Advanced Materials For Hydrogen Production

Advanced Materials for
Renewable Hydrogen
Production, Storage and
Utilization
Edited by Jianjun Liu
ADVANCED MATERIALS
FOR RENEWABLE
HYDROGEN
PRODUCTION, STORAGE
AND UTILIZATION

Advanced Materials for Renewable Hydrogen Production, Storage and Utilization
http://dx.doi.org/10.5772/59520
Contributors
Hailiang Chu, Shujun Qiu, Fen Xu, Lixian Sun, Olaitan Lukman Akanji, Ye Mei, Yuriy Zhirko, Jianjun Liu
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Meet the editor
Professor Jianjun Liu received his Ph.D. in physical

chemistry from the Institute of Theoretical Chemistry,
Jilin University, China, in 2002. He subsequently con-
tinued his research activity in theoretical chemistry as a
postdoctoral fellow at the Cherry L. Emerson Center for
Scientific Computation at Emory University. In 2005, he
moved to the Department of Chemistry and Biochem-
istry of Southern Illinois University as an assistant scientist and lecturer,
working on computational simulation of complex metal hydrides for
hydrogen storage. In 2011, he joined the faculty as a professor at the State
Key Laboratory of High Performance Ceramics and Superfine Microstruc-
ture of Shanghai Institute of Ceramics, Chinese Academy of Sciences.
Professor Liu has been active in various organizations and has coauthored
over 50 papers in journals such as The Journal of the American Chemical
Society as well as four book chapters and delivered over 30 oral research
presentations. Currently, his research focuses on computational simula-
tion of energy conversion and storage materials with an aim to reveal the
relation of their structure and properties and further design and optimize
novel and high-performance materials. His current research activity was
supported by many Chinese national funds.
Contents
Preface XI
Section 1 Introduction 1
Chapter 1 Introductory Chapter 3

Jianjun Liu
Section 2 Hydrogen Production 9
Chapter 2 Characterization and Optical Properties of Layered InSe and

GaSe Crystals Intercalated with Hydrogen and Hydrogen-
Containing Molecules 11
Yuriy Zhirko, Vasiliy Grekhov, Nikolay Skubenko, Zakhar Kovalyuk
and Taras Feshak
Section 3 Hydrogen Storage 51
Chapter 3 Metal Amidoboranes and Their Derivatives for

Hydrogen Storage 53
Hailiang Chu, Shujun Qiu, Lixian Sun and Fen Xu
Chapter 4 Modeling of Hydrogen Absorption/Desorption in a Metal

Hydride Bed Reactor — A Theoretical Study 95
Olaitan Akanji and Andrei Kolesnikov
Section 4 Hydrogen Utilization 119
Chapter 5 Treatment of Hydrogen Bonds in Protein Simulations 121

Ya Gao, Ye Mei and John Z. H. Zhang
Preface
There is a tremendous lack of public appreciation of scientific and technological difficulties

that would be encountered in supplies of energy once fossil fuel sources are acutely deplet‐
ed. The supply is currently adequate, which allows us to develop alternative energy sources,
but the scale of research in physics, chemistry, biology, and engineering needs to be raised,
because it will require sustained efforts to solve the long-term problems of global energy
security and environmental pollution. Hydrogen is regarded as a suitable energy carrier for
sustainable energy schemes with zero emission. In spite of a great deal of scientific and tech‐
nological efforts, many significant challenges still exist. In 2012, InTech publisher invited me
to edit a book titled Hydrogen Storage . This book attracted extensive attention from “hydro‐
gen” researchers. This encouraged me to publish a new book with an aim to cover more
research fields, namely, hydrogen production, storage, and utilization. As is well known,
material issues are a bottleneck in the development of hydrogen economy. Therefore, the
Advanced Materials for Renewable Hydrogen Production, Storage, and Utilization is defined as
our present book title and has tried to present the current research progress in hydrogen
applications to the best of our knowledge.
To achieve this, we reviewed all submitted chapters. The chapters cover three research
fields: hydrogen production, storage, and utilization. In the past decade, computational ma‐
terials science, including first-principles calculations, phase field, and finite element analy‐
sis, made a significant progress in simulating chemical and physical properties of materials.
The Materials Genome Initiative (MGI) involves computation, experiment, and data science
and is playing an important role in developing novel materials. This book targets the reader‐
ship at the professional researcher level. We hope that the book helps in convincing the hy‐
drogen research community of the importance of developing novel hydrogen application
materials by combining theoretical and experimental approaches.
The book could have never been realized without the invaluable assistance of Ms. Iva Lipov‐
ić and Mrs. Ivona Lovrić. Effective communication with them helped to make this book out‐
standing. I would like to acknowledge the valuable input from my colleague Prof. Jiacheng
Wang. I would also like to acknowledge the “One-Hundred-Talent Project,” the “Key Re‐
search Program (Grant No. KGZD-EW-T06)” of the Chinese Academy of Sciences, and the
research grant (no. 14DZ2261200) from the Shanghai government, China, for their financial
support. Most importantly, without the love and encouragement of my family, I could not
have embarked on or finished this book project.
Jianjun Liu
State Key Laboratory of High Performance Ceramics and Superfine Microstructure
Shanghai Institute of Ceramics
Chinese Academy of Sciences
China
Section 1
Introduction
Chapter 1
Introductory Chapter
Jianjun Liu
Additional information is available at the end of the chapter
1. Introduction
1.1. Importance of developing hydrogen energy
As the global consumption of fossil fuels is growing at an alarming and unsustainable rate,
the associated emissions of greenhouse gases and other toxic pollutions are reaching levels
that are environmentally unacceptable. A large challenge of world economic development
requires meeting the demand of energy consumption while reducing emissions of greenhouse
gases and pollutants. Since the sun is our largest and cheapest energy resource, the utilization
of solar energy is considered as the ultimate strategy for solving this problem. It continuously
bombards our planet with solar energy, with 1 h of solar energy equating to more than all of
our annual energy consumption [1]. Among the limited methods for solar energy conversion
and utilization, solar water splitting to make hydrogen has been considered as one of the most
effective and cleanest ways. Hydrogen, as an energy carrier, is widely regarded as a potential
cost-effective, renewable, and clean energy alternative to petroleum, especially in the various
transportation tools [2]. The hydrogen produced by solar energy can then be used by fuel cells
to generate electricity with zero-emission of water. Figure 1 displays the scheme of renewable
energy based on some selected technologies including hydrogen production, storage, and
utilization.
Although a great deal of efforts have been made to develop a sustainable hydrogen economy,
many challenges still exist in many research fields such as hydrogen generation, storage, and
fuel cells in the cyclic system. In order for solar energy to be the major contributor to generate
clean hydrogen, the conversion efficiencies of solar water-splitting devices need to be im‐
proved, for example, developing highly active catalysts for hydrogen/oxygen evolution
reactions. One significant barrier that prevents the widespread use of hydrogen as an energy
source is the lack of efficient hydrogen storage systems. For on-board application, the hydro‐
gen storage system is required to provide the needed quantity of hydrogen with accepted
© 2015 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,
and reproduction in any medium, provided the original work is properly cited.
4 Advanced Materials for Renewable Hydrogen Production, Storage and Utilization
Figure 1. A scheme of renewable energy (solar energy to hydrogen) based on some selected technologies including
hydrogen production, storage, and utilization.
engine. The currently available hydrogen storage systems include compressed hydrogen,
nanomaterials, metal hydrides, and complex metal hydrides. Each can meet some of the
requirements but none of them meets all the requirements for critical applications. Therefore,
developing a compact and efficient hydrogen storage technology is the most technically
challenging for achieving hydrogen economy. Hydrogen fuel cells are a pathway to convert
hydrogen-carried energy into electricity. The development of high-performance fuel cells is
leading to higher efficiencies and cleaner energy utilization than the other conventional
technologies. Costs vary over a wide range, and future cost projections depend on mass
production estimates, driven by the automobile market, in volumes and quantities that do not
represent the volumes of trucks, buses, and trains.
Advances of materials science have generated a significant impact on many technology fields
[3]. Scientists always think, work, and interact to develop and optimize advanced materials
and process in different time and space scales. Developing high-performance materials is
playing an important role in creating new fields of fundamental sciences and promoting
practical technologies. In order to achieve a technological breakthrough in effective renewable
energy conversion from solar energy to hydrogen energy, we need to develop advanced
materials which can be applied in some technologies of hydrogen production, storage, and
utilization. To this end, the potential capabilities of advanced high-performance materials
must be extensively discovered at a more fundamental level.
The specific aim of this book is to provide a fundamental study and in-depth understanding
of mechanisms involved in hydrogen applications. In the past years, there are a few review
books to discuss development of advanced materials in hydrogen production, or hydrogen
storage, or hydrogen fuel cells. However, a comprehensive review in these three aspects is not
found so far. Herein, we intend to provide a complete review in the present and previous
research progresses including discovered materials and research methods in experiment and
computation.
2. Advanced materials in hydrogen production, storage, and utilization
Nano-photocatalysts for hydrogen production plays an important role in enhancing conver‐

sion efficiency from solar energy to hydrogen chemical energy [4]. The highly active catalysts
Introductory Chapter 5
should have suitable band gaps which are favorable to improve the absorbance of abundant
solar light to drive hydrogen and oxygen evolution reactions. In addition, good charge-transfer
ability for electrons and holes and high surface catalytic reactivity for half-reaction are very
important for this kind of photocatalysts.
Loading cocatalysts onto photocatalysts to form hydrogen or oxygen evolution sites have been
considered as an effective method to enhance photocatalytic activity for water splitting. In the
past decades, different kinds of materials such as transition metals and transition metal
compounds (oxides, carbides, nitrides, and sulfides) have been developed as effective
cocatalysts for photocatalytic water splitting [4, 5] Some noble metals such as Pt, Ru, Au, Rh,
etc., and metal oxides such as NiOx, Cr2O3, etc., perform well for water reduction cocatalysts
by entrapping electrons from semiconductor. In addition, some noble metal oxides such as
IrO2 and RuO2 as well as spinel and layer materials such as Co3O4 and LiCoO2 have been found
to have effective water oxidation by entrapping holes [6].
Solid-state nanomaterials for hydrogen storage perhaps offer the best opportunity for meeting
the requirements of on-board applications. Nanoscience and nanotechnology involve studying
and working with matter on a nanometer scale. Nanomaterials with at least one dimension
<100 nm can be in the form of thin films or surface coatings, nanowires and nanotubes, or
nanoparticles. The unique properties of nanomaterials originate from the increased surface
area and quantum effects, both of which relate to the small size. Therefore, reactivity, strength,
and electrical characteristics of nanomaterials may be significantly different from those of
conventional materials. For example, a particle 30 nm in size has only 5% of its atoms on its
surface. When the size is reduced to 3 nm, the particle has 50% of its atoms exposed on the
surface. This makes nanoparticles have a much greater surface area per unit mass than bulk
structures. Both surface area and exposed atoms on the surface could be useful for storing
hydrogen. Therefore, nanotechnology is expected to play a key role in designing high-capacity
solid-state hydrogen storage materials. In fact, the concept of nanoscience and nanoengineer‐
ing has been actively exploited in improving existing hydrogen storage materials and search‐
ing for new hydrogen storage candidates. For example, nanocatalysts have been used to
improve kinetics of hydrogen uptake and release or to improve hydrogen storage capacity
through spillover [7]. Novel building blocks have been proposed to maximize the hydrogen
capacity and optimize the strength of hydrogen binding. Large-surface-area nanomaterials
which offer more host atoms/sites for hydrogen and allow easy access of these sites have been
synthesized, as in materials such as molecular organic frameworks (MOFs) and covalent
organic frameworks (COFs), and show promise as hydrogen storage media [8, 9].
The photoelectrochemical (PEC) water splitting has been considered as the most attractive
method over other hydrogen production approaches. The pioneering work of solar-driven
water splitting in PEC frame consisted of TiO2 anode and Pt cathodes for oxygen and hydrogen
evolution reaction [10]. In fact, TiO2 represents one of the most important semiconductor
materials for PEC water splitting. However, due to its wide band gap, TiO2 cannot absorb
visible and infrared light for solar water splitting. Doping of many metals and non-metals has
been widely adopted to narrow the band gap [11]. In the past decades, many different
nanoengineering methods such as tailoring morphology and composition and interface have
been applied to improve the performance of light absorption of TiO2.
ZnO, another widely used semiconductor, has also been widely investigated as a photoanode
of PEC water splitting. In the past years, different approaches including ion doping and visible
light sensitization with narrow band gap semiconductors have been used to expand the light
absorption region and hence improve the PEC water-splitting performance [12, 13]. Hematite
(α-Fe2O3) is an increasing promising material for solar-driven PEC water-splitting applications
due to its relatively narrow band gap (2.1 eV). However, the poor charge-transfer property of
α-Fe2O3 greatly prevents its efficiency as a photoanode material for splitting water. Similarly,
ion doping and nanocomposition have been extensively applied to improve its charge transfer
property [14].
Nanostructured electrocatalysts for hydrogen fuel cells can harness the chemical energy of
hydrogen to convert electricity at a high-energy conversion efficiency of >70% without
combustion and pollution, owing to the slow kinetics of oxygen reduction reaction on the
cathode, which is primarily responsible for reduced voltage and low conversion efficiency.
The noble metal Pt has been regarded as the most active electrocatalyst for this reaction.
However, the high cost and scarcity of Pt greatly limit the development and widespread
commercial application. In the past two decades, many different catalysts such CrN, WC, and
Mo2C have been studied to replace Pt [15]. Although none of them has a comparative catalytic
activity as Pt, their resource is abundant and available at low cost.
3. Outline of the book
The primary focus of the book is on developing advanced materials for hydrogen production,
storage, and utilization. Unravelling structure-related chemical/physical properties of these
materials plays an important role in designing high-performance materials. The chapter is
concluded with a descriptor of chemical and physical properties of materials.
Chapter 2 presents electron-microscopic, energy-dispersion, and optical (IR-absorption and

low-temperature (4.5 K) photoluminescence) investigations of InSe- and GaSe-layered crystals
intercalated using the below considered methods with various concentrations of hydrogen or
hydrogen-containing molecules such as water, toluene, and alcohol. These materials have
promising applications of these layered matrices (and powders from them) when creating
operation elements of solid hydrogen accumulators. At the same time, these InSe- and GaSe-
layered crystals themselves with different types of conductivity and their thin-layer interca‐
lates as well as other similar compounds can be considered as promising candidates for
creation of various hybrid-layered structures for flat flexible displays. Chapter 3 presents the
extensive studies for understanding hydrogen bonding interaction mechanism in biomole‐
cules, which is favorable to develop hydrogen production technology by biomass approach.
As an example for hydrogen storage, hydrogen desorption/adsorption processes in a metal

hydride bed reactor are simulated using the software COMSOL Multiphysics to study the
Introductory Chapter 7
diffusion and heating of hydrogen and metal hydride powder in both radial and axial
directions. They are presented in Chapter 4. The model consists of a system of partial differ‐
ential equations (PDE) describing two-dimensional heat and mass transfer of hydrogen in a
porous matrix. The influence of the operating parameters such as temperature, pressure,
concentration, permeability, and thermal conductivity on the rate of absorption/desorption of
hydrogen in metal hydride will be fully discussed. The simulation results obtained could be
applied to the on-board hydrogen storage technology, in particular for the hydrogen supply
of a fuel cell for powering of a hydrogen fuel cell vehicle.
Chapter 5 reports a research progress on hydrogen storage based on metal amidoboranes and
their derivatives. Extended from ammonia borane as high-capacity hydrogen storage materi‐
als, thermodynamic tailing of dehydrogenation of metal amidoboranes, metal borohydride–
ammonia borane complexes, and metal amidoboranes ammoniate as well as their derivatives
was studied with emphasis on syntheses, crystal structures, and dehydrogenation properties.
These studies clearly are greatly important to further design novel high-capacity hydrogen
storage materials. In addition, the authors also summarize nanoconfinement and nanocatalysis
of ammonia borane and metal amidoboranes, and their derivatives.
Author details
Jianjun Liu*
Address all correspondence to: [email protected]
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shang‐
hai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China
References
[1] L. Vayssieries, On Solar Hydrogen and Technology, John Wiley and Sons, Singapore,
2009.
[2] S. S. Mao, S. Chen, International Journal of Energy Research 31 (2007) 619–636.
[3] F. D. S. Marquis, Journal of the Minerals Metals and Materials Society 63 (2011) 43.
[4] X. Chen, S. Shen, L. Guo, S. S. Mao, Chemical Reviews 110 (2010) 6503–6570.
[5] S. Shen, J. Shi, P. Guo, L. Uo, International Journal of Nanotechnology 8 (2011) 523–591.
[6] S. Shen, S. S. Mao, Nanophotonics 1 (2012) 31–50.
[7] Y. W. Li, R. T. Yang, Journal of the American Chemical Society 128 (2006) 726–727.
[8] N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O’Keeffe, O. M. Yaghi,

Science 3 (2003) 1127–1129.
[9] S. S. Han, H. Furukawa, O. M. Yaghi, W. A. Goddard, Journal of the American Chemical

Society 130 (2008) 11580–11583.
[10] A. Fujishima, K. Honda, Nature 238 (1972) 37–38.
[11] S. U. M. Khan, M. Al-Shahry, W. B. Ingler Jr., Science 297 (2002) 2243–2245.
[12] A. I. Hochbaum, P. Yang, Chemical Reviews 110 (2010) 527–546.
[13] Y. J. Lin, G. B. Yuan, R. Liu, S. Zhou, S. W. Sheeha, D. W. Wang, Chemical Physics Let‐
ters 507 (2011) 209–216.
[14] K. Sivula, F. Le Formal, M. Gratzel, ChemSusChem 4 (2011) 432–449.
[15] H. Zhong, X. Chen, H. Zhang, M. Wang, S. S. Mao, Appllied Physics Letters 91 (2007)
163103.
Section 2
Hydrogen Production
Chapter 2
Characterization and Optical Properties of Layered InSe

and GaSe Crystals Intercalated with Hydrogen and
Hydrogen-Containing Molecules
Yuriy Zhirko, Vasiliy Grekhov, Nikolay Skubenko,

Zakhar Kovalyuk and Taras Feshak
Abstract
Described in this review are our electron-microscopic, energy dispersion, and optical (IR
absorption and low-temperature (4.5 K) photoluminescence) investigations of layered InSe and
GaSe crystals intercalated using the considered below methods with various concentrations of
hydrogen or hydrogen-containing molecules (HCM) of water, toluene, and alcohol. It has been
shown that these crystals are efficiently intercalated–deintercalated (IC–DIC) not only with
hydrogen but also with HCM. It has been ascertained that the layered crystals kept for a long
term in natural conditions contain molecules of water and carbon dioxide gas in the subsurface
area, where their concentration increases with time. It has been shown that the concentration
of molecules intercalated into the crystal decreases when deepening inside its bulk both along
crystal layers and the normal to them. Also adduced were empirical equations relating
concentration distribution of molecules intercalated into the crystal with the duration of IC–
DIC processes. Ascertained are the optimal dimensions allowing to efficiently perform IC–DIC
of the whole crystal bulk. It has been shown that the IC–DIC process in time has the look of a
hysteresis loop—fast initial growth of the HCM concentration with the following slowdown
when intercalating and fast drop with the following retardation when deintercalating under
permanent evacuation of the chamber with the crystal. The availability of two types of
conductivity in n-InSe and p-GaSe crystals causes some features in the emission spectra of the
crystals intercalated with hydrogen or HCM. In the case of n-InSe crystals, the availability of
HCM results, in the whole, in predominant emission of free excitons, and in the opposite case
of p-GaSe crystals, the recombination of carriers via deep centers becomes predominant.
Keywords: Layered crystals, intercalation, SEM, EDX, photoluminescence
1. Introduction
Unique chemical bonds—strong ion-covalent hybrids-p3-bonds inside crystalline layers and

weak van der Waals ones between layers, which take place in layered InSe and GaSe single
crystals, provide the possibility to introduce foreign atoms and molecules into their interlayer
space by using intercalation. From the practical viewpoint, these crystals and their intercalates
are promising materials for solid-state hydrogen accumulators, electric power, and solar cells
as well as for numerous applications in other tasks.
As it was shown in [1], the electrochemical intercalation of hydrogen into InSe and GaSe
crystals results in changing their physical properties. In particular, spectra of exciton absorp‐
tion in these crystals demonstrate two-dimensional localization of exciton movement inside
the plane of crystal layers, and NMR spectra show resonance absorption of electromagnetic
radiation by hydrogen molecules available both in the interlayer and intralayer spaces of the
crystals. In this case, the chemical shift of the energy level inherent to molecular hydrogen in
these crystals depends both on the hydrogen concentration and crystal temperature, while the
intensity of resonance absorption bands for this hydrogen depends on direction and value
chosen for applied magnetic field relatively to the plane of crystal layers. Calculations
performed using the model of 2D and 3D localization of hydrogen molecules in the layered
crystals showed [1] that the processes of intercalation and deintercalation of molecular
hydrogen take place with participation of full-symmetric optical vibrations in the crystal
lattice, which modulate the width of potential wells and barriers. Results of investigations [1]
also showed that the hydrogen concentration in these crystals reaches considerable values
comparable with the concentration of molecules in the very matrix and in powders of the
crystals the amount of hydrogen molecules after the sufficient duration of intercalation can
exceed the amount of matrix molecules by 2–2.5 times.
The aim of this work was to study changes of physicochemical properties arising in InSe and
GaSe crystals in the course of intercalation with hydrogen, water, and more complex hydrogen-
containing molecules of alcohol and toluene, as well as to obtain information about spatial
distribution of the concentrations inherent to intercalated molecules in these crystals and
dynamics of their deintercalation from the crystals by using the methods of optical and electron
microscopy, energy dispersion, VIS, and IR spectrometry. In Section 2, we have adduced some
(necessary to discuss the results obtained in this work) information about InSe and GaSe
crystals, their physicochemical properties, and ways for the intercalation of simple nonorganic
and organic molecules into these layered crystals. Section 3 describes results of our optical-
microscopic, electron-microscopic, and energy dispersion investigations of InSe and GaSe
crystals intercalated with hydrogen-containing molecules of water, alcohol, and toluene.
Adduced in Section 4 are the results of investigations concerning GaSe crystals kept for more
than 30 years in natural conditions of ambient medium (“aged” crystals). Concentrations and
chemical composition of molecules embedded from ambient medium in the process of natural
intercalation into the subsurface area of the aged crystals are estimated there. Also, the
estimates of spatial distribution inherent to simple nonorganic molecules in the bulk of the
Characterization and Optical Properties of Layered InSe and GaSe Crystals Intercalated with Hydrogen... 13
layered crystals within the volume scales of > 1 cm3 down to < 1∙10–10 cm3 are made in both 2D
and 3D versions. Besides, the results of investigations aimed at infrared light absorption by
the aged GaSe crystals within the range of valence vibrations intrinsic for molecules of water
and carbon dioxide are discussed; adduced are the analytical expressions relating the depend‐
ences of water molecules concentration in these crystals with the duration of their intercala‐
tion–deintercalation; given are recommendations concerning the spatial dimensions of the
crystals from the viewpoint of their efficient application in hydrogen energetics.
Section 5 of the work describes the results of low-temperature investigations aimed at

photoluminescence spectra of InSe and GaSe crystals intercalated with hydrogen molecules
as well as molecules of water, alcohol, and toluene (containing OH and CH groups) with the
purpose to ascertain the influence of their intercalation (including their passivation) on optical
properties of these crystals within the range of the fundamental electron (exciton) transition.
In summary, using the examples of InSe and GaSe crystals, we have presented generalized
conclusions about the character of processes related with the intercalation–deintercalation of
simple nonorganic and organic molecules into the layered crystals as well as their influence
on physicochemical properties of these crystals in the context of applying these layered
matrixes (not containing carbon) in hydrogen energetics.
2. Experimental methods
InSe and GaSe layered crystals considered in this chapter belong to binary compositions A3B6,
in which crystalline layers are composed of four monolayers of Se and In(Ga) atoms, located
one above another, in the sequence Se-In(Ga)-In(Ga)-Se and united together by ion-covalent
hybrid sp3-bonds. Inside these crystalline layers, the orientation of atoms correspond to the
spatial group D3h. In this case, each In(Ga) atom inside the crystalline layer provides the three
nearest Se atoms with two own valence electrons to fill their p-shells, while one remaining
electron together with another excess electron of the adjacent In(Ga) atom forms the completed
s-shell. As a result, orbitals of valence electrons are localized inside the layer and practically
do not overlap with orbitals of valence electrons from neighboring layers. As a consequence,
there is a weak molecular van der Waals bond between these crystalline layers. This clearly
pronounced anisotropy of chemical bonds between crystalline layers as well as inside these
layers allows the intercalation of layered crystals, i.e., introduction of foreign atoms or
molecules into interlayer space of a grown crystal. For instance, in the case of InSe and GaSe
crystals, the volume of van der Waals space (the so-called “van der Waals gap”) is equal to 40–
45% of the total crystal volume, and the internal surface of this space is close to (2–2.5) 103 m2
in 1 cm3.
It is well known [1–4] that InSe and GaSe single crystals grown by the Bridgman method have
four polytypes (β, δ, ε, and γ) that differ between each other by the sequence of packing the
crystalline layers. As a rule, InSe single crystals have the γ-polytype with rhombohedral
(trigonal) crystalline structure (spatial group C53v, the primitive unit cell of which contains one
In2Se2 that comprises three layers). The nonprimitive hexagonal unit cell comprises three
crystalline layers and consists of three molecules In2Se2. GaSe single crystals have ε-polytype.
They belong to the hexagonal crystalline structure (spatial group D13h), the unit cell of which
consists of two Ga2Se2 molecules located in the framework of two crystalline layers.
Parameters of the crystalline lattice inherent to γ-InSe and ε-GaSe crystals are well investigat‐
ed. In the case of ε-GaSe, they are as follows: the lattice parameter along the direction perpen‐
dicular to the layers is C0 = 15.95 Å, and inside the layer plane it is a0 = 3.755 Å [5]. For γ-InSe,
they are, respectively, C0 = 25.32 Å and a0 = 4.001 Å. The distances between the nearest atoms
inside the layer are as follows: CIn-In = 2.79 Å and CIn-Se = 2.65 Å, angle <φ = 119.3°, layer thickness
C1 = 5.36 Å, distance between layers Ci = 3.08 Å, and the distance between the nearest Se atoms
in adjacent layers CSe-Se = 3.80 Å [6].
Undoubtedly, the unique properties of this class of semiconductor compounds, in particular,

