and new developed diaphragms.
Based on modern imaging analyses
techniques, the 3D pore structures aredescribed quantitatively. Reference asbestos
diaphragms consist of a dense solid material,large micro-pores and dense matrix material
with reduced permeability [2]. The influenceofion
conductivity
regardingtheelectrochemical performance is characterized
by impedance spectroscopy [3].

References

Different sets of porous diaphragms made ofdifferent materials were tested in a lab scale
electrolyser regarding cell voltage and purityof the produced gasses hydrogen andoxygen. To establish a link between
diaphragm pore structures, ion conductivity,and gas purity, the diaphragms werestructurally
andelectrochemicallycharacterized by different methods. The
combination of standard electron microscopy[1]

L.Holzer, B. Muench, M. Wegmann, P.
Gasser; J. Am. Ceram. Soc., 89 [8] 25772586 (2006).
[2] D. Wiedenmann, L. Holzer, M. Gobar, U.
Vogt, V. Zakaznova-Herzog, A. Zütter, B.
thGrobéty; 4 Hydrogen & Energy
Symposium, Wildhaus, Switzerland (2010)[3] IR.J.H.G. Van der Stegen; J. App.
Electrochem. 19, 571-579 (1989)

Borne 24.03.1975 in Karlsruhe, Germany. 2004 German Diploma in Mineralogy,
Albert-Ludwigs-Universität, Freiburg im Breisgau, Germany. 2006-2008 research
assistant at the Swiss Federal Laboratories for Materials Testing and Research,
Dübendorf, Switzerland. Since 2009 PhD student at the University of Fribourg,
Switzerland.
D. Wiedenmann
Corresponding author: Daniel Wiedenmann, email: mailto:daniel.wiedenmann@empa.ch, Tel. (+41) (44)823 4862.

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REDUCTION TEMPERATURE IMPACT ON NiO-YSZ CERMETS
MICROSTRUCTURE
Brigita Abakevičienė, Sigitas Tamulevičius
Institute of Materials Science of Kaunas University of Technology, Savanoriu Av. 271, LT-50131
Kaunas, Lithuania
Cermet coatings of yttria stabilized zirconia with nickel (YSZ-Ni) are the most promising for the anodesupported solid oxide fuel cells (SOFC). It is necessary to define the hydrogen reduction process, where
NiO converts to Ni, in order to achieve optimized initial microstructure of the NiO-YSZ cermets. In thisstudy, the influence of hydrogen reduction temperature on NiO-YSZ cermets prepared by screen-printing
method has been investigated.

Experimental procedure
The screen-printing technology was used to
produce NiO-YSZ cermets by mixing NiO
and YSZ powders in variable composition
ratio from 35%:65% to 70%:30% with 5%
increments. NiO-YSZ powders were mixed
with suitable organic additives and printed on
Al2O3 substrate. A 18 µm thick cermets werethen calcined at 1350 °C for 2 h. Hydrogen
reduction on NiO-YSZ anodes wasinvestigated at 300 °C, 600 °C, 800 °C and1000 °C reduction temperatures for 1 h.

Microstructure
The reduction procedure is crucial to theinitial anodic microstructure, while initial
anodicmicrostructure
influences
theperformance of the anodic cell.
The microstructure, elemental composition of
unreduced and reduced NiO-YSZ cermets
with different porosity was analyzed using
scanning electron microscope (SEM) and Xray energy dispersive method (EDX).

Brigita
Abakevičienė

X-ray diffraction (XRD) method was
employed to indentify and quantify thephases of anodic cermets before and after
the reduction. It was found that NiO-YSZ
cermets consist mainly of cubic yttria
stabilized zirconia and nickel oxide phases
and additional cubic nickel phase resulting
from NiO to Ni during the hydrogen
reduction.
In addition to changes in the chemicalcomposition of NiO-YSZ cermets during
reduction, the porosity of the anodes waschanged as well. This was expected since
the specific volume of metallic Ni after
reduction was significantly smaller than thatof NiO [1].
As a result of hydrogen reduction, theporosity increase is clearly demonstrated.

References[1] M. Radovic, E. Lara-Curzio, Acta Materials,
52, 5747-5756 (2004)

Born 5.3.1977 in Alytus, Lithuania. 1999 Bachelor Degree in Physical Science,
Kaunas, Lithuania. 1999 Research work as an exchange student, Christian-Albrecht’sUniversity of Kiel, Germany. 2000 Engineer, Lithuania Energy Institute, Lithuania. 2002
Master Degree in Physical Science, Kaunas, Lithuania. 2003 Junior lecturer, Kaunas
University of Medicine, Lithuania. 2006 Junior lecturer, Physics Department, Kaunas
University of Technology, Lithuania. 2008 Doctor Degree in Physical Science, Poitiers
University, France and Kaunas University of Technology, Lithuania. 2009 Lecturer,
Physics Department, Kaunas University of Technology, Lithuania. 2009 PostDoc
position at Institute of Materials Science of Kaunas University of Technology, Lithuania.

Corresponding author: Brigita Abakevičienė, email: Brigita.Abakeviciene@ktu.lt, Tel. (+370) (37) 313432

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METHANE PRODUCTION THROUGH HYDROGEN FROMRENEWABLE ENERGY
Koji Hashimoto*, Naokazu Kumagai**, Koichi Izumiya**, Zenta Kato**Tohoku Institute of Technology, Sendai, 982-8577 Japan**Daiki Ataka Engineering, Co., 11 Shintoyofuta, Kashiwa, 277-8515 Japan
It is natural that all people in the whole world wish to consume at least the same amount ofenergy as the average amount of energy consumed by a person in developed countries. Thus,
the continuation of the current energy supply system will lead to complete exhaustion of theworld reserves of all fossil fuels and uranium until the middle of this century. The technology tosupply fuels produced from renewable energy, by which all people in the whole world cansurvive without using fossil fuels, should be urgently established. The technology presented
here is to supply renewable energy in the form of methane using carbon dioxide as thefeedstock by the reaction with hydrogen produced by seawater electrolysis.
We are proposing global carbon dioxide
recycling. The electricity necessary for all
people in the whole world will be generated
by solar cells in the deserts. The world totalenergy consumption in 2007, that is, 5.10222
20
x 10 J can be generated in the form ofelectricity by solar cells with 15 % energy
conversion in only 2.00 % of the main-2
deserts on Earth, if 1000 Wm of solar
energy are available for 8 hours a day. Theintermittent and fluctuating electricity will be
used for production of hydrogen by seawaterelectrolysis at nearby desert coasts.
Because there are no infrastructures formass transportation and combustion ofhydrogen, hydrogen will be converted tomethane, that is, the main component of
natural gas, by the reaction with carbon
dioxide at the desert coasts.
Aftercombustion of methane carbon dioxide will
be captured and transported back to thedesert coasts. Among systems in global
carbondioxiderecycling,
seawaterelectrolysis and methane formation by thereaction of carbon dioxide with hydrogen
have not been performed industrially.
We created anodes for oxygen evolution
without chlorine formation in seawaterelectrolysis, energy-saving cathodes forhydrogen production and ideal catalysts formethane formation by the reaction of carbon
dioxide with hydrogen. We constructed a
prototype plant for global carbon dioxide
recycling in 1995 and an industrial scale pilot
plant consisting of seawater electrolysis andcarbon dioxide methanation in 2003.
The current status of creation of key
materials, systems and plants will be shown.
We are now concentrating our efforts to
decease the price of methane by improving
the key materials and systems.

Born 23. 10. 1935 in Tokyo, Japan. 1960 M.Sc. in Chemistry, Tohoku University,
Japan. 1960-1966 Research Associate, Research Institute for Iron, Steel and Other
Metals, Tohoku University. 1966 D.Sc in Chemistry, Tohoku University. 1966 Associate
Professor, Research Institute for Iron, Steel and Other Metals, Tohoku University.
1967-1969 Post Doctorate Fellow, National Research Council, Canada. 1987
Professor, Institute for Materials Research, Tohoku University. 1999 Retirement fromTohoku University. 1999 Professor Emeritus, Tohoku University. 1999 Professor,
Tohoku Institute of Technology, Japan. 2006 Retirement from Tohoku Institute of
Koji Hashimoto Technology. 2006-Present Visiting Researcher, Tohoku Institute of Technology. 2008
Professor Emeritus, Tohoku Institute of Technology.
Corresponding author: Koji Hashimoto, email: koji@imr.tohoku.ac.jp, Tel. (+81) 90-4049-1121

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CO2 Capture from ambient air
Christoph Gebald*,**, Jan Wurzbacher**,
Zimmermann*, Aldo Steinfeld**,***

Philippe

Tingaut*,

Tanja*Empa Materials Science & Technology, Wood Laboratory, 8600 Dübendorf, Switzerland**Department of Mechanical and Process Engineering, ETH Zurich, 8092 Zurich, Switzerland***Solar Technology Laboratory, Paul Scherrer Institute, 5232 Villigen, Switzerland
An amine-modified solid sorbent was developed for CO2 capture directly from ambient air. CO2 adsorption
is carried out at 25°C and atmospheric pressure fro m an air stream with 430 ppm CO2 concentration and
40% relative humidity, while pure CO2 is driven off the sorbent upon heating to 95°C. Th e sorbent showed
to be fully recyclable during cyclic CO2 adsorption-desorption experimental runs.

Most CO2 capture technologies deal with the
scrubbing of CO2 from flue gases [1],although stabilization of global CO2
emissions is unlikely to be achieved without
CO2 capture from atmospheric air [2,3]. The
minimum amount of energy required for gas
separation, given by the Gibbs free energychange of the process, is 5.2kJ/mol for 12%
CO2 concentration in flue gases, and18.9kJ/mol (4 times more energy) for 430
ppm CO2 concentration in air (280 times
more diluted). However, the capture of CO2
from air can be performed conveniently at
locations with high solar energy resources
and coupled to its recycling for the productionof solar liquid fuels [3]. Previous studies
considered adsorbers based on calcium [4],sodium [5,6], amines [7], and ion-exchange
resins [8,9,10].
Herein, an amine-modified solid sorbent wasstudied as CO2 capture structure. Experiments were performed for CO2 adsorption at
25°C and atmospheric pressure using an air
stream with 430 ppm CO2 concentration and
40% relative humidity, followed by pure CO2
desorption upon heating to 95°C. The
sorbent showed to be fully recyclable duringconsecutive CO2 adsorption-desorption cyclic

runs. We describe in detail the experimental
setup and results.
Acknowledgement - This work is being
partially financed by the GEBERT-RÜFSTIFTUNG.

References[1]

Intergovernmental Panel on Climate Change(IPCC), Fourth Assessment Report[2] Sarewitz D., Nelson R., Nature 2008, 456,
(7224), 871-872.
[3] Steinfeld A., Meier A., Encyclopedia ofEnergy, Elsevier Inc., Vol. 5, pp. 623-637,
2004[4] Nikulshina V., Gebald, C., Steinfeld, A.,
Chem. Eng. J. 2009, 146, (2), 244-248.
[5] Zeman F., Aiche J. 2008, 54, (5), 1396-1399[6] Stolaroff J. K., Keith D. W., Lowry G. V.,
Environ. Sci. Technol. 2008, 42, (8), 27282735.
[7] Olah G. A., Goepert A., Meth S., Prakash G.
K. S, WO2008021700-A1[8] Wright A. B., Lackner K. S., Leon-GuerreroE., Ginster U., Catterson T., Madison K.,
Ishikawa R., Grimm G., Malcomson M., Liu,
P, WO2008131132-A1[9] Lackner K. S., Liu P., WO2008061210-A2[10] Lackner K. S., Eur. Phys. J. Special Topics
176, 93–106 (2009)

Born 03. 4. 1983 in Forchheim, Germany. 2009 MSc ETH in Mechanical Engineering with
distinction, Zurich, Switzerland. Visiting scholar at UC Berkeley, USA. 2009 CEO &Founder of Climeworks LLC, Switzerland.

Ch. Gebald
Corresponding author: Christoph Gebald, email: mailto:gebaldc@ethz.ch, Tel. (+41) (44) 632 8974

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Sunfire: 3rd generation Fuels from CO2 and h2O
Christian von Olshausen
SunFire GmbH, Eduard-Suling-Straße 17, 28217 Bremen, Germany www.sunfire.derd

3 generation fuels produced from CO2 and H2O by coupling in renewable energy can provide preferable
energy density, transportation and storage characteristics due to their liquid state. However, at state of theart, energetic efficiency of fuel synthesis from CO2 and H2O is at ~50% (electric energy/fuel energy),
significantly lower than the production of pure hydrogen.[2] SunFire has established a technologicalprocess that can achieve efficiencies above 70%.[1][3] A study has been conducted to evaluate the total
value chain of such a “closed carbon cycle” and to identify commercial potentials.

Synthesis of fuels from CO2 & H2O
For the production of fuels (-CH2-) from CO2
and H2O, both educts need to be reduced.
The required energy can be coupled inelectrically, thermally or from solar light.[1]However, such processes usually start withthe production of pure Hydrogen which isused for reducing CO2 to CO. In a second
step, CO and H2 are mixed to syngas andconverted into -CH2- and H2O. This implies
the need of three molecules H2 for one
compound of -CH2-. Considering thedifference between HHV and LHV for H2O
and the heat losses of the exothermic
synthesis, such a process can practically notexceed an energy efficiency of ~50% withoutsophisticated recuperation.[2]SunFire has developed a technologicalprocess that utilizes electrolysis to produce
Hydrogen, Reverse-Watergas-Shift-Reaction
to reduce CO2 to CO and finally synthesises-CH2- via Fischer-Tropsch. The process canreach efficiencies of ~70% to turn electricenergy into chemical enthalpy of liquid
fuels.[1][3]Value and supply chain
The value chain of a “closed carbon cycle”
has been examined in a study with industrial
and scientific partners. It starts with H2O- andCO2-capture, considers the conversion into
fuels and takes into account all required
logistics for transport and fuel distribution.
As a result, the energetic efficiency of thetotal supply chain (Well-to-Tank) is estimatedrd
to be ~60%. The cost for 3 generation fuels
shall be around 1,2 €/litre Diesel.[3]References[1] Graves C., et al. Sustainable hydrocarbon
fuels by recycling CO2 and H2O with renewable or
nuclear energy. Renew Sustain Energy Rev(2010), doi: 10.1016/ j.rser.2010.07.014[2] CO2 Utlilization Potential, Summary of the jointndrdseminar of BMBF and Siemens 22 -23
September 2009, Bonn, P. 31 ff[3] The SunFire-study is under non-disclosure but
significant details shall be presented in the
symposium.

thBorn October 5 , 1979 in Heidelberg, Germany
1999 Undergraduate work on NECAR – DAIMLER fuel cell cars, Nabern/Teck, Germany
2002 Intermediate Diploma TU Karlsruhe (TH), Germany 2005 Diploma in Industrial
Engineering, TU Dresden, Germany; Exchange student Politecnico di Torino, Turin, Italy
2005 Procter & Gamble, Weiterstadt, Germany 2008 Founder & COO of SunCoal
Industries GmbH, Ludwigsfelde, Germany
2008 – 2010 Leader of SunFire – Feasibility study with scientific & industrial partners
Christian von 2010 Co-Founder & CTO of SunFire GmbH, Bremen, Germany
Olshausen
Corresponding author: Christian Olshausen, email: christian.vonolshausen@sunfire.deTel. (+49) (421) 83 50 55 40

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Formic acid – The key compound in a viable hydrogen storage
systemGábor Laurenczy
EPFL, École Polytechnique Fédérale de Lausanne, ISIC, LCOM, Groupe de catalyse pourl’énergie et l’environnement – GCEE, CH-1015 Lausanne, Switzerland
Hydrogen can be generated very efficiently from formic acid in aqueous phase homogeneous catalytic
reactions, using ruthenium catalysts with water-soluble phosphine ligands. Although this reaction results
only two gas products, heterogeneous catalysts could be advantageous for recycling, especially for diluteformic acid solutions, or for mobile, portable applications. On the other hand, the straightforward reductionof CO2 leads to the production of formic acid, making this system suitable for hydrogen storage.

Introduction
Carbon dioxide is the primary carbon sourcein the atmosphere. One promising approachfor the introduction of CO2 as C1-source insyntheticchemistryisitscatalytichydrogenation to form formic acid or its salts
or adducts.

carbon dioxide and bicarbonate in water are
intensively investigated [2].
Acknowledgment. Swiss National Science
foundation and EPFL are thanked forfinancial support.

References[1]

Experimental
The homogeneous catalytic decomposition of
formic acid and the carbon dioxidehydrogenation reactions have been carriedout under mild experimental conditions inaqueous solutions.

Results and discussion
The water-soluble sulfonato aryl- and aryl/alkylphosphine ligands have been applied
successfully in aqueous-phase ruthenium(II)catalyzed formic acid decomposition intohydrogen and carbon dioxide [1]. Active
catalysts for the benign hydrogenation of

Gábor Laurenczy[2]

C. Fellay, P. J. Dyson, G. Laurenczy, A
Viable Hydrogen-Storage System Based On
Selective Formic Acid Decomposition with a
Ruthenium Catalyst, Angew. Chem. Int. Ed.,47, 3966. (2008); C. Fellay, N. Yan, P. J.
Dyson, G. Laurenczy, Selective Formic Acid
Decomposition for High-Pressure Hydrogen
Generation: A Mechanistic Study, Chem.
Eur. J., 15, 3752. (2009).
G. Laurenczy, F. Joo, L. Nadasdi,
Hydrogenation of CO2 and HCO3 in
Aqueous Solution, Inorg. Chem., 39, 5083.
(2000); C. Federsel, R. Jackstell, A.
Boddien, G. Laurenczy, M. Beller,
Ruthenium-Catalyzed Hydrogenation of
Bicarbonate in Water, ChemSusChem, 3,
1048, (2010)

Born in Békéscsaba, Hungary, 1954. Chemistry M.Sc. at the Univ. Debrecen,
Hungary, 1978. PhD. in Physical Chemistry, Univ. Debrecen, Hungary, 1982.
Habilitation in Inorganic Chemistry, Hungarian Academy of Sciences, 1991. Assistantprofessor, Dept. of Inorganic Chemistry, Univ. Debrecen, Hungary, 1984. Maître
assistant, Université de Lausanne, 1991. Maître d’enseignement et derecherche, Univ. Lausanne, 1997. M. E. R., EPFL, École Polytechnique Fédérale
de Lausanne, 2002. Chairman of the Management Committee of the European
COST D10 Chemistry Action: Innovative Methods and Techniques for Chemical
Transformation, 2001-2002. Chairman of the M. C. European COST D30: High
Pressure Tuning of Chemical and Biochemical Processes, 2002-2007. Visiting
professor, Dept. of Chemistry, University of Bourgogne, France, 2007. Prof. tit. EPFL,
2010. Head of Group of Catalysis for Energy and Environment – GCEE.

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

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Surface Oxidation of Hydrides
Shunsuke Kato1, Andreas Borgschulte1, Michael Bielmann1, Davide Ferri2,
Peggy Rossbach3, Jean-Claude Crivello4, Ye Lu2, Daniel Wiedenmann1,
Kazutaka Ikeda5, Arndt Remhof1, Shin-ichi Orimo6, Andreas Züttel1
1

Empa Materials Science & Technology, Div. Hydrogen & Energy, Dübendorf, Switzerland
Empa Materials Science and Technology, Div. Solid State Chemistry and Catalysis, Dübendorf,
Switzerland
3
Empa Materials Science and Technology, Div. Nanoscale Materials Science, Dübendorf, Switzerland
4
CNRS, ICMPE-CMTR, Thiais, France
5
High Energy Accelerator Research Organization, Tokai, Japan
6
Tohoku University, Institute for Materials Research, Sendai, Japan2

Surface properties of various hydrides, i.e. covalent-like hydride (AlH3), complex metal hydride (Mg2NiH4),
and complex hydride (LiBH4) including the composite system (2NaBH4 + MgH2) were investigated. The
surface processes on the hydrides are discussed with respect to the hydrogen desorption kinetics, surface
oxidation, and catalyst preparation.

Effect of surface oxidation

suppression of diborane formation by the oxides,
e.g. Li2O, on the surface (schematic) [2].

The
surfacecondition,i.e.
surfacecomposition and oxidation state of hydrogenstorage material is crucial to the hydrogen
sorption processes [1].