InSe and GaSe crystals, attract special attention of researchers because the heterostructures
based on them not only possess high photosensitivity and can be applied in solar cells [7–9]
and accumulators of electric energy [10] but are also rather promising for the creation of γ-
radiation sensors, as it follows from [11]. At the same time, as it was shown in recent studies
[1, 12–14] that the layered InSe and GaSe crystals can be applied in hydrogen energetics as
operating elements in solid hydrogen accumulators. The hydrogen concentration in powders
of these crystals can reach values close to х = 5–6, where х is the amount of embedded hydrogen
atoms per one formula unit in the matrix of intercalated crystal.
Figure 1 shows volume images of molecules related to hydrogen, water, alcohol, toluene, or
carbon oxide gas that were embedded into InSe and GaSe crystals by intercalation. The
following methods were used in these cases: electrochemical intercalation, intercalation under
pressure when working with hydrogen, or natural immersion deepening the samples to
solutions of water, alcohol, and toluene, or long-term (for 30 years) keeping the samples in
ambient atmosphere.
Figure 1. Volume images of molecules, namely, hydrogen, water, alcohol, toluene, and carbon oxide gas.
As seen from Figure 1, in their composition, majority of molecules have hydrogen. At the same
time, the molecules of water and alcohol contain the hydroxyl group О-Н, the molecules of
alcohol and toluene–carboxyl group С-Н, and the molecule of carbon oxide –C=O group.
2.1. The method of electrochemical intercalation

The method of electrochemical intercalation with using “pulling” electric field is presented in
Figure 2. It was used when intercalating the crystals with hydrogen. Previous studies [12, 13]
investigated layered InSe and GaSe crystals chemically intercalated with hydrogen, where the
authors used the one-chamber three-electrode cell [1, 15] (see Figure 2a). When current passes
through the cell, the composition of solution is changed due to redox processes taking place
both on operation and on auxiliary electrodes. Products of reactions that go at the auxiliary
electrode get to the zone of operation electrode and can interact with it, which results in
changing its potential and can lead to incorrect determination of the embedded intercalant
concentration.
Therefore, in this work, we used the cell separated by porous membrane spaces of operation
and auxiliary electrodes (Figure 2b). The application of this cell enabled us to separate
processes of oxidation and reduction and to prevent mixing solutions contacting with
operation and auxiliary electrodes.
Figure 2. (a) One-chamber cell; (b) separated cell. The scheme of the electrochemical cell for the intercalation of layered
InSe and GaSe crystals with hydrogen. 1—sample of InSe or GaSe (operation electrode, OE) 2—electrolyte; 3—opera‐
tion electrode; 4—chlorine-silver reference electrode, CE; 5—auxiliary electrode (AE); 6—case of the cell; 7—hole for
the sensor of pH-meter; 8—porous membrane; 9—potentiostate ПИ-50-1.
It is noteworthy that the electrochemical cell used in the process of intercalating the layered
crystals with hydrogen should satisfy the following requirements:
• Material of the cell should not interact with electrolyte. In our case, the cell was made of
silica glass.
• Cell should be hermetic. It is acceptable to use Teflon, vinyl plastic, or chemical-resistant
rubber.
• Space between operation and auxiliary electrodes should be separated with a porous
membrane, for example, with the glass Schott filter.
• Cell design should provide measurements of the electrolyte pH level during the intercala‐
tion process.
When carrying out electrochemical intercalation, InSe and GaSe single crystals were used as
the operation electrode. Their samples had the shape of parallelepiped. In accord with the
method [16], thin copper wire was soldered to the sample from side opposite to that contacting
with electrolyte. Another end of this wire was taken off through the cork and added to the
potentiostat. As a reference electrode, we used the chlorine-silver electrode of industrial
production. A thin platinum wire soldered in glass served as an auxiliary electrode.
To prepare electrolyte, we used concentrated hydrochloric acid of the “chemically pure” grade
diluted in bidistilled water. H ions were embedded into the layered InSe and GaSe crystals as
a result of cathode polarization in galvanostatic conditions (іа = 50–100 μA/cm2) from 1 N HCl
water solution under potentials of the operation electrode that did not allow release of gas-
like hydrogen. The process was carried out like that used in electrolysis bath under permanent
control of the operation electrode potential with using the chlorine-silver electrode deepened
into 1 N HCl solution. In the course of intercalation, the electrolyte pH level was measured
using the pH-meter НІ-8314 through the special hole in the cell cork. The fact of intercalation
with hydrogen ions was confirmed using chemical analysis.
The concentration of embedded hydrogen was determined via the amount of electrical charge
passed through the cell, i.e., using the controlled parameters of intercalation process: the
current density (j) and the duration of the process (t). This process is described by the following
relation [17]:
éa ( t ) + b ( t ) ùû
C0 ( i , t =
) A × eë , (1)
where С0(i, t) is the amount of embedded intercalating ions per unit volume of the crystal; α(t),
β(t) are some linear functions of embedding process duration; і is the current passing through
the cell; and А is the coefficient of proportionality.
The influence of embedded protons concentration on properties of indium monoselenide was
studied using the same group of samples by their step-by-step additional intercalation. This
process was accompanied by a shift of the value of equilibrium electrode potential inherent to
initial material. Taking into consideration the fact that the stationary potential Е for the initial
nonintercalated indium selenide is close to 0.25 V, and data of chemical analysis show that the
higher hydrogen content is corresponded by the higher negative Е value, one can draw a
conclusion that the obtained shift of the equilibrium potential after intercalation is related with
the creation of hydrogen compounds embedded.
2.2. Natural intercalation of InSe and GaSe single crystals
In this work, we also investigated intercalation processes in InSe and GaSe single crystals under
pressure 2 to 5 atm in sealed silica ampoules filled with molecular hydrogen, or using the
natural way by deepening the crystals into chemically pure solutions of water, alcohol, and
toluene. In addition, we studied the samples of GaSe crystals that were kept for 30 years in
ambient atmosphere. To perform physicochemical investigations of naturally intercalated

single crystals, from monocrystalline InSe and GaSe ingots, we cut discs and then prepared
plates with the thickness 3 to 5 mm and lateral dimensions 5 × 5 mm2.
Natural intercalation with hydrogen under pressure was realized within the range of 2 to 5
atm in hermetic cells at the temperature 200°С for 3–4 hours. The natural immersion interca‐
lation of the samples with molecules of water, alcohol, or toluene was performed at room
temperature in silica ampoules by deepening them into chemically pure solutions of corre‐
sponding substances for 35 and 165 days. After finishing the process, the intercalated samples
of InSe and GaSe were withdrawn from solutions.
2.3. The method for the deintercalation of hydrogen from layered crystals
Hydrogen deintercalation from electrochemically intercalated layered HХInSe and HХGaSe

crystals were performed for 3–9 hours at T = 110°C in vacuum under constant pumping out.
It was ascertained that the degree of deintercalation in the HХInSe samples practically linearly
grows with the hydrogen concentration from 60% for x → 0 up to 75–80% for x → 2. When
increasing the hydrogen concentration up to x → 4, the degree of deintercalation in HХInSe
and HХGaSe crystals grows up to 85%. Investigation of powder-like InSe and GaSe crystals
showed that the hydrogen concentration in them can reach the values x = 5–6, while the degree
of deintercalation can reach 90%. Deintercalation of gases from the crystals kept for 30 years
in natural conditions was carried out inside a vacuumed chamber. This method will be
described below, when discussing the results of EDX investigations.
3. Physical properties of InSe and GaSe crystals intercalated with hydrogen

and hydrogen-containing molecules
As it was shown by the previous electron-microscopic investigations of InSe and GaSe crystals
electrochemically intercalated with hydrogen [1], even the 80,000-fold magnification, in the
whole range of investigated hydrogen concentrations x from 0 up to 4, where x is the amount
of molecules per one molecular unit of the matrix, electron images of crystalline surfaces have
no formations of structural defects related with embedding hydrogen into these crystals. At
the same time, small-angle XRD investigations showed [1, 14] that, with increasing the
concentration of intercalated hydrogen, as a result of intercalated hydrogen pressure on the
matrix, there grows deviation of matrix parameters in intercalate HXGaSe from classical values
in GaSe crystals (hexagonal group 9,6/mmm). In particular, for HХGaSe crystals at T = 300 K
and x = 1.0, the parameter C0 is increased by 0.031 ± 0.003 Å from C0 = 15.94 Å up to C0 = 15.971
Å, and the parameter a0 by 0.006 ± 0.003 Å from a0 = 3.753 Å up to a0 = 3.759 Å.
It is noteworthy that, despite essential deviation of the lattice parameter after hydrogen
intercalation from classical values, electron-microscopic images of crystal surfaces remain
practically invariable even for high hydrogen concentrations, and any additional formations
of nonuniformities on surfaces or inside the samples are not observed. At the same time, as it
was ascertained in [1], the samples of GaSe crystals contain residue of the monoclinic phase of
red β-Se, and dimensions of these inclusions do not exceed 1 mkm. The inclusions disappear
after annealing of the crystals in a silica ampoule for 3 hours in vacuum at the temperature Т
= 350°С.
Investigation of EDX spectra taken from surfaces of InSe and GaSe crystals performed using
the scanning microscope Zeiss EVO 50 XVP equipped with the detector INCA ENERGY 450
showed that chemical compositions of these crystals are as follows: 49.3% Se atoms and 50.7%
In atoms in InSe crystals as well as 50.08% Se atoms and 49.92% Ga atoms in GaSe crystals.
3.1. Crystals intercalated with hydrogen-containing molecules
To study the influence of intercalation with hydrogen-containing molecules (HCM) of water,

alcohol, and toluene on the crystals InSe and GaSe, we carried out optical, electron-microscopic
(SEM), and energy-dispersed (EDX) investigations of the samples intercalated with HCM for
35 and 165 days. To reach it, we prepared six samples of InSe and the same amount of GaSe
crystals intercalated naturally with molecules of above substances for 35 and 165 days,
respectively, as well as reference samples of nonintercalated crystals and those electrochemi‐
cally intercalated with hydrogen. When performing this part of work, we used electron
microscopes of the firm TESCAN-SEM VEGA 3, SEM MIRA 3 with an immersion magnetic
lens, two-beam SEM LIRA 3 equipped with energy-dispersed EDX spectrometers X-Max or
BRUKER, as well as optical transmission microscope Primo Star 5 of the firm Carl Zeiss.
As can be seen in Figure 3, after the intercalation of the crystals with HCM (in particular, GaSe
crystals with water for 165 days) even for 1,000-fold magnification in the optical microscope,
one can observe the formation of a bubbled surface. More clearly pronounced such a surface
can be seen in Figure 4 when using 50,000- or 100,000-fold magnification in the electron
microscope SEM MIRA 3 with an immersion magnetic lens.
It is interesting that the same changes with the formation of bubbles after intercalation with
water take place in InSe crystals, too. However, when intercalating the samples InSe and GaSe
with alcohol or toluene, the formation of bubbled surfaces is essentially less pronounced as
compared to the case of water.
It should be noted that under low magnification (Figures 5–7), sample surfaces with clear
images of bubbles border with other surfaces where one can observe quite different formations
(see light areas). For the case of 30,400-fold magnification, these areas are represented in Figure
6 as a color version. As can be seen, under this magnification, they take a look of some bushes
or dendrites located at the crystal surface.
Demonstrated in Figure 7 as an example is the look of the surface for sample 2 (GaSe, H2O, 35
days) obtained in the regime BSE + SE using SEM VEGA 3 with magnification 5,000. As one
can see, after intercalation with water for 35 days, the sample surface is not so developed with
dendrites as compared to that after long-term intercalation.
To ascertain the nature of these dendrites, we perform additional SEM and EDX investigations.
Shown in Figure 8 are SE and BSE images of the GaSe crystal surface after intercalation with
Figure 3. Optical transmission images of the GaSe crystal before (a) and after (b) its intercalation with water for 165
days, obtained using the transmission microscope Primo Star 5 at 1,000-fold magnification.
Figure 4. Obtained using SEM MIRA 3 images of several points on the sample surface for the crystal GaSe (H2O, 165
days) with bubbles and remains of the β-Se phase for the accelerating voltage 5 kV: (a) point 1, magnification 50,000,
scale—1 mkm; (b) point 2, magnification 100,000, scale—0.5 mkm; (c) point 3, magnification 100,000, scale—0.5 mkm.
water for 165 days. Seen there are the dendrites after processing them by using the two-beam
electron microscope SEM LYRA 3. Lateral dimensions of the hollow etched out by the second
beam are close to 9 × 14 mkm, and its depth is 1.5 mkm. It is clearly seen that these dendrites
grows through the surface from the crystal bulk, while their “roots” remain inside the crystal.
Figure 5. BSE + SE images for the surface of the sample GaSe (H2O, 165 days) obtained using SEM VEGA 3 with mag‐
nification 5,000 and accelerating voltage 10 kV. Scale—20 mkm.
Figure 6. BSE + SE images for the surface of the sample GaSe (H2O, 165 days) obtained using SEM VEGA 3 with mag‐
nification 30,400 and accelerating voltage 30 kV. Scale—5 mkm. Color—after computer processing.
Figure 7. BSE + SE images for the surface of sample 2 (GaSe, H2O, 35 days) obtained using SEM VEGA 3 with magnifi‐
cation 5,000 and accelerating voltage 10 kV. Scale—20 mkm.
Figure 8. SEM LYRA 3, magnification 5,000. Scale—20 mkm.
To further ascertain the chemical nature of these dendrites, we use the same microscope SEM
LYRA 3. It enables us to choose one of the dendrite samples that remained on the surface after
cutting the hollow. Using the Ga-ion gun, this sample was fixed on the probe (see Figure 9).
Then the end of the probe was attached to the sample holder, soldered to it by using the same
gun and cut from the probe (Figure 10).
Figure 9. Spatial image of the dendrite fixed on the probe in SEM LYRA 3. Scale—1 mkm. Accelerating voltage 10 kV.
Figure 10. Spatial image of the residue of probe with the dendrite part fixed on the holder in SEM LYRA 3. Scale—20
mkm. Accelerating voltage 10 kV.
The dendrite sample on the probe, obtained in such a manner for EDX investigations, was
transferred to SEM MIRA 3 equipped with the immersion magnetic lens. As seen in Figure
11a, for 150,000-fold magnification the dendrite structure is rather complex in 3D space. Under
500,000-fold magnification and the slope of the subject table 40° relatively to Z-axis, shown in
Figure 11b is the image of one pin of the dendrite. It is clearly seen that the shape of the pin is
close to cylindrical or cone-like. Its diameter at the end reaches 25–50 nm and is narrowed with
the step 15 ± 2 nm. The same electron microscope SEM MIRA 3 enabled us to perform EDX
investigations and ascertain that these dendrites mainly consist of Se atoms and, as seen from
Figure 8, grow from the foreign phase of remaining β-Se.
Figure 11. SE images of surfaces in sample 1 (GaSe, H2O, 165 days) taken from areas with dendrites for very small WD.
Microscope SEM MIRA 3, accelerating voltage 5 kV; magnifications: 150,000-fold (a) and 500,000-fold (b), scales—200
and 100 nm, respectively.
Energy dispersion investigations of GaSe crystal surfaces after water intercalation for 165 days
also enabled to ascertain (see Tables 1 and 2) that in areas of dendrite localization, the oxygen
concentration is approximately 3 times higher than in areas of minor amount of dendrites.
When water molecules are present on the surface of crystals (in particular, GaSe), it can indicate
the formation of developed complexes with β-Se accompanied by Ga2O3 crystallites. As it
follows from the tables, the increase in the Se concentration in these areas also correlates with
these conclusions.
It should be noted that the formation of dendrites at the presence of water is more clearly
pronounced in GaSe crystals than in the InSe ones, which is caused by different types of
conductivity in these crystals. In accord with [18], it is dominance of acceptors over donors in
GaSe crystals that causes precipitation of residual β-Se phases as well as binding and layering
the crystalline layers during growth of these crystals. The results of performed investigations
allow concluding that the formation of bubbled surfaces in the course of intercalation with
HCM is caused by partial layering along the van der Waals gap and filling this space of the
crystal with molecules of water, alcohol, or toluene. It is seen from the example of GaSe that
lateral dimensions of bubbled formations are commensurate with inclusions of residual β-Se
in nonintercalated crystals and lie within the range 0.1 to 1.0 mkm.
Element Series Unn. C norm. C Atom C Error (1 Sigma)

[wt. %] [wt. %] [at. %] [wt. %]
Dendrites
Carbon K-series 0.00 0.00 0.00 0.00
Oxygen K-series 6.16 9.52 33.15 1.03
Gallium K-series 20.63 31.86 25.46 0.63
Selenium K-series 37.96 58.62 41.38 1.23
Total : 64.75 100.00 100.00
Bubbles
Carbon K-series 0.00 0.00 0.00 0.00
Oxygen K-series 2.22 2.80 11.85 0.47
Gallium K-series 33.94 42.77 41.51 0.98
Selenium K-series 43.19 54.43 46.64 1.38
Total : 79.35 100.00 100.00
Table 1. Distribution of chemical elements over the areas with dendrites and bubbles in sample 1
IC duration HCM concentration
H 2O C2H5OH C7H6
35 days 12% 6.0% 5.2%
165 days 25% 12,5% 9,9%
Table 2. HCM concentration in GaSe and InSe intercalates
Similar energy dispersion investigations were carried out using the crystals InSe and GaSe
intercalated with toluene and alcohol for 35 and 165 days. The obtained concentrations of
oxygen atoms after intercalation with water, of oxygen and carbon atoms after intercalation
with alcohol, and of carbon after using toluene enabled us to estimate concentrations of HCM
molecules as well as their dependences on the time of intercalation. The results of calculations
shown in Table 2 confirm that the HCM concentration in the layered InSe and GaSe crystals
grows by two times, when the duration of intercalation is increased from 35 to 165 days. It
allows making the first estimate of the dependence of the HCM concentration in these crystals
on the time of deepening the sample in the respective solutions of HCM by using the following
simple analytical expression
A ( t ) =A0 × A0 × t , (2)
where A(t) is the concentration of molecules intercalated into crystal, A0 is the fitting parameter
for the crystal and solution, and t is the time of intercalation.
3.2. Conclusions
The performed optical, electron-microscopic, and energy-dispersed investigations enabled

authors to ascertain that nonintercalated crystals do not possess stoichiometric composition.
For instance, the chemical composition of crystals InSe and GaSe has the following atomic
ratio: 49.3% Se atoms and 50.7% In atoms in InSe crystals as well as 50.08% Se atoms and 49.92%
Ga atoms in GaSe. It is well correlated with their conductivity, namely, n-type for InSe and p-
type for GaSe. The amount of residual β-Se in the interlayer space of GaSe crystals is much
higher than that in the InSe ones.
It has been ascertained that the concentration of water, alcohol, and toluene molecules even in
the case of the natural intercalation of InSe and GaSe crystals with time can reach considerable
values (x → 1) commensurate with those after electrochemical intercalation.
It has been found that
i. molecules containing hydroxyl group (OH) are embedded into InSe and GaSe crystals
better than molecules containing the only carboxyl group (CH);
ii. contrary to the case of hydrogen, high concentrations of HCM (when x → 1) lead to
the blistering of the crystals and formation of bubbles in the interlayer space, which
are filled with separate HCM or their liquids;
iii. long-term intercalation with HCM (especially with water) results in the formation of
dendrites on the surface of InSe and GaSe crystals, which have a look of bushes
consisting of red monoclinic β-Se that forms (accumulates) in the process of synthesis
of these crystals. Geometrical dimensions of these bushes can reach 2 to 5 mkm. Their
pins have round or oval shape and diameter within the range 25–50 nm, they are
narrowed to their ends with the step 15 ± 2 nm;
iv. since the amount of the residual β-Se in InSe crystals is lower than that in GaSe, the
amount of formed dendrites in them is lower, too;
v. in the areas where dendrites accumulate, one can observe an increased concentration
of HCM.
3.3. Acknowledgement
The authors express their sincere gratitude to the firm TESCAN for the given possibility to
carry out investigations by using the up-to-date samples of electron microscopes as well as to
its co-workers Ph.D. Martin Petrenec, Michal Svoboda, Jiri Dlugos for their assistance in
performing the part of this work, when studying the crystals InSe and GaSe intercalated with
hydrogen-containing molecules.
4. Electron microscopy and energy dispersion investigations of GaSe