Catalyst for hydrogenation of CO2
The hydride Mg2NiH4 was modified byoxidation
andcombininghydrogenabsorption/desorption circles. The preparedcatalyst yields 100% CO2 conversion and100% selectivity to CH4 in the reaction, CO2+ 4H2 → CH4 + 2H2O at 580 K.

References[1][2]
Fig. 1
Mechanism of H2 and B2H6 desorption
from the surfaces of LiBH4 from (a) the cleansurface, and (b) the surface oxidation layer;

S. Kato, M. Bielmann, K. Ikeda, S. Orimo, A.
Borgschulte, A. Züttel, Appl. Phys. Lett, 96(2010) 051912.
S. Kato, M. Bielmann, A. Borgschulte, V.
Herzoga, A. Remhof, S. Orimo, A. Züttel,
PCCP, 12 (2010) 10950.

Born 10. 6. 1976 in Ise, Japan. 2005 Master of Engineering in Applied Science, Tokai
University, Japan. Research into gas-solid reactions: Reactivity of a gas (H2, O2, H2O)
with metal surfaces under ultrahigh vacuum condition. 2005-2007 NEDO research
assistant at Tokai University, Japan, "Advanced metal hydrides with high volume
density of hydrogen". Since 2007 PhD student at Empa, Div. Hydrogen & Energy, andUniversity of Fribourg, Switzerland.

Shunsuke Kato
Corresponding author: Shunsuke Kato, email: mailto:shunsuke.kato@empa.ch, Tel. (+41) (44) 823 4327

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LiBH4 and Ti-Catalyzed Nanocrystalline MgH2 Composite for
Hydrogen Storage
Huaiyu Shao and Michael Felderhoff
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an derRuhr, Germany
Using Ti-catalyzed MgH2 nanocrystalline*
material , a 2LiBH4+nano MgH2 composite
sample shows significantly enhanced kinetics
and different thermodynamics performances
compared to a 2LiBH4+commercial MgH2
composite. Its desorption temperatures are
50-70°Clower
comparedto
2LiBH4+commercial MgH2 composite sample
when desorbed to evacuated space.

studied. It is the first time that three obvious
plateaus are found during the PCI desorption
process of this kind of composites. During*
the PCI desorption of 2LiBH4+nano MgH2
composite, three obvious plateaus areobserved
between357~383°C.
The
desorption reactions for these three plateaus
are MgH2 → Mg + H2, Mg + 2LiBH4 → MgB2
+ 2LiH + 3H2 and 2LiBH4 → 2B + 2LiH + 3H2,
respectively. The reaction Mg + B → MgB2
takes place after the last reaction attemperatures between 357 to 383°C. At 304
and 335°C, two plateaus are found during
the PCI desorption of the 2LiBH4+nano*
MgH2 composite, corresponding to MgH2 →Mg + H2 and 2LiBH4 → 2B + 2LiH + 3H2.

References[1][2]
Fig.1 PCI curves of 2LiBH4+nano MgH2* composite atdifferent temperatures.

Bogdanović B, Liao S, Schwickardi M,
Sikorsky P and Spliethoff B 1980 Catalytic
Synthesis of Magnesium Hydride under Mild
Conditions Angew Chem Int Ed 19 818-9
Shao H, Felderhoff M, Schüth F andWeidenthaler C 2010 Nanostructured Ticatalyzed MgH2 for Hydrogen Storage
Submitted

The reaction pathways during desorption ofthis composite between 304-383°C were

Born 29. 03. 1978 in Jiangsu, China● Apr. 2009-present, Postdoc, Research Group of Prof. Dr. Ferdi Schüth, Department

Huaiyu Shaoof Heterogeneous Catalysis, Max-Planck-Institut für Kohlenforschung, Germany
Supervisor: Dr. Michael Felderhoff● Jul. 2005-Mar. 2009, Postdoc, Energy Technology Research Institute, National
Institute of Advanced Industrial Science and Technology, Japan
Supervisor: Prof. Etsuo Akiba● Ph.D. in Chemistry, Peking University, China, Jun. 2005
● B.S. in Chemistry, Peking University, China, Jul. 2000

Presenting author: Huaiyu Shao, email: shao@mpi-muelheim.mpg.de, Tel. (+49) (208) 306 2449

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New Catalyst for Hydrogen Evolution and Oxygen Reduction
Ib Chorkendorff
Danish National Research Foundation's Center for Individual Nanoparticle Functionality (CINF),
Department of Physics, Building 312, Technical University of Denmark, DK-2800 Kongens
Lyngby, Denmark
A dream device for hydrogen production by water
splitting will be discussed. Here we haveinvestigated new electro-catalysts that – combinedwith semiconductors that can harvest the red partof the solar spectrum – could replace expensive
and scarce materials such as Platinum metals.
Various Molybdenum sulfides and Tungsten
sulfides mimicking nature’s enzymes for hydrogen
evolution will be discussed [1-4]. The optimal
configuration for hydrogen evolution and electronhole separation will also be demonstrated asshown in Figure 1 where an incomplete Mo3S4
Cubane is used for evolving hydrogen.

Figure 1 shows the principle of a dream device
harvesting the solar light and separating the oxygenand hydrogen evolution in a tandem device. The
blowup shows Cubanes deposited on Si-pillars
catalyzing the hydrogen evolution by help of the redpart of the solar spectrum.
Utilizing the hydrogen can be done in a Proton
Exchange Membrane Fuel Cell and here the mostpronounced losses are related to the oxygen
reduction reaction on the cathode side. New
electro-catalysts for the Oxygen Reduction

Reaction (ORR) will also be discussed withparticular focus on alloy catalyst of Pt and earlytransition metals [5].

References[1] B. Hinnemann, P. G. Moses, J. Bonde, K. P.
Jørgensen, J.H. Nielsen, S. Horch, I.
Chorkendorff & J. K. Nørskov “Biomimetic
hydrogen evolution”, J. Am. Chem. Soc. 127(2005) 5308-5309.
[2] T.F. Jaramillo, K.P. Jørgensen, J. Bonde, J.H.
Nielsen, S. Horch, I. Chorkendorff,“Identification of Active Edge Sites forElectrochemical H2 Evolution from MoS2
Nanocatalysts” Science 317 (2007) 100.
[3] T. F. Jaramillo, J. Zhang, B. Lean Ooi, J.
Bonde, K. Andersson, J. Ulstrup, I.
Chorkendorff, “Hydrogen Evolution on
supported [Mo3S4]4+ cubane-type
electrocatalysts” J. Phys. Chem. 112 (2008)
17492-17498.
[4] Y. Hou, B. L. Abrams, P-C.K. Vesborg, M. E.
Björketun, K.Herbst, L. Bech, A. M. Setti, C.
D. Damsgaard, T.Pedersen, O. Hansen, J.
Rossmeisl, S.Dahl, J. K. Nørskov,, and I.
Chorkendorff, “Bioinspired Co-catalysts
Bonded to a Silicon Photocathode for Solar
Hydrogen Evolution “ Submitted (2010).
[5] J. Greeley, I.E.L. Stephens, A.S. Bondarenko,
T. P. Johansson, H. A. Hansen, T. F.
Jaramillo, J. Rossmeisl, I. Chorkendorff, J. K.
Nørskov, “Alloys of platinum and earlytransition metals as oxygen reduction electrocatalysts “, Nature Chemistry 1 (2009) 522.

Born 1955 in Svendborg, Denmark,1982 M.Sc. in Physics and B.Sc. in Chemistry at
Odense University, 1983 Half year stay at the synchrotron DESY, HASYLAB in
Hamburg, Germany, 1985 Ph.D. degree in Physics at the Physics Institute, Odense
University, 1986 Post-doc position with Professor John T. Yates Jr. at the Surface
Science Center, University of Pittsburgh, USA, 1987 Associate Professor at the
Department of Physics, Technical University of Denmark (DTU), 1999 Professor in
Heterogeneous Catalysis, 1999 Director of the Interdisciplinary Research Center for
Catalysis (ICAT), 2005- Director of the Danish National Research Foundation’s “Center
Ib Chorkendorff for Individual Nanoparticle Functionality” (CINF) at the Department of Physics, DTU.
Corresponding author: Ib Chorkendorff, email: ibchork@fysik.dtu.dk, Tel. (+45) 45 25 31 70

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High temperature Steam and Steam / CO2 Electrolysis
Research and Development at the INLCarl Stoots
Idaho National Laboratory, P.O. 1625, Idaho Falls, Idaho, 83415 USA
The Idaho National Laboratory (INL) has been studying the feasibility of using solid oxide fuel cells(SOFCs) as electrolyzers for large-scale, high temperature (efficient) nuclear-powered hydrogenproduction, as well as various other deployment schemes, including coelectrolysis of steam and CO2 forsyngas production. INL’s research and development program includes experimental testing at various
scales, computational fluid dynamics modelling, and process systems analysis. Overall, the use of SOFCs
for hydrogen production appears promising once issues concerning cell durability are solved.

Background
World production of H2 is currently about 42
million tons per year: 48% from natural gas,
30% from oil, 18% from coal, and 4% fromelectrolysis [1]. In other words, 96% of theworld’s hydrogen is produced from fossil
fuels. When fossil fuels are used forhydrogen production, significant quantities of
the greenhouse gas CO2 are produced as a
byproduct.
Obviously this is not asustainable means of satisfying H2 demand
for the future.
The Idaho National Laboratory (INL) has
been assessing the feasibility of using SOFC
technology for high temperature electrolysisof steam for large scale sustainablehydrogen production. In parallel, the INL is
studying the simultaneous electrolysis ofsteam and carbon dioxide for syngas
production. When linked to a nuclear powersource, this technology provides a carbon
neutral means of producing hydrogen via
water splitting or producing syngas / synfuelsfrom water and CO2. High temperatureelectrolysis has an additional advantage ofessentially instantaneous “load following”
capability, as well as fast startup andshutdown times (ramping). The load following
capability of high temperature electrolysis

makes it also an attractive match forrenewable (intermittent) energy sources(wind, solar, etc.) as well.