crystals kept in natural ambient conditions
Presented in this chapter are the results of SEM and EDX investigations aimed at percentage
and distribution of atmosphere gases in GaSe crystals kept for more than 30 years in natural
ambient conditions of the medium geographic belt—in summer at temperatures up to +35°С,
in winter down to –35°С, and air humidity from 30% up to 100%. With this aim, we chose to
cut 30 years ago flat monocrystalline GaSe plates of the 12-mm width and 6-mm thickness,
which were used for preparation of the samples with dimensions 10 × 12 mm and thickness 6
mm (in what follows, the crystals of the first type). Then the results of studying them were
compared with those inherent to the GaSe crystals of the second type—as-grown crystals
nonintercalated and intercalated with water. In detail, the crystals of the second type were
described in the previous chapter.
4.1. SEM and EDX investigations
Energy dispersion (EDX) investigations of the atmosphere gases content in the crystals of the
first type at surfaces containing planes of crystalline layers were performed using the scanning
electron microscope SEM VEGA 3 (TESCAN). As these crystals are semiconductors, the
investigations were performed without deposition of conducting layers on substrates, in the
regime of medium vacuum, when the residual pressure in the column and chamber was close
to 2∙10–2 Pa. Registration of secondary electrons was made using the standard SE detector.
Spectra of γ-radiation were measured using the energy-dispersed analyzer X-Max (OXFORD).
The optical image of the first type of GaSe crystal with the thickness 100 to 150 mkm obtained
using the transmission optical microscope Primo Star 5 with 1,000-fold magnification is shown
in Figure 12. It is seen that, in GaSe crystals of the first type as well as in those of the second
type intercalated with water (see Figure 3 in Chapter 2), volume images contain nonhomoge‐
neities that cannot be observed in as-grown crystals.
EDX investigations enabled to ascertain that the stoichiometric composition of Ga and Se atoms
in the first type of crystals is the same as in as-grown crystals of the second type (studied in
detail in [1]). At the same time, the results of these surface investigations showed the following:
1. There is a great amount of atomic oxygen in the crystals of the first type (see data in Figure
14d) as well as in the crystals of the second type intercalated with water.
Figure 12. (a) Optical image of the first type of GaSe crystal obtained using the transmission optical microscope Primo
Star 5 with 1,000-fold magnification. (b) SE image of the surface obtained for the same crystal under accelerating volt‐
age 12 kV and magnification 8,790 times. Scale—5 mkm.
2. On surfaces of crystals of the first type (Figures 12b and 12a) as well as in the crystals of
the second type intercalated with water (see Figures 4 and 5 in Chapter 2), one can observe
nuclei of residual β-Se phase and dendrites of monocrystalline β-Se.
3. In the bulk of the first type of crystals (Figure. 13b, fresh cleavages at the depth close to 1
mm from the surface), contrary to the second type of as-grown crystals, these nucleation
phases of residual β-Se cannot be already observed.
Figure 13. SE image for small WD taken: (a) from the crystal surface and (b) from the cleavage at the depth 1.1 mm,
obtained at the accelerating voltage 5 kV and magnifications ×44,100 and ×40,300, respectively. Scale—1 mkm.
Figure 14 shows the SE image of the first type of GaSe crystal under accelerating voltage 12
kV and magnification ×2,000. Marked with the point in Figure 14a is the area used for EDX
analysis. The spectrum of X-ray radiation corresponding to transitions of electrons between
inner shells of atoms and analysis of chemical elements made in the virtual program shell
INCA are represented in Figure 14c and in Figure 14d, respectively. It should be noted that
the results adduced in Figures 13a and 13b were obtained in the first day of investigations.
Figure 14. (a) Part of the first type of GaSe crystal and the point in it where EDX analysis was performed; (b) depend‐
ence of the size of analytical area Zm (see the insert) on the accelerating voltage of the probing electron beam, which
was obtained using Eq. (3.3) for oxygen (circles) and carbon (squares); (c) EDX spectrum of the point selected in Figure
14a; (d) chemical composition of elements in point 1 shown on a Figure 14a.
As it is seen from Figure 14d, in the points (and areas) containing no dendrites and residual
phases of β-Se, surfaces of the first type of crystals contain a large amount of carbon and oxygen
atoms. It is known that the Earth atmosphere mainly consists of molecules of nitrogen (78.1%),
oxygen (21), argon (0.9%), water vapors (0.5–1.5%), and carbon dioxide (near 1%). Since, beside
carbon and oxygen, other chemical elements present in the gas composition of the Earth’s
atmosphere were not found on the surface of the first type of GaSe crystals, it allows assuming
that natural subsurface areas of these crystals as well as corresponding areas of the second
type of crystals intercalated with water can contain a large amount of water molecules and
carbon dioxide from ambient atmosphere.
Unfortunately, the data available in this chapter do not allow separating the intrinsic amount
of carbon atoms in crystals of the first type from carbon available in the column and chamber
of the microscope. At the same time, we can assume that the first type of crystal surfaces contain
water and carbon dioxide molecules in approximately the same amounts. It permits us to
exclude carbon from further discussion and to focus on the availability of oxygen. In this case,
it is not excluded the possibility that subsurface area of the crystals in the presence of water
molecules and molecular oxygen is subjected to substitution of Se atoms with the oxygen ones
with the creation of a dielectric coating Ga2O3 in accord with the scheme
2GaSe + 3H 2 O => Ga 2 O 3 + 3H 2 + 2b -Se, (3)

or
2GaSe + 3O 2 => Ga 2 O 3 + 2b -Se. (4)
Previous investigations of the second type of crystals are indicative of the fact that the process
given by Eq. (3) is more preferable on the crystal surface in presence of water since it allows
explaining the growth of dendrites from monocrystalline β-Se in the areas of nucleation phases
of residual β-Se and probably decreasing amount of residual β-Se in the bulk of first type of
crystals. The process given by Eq. (4) in our opinion was happened in a subsurface crystal area.
Despite the described chemical processes of Ga2O3 formation in the crystals of the first and
second types, we assume that the main contribution to EDX spectra corresponding to presence
of oxygen is conditioned by molecules of water and carbon dioxide embedded in the process
of natural (atmospheric or immersion) intercalation into the layered crystal. In this case, as it
follows from data on a Figure 14c, up to two atoms of oxygen are available per one molecule
of Ga2Se2 in the matrix of the first type of crystals.
Since GaSe crystals of the first type contain a large amount of oxygen atoms from the compo‐
sition of H2O and CO2 molecules, the authors performed temporal investigations of the
processes related with the deintercalation of these molecules from the crystals. Every time after
performing the EDX investigations, the first type of crystals remained in the pumped out
chamber of microscope for 1 week. For this time, the residual pressure in the chamber increased
from 2×10–2 up to 2×102 Ра till the next day after measurements and up to 3.5×102 Ра till the end
of the week. Further, the next cycle of measurements was carried out.
Thus, seven cycles of measurements were repeated with the 1-week interval between them.
The results of EDX investigations (by using the accelerating voltages for electrons from 15 to
30 kV) are adduced in Figure 15a, while their averaged voltage values are summarized in Table
3. Also, for comparison, presented in this table are the results of previous EDX investigations
aimed at the second type of crystals after their intercalation with water for 35and 165 days.
K0 - averaged concentrations of water molecules per one formular unit of GaSe crustal in subsurface regionв
1-st type 2-nd type
1 day 1 week 3 weeks 5 weeks 7 weeks 35 days 165 days
108 % 78 % 67 % 33 % 13 % 12 % 25 %
Table 3. The percentage of water determined using the EDX spectra of water intercalates of the layered GaSe[H2O]X
crystals of the first and second types, where Х is the amount of water molecules per one formula unit of the crystal
The performed EDX investigations of the first type of crystals under the values of accelerating
voltages for electrons from 15 to 30 kV showed that, with increasing Zm—depth of penetration
typical for probing electron beam (calculated for oxygen atoms)—from 3.5 up to 13 mkm, the
parameter K0—concentration of oxygen atoms—decreases in the crystal. The increase in the
duration of evacuation also results in decreasing the oxygen concentration in the subsurface
layer (see Table 3 and Figure 15b).
These results are shown in Figure 15a with open squares, rhombs, and circles for the cases of
7-, 21-, and 35-day keeping the first type of crystal in vacuum. The skew cross designates the
water concentration in the subsurface area in the first day of investigations under the acceler‐
ating voltage 12 kV. It should be noted that the analytic area Zm of the probing beam for
chemical elements (in this case: gallium, selenium, oxygen, and carbon) was determined using
the adopted fitting formula
A
Z m = 0.033 × ( E01.7 - EC1.7 ) × , (5)
r ×Z
where E0 is the accelerating voltage (kV), EC is the minimum band emission energy (keV), A is
the atomic mass, ρ is the density (kg/m3), and Z is the atomic number.
Figure 15. (a) Squares, rhombs, and circles correspond to experimental values of the water concentration in the subsur‐
face area of the first type of crystal versus the depth of penetration typical for the probing electron beam in the case of
1-, 3-, and 5-week crystal being in vacuum, respectively. Crosses designate experimental values of the water concentra‐
tion in the first day of measurements at the depth 2.24 mkm as well as on the fresh cleavage at the distance 1,100 mkm
from the crystal surface and in the middle of the crystal at the depth 3,000 mkm obtained from IR investigations. The
curves 1–4 correspond to fitting 2D dependences of the water concentration versus the crystal depth. The dependences
were obtained in accord with Eq. (6) for the case of semi-infinite crystal. (b) The dependence of the fitting parameter Ко
on the duration of keeping the first type of crystal in vacuum for the case of semi-infinite 2D crystal. Curve 1 is approx‐
imation of the parameter К0 dependence on time.
As seen from Figure 15a, with increasing the volume of the analytic area Zm, the concentration
of oxygen atoms in each of these measurements drops with increasing the depth of probing
electron beam penetration into crystal. It allows ascertaining the relation between the param‐
eter K0—concentration of water on the surface of layered crystal and parameter K(z)—its
distribution along the depth in the crystal bulk (z) in the direction perpendicular to crystal
layers in the following form
e × K0 × ln ( z + 1)
K(z) = , (6)
z+1
where e = 2.718... is the Napierian base. Note that this dependence is obtained for the case of
semi-infinite crystal.
As seen from Figure 15a, the curves 1 to 3 both qualitatively and rather well quantitatively
describe experimental values of the water vapor concentration K(z) in the crystal of the first
type as a function of z-distance into the crystal bulk from its surface at fixed K0 values obtained
after 1-, 3-, and 5-week being in vacuum. In Figure 15a, curve 1 plotted for the first day of
measurements is indicative of a fast drop in the concentration of water molecules with depth.
It is also seen (Figure 15a, curve 4) that, with increasing the duration of evacuation, the
experimental values of the water vapor concentration K(z) in the crystal bulk begin to decline
from the theoretical ones. It confirms that water and carbon dioxide molecules faster go out
from subsurface areas and slower from the crystal bulk.
The similar phenomena of decreasing the water concentration are observed on the fresh
cleavages of the first type of crystals (see Figure 13b) when shifting the point of measurements
from an edge to the center. For instance, for the cleavage at the distance z = 1100 mkm from
the surface, the concentration of oxygen (measured immediately after obtaining the fresh
cleavage) is decreased from 5.5% to 4% on the area 500 × 500 mkm located in the center of the
sample down to 1.5–1.1% on the area 50 × 50 mkm in the same center. It indicates that in the
first type of crystals, the concentration of intercalated water and carbon dioxide gas is also
decreased in the lateral plane from the layer edge to its center. These results are shown in
Figure 13a, with the asterisk for the case of the first day measurements on the area 50 × 50 mkm
at the value z = 1100 mkm.
Thus, one can assume that the concentration of H2O and CO2 molecules in the layered crystal
decreases in the crystal bulk when moving from the surface into the bulk to its center—along
the perpendicular and in the plane of crystal layers. Shown for clearness in Figure 16a is the
3D sketch of concentration distribution for H2O and CO2 molecules in the layered crystal with
increasing the depth—along the perpendicular (z-axis) and in the plane of layers (x, y axes).
We suppose that this simultaneous decrease in the concentration when shifting into the bulk
as well as to the center of the sample is caused by the decrease in the amount of H2O and
CO2 molecules penetrating along the layers and perpendicularly to them at presence of
covalent intralayer and van der Waals interlayer forces. Like to the case of molecular hydrogen
intercalation in GaSe and InSe [1], this intercalation of H2O and CO2 molecules takes place due
to participation of A/1-full-symmetric intralayer vibrations of Ga2Se2 molecules.
These A/1 vibrations at room temperature are responsible for changing the width of potential
barriers (interlayer Ga–Se bound) and the widths of 2D (van der Waals gaps) and 3D (interlayer
space) quantum wells where the localization of molecules takes place. In the case of H2O
molecules, the localization of water vapors results in the formation of bubbles inside the
Figure 16. (a) The 3D sketch of distribution inherent to the concentration of water molecules in the layered crystal
within the plane (x, y) and along the perpendicular (z) to crystal layers. Also shown here is the 2D crystal cut in the
plane (y, z). (b) Dependence of the water molecule concentration on the surface of the second type of crystal on the
duration of the intercalation process. The circles and curve 1 correspond to the case of semi-infinite 2D distribution in
accord with Eq. (2); curve 2—for the “thin” crystal with the thickness h = 10 mkm; curve 3—for 3D crystal with the
cube face h = 10 mkm.
interlayer space, as it was shown in the previous chapter. The similar bubbles are also seen in
subsurface areas of the first type GaSe crystals.
Thereof, being based on Eq. (5) describing the distribution of water molecules along the
direction perpendicular to crystal layers (when the crystal is semi-infinite) and on the sketch
for the generalized 3D distribution of the concentration inherent to H2O and CO2 molecules
inside the crystal GaSe, one can estimate the distribution of the concentration K(z) for these
molecules in the case of a real crystal with the thickness z = h. Here, Eq. (5) should be trans‐
formed to the look
e × K0 × ln ( z + 1) e × K0 × ln ( h - z + 1)
K(z)2D = + , (7)
( z + 1) ( h - z + 1)
which reflects the 2D cut of concentration distribution in a three-dimensional crystal. The

integrated value of the molecular concentration for the 2D cut shown in Figure 16a at the fixed
crystal thickness z = h can be defined as
h
K2 D = ò K ( z ) d ( z ). (8)
0
Since in the first approximation one can assume that the distribution K(z) does not depend on
direction within the plane (x, y), the integrated value of specific molecule concentration in the
bulk crystal of a cubic shape with faces h should have the following look
3
K3 D = ( K2 D ) 2 . (9)
In accord with Eq. (8), Figure 17 shows the function for 2D distribution of concentrations for
H2O and CO2 molecules and various values of the crystal thickness h. For convenience,
summarized in Table 4 are also the numeric values of the fitting parameter К0 on the surface
as well as integrated values for the concentration of water molecules K2D in the 2D cut and
K3D in 3D crystal bulk as a function of dimensions inherent to crystal faces (x, y, z).
Figure 17. The 2D cut distribution of the concentration K2D(z) in the case of infinite crystal with the thickness z = h.
As seen from Figures 17a to 17f, with decreasing the thickness of crystal, the integrated
concentration of molecules K2D in the 2D cut (area under the curve) increases from 3.4% for h
= 6000 mkm up to 94% for h = 10 mkm. In this case, the integrated concentration in the bulk
K3D (see Table 4) also increases from 0.63% up to 91%. In addition, the contribution from
opposite faces becomes more essential due to this decrease of geometrical dimensions of the
crystal. In accord with Table 4, it results in a practically 2-fold decrease in the value of К0
parameter that defines the concentration of water molecules on the front face from K0 = 100%
for h = 600 mkm down to K0 = 52% for h = 10 mkm. For clearness, this case is adduced in Figure
17d as superposition of distribution functions K2Z from the opposite crystal faces.
In summary of this discussion, we shall perform juxtaposition of results obtained after EDX
investigations concerning deintercalation (in vacuum) of the first type samples with the similar
data obtained in the process of immersion intercalation of thesecond type samples for the case
of water molecules.
Length – (mkm):
Adjusting concentration of K0 Concentration K2D in case of Concentration K3D in
2D case x = y = ∞, z = h;
on a surfaces for 2D case, (%) 2D cross-section, % 3D case, %
3D case x = y = z = h
6000 100 3.4 0.63
600 99 18.5 38
60 90 67 55
30 80 80 72
20 70 88 83
15 66 92 88
10 60 94 91
5 52 91 87
Table 4. Values of the fitting parameter К0 and specific concentration K2D on thickness (z = h) for the 2D cut (x = y = ∞),
and for the specific concentration K3D for a cube with face dimensions x = y = z = h
4.2. The model of the process for the intercalation–deintercalation of water molecules from
GaSe crystals
In accord with the conclusions obtained in Section 3, the concentration of water intercalated
into the crystal GaSe of the second type is described with the Eq. (2).
Let us consider that the parameters A0 and K0 describing processes of intercalation and
deintercalation of water in GaSe crystals of the first and second types in the crystal subsurface
area are compatible with each other. They unambiguously describe the process of intercala‐
tion–deintercalation of water in layered crystals. (Note that in the case of the second type of
crystals, geometrical dimensions of crystals intercalated with water were 5 × 5 × 1 mm3.) It
follows thereof that in both cases of EDX investigations, the semi-infinite method of interca‐
lation–deintercalation of surfaces took place. Therefore, contribution to the fitting parameters
A0 and K0 from the opposite faces can be neglected. Then the processes of intercalation–
deintercalation in the crystal semi-infinite by its thickness are identical to each other and can
be described as follows
A (t , z ) º K ( z,t ). (10)
where the functions A(t) and K(z) have now the look A(t,z) ≡ K(z,t) = f(z,t). Then Eqs. (6) and
(2) can be transformed to the look
e × K0 ( t ) × ln ( z + 1)
K(z,t) = , a
z+1
and (11)
A ( t , z ) =A0 ( z) × A0 ( z ) × t . b
Thereof, if using the fitting parameter value A0 = 1.63 ± 0.5 obtained to describe water interca‐
lation into semi-infinite crystal of the second type, it follows that A(t) in the subsurface area
will reach the value equal to 100% in t = 6.5 ± 0.5 years. After keeping the sample in water for
30 years, in accord with Eq. (2) and curve 1 in Figure 14b, A(t) will reach the value 215 ± 5%,
which is 2-fold higher than after keeping the sample in ambient atmosphere.
Combining Eqs. (2), (8) and Eqs. (2), (9) with Eqs. (11a), (11b), one can prove that with de‐
creasing the thickness of quasi-infinite crystal down to h = 10 mkm (when the parameter value
of K0 = 50% is sufficient), the function А(t, z) (curve 2 in Figure 14d) will reach 100% in 600 ±
20 days, and when the crystal will be shortened to the cube with faces of 10 mkm, 100%
intercalation will occur in 150 ± 5 days (curve 3, Figure 14b).
Figure 18 shows a generalized process of intercalation–deintercalation of water in crystals

GaSe for the 3D case, when x = y = z = h = 10 mkm. Curve 1 is plotted in accord with Eq. (11b),
and curve 2 is in accord with Eq. (11a). Experimental points correspond to the values shown
in Figure 13b.
Figure 18. Scheme for the process of water intercalation–deintercalation into GaSe crystal. Curve 1 illustrates the proc‐
ess of intercalation in the cubic crystal with the face 10 μm, and curves 2 and 3 describe the process of deintercalation
from the infinite cubic crystal of the thickness 10 μm and cubic crystal with the face 10 μm, respectively. Open circles
show experimental values K0(t) on the surface of the crystal semi-infinite by its width.
As seen from Figure 18, the curve of intercalation–deintercalation looks like a hysteresis loop
—a rather long process of natural intercalation with water is followed by rather fast deinter‐
calation in vacuum under permanent pumping out. It is seen that the initial fast process of
deintercalation at high concentrations is changed for the slow one at low concentrations. To
provide full evacuation of water vapors, it needs period at least three times longer. It should
be noted that curves 1 to 3 in Figure 18 only qualitatively describe these processes. In practice,
these intercalation–deintercalation processes in crystals with small dimensions of faces are
considered by us theoretically and need additional experimental investigations.
Since similar dependences of the water concentration on the duration of intercalation were
also obtained for InSe crystals, we believe that the character of water intercalation–deinterca‐
lation processes in these crystals is analogous to that in GaSe crystals.
Additional investigations of light absorption by GaSe crystals of the first type were per‐
formed within the IR range of 2 to 5 μm, where vibrations of water molecules in the con‐
densed state and in the form of individual molecules as well as the carbon dioxide ones are
active. Dimensions of the studied crystals were identical to those described earlier. The
investigations did not find the bands related with water molecules in the condensed state. At
the same time, after subtraction of contribution made by atmosphere water vapors and carbon
dioxide gas, there remain weak bands related with molecules of H2O and CO2 inside the crystals.
Within the error of experiments (2 cm-1), using the CO2 molecules as an example, one can state
that the intercalation of these molecules into the layered matrix results in neither changes in
frequencies of “fan” vibrations inherent to these molecules nor the changes in the value of
splitting between them.
4.3. Conclusions
The obtained results enabled us to make the following conclusions:
1. The layered crystals are well intercalated with water vapors from Earth atmosphere and
deintercalated in the process of evacuation.
2. Water in the crystals of the first type is available in the molecular state close to that in
Earth atmosphere.
3. Water molecules are in the state that is not bound with the very crystal.
4. Under long-term storage in ambient atmosphere, the concentration of water molecules in
the subsurface area (10–20 mkm) of layered crystals becomes comparable with the
concentration of molecules in the very matrix.
5. In the crystals, volume of which is larger than (1 × 1 × 1) cm3, the integrated concentration
of water molecules under a long-term storage can exceed the concentration of water
vapors in atmosphere by 2 to 3 times.
6. The concentration of H2O molecules sharply drops when deepening inside the crystal
bulk.
7. Decreasing the crystal dimensions down to (10 × 10 × 10) μm3 allows to enhance the rate
of intercalation–deintercalation of water molecules in crystals of these dimensions.
5. Low-temperature investigations of photoluminescence spectra taken

from InSe and GaSe crystals intercalated with hydrogen and hydrogen-
containing molecules: comparative analysis
Photoluminescence spectra of InSe and GaSe crystals nondoped or doped with various
impurities have been rather well studied by many authors for approximately 50 years.
Therefore, being based on the previous results, one can study the influence of intercalation
with hydrogen and hydrogen-containing molecules (HCM) on electron (exciton) excitations
in crystalline matrixes of these crystals. Electron transitions in HCM themselves or in their

compositions from the ground state to the excited one as well as their following radiative
recombination cannot give any contribution to spectra of crystal edge photoluminescence since
their transition energies are much higher than the energy of fundamental transitions in these
matrixes.
Low-temperature spectra of photoluminescence (PL) were measured at T = 4.5 K by using 0.6-

m МДР-23 monochromator with the diffraction grating 1200 mm–1. PL excitation was provided
with stabilized solid semiconductor lasers of the power 100 mW with the wavelengths 532 and
671 nm. To avoid registration of the second orders from the diffraction grating, we used the
edge filters Semrock’s LP03-532RS and LP02-830RS. To detect the useful signal, we used the
photomultipliers ФЕУ-79 and ФЕУ-62 connected via analog–digital converter with PC. The
stabilization of temperature was provided with the accuracy 0.1 K in a liquid helium cryostat
by using the system УТРЕКС designed at the Institute of Physics (NAS of Ukraine). The
spectral slit width during experiments did not exceed 0.2 meV.
When carrying out this part of the work, we used the samples of InSe and GaSe crystals of the
second type of nonintercalated and intercalated with hydrogen, water, alcohol, and toluene in
various concentrations.
5.1. GaSe crystals
Shown in Figures 19a to 19f are the PL spectra of GaSe crystals intercalated with toluene, water,
and alcohol for 35 and 165 days and measured at T = 4.5 K. For comparison, PL spectra of
nonintercalated GaSe crystal (Figure 19g) are shown, as well as the crystal doped with Cd
(concentration 0.01 mass %) and irradiated with γ-quanta possessing the energies from the
range 0 to 34 MeV and doses up to 1014 γ-quanta/cm2 (Figure 19h). The latter crystal was earlier
investigated in [11]. Adduced in the inserts of Fig. 4.1 (b, d, f) are also the 2D sketches of spatial-
coordination ordering inherent to molecules of water, toluene, and alcohol. Figure 19 also
illustrates spatial images of these molecules.
As it can be seen in Figure 19, at the temperature Т = 4.5 K PL spectra of GaSe crystals inter‐
calated with toluene and water, like to the non-doped crystals or those doped with Cd, consist
of emission lines related with free excitons (A-line, λ = 587.8 nm), excitons localized near
stacking faults of crystal layers (Ad-lines), and bound excitons (В1 – В6-lines). Besides, one can
observe there wide doublet bands Р0/, P0 // that, as shown in [11] using the example of GaSe:
0.01 % Cd crystals, are caused by radiative recombination of carriers from direct (DCB) and
indirect (ICD) conduction bands to the acceptor level a1 located at 70 meV above the top of
valence band (VB). In accord with [11], this transition takes place with participation of TO
phonons. The energy positions of peaks А, Ad, B1-B6 lines and doublet of the band P0 are
summarized in Table 5.
As seen from Figure 19, the intercalation of GaSe crystals with toluene and water for 35 days,
if comparing with nonintercalated crystals, results in noticeable changes of PL spectra within
the range of free and bound excitons, namely, the intensity of A-line related with emission of
5.1. GaSe crystals
Shown in Figures 19a to 19f are the PL spectra of GaSe crystals intercalated with toluene, water, and alcohol for 35 and 165
days and measured at T = 4.5 K. For comparison, PL spectra of nonintercalated GaSe crystal (Figure 19g) are shown, as well
38 Advanced Materials
as the for Renewable
crystal doped Hydrogen Production,
with Cd (concentration 0.01 mass %)Storage and Utilization
and irradiated with γ-quanta possessing the energies from the
range 0 to 34 MeV and doses up to 1014 γ-quanta/cm2 (Figure 19h). The latter crystal was earlier investigated in [11].
Adduced in the inserts of Fig. 4.1 (b, d, f) are also the 2D sketches of spatial-coordination ordering inherent to molecules of
water, toluene, and alcohol. Figure 19 also illustrates spatial images of these molecules.
Figure 19. Measured at T = 4.5 K PL spectra of the crystals: a, b—GaSe[C7H8]; c, d—GaSe[H2O]; e, f—GaSe[C2H5OH]
intercalated for 35 and 165 days, respectively; g—GaSe; and h—GaSe:0.01Cd [11].
free exciton in the ε-GaSe crystal grows, while the intensity of Ad lines related with emission
of excitons localized within the ranges of stacking faults in crystal layersops.
It should be noted that the same phenomenon was observed in [11], when doping the crystals
with impurities Cd and Zn available in the concentration 0.01 mass % as well as after their
“radiation annealing” with γ-quanta of the energy from the range 0 to 34 MeV. In accord with
[11], it is related with “curing” the defects by Schottky and by Frenkel, respectively. However,
the effect of increasing the intensity of A-line emission and the respective drop in intensity of
Ad lines is much better observed in the intercalates GaSe[H2O] and GaSe[C7H8] than in the case
of doping with Cd and Zn and the following annealing of these GaSe crystals with γ-quanta.
Wave length of emission line and band peaks (nm)

Crystal
A Ad B1 B2 B3 B4 B5 B6 P0/, P0//
588.1,
GaSe 587.8 588.6, 590.9 592.6 594.1 596.5 599.1 600.4
589.3
588.0,
GaSe[C7H8] – 35
587.8 588.9, 590.5 592.6 593.7 596.4 597.6 600.5
days
589.7
GaSe[C7H8] – 165
587.9 589.2 590.4 592.5 593.5 596.1 597.5 600.2 607.2
days
GaSe[H2O] – 35
587.9 589.5 590.3 592.1 593.2 596.2 597.4 600.3 603.5, 606.9
days
GaSe[H2O] – 165
587.9 590.1 592.6 593.7 596.3 599.0 600.1 603.1, 606.3
days
GaSe[C2H5OH] –
588.9 590.7 593.0 605.8
35 days
GaSe[C2H5OH] –
606.0
165 days
GaSe:0.01Cd and
dose = 1014 γ/cm2) 587.6 588.5 591.5 593.6 600.4 608.0, 612.0
(data from [11])
Table 5. Positions of emission peaks for free and bound excitons at T = 4.5 K typical for GaSe crystals non-intercalated
and intercalated with HCM.
The following growth in the time of intercalation in these solutions for 165 days results in
increasing the emission intensity within the range of P0-bands. Despite the fact that this effect
is more clearly observed in the intercalates GaSe[H2O] (see the dashed line in Figure 19d) than
in the intercalates GaSe[C7H8], the integrated intensity of the emission spectra corresponding
to these intercalates (obtained for 165 days) remains the same as in those intercalated for 35
days.
At the same time, attention is attracted by the fact that the shape of PL spectrum typical for
the crystal GaSe[H2O] intercalated for 35 days is practically identical to that of the crystal
GaSe[C7H8] obtained by intercalation for 165 days. As follows from Table 2 (see Section 3.2),
it correlates with measurements of concentrations of H2O molecules (12.0%) obtained by the
intercalation of GaSe for 35 days and of C7H6 molecules (9.9%) obtained by intercalation for
165 days. Also, we take into account that the redistribution of the emission intensity, which is
observed in the long-wave range of the spectrum, is caused by transitions of carriers from DCB
(P0/) and ICB (P0//) to the a1 acceptor level with participation of TO phonons. However, as it
follows from Figure 19 and Table 6, the energy positions of P0-bands in the case of intercalates
GaSe[H2O] and GaSe[C7H8] are shifted into the high-energy range.
The intercalation of GaSe crystals with alcohol (Figures 19c and 19f) results in practically total
degradation of emission lines related with free excitons and those localized near stacking faults
in crystal layers, as well as excitons bound at point defects. In this case, at Т = 4.5 K, PL spectra
demonstrate only wide weakly structured bands with the peaks at 606.0 ± 0.5 nm (P0/, P0//) and
shoulder close to 614 nm. However, in this case, the integrated intensity of PL spectrum
remains practically the same as those in GaSe crystals intercalated with water or toluene. The
above energy positions of these bands allow their identification with radiative recombination
of carriers from DCB and ICB onto the a1 acceptor level located near 63 meV above the VB top,
which takes place with participation of TO phonons.
According to the data of Table 5, one can show that the energy position of a1 acceptor level
(which for nondoped GaSe crystal is located at 70 meV above the VB top) slows down in the
intercalates GaSe[C7H8], GaSe[C2H5OH] and GaSe[H2O] by 2.7, 6.7, and 15.8 meV, respectively.
5.2. InSe crystals
Shown in Figures 20a to 20f are low-temperature (T = 4.5 K) PL spectra of InSe crystals
intercalated with toluene, water, and alcohol for 35 and 165 days. For comparison, shown in
Figures 20g and 20h are PL spectra of InSe crystals nondoped and doped with Cd at the
concentration 0.01 mass % previously investigated in [19]. The PL spectrum of nondoped InSe
crystal (Figure 20g) is superposition of emission lines that correspond to (i) free excitons (A-
line, λ = 928.0 nm), (ii) excitons located near stacking faults in crystal layers (Ad lines), (iii)
excitons localized in the density-of-state tails (Al lines), and (iv) excitons related with point
defects of crystalline structure (В1–В6 lines), which are related with defects by Frenkel and
Schottky (see [19]).
Contrary to ε-GaSe, InSe crystals have rhombohedral symmetry of the crystalline lattice (γ-
modification), which is lower than that of ε-GaSe [2]. Therefore, the partial disordering of
crystal layers in InSe results in appearance of stacking faults in layers, namely, the areas of
mixed ε- and γ- modifications. In these areas, the band gap is larger than in the areas of pure
γ-modification, and excitons located in the mixed areas possess higher emission energies. The
energy positions of the respective lines and P0-bands at Т = 4.5 K are summarized in Table 6.
The intercalation of InSe crystals with molecules of toluene, water, and alcohol, as well as the
intercalation time, has an essential influence on their optical properties. It is clearly pronounced
(Figures 20a to 20f) in an essential decrease in the emission line intensity of bound excitons
(В1–В6 lines) and in the respective growth of emission lines related with free excitons as well
as excitons bound with stacking faults in layers and in the density-of-state tails. For compari‐
son, it should be noted that the same changes take place (Figure 20h) in PL spectra of InSe
crystals doped with Cd [19] or electrochemically intercalated with hydrogen (see insert in
Figure 20. PL spectra of the crystals at the temperature Т = 4.5 K: a, b—InSe[C7H8]; c, d—InSe[H2O]; e, f—InSe[C2H5OH], intercalated for 35
Figure and
20.165
PLdays,
spectra of the
respectively; crystals
g—InSe; at the [19].
and h—InSe:Cd
InSe:Cd Insert in h—HТ1.0InSe.
temperature = 4.5 K: a, b—InSe[C7H8]; c, d—InSe[H2O]; e, f—
InSe[C2H5OH], intercalated for 35 and 165 days, respectively; g—InSe; and h—InSe:Cd [19]. Insert in h—H1.0InSe.
Contrary to ε-GaSe, InSe crystals have rhombohedral symmetry of the crystalline lattice (γ-modification),
modification), which is lower
than that of ε-GaSe [2]. Therefore, the partial disordering of crystal layers in InSe results in appearance of stacking faults in
Figurelayers,
20h). Thereof,
namely, the areascontrary to γ-
of mixed ε- and γGaSe crystals,
modifications. intercalation
In these with
areas, the band gap hydrogen
is larger than in theor hydrogen-
areas of pure γ-
containing molecules, like to doping with elements of the second group of periodic table,
modification, and excitons located in the mixed areas possess higher emission energies. The energy positions of the
respective lines and P0-bands at Т = 4.5 K are summarized in Table 6.
results in essential improvement of the crystalline lattice in InSe crystals.
Crystal
An increase in theInSetime of927.5
intercalating
929.0 the InSe932.0
crystals
936.0 with
938.0 toluene,
- water, or alcohol leads
Ad A Al B1 B2 B3 B4 B5 B6 IFE
930.0 - -
to improvement of PL spectra: Ad lines begin to dominate, and the emission line of free exciton
typical for γ-modification appears in crystals intercalated with toluene. The value of blue shift
observed for Ad lines in the intercalated crystals relatively to A-line in nonintercalated γ-InSe
reaches the value 1.5 meV. It is also typical that В2–В4 lines corresponding to emission of bound
excitons in the crystals intercalated with water are split. In this case, the split states are located
in the long-wave range relatively standard positions of these lines, and the value of maximum
splitting for these lines approaches to 2.0 meV. It is indicative of a rather complex structure of
defects that provide bonding these excitons.

Crystal
Ad A Al B1 B2 B3 B4 B5 B6 IFE
InSe 927.5 929.0 930.0 932.0 936.0 938.0 - - -
InSe[C7H8] –
927.0 928.5 968.0
35 days
InSe[C7H8] –
927.0 928.0 928.9 935.0
165 days
931.9 938.5
InSe[H2O] – 935.6
926.9 927.9 929.1 - 933.1 939.7 945.0 - -
35 days 936.8
933.9 941.0
InSe[H2O] – 933.3 935.9

927.6 9292.4 929.8 938.7 946.1 951.9 -
165 days 934.3 936.5
InSe[C2H5OH]
927.3 929.1 936.0 957.4 965.3
– 35 days
InSe[C2H5OH]
926.8 928.9 933.5 936.1 937.6 944.2 968.0
– 165 days
InSe:0.01Cd
927.9 - 930.2 - 935.5 - - 950.0 972.0
(data [19 ])
Table 6. Positions of PL lines for free and bound excitons at Т = 4.5 K in nonintercalated and intercalated InSe crystals
Besides, in crystals InSe intercalated with alcohol for not so long time (35 days), one can observe
the wide band peaking at 966 nm that is caused by radiative recombination of free excitons
from indirect conduction band with participation of TO phonons. With increasing the time of
intercalation, this band decays.
5.3. Discussion
The performed investigations of PL spectra of InSe and GaSe crystals intercalated with toluene,
water, and alcohol allows stating that intercalation with HCM that contain carboxyl CH and
hydroxyl OH groups exert different influence on optical properties of these crystals. In InSe
crystals, intercalation with HCM considerably decreases the intensity of emission lines related
with bound excitons, which is a direct confirmation of improvement of the crystalline lattice
as a consequence of decreasing the amount of defects responsible for exciton bonding.
Vice versa, in GaSe crystals, increasing the time of intercalation with water and toluene results
in enhancing the intensity of radiation from bound excitons, while the structure of the line
inherent to free excitons is not practically improved. At the same time, the intercalation of GaSe
crystals with alcohol leads to full disappearance of emission lines both of free and bound
excitons, which is quite opposite to that observed in InSe crystals. In addition, the intercalation
of GaSe crystals with HCM results in lowering the energy position of the а1 acceptor level
relatively to the VB top.
We consider that these differences are caused by peculiarities of covalent bonds inside crystal
layers of these crystals. Thus, InSe crystals are more ionic than the GaSe ones [20]. It defines
the formation of a great number of various defects, which results in appearance of different
type conductivity, namely, n-type in InSe and p-type in GaSe. To expand discussion, let us
consider results of the studies [11, 19], where it was shown that doping the crystals InSe and
GaSe with low concentration of impurities (0.01 mass % of Cd or Zn) and the following
irradiation with γ-quanta results in the growth of integrated intensity of radiative recombi‐
nation. This growth takes place on the background of considerable lowering the PL intensity
of bound excitons relatively to that of free excitons. In this case (see Figure 20), the PL spectrum
of the InSe crystal doped with Cd impurity approaches by its shape and structure to the
spectrum of InSe intercalated with hydrogen, toluene, or alcohol.
Vice versa (see [11, 19]), doping the crystals InSe and GaSe with Ge or Sn results in a sharp
decay of the integrated intensity of radiative recombination. It allows making an assumption
that doping with elements of the second and fourth groups of periodic table influences the
growth of these crystals in a different manner. Moreover, even at low concentrations (0.01 mass
%), impurities of Cd, Zn, Ge, or Sn are nonuniformly distributed in these crystals, and their
concentration can differ almost by one order from one point to another.
At the same time (see [19]), when doping the InSe crystals with Cd or Zn, the type of crystal
conductivity changes from n- to p-type, and in the spectral range after 1.0 mkm (Figure
20h), one can observe the Р1–Р3 emission bands related with carrier transitions from DCB
and ICB to the deep acceptor level as well as transitions between donor and acceptor levels
with participation of optical TO phonons. The similar wide bands are also observed in GaSe
crystals of p-type conductivity after their doping with low concentrations of Cd or Zn
impurities [11, 19].
However, contrary to doping the InSe crystals with Cd or Zn, their intercalation with hydrogen
or HCM leads neither to changing their type of conductivity nor to appearance of new
additional wide bands in the range after 1.0 mkm.
Also in [1], the authors considered the case of passivating the defects with hydrogen atoms in
InSe and GaSe crystals of n- and p-type. According to this work, under electrochemical
intercalation of InSe and GaSe crystals with hydrogen, the latter is embedded into interlayer
and intralayer spaces and recombines there up to the molecular state. At the same time, a small
part of hydrogen remains in the atomic state and passivates point defects in the crystal. When
passivating the donor (see Figures 21a and 21b), proton is localized closer to the defect, while
passivating the acceptor, proton is more movable. It is confirmed by the fact that in EPR spectra
g-factor and the spectral width in HXInSe intercalates are considerably lower than in H XGaSe
ones [1].
Figure 21. a, b – the simplest defects of donor and acceptor type in n-InSe and p-GaSe crystals and the scheme of their
passivation with hydrogen.
In accord with [21], passivation with atomic hydrogen also results in lowering the activation
energy of donor and acceptor levels, since in HXInSe intercalates at low temperatures (Т = 70
К) one can observe the growth by one order in the free electron concentration, and the further
growth of temperature results in exhaustion of the shallow donor level. The additional optical
investigations performed by us also show (see the insert to Figure 20h) that intercalation with
hydrogen improves PL spectra of n-InSe crystals and does not influence on PL spectra of p-
GaSe crystals.
At the same time, when intercalating the crystals with hydrogen, the lattice parameter and
width of the van der Waals gap grow due to embedding the hydrogen molecules into interlayer
and intralayer spaces [1]. The authors of the work [22] investigating the influence of hydrostatic
pressure on lattice parameters in InSe crystals showed that increasing the pressure from 105
up to 8×109 Pa results in essential narrowing the van der Waals gap as a consequence of
decreasing the distance CSe-Se between the two nearest Se atoms located in the adjacent layers
from 0.38 down to 0.33 nm (13%). Inside crystal layers, the distance CIn-In between neighboring
In atoms is decreased from 0.279 down to 0.269 nm (3.58%), and the distance CIn-Se between In
and Se atoms—from 2.65 down to 2.59 nm (2.26%). However, as a consequence of the fact that
the angle φ between atoms Se–In–In grows from 119.3° up to 121.3° (1.5%), the thickness of
crystal layer decreases only by 0.26%—from 0.536 down to 0.5345 nm.
The extrapolation of data from the studies [1, 22] as well as comparison of lattice parameters
of InSe [6, 22] and GaSe [5] with sizes of molecules allows to conclude that the natural
intercalation of these crystals with molecules of water, alcohol, and toluene results in their
embedding into the interlayer space, which causes growth of the van der Waals gap in
respective places. In this case, electrochemical intercalation leads to physical sorption of
hydrogen in crystals (since hydrogen can be deintercalated from InSe and GaSe crystals under
usual evacuation at the temperatures 110–120°С with participation of full-symmetric half-layer
А-phonons able to change the thickness of crystal layers and the intralayer space [1]), while in
the case of natural intercalation with water, alcohol, and toluene there takes place chemical
sorption of molecules in the interlayer space.
To check up general properties and differences that occur in InSe and GaSe crystals after
doping with Cd, Zn, Ge, or Sn atoms, or after intercalation with water, alcohol, and toluene,
let us consider the simplest defects typical for these crystals (Figure 21).
In accord with Figure 21a, the absence of Se atom inside the layer makes it impossible to allocate
2/3 portion of electron charge to each of the nearest atoms for the creation of the natural sp3-
hybrid bond. It is the way with which the simplest (2–) donor arises in n-InSe crystals.
Simultaneously, the absence of Ga atom in p-GaSe crystal (Figure 21b) results in the creation
of the (1+) acceptor state since unpaired s-electron from the nearest Ga atom provides the
hybrid bond with three Se atoms of the upper monolayer.
In the course of doping the p-GaSe crystals with impurities Cd or Zn (Figure 21b), it becomes
possible for Ga vacancies to be substituted with Cd or Zn atoms with the simultaneous creation
of a new (1+) acceptor as a consequence of deficit of one valence electron in Cd or Zn atom.
Then there arises a set of absorption and emission bands in the long-wave spectral range, which
is caused by transitions of carriers from direct and indirect conduction bands on the deep
acceptor level, or by transitions between donor and acceptor levels in p-GaSe:(Cd, Zn) crystals.
Doping the InSe crystals with impurities, Cd or Zn changes their type of conductivity. It
becomes possible (see Figure 21a) when three upper In atoms are simultaneously substituted
with Cd or Zn atoms. This more complex defect becomes the (1+) acceptor. The concentration
of impurities near these defects should be higher since it changes the type of conductivity in
InSe crystals, which by analogy with the p-GaSe:(Cd, Zn) crystals results in appearance of wide
bands in PL spectra of p-InSe:(Cd, Zn) that are caused by radiative recombination of carriers
from DCB and ICB onto the deep acceptor level. Moreover, the availability of another type
defects enables to explain the reason for nonuniform distribution of impurities in these crystals.
In the case of crystals intercalated with HCM, embedded molecules, except hydrogen, contain
either carbon atoms (toluene, alcohol) or hydroxyl group (alcohol, water). The investigations
performed by us showed that the intercalation of p-GaSe and n-InSe crystals with toluene leads
to changes in PL spectra, which are similar to those observed after intercalation with hydrogen.
It allows concluding that passivation of defects with toluene is identical to that with hydrogen.
However, in the case of toluene molecules, hydrogen ions are symmetrically located relatively
to the main axis of the molecule and possess other electro-negativity than those in the methyl
tail. It leads to different positions of toluene molecules in the van der Waals gap of n-InSe and
p-GaSe crystals that contain different defects.
Thus, in n-InSe crystals intercalated with toluene and hydrogen one can observe “curing” the
defects since emission lines of excitons localized on various defects in crystals disappear. By
contrast, in the case of p-GaSe growth of the intercalation time “worsens” crystal quality—
there appear P0-bands, and the emission intensity of bound excitons increases. It can be
possible, when a toluene molecule is differently oriented relatively to (2–) donor and (1+)
acceptor. As the (2–) donor has higher electro-negativity, the toluene molecule approaches to
this defect with its massive benzene ring and becomes more stabilized in space. In the case of
(1+) acceptor, the molecule approaches to the defect with its tail С-Н3. In this situation, there
can take place deviation of the toluene molecule near this defect, which results in decay and
binding the excitons as well as to enhancing radiative recombination via the defect centers of
this crystal.
Unlike to toluene molecules, those of water and alcohol contain the hydroxyl group ОН. In
p-GaSe crystals, it results in essential growth of the P0-band in PL spectra that is caused by
radiative recombination of carriers from DCB and ICB onto the acceptor level а1 with emission
of TO phonons. Besides, the intensity of exciton emission is considerably lowered, since water
and alcohol molecules, being near the (+1) acceptor, essentially disturb the lattice of p-GaSe
crystal.
Contrary to p-GaSe crystals, in n-InSe crystals intercalated with water and alcohol (like those
with embedded hydrogen and toluene) curing the point defects takes place. However, in this
case (2–) donor is passivated with the hydroxyl group. As the water molecule is more sym‐
metric than the alcohol one, and its size practically coincides with that of defect, it can vary
between several symmetric positions relatively to this defect. In the crystal lattice, it results in
splitting the exciton state related with this defect.
5.4. Conclusions
The performed investigations of low-temperature (T = 4.5 K) PL spectra of GaSe and InSe