INL Program
Although high temperature electrolysis
leverages SOFC technology, the concept isstill not ready for commercialization. There
are fundamental differences in the twomodes of operation such that performancecell performance degrades faster in theelectrolysis mode of operation. This issue
has been identified as the major barrier totechnology development. The INL has been
studying and testing various cell designs andmaterials from various manufacturers as wellas performing specialized modeling tounderstand what phenomena are the primarycontributors to cell performance degradation.
INL investigations have included button cell
tests, single cell tests, multi-cell stacks, multistack system tests, as well as computational
fluiddynamics
andsystems-level
simulations.

References[1] www.hydrogenassociation.org/general/faqs.

Born 30. 5. 1961 in Washington D.C., USA. 1984 Engineering Degree in Chemical
Engineering, University of Maryland, USA. 1989 PhD, Chemical Engineering, University of
Maryland, USA. 1990 – Present Research Engineer at the Idaho National Laboratory,
USA.
Carl Stoots
Corresponding author: Email: carl.stoots@inl.gov, Tel. (001) (208) 526-4527.

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Hydrogen Production from Water
M. Guttentag§, B. Probst§, A. Rodenberg#, P. Hamm*#, R. Alberto*§§#

University of Zurich, Department of Inorganic Chemistry , Department of Physical Chemistry ,Zurich, Switzerland
Homogenous photocatalytic water reduction systems known today are often limited both by the stability ofthe participating catalysts in terms of turnover numbers and by their activity in pure aqueous solutions.
Profound knowledge of the mechanism allowed the systematic design of derivatized catalysts to improve
the stability and activity of such a system in water.

Photocatalytic water reduction
A system employing rhenium photosensitizers, cobalt complexes and sacrificial
electron donors was used to producehydrogen with visible light from aqueous or[1]
A detailedorganic media (Scheme 1).
analysis of the hydrogen release allowed to
identify the cobalt species as the stability andrate limiting factor.
O
NN
OC ReI
OC

TEOA
kq

N

O
N
CoII

N
O

N

N

CO

H

H2
N
O

k3
HA+ , e-N
OC ReII
OC

H

H HO
O
N
N
CoIII
N
N
O
O
H
N

k1

N
N

kem

CO

N

hν
ν

OC ReI N
N
OC
CO

O H
N

O
N
CoI

N
H O

N
O

K2
HA +

N

Scheme 1. Proposed photocatalytic cycle

Cobalt macrocyclic complexes are known to
produce hydrogen under reducing conditions[2,3]
upon addition of protons.
However, in thepresent system the turnover numbers arevery limited (<150), most probably due to an

intramolecular metal to ligand hydride shift at
the cobalt centre. By introducing electron
donating or accepting ligands, the reactivityof this hydride could be tuned to increase therate of hydrogen release or to slow down therate of the hydride shift, respectively.
Hydride formation and possible heterolytichydrogen release from such hydrides are
obviously pH dependent. Variation of the pH
therefore plays an important role in theunderstanding of the mechanism.
Detailed mechanistic analysis of the catalytic
cycle as a function of solvent, pH andsynthetic derivatisation of the catalysts will bepresented.

References[1] B. Probst, M. Guttentag, A. Rodenberg, P.
Hamm, R. Alberto, Inorg. Chem., 2010, 49,6453[2] A. M. Tait, M. Z. Hoffman, E. Hayon, JACS,
1976, 98, 86[3] X. Hu, B. S. Brunschwig and J. C. Peters,
JACS, 2007, 129, 8988

Born 24.10. 1983 in Zurich, Switzerland. Matura in 2003 at Kantonsschule Enge. 20042008 Bachelor and Master studies in inorganic chemistry at the University of Zurich.
2005, 2007 and 2009 awards of the Werner-Legat. Since 2009 PhD Student in the groupof Roger Alberto at the institute of Inorganic Chemistry, University of Zürich

Miguel Guttentag
Corresponding author: Miguel Guttentag, email: miguel@aci.uzh.ch, Tel. (+41) (44) 635 4615

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Competitive Chlorine and Oxygen Evolution from Sea Water at
Rutile (110) Surfaces, from First Principle Calculations
I.C. Man, H.A. Hansen, F.A. Pedersen, F.Studt, T. Bligaard, J. Rossmeisl
Center for Atomic-Scale Materials Design Department of Physics, Technical University ofDenmark DK-2800 Kgs. Lyngby (Denmark)Introduction
It is well known that out of all water on Earth
only 2.75 percent is fresh water including
2.05 frozen in glaciers and that the rest of
97.25 is represented by waters having
different degrees of salinity. Electrochemical
water splitting or oxygen evolution reaction(OER) has attracted great interest in the
recent years as a key process in hydrogenproduction from sunlight [1]. Thereby, thisprocess will be performed mostly from waters
with different concentrations of chloride
anions. Despite the fact that the equilibrium
standard potential for Cl2 evolution(1.36 V) is
higher than that of oxygen evolution (1.23 V),
is well known that chlorine evolution (ClER)
is a competitive reaction to that of oxygen
evolution reaction (OER) on the mostsurfaces that perform well for OER [2-3].
Accordingly understanding this process is
crucial in order to desgn catalysts selective
only for oxygen evolution.

Results
Starting from first principle calculation, we willshow the reason why ClER is preferredinstead OER, on the most active surfaces for
OER and which are rutile oxides: IrO2,
RuO2, PtO2, MnO2 etc.
We show that linear correlations between Cl
and O adsorption energies exist, so thecatalysts that are good for oxygen evolution

are also good for chlorine evolution. Using
these relations a generalized phase diagram
was drawn across a potential range, wherebinding energy of oxygen is a descriptor.
cc
ClO and Cl(O)2 will form spontaneously on
the cus sites of IrO2 and RuO2 at thepotential required for chlorine evolution.
Based on the reaction free energies ofintermediates, an electrochemical analogue
to Sabatier analysis is derived for chlorine
evolution and for oxygen evolution and weshow that RuO2 is on top of the volcanoes
followed by PtO2 and IrO2. On all studied
surfaces the potential for chlorine evolution issmaller than the potential for oxygen
evolution, and thereby indicating why Cl2 isthe main product which is produced during
electrochemical water splitting

References
1. Bockris, J.O. and T.N. Veziroglu, Estimates ofthe price of hydrogen as a medium for windand solar sources. International Journal of
Hydrogen Energy, 2007. 32(12): p. 1605-1610.
2. Trasatti, S., ELECTROCATALYSIS IN THE
ANODIC EVOLUTION OF OXYGEN AND
CHLORINE. Electrochimica Acta, 1984.
29(11): p. 1503-1512.
3. Kato, Z., et al., Energy-saving seawaterelectrolysis for hydrogen production. Journal of
Solid State Electrochemistry, 2009. 13(2): p.
219-224.

2004 – Engineering degree in Chemistry, Bucharest, Romania
2006 – Master degree in Biocompatible Substances, Materials and Systems, Bucharest,
Romania
Present – Phd student at CAMD, DTU, Denmark
Email: iman@fysik.dtu.dk
Isabela Man
Corresponding author: Jan Rossmeisl , email: jross@fysik.dtu.dk

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Oxygen Evolution Reaction on Single Crystalline Electrodes
Chinmoy Ranjan

Clean hydrogen obtained from water using electrochemical water splitting.
Splitting involves two steps: oxidation ofwater molecule to form oxygen (anodic
reaction) and protons and then reduction of
protons (cathodic reaction) to obtainhydrogen. The cathodic reaction is very facileand easily happens at various catalysts
whereas the anodic oxygen evolution
reaction is kinetically difficult and currently
uses a huge over potential (to overcome thekinetic barrier) even on state of the art
catalysts.

probing into surface oxidation and surface
modification with occurring with oxygen
evolution reaction and carry out surface
science experiments to understand thenature of oxygen evolving catalysts.
We present our results on comparative
studies on Pt single crystalline electrodes.
We find differences in kinetic behaviours ofvarious surface terminations indicating adissimilar mechanism of oxygen evolution
reaction on these surfaces.

Solution to this problem is essential towards
the successful implementation of a hydrogenbased energy economy.
We investigated electrochemical behavior of
single crystalline surfaces of noble metals

Born 16. 1. 1980 in Cuttack, India. 2002 Masters Degree in Chemistry, Indian Institute ofTechnology Kanpur, India. 2007 PhD in Solid State and Theoretical Chemistry, Cornell
University, USA. 2007-2010 Senior Process Technology Engineer, Intel Corporation,
Portland USA. 2010-Postdoctoral position at Fritz Haber Institute of the Max Planck
Society, Berlin, Germany

Chinmoy Ranjan
Corresponding author: Chinmoy Ranjan email: ranjan@fhi-berlin.mpg.de Tel. 49 (0)30 8413 4500

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Electrochemical Investigation of Advanced Materials Used forDevelopment of Alkaline Electrolyzer’s Diaphragms
J. Stojadinović, M. Gorbar, D. Weidenmann, V. Zakaznova-Herzog, U. Vogt,
A. Züttel
Empa Federal Laboratories for Materials Science & Technology, Dept. Energy, Environment
and Mobility, Div. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland
The alkaline electrolyzers industry is facing the imminent necessity to replace the traditionallyused asbestos diaphragm, with a separator made of advanced environmentally friendly
materials.
The advanced material should fulfill multiple requirements, such as: good gas separation andfast evacuation of the bubbles from the surface, increased ionic conductivity and low cell
overpotential, chemical stability in 25 wt. % KOH solution at 85°C. Also, the material should
possess the mechanical strength, be cost effective and ecologically accepted. The investigationof the effect of porosity on the ionic conductivity of zirconium dioxide, which represents thebasic compound for the development of ceramic diaphragms, is undertaken.

Material development
Zirconium dioxide represents the basic
compound for the development of ceramic
diaphragms. The investigation of theinfluence of different porosity on the ionicresistance of zirconium dioxide based
diaphragms has been undertaken. By varying
the content of carbon as a pore former (0, 20
and 40 vol. % C) during the process ofdiaphragms sintering at the pressure of 36
MPa and the temperature of 1200 °C,
different porosity is obtained.

Ionic resistivity
Ionic conductivity of developed materials wasdetermined by electrochemical impedance
spectroscopy (EIS). Two compartment, fourelectrodes electrochemical cell served for
EIS
measurements
using
Zahnerpotentiostat. Measurements were performed

in 25 wt. % KOH solution at ambient
temperature, by sweeping frequencies from
1 MHz to 10 mHz in potentiostatic mode.
Different techniques, such as gas adsorption(BET), mercury intrusion porosimetry (MIP),
and scanning electron microscopy (SEM)
served for micro-structural characterization(porosity determination)ofdeveloped
diaphragms.
EIS spectra showed the purely resistive
behaviour of investigated diaphragms.
Diaphragms conductivity as a result of thesemeasurements was correlated to thematerials porosity and tortuosity.

References[1] Zeng K., Zhang D., Progress in Energy andCombustion Science 36, 2010, pp. 307Vermeiren[2] Ph., Mereels J.P., Cleaes A., Beckers H.,
International Journal of Hydrogen Energy, 34,2009, pp. 930

MSc Degree in Energy and Process Engineering in 1998 at the University ofKragujevac, Serbia, on the topic of heat pump and solar cell system for water heating,and MSc in Tribology in 2004 at the same University. In 2009 obtained a PhD degree
at The Swiss Federal Institute of Technology in Lausanne, Materials Science Institute,on the topic of electrochemical and tribocorrosion investigation of micro-electronic
metals. In December 2009 joined the Division of Hydrogen and Energy at EMPA, on
the project New membranes for alkaline electrolyzers.
J. Stojadinović
Corresponding author: Jelena Stojadinović, email: jelena.stojadinovic@empa.ch, Tel. (+41) (44) 823 4087

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Hydrogen Adsorption in Advanced Carbon Materials
Philippe Mauron1, Daniele Pontiroli2, Marcello Mazzani2, Mauro Riccò2, Arndt
Remhof1, Andreas Züttel1
1

Empa. Swiss Federal Laboratories for Materials Science and Technology, Dept. Energy,
Environment and Mobility, Div. Hydrogen & Energy, CH-8600 Dübendorf, Switzerland

2

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

Due to the fact that the physisorption energy of hydrogen on carbonaceous materials is low and on theother hand the chemical binding energy of hydrogen is too high, different approaches are attempted toincrease the physisorption energy to usable values (30-40 kJ/mol H2). For the hydrogen adsorption on
carbonaceous materials it is known that the gravimetric hydrogen density is proportional to the specific2surface BET area of the material. 1.5 mass% per 1000 m /g were determined electrochemically at room
temperature [1]. The hydrogen adsorption on different materials like a-C, graphene, LiXC60 and MgxC60 and
was investigated.

Introduction
The hydrogen binding energy increases on
curved carbon sheets due to the rehybridiza2
3
tion from sp to sp of the carbon network [3,4]. The binding energy can further be increased by charging the surface e.g. charged
C60 [5]. An interaction between H2 and metal
ions is also established by electro-static ororbital interaction (Kubas [6]).

Experimental
Graphene was produced via exfoliation ofgraphite oxide or by solvothermal synthesis.
The MxC60 was synthesized by mixing C60
powder directly with the metal and subsequent heat treatment [7]. The hydrogen adsorption in a-C, graphene, LixC60 and MgxC60
was investigated volumetrically. Dependingon the material, the hydrogen adsorption wasinvestigated between 77 and 873 K andhydrogen pressures up to 100 bar. The BET
surface area of the material was determined
and compared with the hydrogen uptake.

References[1] A. Züttel, P. Sudan, Ph. Mauron, T.
Kiyobayashi, Ch. Emmenegger, L.
Schlapbach, Int. J. Hydrogen Energy 27, 203(2002).
[3] P. Ruffieux, O. Gröning, M. Bielmann, Ph.
Mauron, L. Schlapbach, P. Gröning, Phys.
Rev. B 66, 245416 (2002).
[4] H. Cheng, A.C. Cooper, G.P. Pez, M.K.
Kostov, P. Piotrowski, S.J. Stuart, J. Phys.
Chem. B 109, 3780 (2005).
[5] M. Yoon, S. Yang, E. Wang, Z. Zhang, Nano
Letters 7, 2578 (2007).
[6] G.J. Kubas, J. Organomet. Chem. 635, 37(2001).
[7] M. Ricco, T. Shiroka, M. Belli, D. Pontiroli, M.
Pagliari, G. Ruani, D. Palles, S. Margadonna,
M. Tomaselli, Phys. Rev. B 72, 155437 (2005).

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, email: philippe.mauron@empa.ch, Tel. +41 44 823 4099

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Hydrogen interaction with graphene probed by µSR
Daniele Pontiroli, Marcello Mazzani, Mauro Riccò
Dipartimento di Fisica, Università degli Studi di Parma, Parco Area delle Scienze 7/A, 43124 Parma, Italy
The interaction of hydrogen with defective graphene produced via chemical methods is investigated bymuon spin relaxation spectroscopy. In-plane defects could dissociate the hydrogen molecule and absorb
up to two hydrogen atoms at the same site. An unexpected mobility of the hydrogen atoms absorbed onto
the graphene surface is inferred by the experimental data.

Hydrogen in graphene
The recent Nobel prized discovery ofgraphene has renewed the interest towards
carbon based materials for hydrogen storage
applications. Thanks to the huge specificsurface, the light weight and the exceptional
mechanical properties, optimised graphenebased systems are expected to bear goodreversibility, fast kinetics and high capacity,
as suggested by the studies on metal
decorated nanostructures and GOFs [1,2].

Synthesis
Gram quantities of graphenes are obtained
from the thermal reduction of graphite oxide(GO). GO is produced with Brodie method(oxidation of graphite with fuming HNO3 andKClO3). Hydroxyl, epoxide and carboxylgroups attached on the graphene sheets arethen removed by thermal shock at 1320 K in
vacuum and their desorption allows to
separate the single graphene layers. Anintermediate partial reduction with NaBH4
allows to control the amount of in-plane
defects in the graphene sheets. Graphenesamples may then be treated in H2 (or D2)
flux at different temperatures (from 973 to1273 K) and thoroughly characterised.

µSR on graphene
Both in-plane defects (vacancies) and edges
in graphene sheets are known to promote thedissociative
absorptionofmolecularhydrogen (dissociation barrier of 1.1 eV [3])and to easily absorb atomic hydrogen.
We investigated the samples with Muon Spin
Relaxation Spectroscopy (µSR), techniquewhich consists in implanting muons(chemically analogous to light hydrogen
nuclei) in the sample and following their spin
evolution. Data show that up to 30% of
implanted muons experience the dipolar fieldof a µ-H entangled state with dµ-H = 1.75Å,suggesting that up to two hydrogen atoms
could saturate an in-plane carbon vacancy ina stable configuration. Moreover, theunexpectedly high capture cross-section, if
compared with the estimated number ofdefects in the graphene planes (of the orderof 100 ppm), suggests that muons (andhence also hydrogen atoms) could easily
diffuse onto the graphene plane before being
trapped by the defects.

References[1] J. W. Burress, S. Gadipelli, J. Ford, J. M.
Simmons, W. Zhou and T. Yildirim, “Graphene
Oxide Frameworks Materials: Theoretical
Predictions and Experimental Results”,
Angewandte Chemie, 2010, Volume 122, 1-4.
[2] H. Lee, J. Ihm, M. L. Cohen and S. G. Louie,“Calcium-Decorated Graphene-Based
Nanostructures fo Hydrogen Storage”,
NanoLetters, 2010, Volume 10, 793-798.
[3] A. Allouche and Y. Ferro, “Dissociative
adsorption of small molecules at vacancies on
the graphite (0 0 0 1) surface”, Carbon, 2006,
Volume 44, 3320-3327.

Corresponding author: Marcello Mazzani, email: marcello.mazzani@fis.unipr.it , Tel. +3905219052

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Neutron total Diffraction for structural studies ofhydrogen storage materials
Toshiya Otomo
Neutron Science Division, Institute of Materials Structure Science, High Energy Accelerator
Research Organization, Ibaraki, Japan
New neutron total diffractometer, NOVA, was constructed at J-PARC (Japan Proton Accelerator Complex)
for structural analysis of hydrogen storage materials. NOVA observes powder diffraction and small-angle
scattering simultaneously. It is at the final commissioning phase and recent results obtained by NOVA
show its usefulness for hydrogen materials study.

Neutron total diffractometer, NOVA
Neutron diffraction technique is a powerfulprobe to observe and analyze hydrogen
position in materials. “Total scattering” is atechnique that had been developed for
disordered materials studies and is now
widely used to observe non-crystalline
features in materials. The word, “total”, camefrom obtaining real-space pair correlation
function, which contains every atomic
correlation,
byFouriertransforming
measured diffraction pattern. A neutron total
diffractometer, NOVA, was constructed at JPARC to observe hydrogen storage
materials.

Study
of
hydrogenmaterials by NOVA

storage

By adapting neutron total scattering tohydrogen storage materials, variety ofstructural information such as hydrogenhydrogen correlation even in disorderedphase can be analyzed. One of the mostprominent features of NOVA is the ability toanalyze structures of amorphous and liquids
structure as well as crystalline structure. To
observe hydrogenation and dehydrogenation
process, in-situ sample environments suchas H2/D2 gas atmosphere (up to 10 MPa, 50
K ~ 473 K) and high-temperature (up to 1373
K) have been equipped on NOVA. As a total
diffractometer, NOVA covers a wide
-1
momentum transfer range, 0.01 Å < Q <-1
100 Å in one measurement. This wide-Q
measurement ability is also useful for mesostructure and nearest atomic correlation
simultaneously. Based on the high neutron
flux of J-PARC, real-time observation of nonequilibrium state is feasible.
During the commissioning of NOVA, several
samples were measured to confirm
instrument performance. Some of recent
results including VD1.8, AlD3 and LiAl(NH2)4
will be presented.
This work was supported by NEDO under“Advanced Fundamental Research Projecton Hydrogen Storage Materials” (HydroStar)

Born 5. 9. 1965 in Japan. 1993 Dr. of Engineering from Tohoku University and Post
Doctoral fellow at Institute for Material Research, Tohoku Univ. 1994 Research
associate, High Energy Physics Laboratory (former name of High Energy Accelerator
Research organization, KEK). 2003 Associate Professor, KEK. 2008 Professor, KEK.
2009 Guest Professor at IMR, Tohoku University in Sendai, Japan. Guest Professor at
Kyushu University in Fukuoka, Japan. 2009- Member of the council of Japanese
Neutron Scattering Society.
Toshiya Otomo

Corresponding author: Toshiya Otomo, email: mailto:toshiya.otomo@j-parc.jp, Tel. (+81) (29) 864 5615

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What can we learn from EXAF’s for hydrogen storage
materials?
Q. Zhenga,b, S. S. Tatipartib, J. H. Bitterb, P. E. de Jonghb, B. Damaa

Chemical Engineering, Technical University Delft, Julianalaan 136, 2600 GA Delft, The
NetherlandsbInorganic Chemistry and Catalysis, Debye Institute for Nanomaterials Science, Utrecht
University, Sorbonnelaan 16, 3584 CA Utrecht, The Netherlands
Extended x-ray absorption fine structure (EXAFS) is an element specific method to provide information
about the local structure, such as the nature and number of surrounding atoms around an absorber atoms
and their interatomic distances. Here, we show the strengths of EXAFS for hydrogen storage research
for two show cases i.e., nano sized Mg-Ni supported on carbon scaffold [1] and Ti-doped Mg2Ni thin film
systems [2]. EXAFS was applied to characterize the local structure of Ni upon hydrogen cycling.