crystals intercalated with hydrogen-containing molecules (HCM) of water and alcohol, their
comparison with the spectra of GaSe and InSe crystals intercalated with hydrogen or doped
with impurities Cd, Zn, Ge, Sn [11, 19], as well as review of the simplest defects carried out in
discussion for the crystals of n- and p-type enabled to explain differences of optical properties
inherent to p-GaSe and n-InSe crystals and to draw the following conclusions:
i. HCM are predominantly located in the interlayer space and passivate point defects
of p-GaSe and n-InSe crystals.
ii. The availability of two conductivity types, namely, p-type in GaSe and n-type in InSe,
leads to different influence on their optical properties.
In particular, in p-GaSe crystals intercalation with HCM possessing the OH group results in
considerable disturbance of the crystalline lattice around the (+1) acceptor, as a consequence
of which emission lines inherent to free and bound excitons disappear, while radiative
recombination of carriers from DCB and ICB onto the a1 acceptor level located at 70 meV above
the VB top grows. This effect of increasing the intensity of radiative recombination of carriers
from DCB and ICB onto the a1 acceptor level in p-GaSe is observed with increasing the
intercalation time as well as when transferring along the direction toluene → water → alcohol.
When transferring from nonintercalated GaSe to the HCM-intercalated ones along the set GaSe
→ GaSe[C7H8] → GaSe[C2H5OH] → GaSe[H2O], the energy position of the a1 acceptor level in
the forbidden gap is lowered in accord with the sequence 70 → 67 → 63 → 56 meV. By analogy
with the p-GaSe and n-InSe crystals intercalated with hydrogen, it has been made an assump‐
tion that the observed lowering the position of activation energy for the a1 acceptor level is
caused by passivation of this defect with HCM.
By contrast, in n-InSe crystals intercalated with HCM, one can observe curing the point defects,
predominantly (2–) donors, which results in the growing intensity of emission lines related
with free excitons and practically full disappearance of lines inherent to bound excitons as well
as emission bands of indirect free excitons with participation of optical phonons. In this case,
the effects of curing the defects in n-InSe are more clearly pronounced after intercalation with
HCM containing the molecules of carboxyl group (CH) or molecular hydrogen than in those
with the hydroxyl group (ОН)–water or alcohol.
Also, after the intercalation of n-InSe crystals with water, splitting the emission lines of bound
excitons is observed, which is caused by splitting the exciton states related with the (2–) donors.
However, intercalation with HCM does not practically change the integrated intensity of
radiative recombination for excitons and free carriers in p-GaSe and n-InSe crystals.
6. Summary
In this review, in the wide energy range from energies of electron transitions between inner
shells of intercalated atoms and those typical for energies of electrons providing valence bonds
in the crystalline matrix down to the energies of intrinsic vibrations of atoms (nuclei) of
molecules intercalated into the matrix, we have presented the results of investigations by using
electron-microscopic, energy-dispersive, and optical methods. These methods allow to study
spectra within the range of fundamental electron transitions in the matrix as well as in the
range of IR vibrations of intercalated molecules in layered InSe and GaSe crystals with
embedded molecular hydrogen or hydrogen-containing molecules (HCM) of water, alcohol,
and toluene. Described also have been the methods for the intercalation and deintercalation
of HCM.
It has been shown that these crystals in the course of intercalation free take (and during
deintercalation release) not only atomic hydrogen but also HCM. This process takes a look of
a hysteresis loop—it is retarded during intercalation and is faster during deintercalation when
heating and evacuating in a vacuum chamber. Adduced have been the empirical equations
relating these two processes and their temporal estimates. We have also determined the
optimal dimensions of the crystals (including their powders) to accelerate the process of
intercalation–deintercalation.
As InSe and GaSe crystals are characterized by two different types of conductivity, it results,
when intercalating with hydrogen and HCM, in predominant recombination of free and bound
excitons in n-InSe crystals, while in p-GaSe crystals processes of free carrier recombination via
impurity levels are predominant. These processes have no effect on the integrated intensity of
emission from the crystal within the range of fundamental transitions, since the energy of
valence electron transitions for HCM lies in the UV range.
The results obtained in this work with account of the conclusions made by us in [1] are
indicative of promising applications of these layered matrixes (and powders from them) when
creating operation elements of solid hydrogen accumulators. At the same time, these layered
InSe and GaSe crystals themselves with different types of conductivity and their thin-layer
intercalates as well as other similar compounds can be considered as promising candidates for
the creation of various hybrid layered structures for flat flexible displays. The obtained in this
work results for various cases of volume dimensions, conditions and terms of their operation
can be used for solving these tasks, too.
Acknowledgements
Performing these investigations became possible owing to the project no. 0108U000252 within
the framework of the departmental subject area in the National Academy of Sciences of
Ukraine in accord with the Program for Scientific Instrument Engineering.
Author details
Yuriy Zhirko1*, Vasiliy Grekhov1, Nikolay Skubenko1, Zakhar Kovalyuk2 and Taras Feshak2
*Address all correspondence to: [email protected]
1 Institute of Physics National Academy of Sciences of Ukraine, Kiev,, Ukraine
2 Chernivtsy Department of the Institute for Material Science Problems National Academy
of Sciences of Ukraine, Chernivtsy, Ukraine
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Section 3
Hydrogen Storage
Chapter 3
Metal Amidoboranes and Their Derivatives for

Hydrogen Storage
Hailiang Chu, Shujun Qiu, Lixian Sun and Fen Xu
Abstract
As potential hydrogen storage mediums, ammonia borane and its derivatives have
been paid an increasing attention owing to their higher hydrogen capacities and facile
dehydrogenation properties under moderate conditions. In this chapter, we presented
extensive studies on thermodynamic tailoring of dehydrogenation of metal amidobor‐
anes, metal borohydride-ammonia borane complexes, and metal amidoborane am‐
moniates as well as their derivatives, with special focus on the syntheses, crystal
structures, and dehydrogenation properties. Finally, future perspective was given to‐
ward the practical applications.
Keywords: Hydrogen storage, dehydrogenation, metal amidoborane, B-N-containing

compounds, thermodynamics, kinetics
1. Introduction
Mainly driven by two global issues of energy crisis and environmental pollution, great
attention to a relatively new concept of the hydrogen economy has been paid in the last
decades. However, hydrogen storage is one of bottlenecks in hydrogen economy. Generally,
the materials with high hydrogen content have received an increasing interest for chemical
storage concepts. As a chemical hydride, ammonia borane (NH3BH3, AB) has attracted
significant attentions owing to the extremely high hydrogen capacity up to gravimetric density
of 19.6 wt% and volumetric density of 146 g H2 L-1 [1]. Unlike metal borohydrides, solid
crystalline AB is not very sensitive to air at ambient condition. In AB molecules, there are both
hydridic H atoms in BH3 groups and protic H atoms in NH3 groups. Consequently, the
chemical potential of the interaction between protic Hδ+ and hydridic Hδ- to the formation of
hydrogen has been known as one of the prime driving powers for hydrogen release [2,3].
However, the relatively high kinetic barriers are observed in its multistep decomposition,
which heightens the temperatures for hydrogen release more than 100 °C [4,5]. Other disad‐
vantages of AB dehydrogenation consist of the discharge of some detrimental by-products
(borazine and ammonia) and severe sample expansion and foaming. Moreover, the intrinsic
exothermicity of dehydrogenation reveals that reversible hydrogenation under moderate
conditions is thermodynamically impracticable. In recent years, a number of techniques
including nanoconfinement [6-8], using ionic liquid medium [9], and catalytic modifications
[10-14] were successfully employed in extensive studies. More importantly, another strategy
proposed to improve the properties of AB thermolysis is the formation of metal-substituted
AB-compounds, i.e., metal amidoboranes (MABs), which have been proven to be a practical
method for tuning the dehydrogenation thermodynamics of AB [15-20]. Because of the quite
high hydrogen content and reasonable dehydrogenation properties, this new type of materials
has been paid intensive attention and grown to become one of the likeliest candidates for
storing hydrogen.
In this chapter, we briefly summarize the recent progress of nanoconfinement and nanocatal‐
ysis of AB, metal amidoboranes (including single- and mixed-metal amidoboranes), and their
derivatives (including metal amidoborane ammoniates, metal borohydride-ammonia borane
complexes, and other complexes related to AB or MAB), with a particular emphasis on the
synthesis, crystal structure, and dehydrogenation.
2. Nanoconfinement of AB
The pioneering work on AB nanoconfined in porous materials was performed by Autrey and
his coworkers [6]. They loaded AB into SBA-15 (a kind of mesoporous material with specific
surface area of about 900 m2 g−1, pore size of 7.5 nm in diameter, and porous volume of 1.2
cm3 g−1) by impregnating SBA-15 in a saturated methanol solution of AB. The obtained sample
was determined to contain 50 wt% AB (denoted as AB:SBA-15). Compared to pristine AB, the
sample nanoconfined in SBA-15 has two significant differences, as shown in Figure 1. First,
the dehydrogenation peaks shifted to lower temperatures. Second, the great suppression of
borazine evolution was successfully achieved, which indicates that the dehydrogenation
reaction is probably tuned. The change of reaction pathway was further verified by differential
scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments. From
isothermal DSC test, the dehydrogenation reaction enthalpy of AB:SBA-15 was found to
significantly reduce to 1 ± 1 kJ (mol AB)−1, compared to pristine AB of 21 ± 1 kJ (mol AB)−1. Also,
NMR tests showed that the post-dehydrogenated product was only polyaminoborane (PAB)
for AB:SBA-15 upon heating to 85 °C, which is different from pristine AB.
Isothermal dehydrogenation showed that the releasing rate of hydrogen from AB:SBA-15 was
much more rapid than that from pristine AB. As an example, it needed less than 10 min for
AB:SBA-15 to reach 50% reaction conversion at 80 °C, while 290 min for pristine AB. Also, a
much lower activation energy of 67 ± 5 kJ mol−1 was determined for dehydrogenation from
AB:SBA-15. However, the total amount of released hydrogen was undoubtedly sacrificed after
AB loading into SBA-15, which was not specifically mentioned in their work.
Metal Amidoboranes and Their Derivatives for Hydrogen Storage 55
Figure 1. TPD/MS tests of AB nanoconfined in SBA-15 (AB:SBA-15). For comparison, neat AB was also included. Re‐
produced from Ref. [6] with permission.
In another study [7], carbon cryogel with specific surface area of 300 m2 g−1, pore diameter in
the range of 2-20 nm, and pore volume of 0.7 cm3 g−1 was selected as a nanoscaffold to
incorporate AB. Sample with a loading of 24 wt% AB into carbon cryogel was obtained
(denoted as C−AB nanocomposite) by wet impregnation using tetrahydrofuran (THF) as
solvent. Nitrogen physisorption test revealed that there is a loss of ~30% in pore volume after
loading AB. From Figure 2, it was found that carbon cryogel as a nanoscaffold exhibited an
even more pronounced effect on dehydrogenation than SBA-15. The peak for hydrogen release
shifted to a low temperature of ~90 °C, and no signal for borazine was observed throughout
the experiment. However, the total amount of released hydrogen was significantly less than
that from pristine AB (9 wt% vs. 13 wt%). When confined in carbon cryogel, AB underwent
the expected reactions for dehydrogenation. Unexpectedly, the enthalpy of dehydrogenation
reaction for C−AB nanocomposite was determined to be an extremely high value of ~120 kJ
mol−1 (compared to pristine AB of 21 ± 1 kJ mol−1 and AB:SBA-15 of 1 ± 1 kJ mol−1). However,
it remains so far unclear what caused the tremendous increase in reaction enthalpy. The
authors suggested that the improvements (for AB loaded into both carbon cryogel and SBA-15)
were ascribed to the increase of defect sites and surface energy of AB, resulting from nano‐
confinement and/or the possible catalysis by the terminal SiO−H groups in SBA-15 and
carboxylic groups in carbon cryogel. For carbon cryogel used as a nanoscaffold, the smaller
the pore diameter, the lower the temperature for the dehydrogenation. In-depth studies of
pore size effect on the structure and dehydrogenation are needed in the forthcoming research.
Figure 2. (A) DTA, MS for (B) H2 and (C) borazine of AB nanoconfined in carbon cryogel (C-AB nanocomposite) at 1
°C/min. For comparison, neat AB was also included. Reproduced from Ref. [7] with permission.
As a newly developed kind of porous material, metal-organic frameworks (MOFs) consist of

polydentate organic ligands and metal ions, achieving 3D extended frameworks [21,22]. A
unique feature of MOFs is its adjustable porosity, which enables it with special properties like
the combination of active metal sites and nanoporosity. Taking advantage of its porosity, an
MOF-confined AB system was successfully synthesized by an infusion method using a solvent
of methanol [23]. Y(BTC)(H2O)⋅DMF (denoted as JUC-32-Y) was used as a nanoscaffold
because of its high specific surface area, suitable pore size, and high thermal stability. Most
importantly, it has many unsaturated metal sites after the removal of the terminal H2O upon
heating at 300 °C under vacuum (Figure 3A). After loading AB in 1:1 molar ratio, the framework
of JUC-32-Y retained its integrity, even after dehydrogenation of AB/JUC-32-Y. Temperature
programmed desorption coupled with mass spectrometry (TPD-MS) results shown in Figure
3B demonstrated that the dehydrogenation of AB/JUC-32-Y started at a lower temperature of
~50 °C, with a peak at 84 °C for most rapid releasing rate, which has a reduction of 30 °C in
comparison with pristine AB. Furthermore, no volatile products such as B2H6, NH3, and
borazine were detected during the decomposition process. The suppression of ammonia was
ascribed to the existence of unsaturated coordination of Y3+. Figure 3C indicates a notable

improvement of the dehydrogenation kinetics of AB/JUC-32-Y. At 95 °C, 10.2 wt% H2 could
be released in initial 10 min while 8.0 wt% H2 at a reduced temperature of 85 °C. Pristine AB
displayed no emission of any hydrogen under same conditions. Note that AB/JUC-32-Y could
release ~13 wt% H2 at 95 °C within 3 h, corresponding to 2 Eq of H2 in pristine AB.
Figure 3. (A) 3D images of (a) JUC-32-Y and (b) AB/JUC-32-Y. Views of 1D chains of JUC-32-Y (c) before and (d) after
removal of terminal H2O and (e) after interaction with AB. Y: bright blue; C: gray; O: pink; N: blue; and B: purple. (B)
TPD-MS and (C) Isothermal dehydrogenation of AB/JUC-32-Y. For comparison, neat AB was also included. Repro‐
duced from Ref. [23] with permission.
Soon afterward, Gadipelli et al. [24] reported the confinement of AB in Mg-MOF-74 with 1D
pores (denoted as AB/Mg-MOF-74), in which the dehydrogenation kinetics had a remarkable
improvement under 100 °C. Furthermore, in the released hydrogen, the detrimental concom‐
itants such as ammonia, borazine, and diborane were not detectable throughout the dehydro‐
genation process. More importantly, owing to the relatively high specific surface area of 1100
m2 g−1 and low atomic weight of metal cation, Mg-MOF-74 could contain about 26 wt% AB
determined by theoretically structural optimization, while only about 8 wt% AB in JUC-32-Y
[23]. Almost 14 wt% of pure H2 could be released at a temperature of 125 °C in one hour for
the AB/Mg-MOF-74 sample, which exceeded 13 wt% of H2 (2 Eq) from pristine AB. Further
systematic investigation showed that the dehydrogenation kinetics of AB/Mg-MOF-74 were
very dependent on the loading amount of AB. Other MOFs such as Ni-MOF-74 and HKUST-1
were also tried in this work. However, the structures collapsed with AB loading, which enabled
them to be unsuitable for serving as a nanoscaffold. In our related study [25], new tactics for
loading AB in MIL-101 (AB/MIL-101) or Ni-modified MIL-101 (AB/Ni@MIL-101) were
proposed through wet impregnation. As shown in Figure 4, the dehydrogenation of AB/
MIL-101 proceeded without an induction period or any detectable borazine and diborane, but
with some ammonia. For the case of AB/Ni@MIL-101, the dehydrogenation peak for the most
rapid rate was reduced to a lower temperature of 75 °C. Furthermore, the detrimental by-
products of borazine, diborane, and ammonia were not detected during the whole experi‐
ments. Theoretical calculations indicated the establishment of B−O and Cr−N bonds and the
existence of strong interaction between MIL-101 and NH2BH2 species, which could facilitate
the dehydrogenation.
Figure 4. TPD-MS of AB, AB/Ni@MIL-101, and AB/MIL-101. Reproduced from Ref. [25] with permission.
3. Nanocatalysis of AB
Ni1-xPtx (x = 0-0.12) hollow spheres were prepared with an assistance of a template called as
poly(styrene-co-methacrylic acid) and then used as catalysts for generating hydrogen from AB
[26]. The morphology and the composition of the obtained Ni0.88Pt0.12 sample were shown in
Figure 5. There are both broken and intact hollow spheres appeared in the sample. TEM images
revealed that the porous shells of hollow spheres with a thickness of 20-40 nm contained many
smaller nanowhiskers and nanoparticles, which enabled the increase of specific surface area
of hollow spheres. Then the hollow spheres with a chemical composition of Ni0.88Pt0.12 were
introduced into a methanol solution of AB. The mixture was vacuumed to obtain a dry solid
sample with homogeneous loading of about 1.8 wt% Pt. TPD tests in Figure 6 showed that the
onset temperature for hydrogen release was reduced to about 56 °C and the peak shifted to
about 100 °C.
A “co-precipitation” process was developed using a typical wet-chemical method for

fabricating nanoalloy to catalyze AB dehydrogenation [27]. Typically, a mixture of 2.0 mol
% of CoCl2 and 10 mL of THF was stirred by ultrasound at room temperature. Then AB
was introduced into the resultant THF solution, which was immediately distilled under a
Figure 5. (a) SEM image, (b, c, d) TEM images, and (e) HRTEM image and (f) EDX spectrum of Ni0.88Pt0.12 hollow
spheres. Reproduced from Ref. [26] with permission.
reduced pressure at room temperature. Finally, the Co-doped sample was obtained after
continuous evacuation to eliminate the rest of THF. Ni-doped sample could be prepared
in the same way. The size of most Ni and Co particles was below 3 nm, which indicated
the peculiarity of the “co-precipitation” method in synthesizing nanoscaled metal cata‐
lysts. TPD-MS curves in Figure 7A showed that the catalyst-doped AB started to release
H2 at a very low temperature of 50 °C and exhibited broad dehydrogenation processes
peaked at about 113 °C. Isothermal dehydrogenation test indicated that nearly 1 Eq of H2
was released from the catalyst-doped AB at 59 °C without any induction period (Figure
7B). However, after being held at this temperature for more than 24 h, there was no
evolution of any H2 from pristine AB. Moreover, the detrimental by-product of borazine
and sample forming were not observed during the catalytic dehydrogenation. Deter‐
mined by the Kissinger model, the activation energy Ea was reduced to 117 and 123 kJ mol
−1
for Co- and Ni-doped AB. For the case of Co-doped AB, from electron paramagnetic
resonance (EPR) characterization, Co2+ was partially reduced in the preparation, which was
regarded as the catalytically active species for AB dehydrogenation.
Figure 6. TPD-MS of AB mixed with Ni0.88Pt0.12 hollow spheres (red line). For comparison, neat AB (black line) was also
included. Reproduced from Ref. [26] with permission.
Figure 7. (A) TPD-MS of pristine and 2.0 mol% Co- or Ni-doped AB samples: (a) H2 signal and (b) borazine signal. (B)
Isothermal hydrogen release tests at 59 °C on (a) pristine, (b) Co-doped, and (c) Ni-doped AB samples. Reproduced
from Ref. [27] with permission.
Because the chlorides of cobalt and nickel as precursors have better performance in catalyzing
the dehydrogenation of AB, FeCl3 and FeCl2 were tried in the following studies [28,29].
Different amounts of FeCl3 or FeCl2 were introduced in solid AB using a “co-precipitation”
method. Generally, FeCl3 exhibited much better performance in catalyzing AB dehydrogena‐
tion than FeCl2. Because of the formation of FeB nanoalloy in particle size of 2-5 nm, AB doped
with 5 mol% FeCl3 gave excellent performance with an onset temperature for hydrogen release
at about 55 °C. Volumetric release tests (Figure 8) showed that FeCl3-doped AB evolved H2
immediately at 60 °C without an induction period observed. With the increase of temperature
to 80 °C and 100 °C, it could release more than 1.2 and 1.5 Eq of H2, respectively. Also, sample
foaming upon heating and the by-products (borazine and ammonia) were significantly
suppressed. More importantly, crystalline linear polyaminoborane (PAB) was found upon
dehydrogenation of FeCl3-doped AB, which was the first case on the preparation of crystalline
PAB through solid-state reaction. Theoretical calculations showed that the growth of crystal‐
line PAB may follow the dehydrogenation-chain growth mechanism. When the loading
amount of FeCl3 was reduced to 2.0 mol%, the optimal performance of the formation of
crystalline PAB was achieved.
Figure 8. Volumetric release of 5.0 mol% FeCl3-doped AB samples (□). For comparison, pristine AB (▲) was also in‐
cluded as a reference. Reproduced from Ref. [28] with permission.
As shown in Figure 9, a nanocomposite of AB/Li-CMK-3 was successfully synthesized by an

impregnation method, i.e., AB loaded into a Li-doped CMK-3 (a class of carbon material with
an ordered mesoporous structure) [30]. It could release more than 7 wt% H2 at 60 °C, which
was ascribed to the synergy between catalytic effect and nanoconfinement in AB/Li-CMK-3
system. These effects resulted in a significant enhancement of the dehydrogenation kinetics
and a great suppression of detrimental by-products. In reference [31], two novel catalysts based
on MOFs (denoted as MOF1cat and MOF2cat) were developed, in which in situ-formed metal
Ni and the retained frameworks greatly promoted their catalytic activity. Loading with only
1.0 mol% catalyst in AB would give rise to higher dehydrogenation capacity, more rapid
hydrogen releasing rates, lower onset temperature, and much less reaction exothermicity. At
90 °C, about 8 wt% H2 could be released from catalyzed samples. The reaction enthalpies of
AB dehydrogenation catalyzed by MOF1cat and MOF2cat were determined to be −4.3 and

−7.9 kJ mol−1, respectively, much less than −21 kJ mol−1 for pristine AB. The apparent activation
energies of 131 and 160 kJ mol−1 were also much lower than 184 kJ mol−1 for pristine AB.
Figure 9. Schematic model of AB/Li-CMK-3 nanocomposites (AB: dark gray spheres; Li: light gray spheres; CMK-3
substrate: gray rod). Reproduced from Ref. [30] with permission.
Other catalysts consisting of noble metals were fabricated. For instance, the catalytic dehy‐
drogenation properties of AB by carbon nanotubes functionalized with Pt nanoparticles
(denoted as Pt@CNTs) were reported, in which Pt@CNTs was synthesized through an
“ammonia-deliquescence” method [32]. From Figure 10, AB/Pt@CNTs had two peaks for
hydrogen release at temperatures of about 108 °C and 150 °C. Furthermore, great suppression
of borazine and no sample foaming and expansion were observed during the whole dehydro‐
genation. Of particular concern is achieving much less exothermicity for dehydrogenation.
Meanwhile, AB/Pt@CNT had ameliorative dehydrogenation kinetics, i.e., releasing 1 Eq of
H2 in 5 h at 70 °C, which was evidenced by the reduced activation energy of 106.2 kJ mol−1. It
was also indicated that the combination of the nanoconfinement of AB into CNTs and the
synergetically catalytic effects of Pt nanoparticles and CNTs were primarily responsible for
enhancing the dehydrogenation properties. In addition, Pd, Pt, and Ni nanoparticles well
deposited on MCM-48 (a silica-based material with mesoporous structure) were developed by
a magnetron sputtering technique [33]. Then the resultant catalysts were introduced into AB
by impregnation method using anhydrous diethyl ether as solvent and displayed obvious
catalytic effects for hydrogen release from AB. For example, the onset temperature for
dehydrogenation was about 93 °C for AB/MCM-48-Pd (weight ratio of 2:1), with a shift of 12
°C to reduced temperature compared with pristine AB. For all samples catalyzed by well-
dispersed Pd, Pt, and Ni nanoparticles on MCM-48, borazine as a detrimental by-product was
significantly suppressed, and there was no foaming and expansion during dehydrogenation
process.
Figure 10. TPD-MS of pristine AB and loaded AB/Pt@CNTs. Reproduced from Ref. [32] with permission.
4. Metal amidoboranes, MABs
In 1938, sodium amidoborane (NaNH2BH3, NaAB, similarly hereinafter for other amidobor‐
anes) was initially prepared by a reaction of borane etherate with sodium and ammonia [34].
For the case of lithium amidoborane (LiNH2BH3, LiAB), it was synthesized through deproto‐
nation of AB in THF using n-butyllithium at 0 °C and then used as a reducing reagent [35].
However, the crystal structure of LiAB and NaAB was not reported until 2008 [36-38]. A solid-
state synthetic method was developed for MABs through controlled mechanical ball milling
AB with MH (M = Li or Na) in an equivalent molar amount. Calcium amidoborane
(Ca(NH2BH3)2, CaAB) was prepared by a wet-chemical reaction between AB and CaH2 in THF
[39]. As a matter of fact, CaAB⋅2THF rather than pure CaAB was obtained in final product due
to the strong coordination of THF with Ca2+. Wu et al. [38] synthesized solvent-free CaAB by
ball milling solid-state CaH2 and AB. More recently, some new MABs such as potassium
amidoborane (KNH2BH3, KAB) [40], strontium amidoborane (Sr(NH2BH3)2, SrAB) [41], and
yttrium amidoborane (Y(NH2BH3)3, YAB) [42] were successfully synthesized. In general, there
are two synthetic approaches for the preparation according to the reported MABs, i.e., solid-
state mechanical ball milling and wet-chemical synthesis. In solid-state ball milling method,
the chemical interaction between protic H and hydridic H was regarded as one of main driving
forces for hydrogen release [43-45]. It should be pointed out that the milling conditions are
crucial during the synthesis of MABs because of their lower temperatures for dehydrogena‐
tion. In a wet-chemical reaction, the adducts rather than pure MABs are always obtained
because the solvent is easily coordinated with amidoborane, especially alkaline-earth metal
amidoboranes [39]. Because of relatively strong combination between solvent molecules and
metal cations, special procedures are needed for removal of solvent, during which the
decomposition of MABs should be avoided.
4.1. Lithium amidoborane (LiNH2BH3, LiAB) and sodium amidoborane (NaNH2BH3, NaAB)
As mentioned above, LiAB or NaAB could be prepared by carefully milling a mixture of AB

and an equivalent LiH or NaH. LiAB crystallizes in an orthorhombic cell (space group Pbca)
with lattice parameters of a = 7.11274(6) Å, b = 13.94877(14) Å, and c = 5.15018(6) Å (Figure 11)
[36]. Moreover, NaAB is an isostructural compound with LiAB and the lattice parameters are
a = 7.46931(7) Å, b = 14.65483(16) Å, and c = 5.65280(8) Å [36]. In their crystal structures, the
bond lengths of Na-N and Li-N are 2.35 and 1.98 Å. The substitution of one H atom in NH3
group by Li+ gave rise to the slight shortening of bond length for B-N (1.56 Å) compared to
that in AB (1.58 Å) [46]. Moreover, the B-H distance is 1.079 Å in LiAB and 1.245 Å averagely
in NaAB, which are different from that that in AB (1.11 Å) [47]. The establishment of an ionic
Li-N or Na-N bond and the resulting reinforce of B-N bond in [NH2BH3]- group in LiAB or
NaAB resulted in an improved dehydrogenation properties. LiAB and NaAB started to release
H2 at 85 °C and had a peak at about 90 °C [36,37]. In addition, no borazine was detectable
during the dehydrogenation. Furthermore, the heat for dehydrogenation from LiAB and NaAB
was determined to be ~-3 and -5 kJ (mol H2-1), remarkably less exothermic than that of pristine
AB (-21 kJ (mol H2-1)) [4]. At 91 °C, about 7.4 and 11 wt% H2 could be released from NaAB and
LiAB, respectively (Figure 12).
LiAB could also be synthesized by reaction of LiH and AB in THF after the evolution of 1 Eq
of H2. Surprisingly, it then releases another 2 Eq of H2 in THF at a lowest temperature of 40 °C
reported so far [48]. The dehydrogenation of LiAB in THF was determined to be zero-order
based on the concentration of LiAB. However, the dehydrogenation mechanism is still unclear
and needs further investigations. Through an electrospinning technique, LiAB nanoparticles
were well dispersed in carbon nanofibers (denoted as LiAB@CNFs), which had onset and peak
temperatures of about 40 °C and 80 °C, significantly lower than pristine LiAB. Upon heating
to 100 °C, all hydrogen in LiAB of 10.6 wt% could be released in only 15 min [49]. For the case
of NaAB, it could also be prepared through a wet-chemical method by reacting AB with NaH
at -3 °C or with NaNH2 at 25 °C in THF [50]. After dehydrogenation of LiAB or NaAB, the solid
residues were found to be poorly crystalline phases. A following study indicated that solid
NaH was detected for NaAB [50]. However, a recent investigation on the post-dehydrogenated
products of NaAB at 200 °C suggested that except NaH, an amorphous phase with the chemical
composition of Na0.5NBH0.5 (or regarded as a mixture of NaNBH and h-BN) was identified by
NMR technique [51]. Unfortunately, the results from Fijałkowski et al. [52] showed that a
substantial amount of NH3 was released during synthesis by ball milling and the following
thermal decomposition of NaAB.
Figure 11. Crystal structure of LiAB. B: orange spheres; N: green spheres; H: white spheres; and Li: red spheres. Repro‐
duced from Ref. [36] with permission.
4.2. Lithium amidoborane-ammonia borane (LiNH2BH3⋅NH3BH3, LiAB⋅AB) and β-LiAB
Careful exploration by XRD technique during ball milling of AB and LiH (in 1:1 molar ratio)
indicated a stepwise process in LiAB formation [53]. A new complex hydride of lithium
amidoborane-ammonia borane (LiNH2BH3⋅NH3BH3, LiAB⋅AB) was formed as an intermedi‐
ate [38,53]. Pure LiAB⋅AB could be prepared by ball milling a mixture of AB/LiAB or 2AB/LiH
[54]. It crystallizes in a monoclinic cell (space group P21/c) with lattice parameters of a =
7.0536(9) Å, b = 14.8127(20) Å, c = 5.1315(7) Å, and β = 97.491(5)°. There is the intergrowth of
AB and LiAB layers in crystal structure of LiAB⋅AB. As shown in Figure 13, each Li+ is bonded
with one N atom from [NH2BH3]- with a Li-N bond in 2.05 Å and coordinated with hydrogen
atoms from BH3 group in two LiAB and one AB. The dihydrogen bonding of NH⋅⋅⋅HB is 1.902
Å in AB layer. About 14.0 wt% H2 could be released at 228 °C from LiAB⋅AB after its melting
with an onset temperature of 58 °C. Furthermore, another allotrope of β-LiAB was found
during ball milling process. Interestingly, it transformed from initially formed α-LiAB and
could transform to α-LiAB upon extended milling [53]. β-LiAB also crystallizes in an ortho‐
rhombic cell (space group Pbca) with lattice parameters of a = 15.15 Å, b = 7.726 Å, and c = 9.274
Å. However, its unit cell has a double volume of α-LiAB, in which two alternative LiAB layers
were observed along the a axis. The coordination of Li+ was found to be distortedly tetrahedral
Figure 12. Isothermal dehydrogenation of LiAB, NaAB, and post-milled AB samples at about 91 °C. Reproduced from
Ref. [36] with permission.
in β-LiAB due to different distances for Li1-B and Li2-B (Figure 13b). The bond length of Li-N
(1.93 and 2.04 Å for Li1-N and Li2-N) is similar to that in α-LiAB (1.98 [36] or 2.02 Å [53]). Both
allotropes of LiAB displayed identical dehydrogenation behaviors, i.e., 10.8 wt% H2 could be
released at 180 °C [53].
Figure 13. Coordination of Li+ in (a) α-LiAB, (b) β-LiAB, and (c) LiAB⋅AB. Li: purple spheres; B: brown spheres; N:
blue spheres; and H: white spheres. Reproduced from Ref. [53] with permission.
4.3. Potassium amidoborane (KNH2BH3, KAB)
Through the reaction of AB with an equivalent KH, polycrystalline KAB was synthesized in
THF, while single crystal was obtained in a mixed solvent of diglyme and hexane at room
temperature [40]. Similar to LiAB and NaAB, KAB crystallizes in an orthorhombic cell (space
group Pbca) with lattice parameters of a = 9.4304(1) Å, b = 8.26112(1) Å, and c = 17.3403(2) Å.
However, different from Li+ in LiAB and Na+ in NaAB, K+ is octahedrally coordinated by
[NH2BH3]- groups with the formation of three K-N bonds (3.0207-3.1345 Å) and three
K⋅⋅⋅BH3 coordinations (Figure 14A). The distance of closest NH⋅⋅⋅HB (2.265 Å) in KAB is
smaller than those in LiAB (2.372 Å) and NaAB (2.717 Å). As shown in Figure 14B, an endo‐
thermic peak for melting was observed before an exothermic event for hydrogen release. It
could release 1.5 Eq of H2 (6.5 wt%) at ~80 °C. With the temperature increase to 160 °C, another
0.5 Eq of H2 was released. No ammonia or borazine was detected throughout the dehydro‐
genation.
Figure 14. (A) Crystal structure of KAB. K: green spheres; N: blue spheres; B: cream spheres; and H: white spheres. (B)
(a) DSC and (b) IGA data for KAB decomposition. Reproduced from Ref. [40] with permission.
4.4. Magnesium amidoborane (Mg(NH2BH3)2, MgAB)
MgAB is supposed to be a promising material for storing hydrogen because it has a hydrogen
content of 11.8 wt%. However, it is unsuccessful to prepare crystalline MgAB either by ball
milling method or via wet-chemical method until the beginning of 2013. MgAB was synthe‐
sized through aging treatment of post-milled 2AB/MgH2 or 2AB/Mg powder, in which the
formation of MgAB was not a straightforward process but experienced a prerequisite step of
phase transition [55]. However, the crystal structure was failed to solve. In 2010, its structure
was successfully proposed through theoretical simulation [15]. MgAB has a monoclinic cell
(space group C2) with lattice parameters of a = 8.5772 Å, b = 5.6048 Å, c = 5.6216 Å, and β =
85.8476°. Two Mg-N bonds with the length of 2.111 Å and two Mg⋅⋅⋅BH3 coordinations are
around Mg2+ (Figure 15). As a stable compound at room temperature, MgAB could release ~10
wt% H2 at 300 °C, without volatile by-products detectable [55].
Figure 15. Simulated crystal structure of MgAB. Mg: green spheres; N: blue spheres; B: orange spheres; and H: white
spheres. Reproduced from Ref. [15] with permission.
4.5. Calcium amidoborane (Ca(NH2BH3)2, CaAB)
Due to the strong coordination between solvent and metal cation, CaAB⋅2THF adduct rather
than pure CaAB was first synthesized through reacting CaH2 with two equivalent AB in THF
[39]. The specially octahedral coordination of Ca2+ with two NH2, two BH3, and two O resulted
in an extended chain-like structure. After desiccation under a dynamic flow of argon, about
10% remaining THF was evolved from 70 °C to 105 °C, and hydrogen was released mainly
from 120 to 245 °C. Another adduct of [(DIPP-nacnac)CaNH2BH3(THF)2] was also reported
[56], in which Ca2+ is octahedrally coordinated to DIPP-nacnac [(2,6-
iPr2C6H3)NC(Me)C(H)C(Me)N(2,6-iPr2C6H3)] bidentate ligand, [NH2BH3]-, THF. Using
mechanical milling method from CaH2 and two equivalent AB, Wu et al. [38] synthesized a
solvent-free CaAB, which crystallizes in a monoclinic cell (space group C2) with lattice
parameters of a = 9.100(2) Å, b = 4.371(1) Å, c = 6.441(2) Å, and β = 93.19°. Ca2+ is octahedrally
coordinated through two Ca-N bonds with the length of ~2.466 Å and four coordinations of
Ca⋅⋅⋅BH3 with the distance in the range of 2.87-3.03 Å (Figure 16). Different from the CaAB
adducts, there are two steps for hydrogen release with peaks at 100 and 140 °C. Upon heating
to 250 °C, 2 Eq of H2 was released with the solid residues in amorphous state.
Figure 16. (Top) Crystal structure of CaAB. Ca: orange spheres; B: green spheres; N: blue spheres; and H: white
spheres. (Bottom) Coordination environment of Ca2+. Reproduced from Ref. [38] with permission.
4.6. Strontium amidoborane (Sr(NH2BH3)2, SrAB)
Through reacting SrH2 with AB in a 1:2 molar ratio, SrAB was successfully synthesized by
moderate milling and the following heating treatment at 45 °C [41]. Similar to CaAB, SrAB also
crystallizes in a monoclinic cell (space group C2) with lattice parameters of a = 8.1660(4) Å, b
= 5.0969(3) Å, c = 6.7258(4) Å, and β = 94.392(4)°. Sr2+ is octahedrally coordinated by
[NH2BH3]- groups to form two Sr-N bonds with a length of 2.68 Å and four Sr⋅⋅⋅BH3 coordi‐
nations (Figure 17). Upon heating, SrAB started to decompose into H2 and Sr(NBH)2 at about
60 °C. In an isothermal dehydrogenation performed at a temperature of 80 °C, 4 Eq of H2 could
be rapidly released in a few minutes. However, the evolved hydrogen was contaminated by
undesirable by-products of NH3 and B2H6 evolved from the decomposition of the resulting
Sr(NBH)2.
Figure 17. Crystal structure of SrAB. Sr: red spheres; N: yellow spheres; and B: blue spheres. Reproduced from Ref.
[41] with permission.
4.7. Yttrium amidoborane (Y(NH2BH3)3, YAB)
Ball milling YCl3 with three equivalent LiAB gave rise to the formation of YAB [42]. In fact, it
was a homogenous mixture with a side product of LiCl, which is very difficult to separate.
YAB has a monoclinic cell (space group C2/c) with lattice parameters of a = 13.18902(63) Å, b =
7.82233(38) Å, c = 14.874274(68) Å, and β = 92.42620(40)°. However, it was thermodynamically
unstable and spontaneously decomposed in several days at room temperature. A large amount
of H2 with NH3 impurity was released from freshly prepared sample upon heating to 250 °C.
Motivated by the synthesis of YAB, the attempt to synthesize iron (III) amidoborane
(Fe(NH2BH3)3, FeAB) through metathesis of FeCl3 and three equivalent LiAB in THF was
unsuccessful [57]. Instead of FeAB formation, 1.5 Eq of H2 was released and a black solid
containing LiCl was produced. Meanwhile, Fe3+ was reduced during dehydrogenation
evidenced by Mössbauer and XAFS characterizations.
4.8. Na[Li(NH2BH3)2]
Na[Li(NH2BH3)2] was reported to be the first mixed-cation amidoborane, which was prepared
by milling a mixture of NaH/LiH/2AB performed on a high-energy disk mill [58]. It crystallizes
in a triclinic cell (space group P1̄) with lattice parameters of a = 5.0197(4) Å, b = 7.1203(7) Å, c
= 8.9198(9) Å, α = 103.003(6)°, β = 102.200(5)°, and γ = 103.575(5)° [58]. As shown in Figure
18B, Na+ is octahedrally coordinated with H atoms from BH3 groups with different Na-H
distances, while Li+ is tetrahedrally coordinated by one H atom from BH3 group and three N
atoms from NH2 groups. In addition, the formed chains of dimeric [Li(NH2BH3)2]2- anions
linked through Li⋅⋅⋅H coordinations were found in Na[Li(NH2BH3)2]. Thus, Na[Li(NH2BH3)2]
was regarded as an ionic compound composed of Na+ and [Li(NH2BH3)2]2-, which is totally
different from NaAB and LiAB. Na[Li(NH2BH3)2] decomposed exothermally from 75 °C to 110
°C with 6.0 wt% H2 released. An additional 3.0 wt% H2 could be released in the temperature
range of 110-200 °C. During its decomposition, there was an evolution of ammonia [58]. One
year later, Li et al. [59] prepared Na[Li(NH2BH3)2] through a wet-chemical method, i.e.,
recrystallizing a mixture of LiAB/NaAB (1:1 molar ratio) or reacting AB with a post-milled
mixture of LiH/NaH (1:1 molar ratio) in THF. However, Na[Li(NH2BH3)2] was theoretically
determined to be in an orthorhombic cell (space group of Pca21) with lattice parameters of a =
14.639 Å, b = 7.169 Å, and c = 5.367 Å, which is significantly different from the structure
determined experimentally. For example, the coordination environments of Li+ and Na+ are
similar in its simulated structure, i.e., surrounded by one N atom from [NH2BH3]− and six H
atoms from [NH2BH3]− (Figure 18A). Furthermore, the calculated free energy ΔG(x) indicated
that all of the studied compositions in NaxLi1−xNH2BH3 except x = 0.125 were also thermody‐
namically favored [59].
Figure 18. Crystal structure of Na[Li(NH2BH3)2] determined theoretically (A) and experimentally (B). Coordinations of
Li+ and Na+ are displayed under each structure. Li: big red spheres; Na: big yellow spheres; N: small light blue spheres;
B: small green spheres; and H: small pink spheres. Reproduced from Ref. [59] with permission.
4.9. NaMg(NH2BH3)3
Almost at the same time, another dual-metal (alkali metal and alkaline-earth metal) amido‐
borane, namely, NaMg(NH2BH3)3, was reported [60]. It was prepared by mechanically milling
3AB/NaMgH3 powdery mixture and the following treatment at 45 °C according to the reaction
equation: 3NH3BH3 + NaMgH3 → NaMg(NH2BH3)3 + 3H2. From its SR-XRD pattern,
NaMg(NH2BH3)3 was ascribed to a monoclinic cell (space group P21 or P21/m) with lattice
parameters of a = 17.011 Å, b = 9.432 Å, c = 9.398 Å, and β = 115.99°. However, the detailed
crystal structure was unsuccessfully solved in reference [60]. For the post-milled 3AB/
NaMgH3 without heating treatment, there were two steps for dehydrogenation. It started to
release H2 exothermically at around 50 °C for the first step with yielding about 3.5 wt% H2,
which agrees well with the amount of hydrogen released during heating treatment at 45 °C.
Therefore, it could be concluded that the first step for dehydrogenation gave rise to the
formation of NaMg(NH2BH3)3 and the second one was for its own dehydrogenation with the
beginning at about 140 °C and the most rapid release rate at about 170 °C. No volatile by-
products and sample foaming were observed during the decomposition process upon heating
to 250 °C. It is worth noting that the dehydrogenation was determined to be of mild endo‐
thermicity of 3.4 kJ (mol H2)-1, which is the first case reported so far and entirely different from
the exothermic dehydrogenation for monometal amidoboranes of NaAB and MgAB. This
indicates that dual-cation combination in amidoboranes plays a vital role in altering their
dehydrogenation thermodynamics. From thermodynamic point of view, the endothermic
dehydrogenation provides a possibility to achieve rehydrogenation at moderate conditions.
However, in this study, it was unsuccessful to recharge the solid residual at moderate
conditions.
4.10. Na2Mg(NH2BH3)4
Na2Mg(NH2BH3)4 was first synthesized by ball milling a mixture of NaH/MgH2/2AB [61]. It

was identified to have a space group of I41/a and approximate lattice parameters of a = 9.415
Å and c = 12.413 Å. The crystal structure illustrated in Figure 19 shows that Mg2+ is coordinated
with four [NH2BH3]− groups via Mg-N bonds (2.104 Å) to form [Mg(NH2BH3)4]2− tetrahedron.
Na+ is octahedrally coordinated only with six BH3 groups with the distances of Na-B ranging
from 2.900 to 3.634 Å. The distances of Na-H coordinations between Na+ and its close hydridic
H in BH3 groups are in the range of 2.383-2.943 Å. As a consequence, Mg2+ and Na+ are linked
through different coordinations with both ends of the bridging [NH2BH3]− groups and form
an ordered structure in coordinations. Na2Mg(NH2BH3)4 had an onset temperature for
dehydrogenation at ~65 °C and a total amount of 8.4 wt% H2 was released upon heating to 200
°C, with contamination by trace amount of borazine and ammonia. In another paper [62], a
wet-chemical method was proposed to synthesize pure Na2Mg(NH2BH3)4. Typically, a solid
mixture of Mg(NH2)2/2NaH/4AB was introduced into THF. After 0.7 Eq of gaseous products
(H2 and NH3) was released, pure Na2Mg(NH2BH3)4 as the precipitate was obtained through
filtration, which agrees well with the one synthesized by ball milling method [61].
4.11. K2Mg(NH2BH3)4
K2Mg(NH2BH3)4 was synthesized by ball milling method according to the reaction equation:
2Mg(NH2BH3)⋅NH3 + 2KH → K2Mg(NH2BH3)4 + Mg(NH2)2+ 2H2 [62]. Similarly,
Na2Mg(NH2BH3)4 could also be prepared through this procedure. However, as a by-product,
Mg(NH2)2 is very difficult to separate or remove. K2Mg(NH2BH3)4 crystallizes in a tetragonal
cell (space group I41/a) with lattice parameters of a = b = 9.5974(17) Å and c = 13.581(4) Å. As
shown in Figure 20, Mg2+ is tetrahedrally coordinated with four N atoms (2.115 Å for Mg−N
bond length) from four [NH2BH3]− groups to form [Mg(NH2BH3)4]2− species. Unlike Mg2+,
without the formation of K−N bond, K+ is octahedrally coordinated by six [Mg(NH2BH3)4]2−
groups through six K⋅⋅⋅BH3 coordinations with K-B distances ranging from 3.361 to 3.617 Å.
Due to the difficulties in the removal of Mg(NH2)2 from the products, the dehydrogenation
Figure 19. Crystal structure of Na2Mg(NH2BH3)4. Na: pink spheres; Mg: yellow spheres; N: blue spheres; B: orange
spheres; and H: white spheres. Reproduced from Ref. [61] with permission.
was measured based on the composite of [M2Mg(NH2BH3)4 + Mg(NH2)2, (M = Na, K)] [62]. A
very small amount of NH3 was released from room temperature to 150 °C before dehydro‐
genation for both composites, with a mass loss of 3.7 and 3.8 wt%. Hydrogen was released
with the most rapid rate at about 158 and 153 °C for [K2Mg(NH2BH3)4+Mg(NH2)2] and
[Na2Mg(NH2BH3)4+Mg(NH2)2] composites, respectively. Most important of all, both compo‐
sites exhibited the endothermic dehydrogenation in open system, i.e., 5.2 kJ (mol H2)-1 for
[Na2Mg(NH2BH3)4+Mg(NH2)2] and 7.0 kJ (mol H2)-1 for [K2Mg(NH2BH3)4+Mg(NH2)2]. A total
amount of about 7 and 7.8 wt% H2 was achieved upon heating to 285 °C for these two com‐
posites. However, the role of Mg(NH2)2 remains unknown in inducing endothermic dehydro‐
genation of composites. Further research into the interaction between amide and dual-metal
amidoborane is needed.
4.12. (Li,Al) amidoborane