The Mg-Ni carbon systems [1] were preparedby melt infiltration of MgH2 under H2 pressure
into the nano pores of a carbon scaffold.
On/in this carbon first 12 wt% Ni was
deposited. TEM results show that the size of
Mg-Ni particles is only a few nanometers
thus too small to be visualized by XRD. Ni Kedge EXAFS was measured upon hydrogen
cycling. For the hydrogenated state, Mg2NiH4
and very small Ni particles (CN = 2.9) weredetected. After dehydrogenation, the phases
were deduced to be agglomerated Ni
particles with a CN of 8.2 together with Mg2Ni
particles (CN Ni-Mg = 3.9). Afterrehydrogenation the Ni-Ni coordination
number decreased again to 2.1. This
structural reversibility parallels that of thehydrogen storage reversibility.
For the Ti-doped Mg2Ni thin film system [2],hydrogenography shows that the hydride
formation enthalpy of Mg-Ni is drasticallyaltered upon Ti doping. Also, density
functional theory (DFT) calculation results
indicate that the destabilization mechanismof Mg-Ni-H system by Ti doping is due to theformation of Mg2Ni and Ti-Ni intermetallics inthe as-deposited state, which transform intoa metastable Ti-doped Mg2NiH4 phase uponhydrogenation [3].
Our Ni K-edge EXAFS results show that for
the as prepared state of Mg-Ni-Ti, the phases
are indeed Mg2Ni and Ti-Ni intermetallics.
After hydrogenation, we deduce thepresence of a Ti-doped Mg2NiH4 in which Ti
substitutes the Mg positions. The model for
the Ti-doped Mg2NiH4 matches very well withthe experimental data.

References[1] R. Bogerd R, P. Adelhelm, J.H. Meeldijk, K.P.
de Jong, P. E. de Jongh, Nanotechnology, 20,
204019 (2009).
[2] R. Gremaud, C.P. Broedersz, D.M. Bosa, A.
Borgschulte, P. Mauron, H. Schreuders, J.H.
Rector, B. Dam, R. Griessen, Adv. Mater. 19,
2813 (2007)[3] C. P. Broedersz, R. Gremaud, B. Dam, R.
Griessen, O. M. Lovvik, Phys. Rev. B
77, 024204 (2008)

Born 16. 6. 1976 in Hebei, China. 1999 Bachelor Degree in Nonferrous Metallurgy fromCentral South University, Changsha, China. 2004 Master Degree in Materials Sciencefrom Central South University, Changsha, China. 2009 PhD Degree in Materials
Physics and Chemistry from Shenyang National Laboratory for Materials Science(SYNL), Institute of Metal Research, Chinese Academy of Sciences. 2009 Post doc at
Delft University of Technology and Utrecht University.
Qiang Zheng
Qiang Zheng, email: mailto:q.zheng@tudelft.nl, Tel. (+31) (15) 27 83891

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Mg-based optical Hydrogen sensors
Valerio Palmisanoa, Matteo Filippia,b, Andrea Baldia, Martin Slamanb,a, Herman
Schreudersa, Bernard DamaDepartment of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BLb
Delft, The Netherlands. Department of Physics and Astronomy, Condensed Matter Physics,
Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam, The Netherlands.

The equilibrium pressure of the hydride formation of Pd-capped Mg thin films can be tuned by varying the
Mg thickness. This remarkable property combined to the large optical change upon hydrogen absorption(switchable mirror effect) can be exploited in order to make a Mg-based optical sensor able to measure acontinuous range of hydrogen partial pressures. Such a device works also in reflectance, providing a direct
reading by human eye.

Optical hydrogen sensor
The development of hydrogen based energy
systems drives the research for reliable safe
and cheap hydrogen sensors.
Conventional hydrogen sensors make use ofelectrical leads which may induce sparks andprovide a cause for ignition. Optical sensors
operate safely in hazardous atmospheres thanks to the possibility of separating theoptical read-out from the sensing area. The
fiber optics hydrogen detector represents a
unique combination of small dimensions, lowcost, and safe operation but it only indicates
whether the hydrogen pressure overcomes
the threshold level, set by the nature of themetal hydride sensing layer [2].
We designed a sensor which exploits the
thickness dependence of the equilibriumpressure of Pd-capped Mg thin films. The
device basically consists of a sensing Mglayer with a thickness gradient along thelongitudinal direction. Such a device shows a
one-to-one relationship between the lateralprogression of a visible optical change along
the Mg gradient and the H2 partial pressurevarying in the range between 200 and 4000
Pa. The optical change of the Mg layer
during the metal-hydride transition can also
be detected in reflection, thereby allowing for
multifiber applications.

References[1] M. Slaman, B. Dam, H. Schreuders, R.
Griessen, Sens. Actuators B 123 (2007) 538–
545
[2] A. Baldi, M. Gonzalez-Silveira, V. Palmisano,
B. Dam, R. Griessen, Phys. Rev. Lett. 102,
226102 (2009)[3] V. Palmisano, M. Filippi, A. Baldi, M. Slaman,
H. Schreuders, B. Dam, Int. J. Energy 35(2010) 12574-12578

Born 26. 2. 1980 in Rome, Italy. 2003 Master student at the ESRF in Grenoble,
France. 2004 Master Degree in Physics, Rome, Italy. 2008 PhD in Physics inRome, Italy. 2008 Post doc at the Vrije Universiteit Amsterdam, Netherlands. 2009
Post doc at the Delft University of Technology, Netherlands.

Valerio PalmisanoCorresponding author: Valerio Palmisano, email: v.palmisano@tudelft.nl, Tel: +31 15278 2676

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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 the isotope effecton the electronic structure of hydrides. Furthermore, the effect of anharmonicity and DebyeWaller factor on superconductivity of PdHx and PdDx have been studied by Ronald before hedeveloped a semi-empirical model for the heat of solution of hydrogen in transition metals. He
also studied the trapping energy for hydrogen on lattice defects as well as the heat of solution ofdisordered transition metals. The volume expansion upon hydrogen absorption, the Gorskyeffect, the diffusion, 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 theworld of high pressure hydrogen and described the properties of hydrides formed at very highpressure as well as the properties of hydrogen gas in a wide temperature and pressure range.
During the intense investigation of superconductors and metal hydrides under high hydrogenpressure in a diamond anvil cell, Ronald has discovered the switchable optical properties ofyttrium and lanthanum hydride films. This has then stimulated 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 the determination of the thermodynamic parameters e.g. stability andkinetics of the hydrides. Furthermore, new applications for hydrides as hydrogen detectors andoptical filters 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 the investigation of theHall effect, electrical transport and magnetic susceptibility of liquid rear earth elements like
Cerium. 30 years ago in 1970 he was coauthor with Busch and Waldirich on a paper about thehydrides of La-Ni compounds. LaNi5 was subsequently investigated in view of the structure,surface segregations, hydrogen occupation of interstitial sites and as electrode material.LaNi5 isstill the base material for most of the electrochemical applications of metal hydrides today. The
work on LaNi5 was complemented by the research on FeTi. Louis Schlapbach realized theimportance of the surface composition for the hydrogen sorption process and he was able todescribe 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 the formation of
metallic clusters as superparamagnetic particles acting as the active sites in hydrogendissociation and recombination. The investigation of the surface of metal hydrides was further
intensified by means of X-ray photoelectron spectroscopy. Louis Schlapbach was the firstscientist correctly describing the activation process of a metal hydride and, furthermore, tomodel the chemical composition and states of the elements in a surface profile. He also
succeeded to analyze the electronic structure of raere earth elements and their hydrides bymeans 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 book chapters 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 mostrecently Gary investigated the hydrogen desorption behavior of AlH3 and explaned themechanism 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 in acontrolled 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 thehydride 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 sciencee.g. “Role of strain and ligand effects in the modification of the electronic and chemical
properties of bimetallic surfaces”; 3) Nanostructures and materials properties e.g. Atomic-scale
imaging of carbon nanofiber growth”; 4) Heterogeneous catalysis e.g. “Ammonia synthesis fromfirst 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 fuelcell 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 theunderstanding 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

Prof. Rüdiger Bormann investigated 20 years ago the free energy of metallic glasses, metastable
crystalline and amorphous alloys as well as the thermodynamics and kinetics of the amorphous phaseformation by mechanical alloying. This was the basis for the investigation of Mg and Mg-Ni hydrides andthe thermodynamics of nanoscale magnesim hydride. The discovery catalytic effect of metal oxides on thehydrogen sorption kinetics of magnesium was a great step forward in the development of hydrogenstorage materials. Furthermore, very important was also the interpretation of the role of the grainboundaries for the diffusion of hydrogen in the passivating hydride phase formation. Recently the discoveryof the so called reactive hydride composites by the combination of two hydrides has opened a new field ofmaterials design for hydrogen 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 thefields 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 theHydrogen Decrepitation (HD) process to the 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 fabricationof NdFeB sintered magnets. These materials are playing a vital role in the production of energy
efficient electric drives, actuators and generators. The latest development within the group is theuse of the HD process in the recycling of 2/17 and NdFeB magnets. His research also made avery significant contribution to the development and understanding of the Hydrogenation,
Disproportionation, Desorption and Recombination (HDDR) process which enabled coercive
powder and hence bonded magnets to be formed from bulk NdFeB alloys. He has publishedover 500 scientific papers and edited and co-edited a number of books. During these years hehas successfully supervised around 120 postgraduate students, many of whom are still working
in applied materials science and occupy senior positions in industry, government and academia
throughout the world. Since stepping down as group leader and head of school he has focusedhis 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 isserving to highlight the huge potential of magnets and hydrogen in the drive towards asustainable 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 of climate change and resource
depletion. He continues to be very active in this campaign which he considers to be ofparamount importance. Therefore, we aword Prof. Rex Harris with the Science of Hydrogen &Energy prize 2010.

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SCIENCE OF HYDROGEN & ENERGY AWARD 2010
Rainer Kirchheim was born May 24, 1943 in Halle/Saale,
Germany. He studied Physics at the University of Stuttgart from
1966-1971 and received the diploma for the work
“Electrochemical studies of oxygen solid solutions in high melting
metals” at the Max-Planck-Institut für Metallforschung/Universityof Stuttgart. He received his Ph.D. for the thesis entitled “Thermoand electrotransport of oxygen and nitrogen in Va metals “ fromthe
UniversityofStuttgart,
Max-Planck-Institut
fürMetallforschung in 1973. In 1988 he received the Habilitation“Measurements and modelling of hydrogen solubility anddiffusivity in disordered metal lattices“ from the University of
Stuttgart, Faculty of Chemistry Metallurgy.
Since 1993 he is Full Professor (Gustav Tamman Chair)Prof. Dr. Rainer Kirchheim University of Göttingen Göttingen Germany and Director GeorgAugust-Universitaet Goettingen, Institut für Materialphysik
Göttingen Germany .
Prof. Rainer Kirchheim has investigated 30 years ago oxygen in metals, especially diffusion,
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 niobium in palladium. He developed
an electrochemical method for the measurement of the hydrogen diffusion in palladium andpalladium alloys and performed fundamental studies on the diffusion mechanism of interstitial
species. The interaction of hydrogen with dislocations in palladium and the interpretation with amodel based on the Fermi-Dirac distribution are of great importance for the understanding of theinterstitial site occupation of hydrogen in alloys and amorphous metals.
For the enormous contributions on the hydrogen dynamics and thermodynamics in metals aswell as the hydrogen interaction with dislocations, grain bounderies and interfaces 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 Chemistry of
the National Research Council in Canada.
From 1987 to 1999 he was a Professor in the Institute for Materials
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 toreview articles and book chapters. He has worked on corrosion-resistant alloys, electrolysis,
especially he pioneered the electrolysis of seawater. He tailored the catalysts for carbon dioxidemethanation, in particular, he has built a prototype plant for global CO2 recycling in 1995 on theroof 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 of carbon dioxide with hydrogen, carbon dioxide recovery at an energy
consuming district, and transportation of carbon dioxide. The plant uses tailored key materials
with high performance and durability, that is, cathodes for hydrogen production, anodes for only
oxygen evolution without chlorine evolution in seawater electrolysis, and catalysts for rapid andselective production of methane by the reaction of carbon dioxide with hydrogen. 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 of Technology which is the minimum unit of industrial scale forseawater electrolysis and carbon dioxide methanation.
He is in the Editorial Board of "Corrosion Science", a Member of NACE International, theElectrochemical Society and the International Society of Electrochemistry. Member of Japan
Society of Corrosion Engineering, the Japan Institute of Metals, the Surface Finishing Society ofJapan, the Iron and Steel Institute of Japan, the Electrochemical Society of Japan, the Societyof Chemical Engineers, Japan, the Chemical Society of Japan, and other scientific societies inJapan.
He received many awards among those also The Electrochemical Society Fellow Award in 1997
in recognition of contribution to the advancement of science and technology, for leadership inelectrochemical and solid state science and technology and for active participation in the affairsof the Electrochemical Society, Inc.
We award Prof. Koji Hashimoto for his outstanding work on the production of hydrogen and theuse of hydrogen for the reduction of CO2 with the Science of Hydrogen & Energy prize 2011.

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PARTICIPANTS

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ABAKEVICIENE Brigita, Dr.
P12

KAUNAS UNIVERSITY OF TECHNOLOGY email: Brigita.Abakeviciene@ktu.lt
INSTITUTE OF MATERIALS SCIENCE
Tel: +370 37 313432
SAVANORIU AVE. 271
Fax: +370 37 314423
LT-LT-50131 KAUNASALBERTO Roger, Prof. Dr.
G01

University of Zurich
Institute of Inorganic Chemistry
Winterthurerstr. 190
CH-8057 Zürich

email: ariel@aci.uzh.ch
Tel: 044 6354631
Fax:

ATAMAS Alexander, Dr.
P01

Leiden University
Theoretical Chemistry
Einsteinweg 55
NL-2333 CC Leiden

email: atamasa@chem.leidenuniv.nl
Tel:
Fax:

BERKE Heinz, Prof. Dr.
O11

University of Zurich
Institute of Inorganic Chemistry
Winterthurerstrasse 190
CH-8057 Zurichemail: hberke@aci.uzh.ch
Tel: +41 44 635 4680
Fax: +41 44 635 6803

BIELMANN Michael, Dr.
O10

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

email: michael.bielmann@empa.ch
Tel: +41 44 823 4342
Fax: +41 44 823 4022

BLANCHARD Didier, Dr.
O04

Risoe-DTU
AFM
Building 228, P.O. Box 49
DK-4000 Roskilde

email: didier.blanchard@risoe.dk
Tel:
Fax:

BORGSCHULTE Andreas, Dr.
O02

Empa
H2E
Überlandstrasse 129
CH-8600 Dübendorf

email: andreas.borgschulte@empa.ch
Tel: +41 44 823 4639
Fax: +41 44 823 4022

CALLINI Elsa, PhD Student
O29

University of Bologna
Physics Department
viale C. Berti-Pichat 6/2
I40127 Bologna

email: elsa.callini@unibo.it
Tel: +39 51 209 5298
Fax:

CAPUTO Riccarda, Dr.
I10

ETHZ
Laboratorium für Anorganische Chemie
HCI H 139, Wolfgang-Pauli-Str. 10-8093 Zürich

email:
riccarda.caputo@inorg.chem.ethz.ch
Tel:
Fax:

CHORKENDORFF Ib, Prof. Dr.
I08

CINF
DTU Physics
Fysikvej, Bldg. 312
DK-2800 Kgs. Lyngby

email: ibchork@fysik.dtu.dk
Tel: +4545253170
Fax:

CORNO Marta, Dr.
O05

University of Turin
Chemistry Department
via Giuria 7
IT-10125 Torino

email: marta.corno@unito.it
Tel: 00390116704597
Fax: 00390112364596

CYVIENE Jurgita, Dr.
P02

Kaunas University of Technology
Department of Physics
Studentu str. 50
LT-LT-51368 Kaunas

email: jurgita.cyviene@ktu.lt
Tel: +37037300346
Fax: +37037456472

DE JONGH Petra, Prof. Dr.
I02

Utrecht University
Inorganic Chemistry and Catalysis
Sorbonnelaan 16
NL-3584 CA Utrecht

email: P.E.deJongh@uu.nl
Tel: +31 30 2536766
Fax: +31 30 2711027

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EKINS Paul, Prof. Dr.
I01

Energy and Environment Policy UCL Energy email: p.ekins@ucl.ac.uk
Institute
Tel:
University College London Central HouseFax:
14 Upper Woburn Place
UK-WC1H0NN London

FUMEY Benjamin, Dipl. Ing.
G02

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

GAO Jinbao, PhD Student
G08
Sorbonnelaan 16
NL-3584 CA UTRECHT

email: benjamin_fumey@kastanet.org
Tel: +41 33 437 3840
Fax:
email: J.GAO@uu.nl
Tel:
Fax:

GEBALD Christoph, PhD Student Climeworks GmbH
I07
Toblerstrasse 36
CH-8044 Zürich

email: gebaldc@ethz.ch
Tel: +41 76 468 1249
Fax:

GIANOLA Corinne,
G03

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

email: corinne.gianola@empa.ch
Tel: +41 44 823 4692
Fax: +41 44 823 4022

GORBAR Michal, PhD Student
P03

EMPA
138 H&E
ueberlandstrasse 129
CH-8600 duebendorf

email: michal.gorbar@empa.ch
Tel: +41 44 823 4301
Fax:

GRZECZKA Grzegorz, Dr.
P04

Polish Naval Academy

email: g.grzeczka@amw.gdynia.pl
Tel:
Fax:

Smidowicza 69
PL-81-103 Gdynia
GUTTENTAG Miguel, PhD Student University of Zurich
O21
Inorganic Institute
Winterthurerstr. 190
CH-8057 Zürich

email: miguel@aci.uzh.ch
Tel: +41 76 349 4289
Fax:

HAJIHASHEMI Sara,
G05

Islamic Azad University
IT and Computer
Parvin- Azarbahram
IR-8199886699 Esfahan

email: s_hashemi2004@yahoo.com
Tel: +98-9131101856
Fax:

HASHIMOTO Koji, Prof. Dr.
I06

Tohoku University
Institute for Materials Research
Tohoku Institute of Technology
JP-982-8577 Sendai

email: koji@imr.tohoku.ac.jp
Tel: +98-9131101856
Fax:

KATO Shunsuke, PhD Student
O19

Empa
Mobility, Energy and Environment
Ueberlandstr. 129
CH-8600 Duebendorf

email: shunsuke.kato@empa.ch
Tel: +41 44 823 4327
Fax: +41 44 823 4022

KAZEMPOOR Pejman, Dr.
P05

Tarbiat Modares University
Mechanical Engineering
Parvin- Azarbahram
IR-8199886699 Esfahan

email:
pejman.kazempoor@hotmail.com
Tel: +98-9124389239
Fax:

KHAMIS Ibrahim, Dr.
O16

IAEA
Department of Nuclear Energy
Wagramer strasse 5AT-1400 Vienna

email: i.khamis@iaea.org
Tel: +43-1 2600 22822
Fax: +43-1 2600 29598

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KLASSEN Thomas, Prof. Dr.
I04