Bimetallic (Li,Al) amidoborane was prepared by ball milling of 4AB/Li3AlH6 mixture [63]. It
was also observed after heating a post-milled mixture of LiAlH4/AB at 170 °C [64]. The
information of crystal structure was not reported in both references [63,64]. It could release
about 10 wt% H2 at 200 °C, with a significant suppression of volatile by-products. The post-
dehydrogenated products of (Li,Al) amidoborane could be regenerated through reduction by
hydrazine in liquid ammonia. Around 3.5 wt% H2 was released upon heating to 400 °C,
corresponding to a 35% regeneration yield [63].
5. Metal amidoborane ammoniates
Ammonia was a hydrogen-rich compound (17.7 wt%). As a strong Lewis base, it is used as a
ligand to form amine complexes with various compounds for hydrogen storage [65-69]. It is
Figure 20. Crystal structure of (a) K2Mg(NH2BH3)4, (b) Na2Mg(NH2BH3)4, (c) Coordination of Mg2+, and (d) Coordina‐
tion of K+. Reproduced from Ref. [62] with permission.
noted that because of the difference in electronegativity, positively charged H in NH3 can
interact with protic H in metal amidoboranes and borohydrides for facilitating hydrogen
release.
5.1. Lithium amidoborane ammoniate (LiNH2BH3⋅NH3, LiAB⋅NH3)
A new hybrid material with the formula of LiNH2BH3NH3 was produced from the mixed AB
and LiNH2 in a 1:1 molar ratio, which can be treated as a monoammoniate of LiAB. It rapidly
released 11.9 wt% H2 under 250 °C, with the most rapid rate observed at 60 °C [70]. In fact,
LiAB⋅NH3 was synthesized by reacting LiAB with an equivalent NH3 [71]. At room tempera‐
ture, it is a sticky matter in an amorphous state. Upon cooling to −20 °C, LiAB⋅NH3 becomes
a solid and crystallizes in an orthorhombic cell (space group Pbca), which has the lattice
parameters of a = 9.711(4) Å, b = 8.7027(5) Å, and c = 7.1999(1) Å. However, the crystal structure
was not reported in reference [71]. At room temperature, LiAB⋅NH3 decomposed into
ammonia and LiAB under vacuum. However, at temperatures more than 40 °C, favorable
dehydrogenation was observed. Volumetric release test showed that about 6.2 wt% H2 could
be released at 70 °C under argon, while 11.2 wt% H2 at 60 °C under ammonia.
5.2. Calcium amidoborane diammoniate (Ca(NH2BH3)2⋅2NH3, CaAB⋅2NH3)
In 2009, Chua et al. [72] reported the synthesis, structure, and dehydrogenation of
CaAB⋅2NH3. They provided two synthesizing methods, i.e., ball milling of Ca(NH2)2/2AB
mixture and reacting CaAB with two equivalent NH3. It crystallizes in an orthorhombic cell
(space group Pna21) with lattice parameters of a = 18.673(3) Å, b = 5.2283(8) Å, and c = 8.5748(12)
Å. Figure 21 shows that each Ca2+ has octahedral coordination through two Ca⋅⋅⋅NH3
coordinations (2.517 and 2.521 Å), two Ca⋅⋅⋅BH3 coordinations (2.650 and 2.807 Å), and two
Ca-N bonds (2.397 and 2.521 Å), which results in a bonding network of NH⋅⋅⋅HB dihydrogen
due to NH3 coordinations. CaAB⋅2NH3 decomposed into CaAB and 2 Eq of NH3 under 100 °C
in an open system. On the contrary, in a closed reactor, H2 rather than NH3 was released
predominantly due to the existence of NH3 equilibrium pressure, with an onset temperature
at ~70 °C. Almost 9 wt% H2 could be released upon heating to 300 °C. Compared to CaAB, the
onset temperature has a 50 °C reduction and the dehydrogenation capacity at 300 °C has a 2
wt% increase.
Figure 21. Crystal structure of CaAB⋅2NH3. Ca: green spheres; N: blue spheres; B: pink spheres; and H: white spheres.
Reproduced from Ref. [72] with permission.
5.3. Calcium amidoborane monoammoniate (Ca(NH2BH3)2⋅NH3, CaAB⋅NH3)
CaAB⋅NH3 was prepared by ball milling a mixture of CaNH/2AB [73]. Alternatively, ball
milling a mixture of Ca(NH2)2/CaH2/4AB could also give rise to the formation of CaAB⋅NH3
with accompanying 2 Eq of H2 released. It crystallizes in a monoclinic cell (space group of P21/

c) with lattice parameters of a = 10.5831(14) Å, b = 7.3689(11) Å, c = 10.2011(13) Å, and β =
120.796(6)° [73]. Unlike CaAB⋅2NH3, Ca2+ in CaAB⋅NH3 has a geometry of trigonal bipyramid
(Figure 22), in which Ca2+ is surrounded by two NH2 from [NH2BH3]− groups through Ca-N
bonds (2.400 and 2.465 Å), two BH3 from [NH2BH3]− groups through Ca⋅⋅⋅BH3 interactions
(2.669-3.182 Å), and one NH3 through Ca⋅⋅⋅NH3 interaction (2.472 Å). The special structure
resulted in the network of NH⋅⋅⋅HB dihydrogen bond. TG-DSC-MS tests revealed that NH3
was predominantly released under 100 °C with a weight loss of 12.6%, while 6.2 wt% H2 was
solely released from 100 to 300 °C. Compared with the theoretical value for deammoniation
of CaAB⋅NH3 (~14.5 wt%) and for dehydrogenation of CaAB (~8 wt%), some NH3 should
participate in dehydrogenation under 100 °C, which is evidenced by the concurrent release of
H2 from MS. However, in a closed reactor, hydrogen release in two steps was observed with
an exothermic event detected in the first step. At 300 °C, 6 Eq of H2 (~10.2 wt%) could be
released, in which the amount of by-product NH3 is less than 0.1 Eq.
Figure 22. A) Crystal structure of CaAB⋅NH3. (B) Coordination of Ca2+. Ca: green spheres; N: blue spheres; B: pink
spheres; and H: white spheres. Reproduced from Ref. [73] with permission.
5.4. Magnesium amidoborane monoammoniate (Mg(NH2BH3)2⋅NH3, MgAB⋅NH3)
Ball milling a mixture of Mg(NH2)2/2AB could give rise to the formation of magnesium
amidoborane diammoniate (Mg(NH2BH3)2⋅2NH3, MgAB⋅2NH3). Unlike solid CaAB⋅2NH3,
MgAB⋅2NH3 is a liquid matter at ambient condition. Upon releasing 1 Eq of NH3, solid
MgAB⋅NH3 was formed [74]. Alternatively, MgAB⋅NH3 could also be prepared by ball milling
a mixture of MgNH/2AB [74]. In a monoclinic cell (space group of P21/a), MgAB⋅NH3 has the
lattice parameters of a = 8.8815(6) Å, b = 8.9466(6) Å, c = 8.0701(5) Å, and β = 94.0744(48)°. As
shown in Figure 23, each Mg2+ has a tetrahedral coordination, in which Mg2+ forms two Mg-N
bonds (2.104 and 2.129 Å) with the adjacent [NH2BH3]− groups, a Mg⋅⋅⋅NH3 coordination
(2.157 Å) with the adjacent NH3, and a Mg⋅⋅⋅BH3 coordination (2.126 Å) with the adjacent
[NH2BH3]− group. In MgAB⋅NH3, a dihydrogen bonding network was established through the
interactions of NH⋅⋅⋅HB between NH3 and BH3 groups. Different from CaAB⋅2NH3 and
CaAB⋅NH3, the decomposition of MgAB⋅NH3 in an open system exhibited direct desorption
of H2 instead of NH3, indicating easier interaction between Hδ+ in NH3 and Hδ- in BH3 to the
formation of H2 or stronger Mg⋅⋅⋅NH3 coordination. Hydrogen release of MgAB⋅NH3 started
at about 50 °C, with 5.7 Eq of H2 (11.4 wt%) released up to 300 °C. An amorphous solid residue
with chemical composition of MgB2N3H was left. NH3 was undetectable during the whole
dehydrogenation process, which evidenced the complete conversion of NH3.
Figure 23. (a) Crystal structure of MgAB⋅NH3, and (b) Coordination of Mg2+. Mg: green spheres; N: blue spheres; B:
orange spheres; and H: white spheres. Reproduced from Ref. [74] with permission.
6. Metal borohydride-ammonia borane complexes
6.1. 2LiBH4⋅NH3BH3, 2LiBH4⋅AB
In 2010, the first metal borohydride-ammonia borane complex, namely, 2LiBH4⋅AB, was
reported [75]. It was synthesized by ball milling AB with two equivalent LiBH4 and had an
orthorhombic structure (space group Pnma) with lattice parameters of a = 8.3118(8) Å, b =
12.428(1) Å, and c = 6.5944(7) Å. Figure 24 shows that there are alternating layers of borohydride
and AB in 2LiBH4⋅AB. And Li+ and BH4− in the layer of borohydride remain their original
configuration in pristine LiBH4. Li+ has a tetrahedral coordination with one AB and three
BH4− groups. The distances between Li and H in BH4− are in the range of 2.023-2.246 Å,
analogous to those between Li and its two close hydridic H in AB (2.078 and 2.321 Å). The
BH⋅⋅⋅HN distances between BH4− and its nearby AB range from 2.248 to 2.254 Å, whereas the
BH⋅⋅⋅HN distance between the adjacent AB is 2.439 Å. Such a weak BH⋅⋅⋅HN interaction in
AB layers may be ascribed to the reinforced interactions of AB with the nearby H in BH4− and
also with Li+. Consequently, the intercalation of AB molecules into the crystal structure of
LiBH4 is basically stabilized by the interactions of AB with Li+ and BH4−. There were two steps
for dehydrogenation of 2LiBH4⋅AB, i.e., the first step occurring at 105-135 °C and the second
one at 360 °C, which are determined to be the dehydrogenation of pristine AB and LiBH4,
respectively. In addition, the suppression of ammonia was achieved compared with pristine
AB. It is worth noting that the dehydrogenated products of 2LiBH4⋅AB could reabsorb 2.4 wt
% H2 at 400 °C under 82 bar H2 pressure. In contrast, MBH4-AB (M = Na, K) do not form new
compounds during mechanochemical treatment [76].
Figure 24. Crystal structure of (a) 2LiBH4⋅AB and (b) Ca(BH4)2⋅AB. Coordination of (c) Li+ and (d) Ca2+. Li: pink
spheres; Ca: orange spheres; B: green spheres; N: blue spheres; and H: white spheres. Reproduced from Ref. [75] with
permission.
6.2. LiBH4⋅NH3BH3, LiBH4⋅AB
LiBH4⋅AB was prepared by mechanically milling AB with an equivalent LiBH4 [77]. It

crystallizes in a monoclinic cell (space group P21) with lattice parameters of a = 14.3131 (11) Å,
b= 4.3634 (5) Å, c= 15.3500(13) Å, and β= 90.325(11)°. In LiBH4⋅AB, there are LiBH4 columns
running along the b axis (Figure 25), which is notably different from 2LiBH4⋅AB. LiBH4
columns are segregated by the adjacent AB molecules and thus lose the structural similarity
to pristine one. In such an arrangement, Li+ has two different coordination environments, both
of which have a trigonal-planar coordination. One is coordinated by two BH4− and AB groups
and the other by three BH4− groups. The unique coordination of Li+ results in the remarkable
variations of the interactions of Li+ with its adjacent anions. For example, the distances of Li−B
are ranging from 2.22 to 2.81 Å. While the distances between Li and its two close hydridic H
in AB are 1.78 and 2.07 Å, much smaller than those in 2LiBH4⋅AB (2.08 and 2.32 Å) [75], which
indicates a stronger interaction between AB and Li+. The BH⋅⋅⋅HN distances between AB and
the adjacent BH4− are in a range of 1.85−2.31 Å, and those between nearby AB in AB layers are
1.86−2.39 Å, which demonstrates the presence of strong dihydrogen bonding throughout
LiBH4⋅AB. For thermolysis, LiBH4⋅AB first decomposed into 2LiBH4⋅AB and AB at about 54
°C and then exhibited a three-step dehydrogenation, with release of a total amount of ~15.7 wt
% H2 upon heating to 450 °C. Interestingly, h-BN was found to form in the post-dehydrogen‐
ated product at a moderate temperature of 450 °C (compared with other methods for h-BN
preparation), which resulted in the improved rehydrogenation and the following dehydro‐
genation properties of LiBH4⋅AB sample.
6.3. Ca(BH4)2⋅NH3BH3, Ca(BH4)2⋅AB
Ca(BH4)2⋅AB was prepared by ball milling Ca(BH4)2 with an equivalent of AB, which had an
orthorhombic cell (space group Aba2) with lattice parameters of a = 8.265(1) Å, b = 13.478(2) Å,
and c = 8.136(1) Å [75]. Each Ca2+ has an octahedral coordination, surrounded by two AB
molecules with Ca−B distances ranging from 2.899 to 2.923 Å and four BH4− groups (Figure
24). Unlike 2LiBH4⋅AB, the BH⋅⋅⋅HN distance between neighboring AB in AB layers of
Ca(BH4)2⋅AB is 1.735 Å, which indicates more powerful dihydrogen bonding. Through
dihydrogen bonding, AB also interacts with its adjacent BH4− with the BH⋅⋅⋅HN distances of
1.986−2.037 Å. Furthermore, the distances between Ca2+ and its two close hydridic H of AB are
2.441 and 2.504 Å, similar to those between Ca2+ and H in BH4− (2.412−2.477 Å). As a conse‐
quence, different from 2LiBH4⋅AB, AB layers and Ca(BH4)2 layers are interlaced primarily by
dihydrogen bonding in Ca(BH4)2⋅AB. For the case of hydrogen release, it has similar dehy‐
drogenation behaviors with 2LiBH4⋅AB, i.e., independent dehydrogenation of AB and
Ca(BH4)2 was observed, although the dehydrogenation temperature was slightly reduced to
some extent.
6.4. Mg(BH4)2⋅2NH3BH3, Mg(BH4)2⋅2AB
Mg(BH4)2⋅2AB was prepared by ball milling Mg(BH4)2 with 2 equivalent AB [78,79]. It has an
orthorhombic unit cell (space group P212121) with lattice parameters of a = 14.4135(2) Å, b =
13.2084(2) Å, and c = 5.1118(1) Å. As shown in Figure 26, each Mg2+ has a tetrahedral coordi‐
Figure 25. (a) Crystal structure of LiBH4⋅AB. (b) Li+ coordination. (c) Schematic arrangement of LiBH4 and AB compo‐
nents in the crystal structure. Li: yellow spheres; B: green spheres; N: blue spheres; and H: white spheres. Reproduced
from Ref. [77] with permission.
nation, surrounded by two BH4− groups and two AB groups with Mg-B distances in the range
of 2.394−2.500 Å. The distances between Mg2+ and its close H in AB range from 2.062 to 2.106
Å, while the distances between Mg2+ and its close H in BH4− are in the range of 1.987-2.033 Å.
Between AB and its nearby BH4− groups, there are BH⋅⋅⋅HN dihydrogen bonds with the
distances in the range of 2.210-2.274 Å. Mg(BH4)2⋅2AB melted at 48 °C and started to release
H2 at 75 °C [79]. It had a broad dehydrogenation peak at 126 °C with a releasing trace amount
of NH3, B2H6, and borazine. The following dehydrogenation in the range of 200-400 °C was
observed with two peaks at 297 °C and 340 °C. Volumetric release tests implied that the
dehydrogenation behaviors of Mg(BH4)2⋅2AB look like a combination of pristine AB in 30-200
°C and Mg(BH4)2 in 200-400 °C.
Figure 26. Crystal structure of (a) Mg(BH4)2⋅2AB and (b) Mg(BH4)2⋅2NH3⋅AB. Coordination of Mg2+ in (c)
Mg(BH4)2⋅2AB and (d) Mg(BH4)2⋅2NH3⋅AB. Mg: red spheres; B: pink spheres; N: blue spheres; and H: white spheres.
Reproduced from Ref. [78] with permission.
6.5. Al(BH4)3⋅NH3BH3, Al(BH4)3⋅AB
Al(BH4)3⋅AB was synthesized through a reaction between Al(BH4)3 and an equivalent AB

in a closed reactor at room temperature for 3 days, which could be accelerated by ball
milling [80]. The resulting white crystals of Al(BH4)3⋅AB revealed two polymorphs: the low-
temperature α-phase and the high-temperature β-phase. Pure α-phase was found only in
fresh samples, and it slowly transformed to β-phase at room temperature. Pure β-phase was
obtained upon heating α-phase to about 62 °C with 1 °C min−1, and it could not trans‐
form back to α-phase even cooling to -173 °C. Both phases crystallize in monoclinic cells
with space group of P21/c and Cc for α- and β-phase, respectively. α-phase has the lattice
parameters of a = 7.8585(2) Å, b = 6.86473(14) Å, c = 15.7136(8) Å, and β = 96.429(4)°, while
β-phase of a = 10.8196(8) Å, b = 7.2809(4) Å, c = 11.3260(9) Å, and β = 107.695(8)°. The crystal
structures of Al(BH4)3⋅AB in α-phase and β-phase are shown in Figure 27. In both struc‐
tures, Al3+ is coordinated with one AB and three BH4− to form a distorted tetrahedron of
AlB4. The interactions of NH⋅⋅⋅HB between NH3 and BH4− groups were formed in
Al(BH4)3⋅AB to sustain its 3D structure. The distances between Al and B in BH4− narrow‐
ly range from 2.21 to 2.23 Å, while the distance between Al and B in BH3 from AB is 2.31
Å. The distances between Al and H in BH4− are in the range of 1.65 −1.81 Å, while the
distances between Al and H in BH3 range from 1.86 to 1.96 Å. The thermal decomposi‐
tion of Al(BH4)3⋅AB at 70 °C gave rise to the release of 2 Eq of H2 (5 wt%), with a unique
intermediate found in [6H + 1H] coordination of Al3+. It is worth noting that the endother‐
mic dehydrogenation of Al(BH4)3⋅AB (39 kJ mol−1) was achieved.
7. Other derivatives
7.1. Mg(BH4)2⋅2NH3⋅NH3BH3, Mg(BH4)2⋅2NH3⋅AB
Mg(BH4)2⋅2NH3⋅AB was prepared by ball milling Mg(BH4)2⋅2NH3 with an equivalent AB

[78]. It had a tetragonal cell in space group of P4bm and the lattice parameters of a = 9.4643(8)
Å and c = 5.5229(8) Å (Figure 26). Each Mg2+ is tetrahedrally coordinated by two BH4− with
Mg-B distance of 2.30 Å and two NH3 groups with Mg-N distance of 2.14 Å. NH3 groups
interact with their close BH4− and AB groups through the formation of BH⋅⋅⋅HN dihydro‐
gen bonds(1.821-2.368 Å). Different from Mg(BH4)2⋅2AB, Mg(BH4)2⋅2NH3⋅AB exhibited
significant depression of by-products and tremendously improved H2 release. The onset
dehydrogenation was reduced to 75 °C, and about 9.6 wt% H2 could be released by 170 °C.
Upon heating to 400 °C, a total amount of 13.8 wt% H2 was desorbed.
For dehydrogenation improvement, Zr(BH4)4⋅8NH3 was ball milled with four equivalent AB.
Although no new compound formed after ball milling and the subsequent heating treatment,
it had an onset temperature at about 60 °C for dehydrogenation and could release 7.0 wt%
H2 at 100 °C in 45 min [81].
Figure 27. Crystal structure of Al(BH4)3⋅AB: (a) α-phase and (b) β-phase. Reproduced from Ref. [80] with permission.
7.2. LiCa(NH2)3(BH3)2
LiCa(NH2)3(BH3)2 was reported to be prepared by ball milling CaAB with an equivalent

LiNH2 [82]. Primary analysis showed that it crystallized in a monoclinic cell with lattice
parameters of a = 7.3021 Å, b = 12.5513 Å, c = 5.0595 Å, and β = 120.98°. However, the detailed
crystal structure was not given. The onset temperature for dehydrogenation was at about 50
°C and a total amount of 6.8 wt% H2 could be released exothermically upon heating to 300 °C,
without the detectable borazine and diborane.
7.3. Sodium aminodiborane (NaNH2(BH3)2)
NaNH2(BH3)2 with an infrequent NH2(BH3)2− anion was first reported by Girolami and
coworkers in 2010 [83]. It was synthesized by the reduction of AB with excess Na in THF at
room temperature and the following reflux. However, the target compound failed to isolate
from the resulting THF adduct. In a very recent paper [84], solvent-free NaNH2(BH3)2 was
prepared by reacting NaNH2 and two equivalent AB in THF. In a closed reactor,
NaNH2(BH3)2 could release 2 Eq of H2 (6.0 wt%) at 271 °C, forming solid products of NaBH4
and highly condensed polyborazylene.
7.4. LiNH2BH3⋅LiBH4, LiAB⋅LiBH4
LiAB⋅LiBH4 was synthesized by ball milling LiAB with an equivalent LiBH4 [85]. It was
ascribed to an orthorhombic cell (space group Pbca) with lattice parameters of a = 9.2824(18)
Å, b = 14.3092(28) Å, and c = 7.6194(12) Å. In LiAB⋅LiBH4 structure shown in Figure 28,
alternative LiAB and LiBH4 layers are stacked along the b axis. A strong interaction is resulting
from the formed ionic bonds by Li + with [NH2BH3]− and BH4−. Li+ has two tetrahedral coordi‐
nation environments. One is surrounded by one BH3 of [NH2BH3]− and three BH4−, while the
other by one NH2 of [NH2BH3]−, one BH4−, and two BH3 of [NH2BH3]−. Furthermore, the
BH⋅⋅⋅HN dihydrogen bondings range from 2.181 to 2.387 Å. However, the detailed dehydro‐
genation behavior of this compound was not given, although it had a similar process to 2LiAB/
LiBH4 reported in detail.
7.5. M(BH3NH2BH2NH2BH3), M = Li or Na
Preparation of M(BH3NH2BH2NH2BH3) (denoted as M(B3N2), M = Li or Na) was performed

through a wet-chemical method in THF, according to the reaction: MH + 3NH3BH3 →
M(BH3NH2BH2NH2BH3) + NH3 + 2H2 [86]. As stable white solids at room temperature,
Li(B3N2) crystallizes in a tetragonal cell (space group P4̄2c ) with lattice parameters of a = 4.02(1)
Å and c = 16.95(5) Å, while Na(B3N2) in a hexagonal cell (space group P63/m) of a = 4.3392(2)
Å and c = 17.853(6) Å. Both crystal structures are shown in Figure 29. In Li(B3N2), each layer
of Li+ is linked by (BH3NH2BH2NH2BH3)−. Li+ is tetrahedrally coordinated with four H atoms
from terminal BH3. The shortest distance between Li and H is 2.0 Å, and the average B-N bond
length in (BH3NH2BH2NH2BH3)− is about 1.59 Å. The twisty (BH3NH2BH2NH2BH3)− were
observed to lie along the c axis in Li(B3N2). It is worth noting that there is no interactions of
BH⋅⋅⋅HN between neighboring (BH3NH2BH2NH2BH3)−. For the case of Na(B3N2) structure,
there are some similarities to Li(B3N2), i.e., Na+ layers perpendicular to the c axis separated by
twisty (BH3NH2BH2NH2BH3)−. The most obvious difference is the fact that Na+ is coordinated
with eight H atoms with the closest Na-H distance of 2.22(9) Å. Upon heating, M(B3N2)
decomposed exothermally into MBH4 and H2. As an example, Li(B3N2) had a weight loss of
5.0 wt% at 140 °C, contributed to hydrogen release without any ammonia or other impurities.
Figure 28. (a) Crystal structure of LiAB⋅LiBH4 and (b, c) Coordination of Li+. Li: green spheres; N: blue spheres; B: cyan
spheres; and H: pink spheres. Reproduced from Ref. [85] with permission.
Figure 29. Crystal structure of Li(B3N2) and Na(B3N2): Li: green spheres; Na: yellow spheres; B: red spheres; N: blue
spheres; and H: grey spheres. Reproduced from Ref. [86] with permission.
8. Conclusions
In this chapter, metal amidoboranes, metal borohydride-ammonia borane complexes, and

metal amidoborane ammoniates as well as their derivatives were summarized with focus on
their structures and dehydrogenation properties. In addition, nanoconfinement and nanoca‐
talysis of AB for improving the dehydrogenation were also included. From scientific point of
view, some new B−N-containing compounds and their crystal structures were reported, which
enriches the chemistry of the scope of B and N elements. For the case of practical applications,
the fast dehydrogenation rate at around 60 °C and the stability under 40 °C is one of the most
important targets. Due to the difficulties in reversible hydrogenation of AB-related materials,
off-board regeneration of spent fuel with high-energy efficiency is another issue to be solved.
This would make it vitally important for altering the dehydrogenation thermodynamics from
exothermicity to endothermicity. What is exciting is the fact that some cases of endothermic
dehydrogenation were observed [60,62,80]. In this regard, it is indispensable for material
design. That means that both a large number of experimental studies and the related theoretical
calculations are urgently needed in the future. Moreover, catalytic modification should be
considered for the dehydrogenation kinetics. In addition, how to eliminate the un-wanted by-
products including ammonia, diborane, and borazine in the evolved hydrogen is also a critical
issue, which needs special attention to be given because they are detrimental to proton
exchange membrane (PEM) fuel cell, especially ammonia even with trace amount. As an
example, there is a controversial debate of NaAB dehydrogenation for ammonia contamina‐
tion [36,49,51]. Therefore, the mechanism for NH3 formation during dehydrogenation is
another task of further study.
Acknowledgements
The related research in this chapter was financially supported by the National Natural Science
Foundation of China (51361006, 51401059, 51461010, 51361005, and 51371060), the Guangxi
Natural Science Foundation (2014GXNSFAA118043, 2014GXNSFAA118333,
2013GXNSFBA019034, and 2013GXNSFBA019239), and the Guangxi University Research
Project (YB2014132). This work was partially sponsored by Guangxi Collaborative Innovation
Center of Structure and Property for New Energy Materials.
Author details
Hailiang Chu1,2*, Shujun Qiu1,2, Lixian Sun1,2 and Fen Xu1,2
1 Guangxi Key Laboratory of Information Materials, Guilin University of Electronic