Helmholtz-Zentrum Geesthacht
Centre for Materials and Coastal Research
Max-Planck-Strasse 1
D-21502 Geesthacht

email: klassen@hzg.de
Tel: +49-(0)-4152-87-2562
Fax: +49-(0)-4152-87-2636

LAURENCZY Gabor, Prof
O18

EPFL
SB ISICEPFL BCH 2405
CH-CH-1015 Lausanneemail: Gabor.Laurenczy@epfl.ch
Tel: +41 21 693 9858
Fax: +41 21 693 9780

LINDEMANN Inge, PhD Student
O12

IFW Dresden

email: I.Lindemann@ifw-dresden.de
Tel:
Fax:

Helmholtzstraße 20
DE-01069 Dresden
LINDER Marc , Dr.
O09

German Aerospace Center - DLR e.V.
Institute of Technical Thermodynamics
Pfaffenwaldring 38-40
DE-70568 Stuttgart

email: marc.linder@dlr.de
Tel:
Fax:

LOHSTROH Wiebke, Dr.
I03

Karlsruhe Institute of Technology
Instritute of Nanotechnology
Hermann-von-Helmholtz-Platz 1
DE-76344 Eggenstein-Leopoldshafen

email: wiebke.lohstroh@kit.edu
Tel: +49 7247 82 6377
Fax:

MAISSEU André, Prof. Dr.
O30

IJNHPA
Editor in chiefrue de Morges, 64
CH-1110 Morges

email: a.maisseu@bluewin.ch
Tel:
Fax:

MAN Isabella, PhD student
O22

email: iman@fysik.dtu.dk
Tel:
Fax:
-

MARTELLI Pascal, PhD Student
O01

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

email: pascal.martelli@empa.ch
Tel: +41 44 823 4082
Fax: +41 44 823 4022

MAURON Philippe, Dr.
O25

Empa
Hydrogen & Energy
Ueberlandstrasse 129
CH-8600 Dübendorf

email: philippe.mauron@empa.ch
Tel: +41 44 823 4099
Fax:+41 44 823 4022

MAZZANI Marcello, PhD Student
O26

Univeristy of Parma
Physics
Parco Area delle Scienze, 7/A
IT-43100 Parma

email: mazzani@fis.unipr.it
Tel: +393282651386
Fax: +390521905223

MILANESE Chiara, Dr.
O15

University of Pavia
Department of Physical Chemistry
Viale Taramelli, 16
IT-I-27100 Pavia

email: chiara.milanese@unipv.it
Tel: +39 0382 987670
Fax: +39 0382 987670

MULLER Jiri, Dr.
O13

IFE

email: Jiri@ife.noTel: -47 63 80 61 85
Fax:

Instiuttveien 8
NO-NO-2027 Kjeller
NESPER Reinhart, Prof. Dr.
G06

ETH Zürich
Laboratorium für Anorganische Chemie
HCI H 139, Wolfgang-Pauli-Str. 10
CH-8093 Zürich

email:
reinhard.nesper@inorg.chem.ethz.ch
Tel: (+41) (44) 632 3069
Fax: (+41) (44) 632 1149

ORIMO Shin-Ichi, Prof. Dr.
I05

Tohoku University
Institute for Materials Research
2-1-1 Katahira
JP-980-8577 Sendai

email: orimo@imr.tohoku.ac.jp
Tel: +81 22-215-2093
Fax: +81 22-215-2091

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OTOMO Toshiya, Prof
I11

Stoos, Switzerland 2011

High Energy Accelerator Research
Organization
Institute of Materials Structure Science
1-1 OhoJP-305-0801 Tsukuba
Delft University of Technology
Chemical Engeneering
Julianalaan
NL-2628 BL De Delftemail: toshiya.otomo@j-parc.jp
Tel:
Fax:

PATZKE Greta, Prof. Dr.
G08

University of Zürich
Institute of Inorganic Chemistry
Winterthurerstrasse 190
CH -8057 Zürich

email: greta.patzke@aci.uzh.ch
Tel: +41 44 63 54691
Fax: +41 44 63 56802

PHUNG Bac, Dr.
P06

National Institute of Advanced Industrial
ScienceNanosystem Research Institute
IST Tsukuba Central 2, 1-1-1 Umezono
JP-305-8568 Tsukuba
Università di Parma
Dipartimento di Fisica
Via G. Usberti, 7/aIT-43124 Parma

email: phung.bac@aist.go.jp
Tel: ++31 15 27 83891
Fax: ++31 15 27 87421

RANJAN Chinmoy, Dr.
O23

Fritz Haber InstituteInorganic Chemistry
Faradayweg 4-6
DE-14195 Berlin

email: ranjan@fhi-berlin.mpg.de
Tel:
Fax:

REMHOF Arndt, Dr.
O06

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

email: arndt.remhof@empa.ch
Tel: +41 44 823 4369
Fax:RICCÒ Mauro, Prof. Dr.
G08

Università di Parma
Dipartimento di Fisica
Via G. Usberti 7/a
IT-43124 Parma

email: mauro.ricco@fis.unipr.it
Tel: +39 3496609300
Fax: +39 0521905223

SHAO Huaiyu, Dr.
O20

Max-Planck-Institut für Kohlenforschungemail: shao@mpi-muelheim.mpg.de
Tel: +49.208.306-2449
Fax:

PALMISANO Valerio, Dr.
O28

PONTIROLI Daniele, Dr.
P07

Kaiser-Wilhelm-Platz 1
DE-D45470 Mülheim an der Ruhr
SHEPTYAKOV Denis, Dr.
G08

Laboratory for Neutron Scattering
Paul Scherrer Institut
CH-5232 Villigen PSISHIM Jae-Hyeok, Dr.
P08

Korea Institute of Science and Technology
39-1 Hawolgok-dong, Seongbuk-gu
KR-136-791 Seoul

email: v.palmisano@tudelft.nl
Tel: +31 15 27 83891
Fax: +31 15 27 87421

email: Daniele.Pontiroli@fis.unipr.it
Tel: +39 3282630760
Fax: +39 0521 905223

email: denis.sheptyakov@psi.ch
Tel:
Fax:
email: jhshim@kist.re.kr
Tel: +82-2-958-6760
Fax:

STOJADINOVIC Jelena, Dr.
O24

Empa
Abt. 138Überlandstrasse 129
CH-8600 Dübendorf

email: jelena.stojadinovic@empa.ch
Tel:
Fax:

STOOTS Carl, Dr.
I09

Idaho National Laboratory
Thermal Sciences
PO 1625
US-83415 Idaho Falls

email: carl.stoots@inl.gov
Tel: 001-208-526-4527
Fax:

SZYMAK Piotr, Dr.
P09

Polish Naval Academy

email: p.szymak@amw.gdynia.pl
Tel:
Fax:

Smidowicza 69
PL-81-103 Gdynia

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TAMULEVICIUS Sigitas, Prof. Dr. KAUNAS UNIVERSITY OF TECHNOLOGY email: Sigitas.Tamulevicius@ktu.lt
G04
INSTITUTE OF MATERIALS SCIENCE
Tel: +370 37 313432
SAVANORIU AVE. 271
Fax: +370 37 314423
LT-LT-50131 KAUNASTORRES Alondra, PhD Student
P10
Prins Mauritsstraat 46
NL-2624 ST Delftemail: alondra_t@hotmail.com
Tel:
Fax:

VOGT Ulrich, Dr.
O08

EMPA
Hydrogen & Energy
Ueberlandstr. 129
CH-8600 Duebendorf

email: ulrich.vogt@empa.ch
Tel: +41 44 823 4160
Fax: +41 44 823 4150

VON OLSHAUSEN Christian, Dr.
O17

SunFire GmbHCTO
Eduard-Suling-Straße 17
DE-28217 Bremen

email:
christian.vonolshausen@sunfire.deTel: +49 421 83 50 55 40
Fax: +49 421 83 50 55 10

WALTON Allan, Dr.
O14

University of Birmingham
Metallurgy and Materials
Elms Road
GB-B15 2TT Birmingham

email: a.walton@bham.ac.uk
Tel: +44 121 414 3960
Fax:

WIEDENMANN Daniel, PhD
Student
P11

EMPA
138
Überlandstrasse 129
CH-8600 Dübendorf

email: daniel.wiedenmann@empa.ch
Tel: 4630
Fax: 4022

YAN Yigang, Dr.
O03

Tohoku University
Institute for Materials Research
2-1-1 Katahira, Aoba-ku
JP-980-8577 Sendai

email: yg-yan@imr.tohoku.ac.jp
Tel: +81 22 215 2094
Fax: +81 22 215 2091

ZHENG Qiang, Dr.
O27

Delft University of technology
Chemical Engineering
Julianalaan 136
NL-2628 BL Delftemail: Q.Zheng@tudelft.nl
Tel:
Fax:

ZÜTTEL Andreas, Prof. Dr.
O07

EMPA
Hydrogen & EnergyÜberlandstrasse 129
CH-8600 Dübendorf

email: andreas.zuettel@empa.ch
Tel: +41 44 823 4038
Fax: +41 44 823 4022

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Information

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

Map of the region Schwyz-Stoos

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Travel to Stoos from Zürich airport:
Please go to the ticket counter in the airport and ask for a ticket to Stoos (roundtrip). Pleasealso ask the person at the counter to print you the timetable for your connection e.g.:
So, 23.01.11
Zürich Flughafen
ab 14:13
3
IC 726, InterCity BZ RZ
Zürich HB
an 14:23 17
walk from track 17 to track 4
Zürich HB
ab 14:35
4
IR 2345, InterRegio
Zugan 15:01
4
change to train on opposite side of platformZug
ab 15:05
3
S2 21247, S-Bahn Linie 2
Schwyzan 15:33
2
the bus is parked in front of the station
Schwyz, Bahnhof
ab 15:36
Bus 1, Richtung: Muotathal, Hölloch
Schwyz, Schlattli
an 15:54
the bus stops in front of the cable car station, show your ticket at the counter
Schlattli SSSF
ab 16:10
FUN 19, Standseilbahn
Stoos
an 16:18
Dauer: 2:05

EMERGENCY TELEPHONE NUMBERS
POLICE

117

FIRE FIGHTERS

118

AMBULANCE144

RESCUE HELICOPTER

1414

Corinne Gianola

076 398 9985

Andreas Züttel

079 215 4601

Hotel Stoos, Reception

041 817 44 44

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