Technology, Guilin, PR China
2 School of Materials Science and Engineering, Guilin University of Electronic Technology,

Guilin, China
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Chapter 4
Modeling of Hydrogen Absorption/Desorption in a

Metal Hydride Bed Reactor — A Theoretical Study
Olaitan Akanji and Andrei Kolesnikov
Abstract
Hydrogen has been considered as an alternative source of fuel to the fossil fuel in
future, most especially, for mobile applications. However, a requirement is the safe,
efficient and compact on- board storage of hydrogen. Reversible storage in metal
hydride is promising, but adequate knowledge of materials system fulfills all
requirements regarding hydrogen content is a major drawback, release temperature,
and reversibility simultaneously. Hydrogen absorption- desorption in a metal
hydride bed reactor can be modeled using different software such as FLUENT, CFD-
ACE, and COMSOL Multiphysics. This book chapter will focus on the use of software
COMSOL Multiphysics to simulate the diffusion and heating of hydrogen and metal
hydride powder in both radial and axial directions. The model consists of system of
partial differential equations (PDE) describing two-dimensional heat and mass
transfer of hydrogen in a porous matrix. The influence of the operating parameters
Temperature, Pressure, Concentration, Permeability and Thermal Conductivity on
the rate of absorption-desorption of hydrogen in metal hydride will be fully discussed.
The simulation results obtained could be applied to the on - board hydrogen storage
technology, in particular for the hydrogen supply of a fuel cell for powering of a
hydrogen fuel cell vehicle.
Keywords: Hydrogen, Storage, Metal hydride, Absorption, Desorption
1. Introduction
The excessive demand of Energy across the globe has risen sharply over the last decade. Today,
fossil- fuel- based sources of energy are being depleted at a fast rate because of the ever
increasing energy demand and consumption. In addition, fossil- fuels are contributing to both
greenhouse gas emissions and global warming [1]. Due to these hazardous effects, there should
be an urgent need for alternative and cleaner fuels which will be toxin free and environmentally
friendly. Hydrogen energy seems to be the best alternative for the future to replace the fossil
fuel and it already has several applications such as in heat pumps and automotive industries.
One of the main problems in large usage of hydrogen in automotive industry is the storage
problem. The conventional hydrogen storage methods in use for hydrogen gases are gas
compression and liquefaction. These storage methods are impractical since the former requires
very heavy gas tank and the latter is too expensive to be implement in public vehicles. Storing
hydrogen in metal hydride beds as a chemical compound appears to be method of hydrogen
storage in near future, and as this has received much interest recently [2]. There are several
important challenges to overcome before hydrogen can become a viable fuel. Only 1% of the
hydrogen is available as molecular hydrogen gas while the majority is present in the form of
water or hydrocarbons. The large- scale production of hydrogen from water or chemical
compounds in an efficient and clean method remains a challenge. Another challenge is storage
volume. Although hydrogen has high energy content by weight (three times that of gasoline),
its energy content by volume is only one-tenth that of gasoline. The process is major storage
volume problem in automotive and other mobile systems with stringent volume constraint. A
third challenge is hydrogen transport to filling stations. Because of the low density of hydro‐
gen, finding an economical way of transporting large amounts of hydrogen to various locations
is quiet illusive. The fourth challenge is the use of hydrogen as a fuel in producing clean energy
that would justify its wide acceptance in the market [1]. Hydrogen can be used to produce
energy either by burning with oxygen in air (e.g. internal combustion engine) or by electro‐
chemical reaction with oxygen using fuel cells. Fuel cells are both energy efficient and virtually
pollution free compared to internal combustion engines. The choice of energy production
method is dictated mainly by cost and application. A promising alternative method of storing
hydrogen in a fuel cell is solid-metal hydride storage utilizing metal hydride to absorb/desorbs
hydrogen at a relatively low pressure(<20-bar), which offers safety and cost advantage, but the
obvious disadvantage of weight for hydrogen onboard storage. Efficient release of hydrogen
gas in the metal hydride reactor should meet the need for fast load variation in order to build
and satisfy such hydrogen systems. The physics of the transport process coupled with reaction
kinetics are very important such as hydrogen mass flow in the hydride bed, heat transfer within
the bed and local hydrogen absorption rate. - [3]. Several mathematical models for analyzing
hydrogen absorption/desorption in metal hydride beds were presented in the literature:
Jemni and Nasrallah [3] presented a model for the two-dimensional transient heat and mass
transfer within a cylindrical reactor. The influence of some parameters (reactor radius,
temperature and inlet pressure) on the dynamic reactor performance was determined.
Aldas et al. [4] extended the mathematical model of jemni and Nasrallah to three- dimensions
demonstrating that hydrogen flow significantly influences the temperature profile in the
system
Mayer et al. [5] - developed a one- dimensional model which showed that heat and mass
transfer are key factors affecting reaction rate in the reactor.
Modeling of Hydrogen Absorption/Desorption in a Metal Hydride Bed Reactor — A Theoretical Study 97
Nakawaga et al.[6]- predicted the transient heat and mass transfer phenomenon through the
hydride bed by using a two-dimensional mathematical model with hydriding and dehydrid‐
ing kinetics.
2. Methodology
Those equations, which represent the mathematical model of hydrogen absorption/desorption

in metal hydride, are stated here, and implemented in COMSOL MULTIPHYSICS software to
validate the experiment performed by Jemni et al. [9] and the following parameters were
determined:
• Temperature variation during charging and discharging of hydrogen in metal hydride
reactor
• Variation in the density of metal hydride in the reactor during hydrogen charging and
discharging
• Variation in the pressure of hydrogen in metal hydride reactor during charging and
discharging
• Variation in the flow rate of the gas at the outlet of the metal hydride reactor
2.1. Mass balance
The mass conservation equation of the solid metal hydride is presented as follows:
¶r
(1 - e ) ¶ts =
m (1)
In Equation (1), the left side represents the accumulation/dissipation term for mass of metal
hydride, and the term on the right side represents mass of metal hydride release during
adsorption/desorption.
Mass balance equation for hydrogen gas is given by equation (2):-
¶r g
e
¶t
( )
+ Ñ r gug = m (2)
∂ ρg
In Equation (2), the term - ε ∂ t - represents accumulation/dissipation term for hydrogen gas
release during adsorption/desorption and the second term on the left side represents convec‐
tion transfer. The term on the right side represents amount of hydrogen gas release during
absorption/desorption.
K
u=
g
ÑP (3)
mg g
Equation (3) is called Darcy equation, and the velocity of hydrogen gas is calculated from this
equation. The equation term on the left side represents the velocity of the gas and the right-
hand side of the equation represents Darcy expression.
æ E ö Pg - Peq
=m Cd exp ç - d ÷ rs (4)
ç RgT ÷ Peq
è ø
The hydrogen release/consumption due to absorption/desorption is given by Equation (4).The

term on the left side represents the amount of hydrogen gas released during absorption/
desorption and the equation term on the right side represents the kinetic of absorption/
desorption of hydrogen.
2.2. Momentum balance and equilibrium pressure
Jemni et al. [3],- proposed the following equilibrium pressure equation
DH DS é æ C 1 öù b
( )
ln Peq = -
RT R
+ (j - f0 ) tan êp çç - ÷÷ ú + (5)
ëê è C m 2 ø úû 2
In Equation (5), the term on the left side represents equilibrium pressure. Vant Hoff derived
the right- hand side expression, the second term to the right is known as plateau value, and
the last term to the right is called hysteresis value.
( ) + Ñ æç - r
¶ r ge K ö
ÑPg ÷ = 0 (6)
¶t ç g
mg ÷
è ø
Equation (6), - represents the momentum balance, the first term to the left represents change
in momentum due to non-stationary equilibrium and the second term to the left represents
momentum change due to absorption inside the porous medium.
2
æ e ö
= C k × dp2 ç
K ÷
è1-e ø
Permeability K and porosity are related Equation (6) above, where dp is metal hydride particle
diameter and constant Ck=2.37x10-3.
2.3. Energy balance
Energy balance is written in assumption that porous metal hydride bed and hydrogen gas are
having the same temperature.
Energy balance equation (7) describes temperature evolution of the hydrogen porous bed
system-:
dæ r RT ö
ç er gC pgT + ( 1 - e ) r sC psT - e g
dt çè
( )
÷ + Ñ r gC pguT - leÑT + ( 1 - e )( -DH ) r s m = 0
M H2 ÷ø
(7)
The first term in Equation (7) to the left represents unsteady heat change in the system, and
second term to the left represents heat change in the system due to conduction and third term
to the left represents heat release/consumption due to chemical reaction in absorption-
desorption processes.
Effective thermal conductivity of metal hydride bed is expressed as:
le = elg + (1 - e )ls (8)
2.4. Conclusion
The dynamic model of the process incorporates coupling between hydrogen adsorption/
desorption, flow in porous media, and heat transfer in porous media and gas. The model also
assumes thermal equilibrium between metal hydride (solid phase) and hydrogen (gas phase).
The equations are implemented in computational software COMSOL 4.0a to solve for de‐
pendent variables such as temperature, metal hydride density, gas pressure, and velocity of
the gas.
2.5. Building the geometry
The geometry for the MHHST was presented as a cylindrical reactor where hydrogen is
adsorbed/desorbed in/out of metal-hydride powder stored in the reactor. Because of axial
symmetry, 2D model was used.
In COMSOL software, the geometry was built in the form of rectangles, and final geometry
was developed by the Boolean operations: forming union of three different rectangles and then
finding the Boolean differences.
One rectangle represents domain for hydrogen, the second rectangle represents the domain
for metal-hydride that will absorb/desorbs hydrogen, and the third rectangle represents the
domain that will supply heat to the system. The material used in for the tank walls is copper
due to its high conductivity. Copper walls were built as an envelope surrounding the metal
hydride rectangles. The contour line of the tank was built from certain geometrical points. The
points have different coordinates listed in the Table 1. The geometry of the tank is shown in
Figure 1. It can be seen that the tank has two radial ribs/fins for better thermal management.
Figure 1. Schematic of Metal hydride reactor.
R- coordinates Z- coordinates
0.025 0
0.025 0.05
0.025 0.075
0.025 0.15
0.025 0.175
0.025 0.24
0.05 0.05
0.05 0.075
R- coordinates Z- coordinates
0.05 0.15
0.05 0.175
Table 1. Geometry Coordinates
2.6. Computational mesh
Figure 2 shows the mesh of the MHHST and different boundaries. The portion of the MHHST
is taken as rectangular shape that comprises two computational domains (1 and 2). Domain 1
represents metal hydride insulated with copper body (Domain 2), which serves as a conductor
to supply/remove heat from metal hydride bed. The heat is supplied to metal hydride (or
removed) through the copper walls.
Figure 2. Computational Mesh.
2.7. Boundary conditions
The boundary conditions are described in Figure 3.

Figure 3. Boundaries within MHHST during hydrogen absorption and desorption
Figure 3. shows different boundaries within MHHST. Each boundary

Illustrates the heat and mass transfer of hydrogen during absorption and desorption.
The Following types of boundary conditions were used.
For modeling of heat transfer during absorption:
a. inlet/outlet −Boundary 12
b. wall − Boundary 9, 14...
c. flux − Boundary 9...
d. isolation − Boundary 9...
For modeling of momentum transfer during absorption:
a. inlet/outlet
b. wall
c. flux
d. isolation
For modeling of hydrogen diffusion during absorption:

a. inlet/outlet Pressure P = 40_bar_(absorption) or 10_bar_(desorption)
b. wall - C=Cwall = 293_K
c. flux Q=...h.(Text- T) mol/m2
d. isolation - dC/dz= 0
For modeling of heat transfer during desorption:
a. inlet− outlet − Boundary 12
b. wall−Boundary 9,Boundary 14, Boundary 16, T=293_K
c. flux – boundary 9 Q=...h.(Text- T) W/m2
d. Isolation – Boundary 9,Boundary 10, Boundary11−. dT/dz = 0

For modeling of momentum transfer during desorption:
a. inlet/outlet
b. Wall
c. Flux
d. Isolation
For modeling of hydrogen released during desorption:
a. inlet/outlet Pressure P =8_bar
b. wall, C=Cwall = rho_sat/Mg (mol/m3)
c. flux Q= h.(Text-T) (mol/m3)/m2
d. isolation, dC/dz=0
2.8. Initial conditions
At the beginning of the absorption, the system is at 293_K and the hydrogen is injected at the
top of the system (Boundary 12) with the pressure P= 40_bar, then the hydride absorbs and
the exothermic reaction raises the temperature.
At the beginning of the desorption, the system is at 333_K and the hydrogen is released from
the MHHST through the outlet of the system (Boundary 12) with the pressure P= 10_bar. The
temperature decreases slowly within the tank, due to the endothermic reaction, then hydrogen
desorbs slowly from the hydride.
2.9. Simulation variables, parameters, and function used
The mathematical model is applied to the geometry built above and various variables param‐
eter and functions used from the experimental work performed by Jemni et al (1995) are
defined specifically and solved with the aid of COMSOL MULTIPHYSICS software. The
density of metal hydride presented in the table for this research work is bulk densities (Table
2)
rho_s 6360_[kg/m^3] Bulk density of metal hydride at saturation
rho_emp − 6000[kg/m3] Bulk density of metal hydride
Cps − 419[j/kg/k] Solid- specific heat capacity
Cpg − 14890[j/kg/k] Gas- specific heat capacity
k_e − 1.32[w/m/k] effective thermal conductivity
K − 1e_08 permeability
epsilon 0.5 porosity
Mg 2.01588_03_[kg/mol] hydrogen molecular weight
Rg − 8.314[J/mol/k] universal gas constant
ca − 59.187_[1/s] absorption constant
cd − 9.57_[1/s] desorption constant
Ea − 21179.6[J/mol] absorption activation energy
Ed − 15473_[J/mol] desorption activation energy
T_ini − 293_[k] initial temperature
P_ini 156000_[Pa] initial pressure
deltaH −1.539e+07_[J/kg] heat of formation in abs/des reaction
eta − 9.2e-06_[Pa*S] dynamic viscosity
h1 − 150_[w/m /k] 2
heat source
v_out − 1.098_[m/s] outlet velocity
Po − 18_[bar] initial Pressure
P − 50_[bar] Pressure
Pg − P_[Pa] gas pressure from Darcy
Cps − 419_[j/kg/K] Solid specific heat capacity
Table 2. Variables and function used in simulation (Jemni et al. [3])
The developed mathematical model included the following variables and functions, which
were used to simulate heat and mass transfer inside hydrogen storage tank. The variables and
functions are listed in the Table 3 below.
T_ini 293_[K] Initial temperature
p_ini 143,220_[Pa] Initial pressure
c_ini rho_emp/Mg Initial concentration
rho_s c.*Mg Current density of solid MH
rho_sat 8527_[kg/m ] 3
Saturated density
rho_emp 8400_[kg/m3] Empty density
Cps 419_[J/kg/K] Solid specific heat
Cpg 14890_[J/kg/K] Gas specific heat
k_e 1.32_[W/m/K] Effective thermal conductivity
K 1e-08_[m^2] Permeability
deltaH -1.539e+07_[J/kg] Heat of formation in abs/des reaction
epsilon 0.5 Porosity of the gas
Mg 2.01588e-03[kg/mol] H2 mol weight
Rg 8.314[J/mol/K] Universal gas constant
Ca 59.187[1/s] Absorption constant
Cd 9.57[1/s] Desorption constant
Ea 21179.6[J/mol] Absorption activation energy
Ed 15473_[J/mol] Desorption activation energy
Pg p Gas pressure
Peqa 1000[Pa]*exp(17.6083704.6[K]/T) Equilibrium pressure of absorption
Peqd 1000[Pa]*exp(17.4783704.6[K]/T) Equilibrium pressure of desorption
m_des_fin if(Pg<Peqd,Cd*exp(Ed/(Rg*T)) Mass source during desorption process

*(g-Peqd)/Peqd*(rho_s-rho_emp),0)
m_abs_fin if(Pg"/>=Peqa,(Ca*exp(Ea/(Rg*T)) Mass source during absorption process

*log(Pg/Peqa)*(rho_sat-rho_s)),0)
m1 if(abs(m_des_fin)"/ Auxiliary term

>abs(m_abs_fin),m_des_fin,m_abs_fin)
M if(((m_des_fin==0)&&(m_abs_fin==0)), Total mass source/sink

0,m1)
Table 3. Simulation variables and functions
2.10. Model verification
To validate the model, the results of Jemni et al.[3] were used. The simulation results obtained
were compared with one obtained by Jemni et al. [10]. The comparison of the axial temperature
distribution in the paper of Jemni and the calculated results shows agreement with each other.
(Figure 4).
Further modification of simulation variables and functions used by Jemni et al. with intro‐
duction of some conditions upon simulation produced similar results, which can be shown in
the Figures 5 and 6. The main body of results obtained in current research is given in the
following Chapter.
Figure 4. Axial temperature distribution in metal hydride reactor. 1 – Experiment (Jemni et. al. [3]-), 2 – calculations.
Figure 5. Time evolution of temperature in metal hydride reactor during absorption at point with coordinates [0.08,
0.14] during the 600-s period.
Figure 6. Time evolution of temperature in metal hydride reactor during desorption at point with coordinates [0.08,
0.14] during the 600-s period.
There is a significant - agreement between the results obtained by Jemni et al. [3], and the
simulation for this work, for both absorption and desorption process. While Jemni et al. [10]
used the cylindrical tank as a reactor for metal hydride hydrogen storage, in this work, most
of the simulations were performed for the reactor with - rectangular fins.
3. Results and discussion
3.1. Dynamics of absorption process

Absorption process was simulated for hydrogen storage tank filled with AB5 type metal
hydride. The geometry of the tank and the boundary conditions were described in the sections
3.1 and 3.3. The position of the sensor (measurement point) for temperature, pressure, velocity,
and density has the following coordinates: radial coordinate r=0.08 m, axial coordinate z=0.14
m, which is approximately in the center of the metal hydride bed(Domain 1).
3.1.1. Temperature time distribution

Figure 7. illustrates the temperature distribution of hydrogen in MHHST during absorption
at point [0.08, 0.14] of the bed. The simulation results show a gradual increase in temperature
at different time interval. The total simulation time was taken to be 600_s. The temperature at
initial stage of the reaction was very slow but started to increase gradually from 200_s to 600_s,
due to the exothermic nature of the reaction between hydrogen and metal hydride. More heat
has been release into the bed and this tends to increase the temperature of the heating fluid.
A maximum temperature of 313K within the bed was reached.
Figure 7. Time evolution of temperature in metal hydride reactor at point with coordinates [0.08, 0.14] during the 600-s
period.
3.1.2. Pressure distribution
Figure 8. shows the pressure variation with time at point [0.08, 0.14] within the MHHST during
absorption reaction of hydrogen. It was observed that there is an increase in the pressure in
the bed during absorption process at various simulation times. More hydrogen was absorbed
due to increase in temperature and pressure in the MHHST bed, which was due to the
exothermic nature of the reaction. The pressure increased gradually from initial stage of the
reaction, which was 0_s to final time of 600_s. At this time, the maximum pressure was reached
in the bed, which is closer to the equilibrium pressure. The equilibrium pressure is
1000_[Pa]*exp[17.6083704.6[K]/T], in which the temperature T is 273_K, the temperature in the
middle of the reactor. Lower temperature yields more hydrogen,and the heat released during
reaction slows down subsequent reaction for higher coolant temperature. In addition, the
higher the charging pressure, the faster the reaction rate.
Figure 8. Time evolution of pressure in metal hydride bed at point with coordinates [0.08, 0.14] during the 600-s
3.1.3. Concentration distribution

Figure 9. illustrates the changes in the concentration of metal hydride when it absorbs
hydrogen at different time intervals. It was observed that the mass of metal hydride that was
loaded inside the bed changes with time gradually. At initial stage of the reaction, the
concentration of metal hydride is 4.2, this value reduces to 4.225x106 at the final simulation
time of 600_s. It can be concluded that at increasing time of the simulation, the concentration
of metal hydride in the bed will decrease further when fully absorbed hydrogen.
3.1.4. Hydrogen flow rate during absorption

Figure 10. illustrates the flow rate of hydrogen into MHHST at different time interval during
absorption. The flow of hydrogen into the metal hydride tends to increase with time. At the
point [0.08, 0.14] of the bed, the flow rate started to increase from 0 to 0.0025kg/s and further
increased to the maximum flow at a simulation time of 600s, where there is a larger absorption
of hydrogen in MHHST. It can be concluded that flow rate of hydrogen into MHHST tends to
increase with an increasing simulation time and a larger heat transfer coefficient values.
Figure 9. Time evolution of metal hydride concentration at the point with coordinates [0.08, 0.14] during the 600-s period
Figure 10. Flow rate of hydrogen in metal hydride during absorption in simulation time 600-s.
3.2. Dynamics of desorption process
3.2.1. Temperature time distribution during desorption
Figure 11 shows, the changes in the temperature at different times during the hydrogen
desorption from MHHST. Due to the endothermic nature of the reaction, the desorption of
hydrogen at initial stage, which is 0_s is very slow, and the temperature value was noticed to
be 293_K, which is the initial temperature of the simulation. As the time increases, the
temperature along the MHHST also tends to increase. This is happening up to the 600s. At that
time the temperature increases rapidly to much higher values. After a long time the system
comes down to thermal equilibrium with the heating fluid. It can be concluded that desorption
occurs very fast at higher temperatures with an increase of operating time.
Figure 11. Time evolution of temperature in metal hydride reactor at point with coordinates [0.08, 0.14] during 600s
period.
3.2.2. Pressure time distribution during desorption
Figure 12 shows that pressure distributions at the point [0.08, 0.14] within the MHHST during
desorption with initial gas phase pressure are set to be 10_bar, which is equal to equilibrium
temperature at 293_K (initial bed temperature). Although the MHHST is operated at 8_bar at
the start, the simulation shows that before the average pressure approaches the equilibrium
value, only the small amount of hydrogen in gas phase is released and there is no desorption
in this period. From Figure 12, we can see that there is initial pressure drop from 8bar to the
equilibrium pressure. The focus was based on what happened when desorption start (t=0). The
discharging pressure is set to be 1_bar.desorption rate increases as the coolant temperature
increases, since hydrogen desorption in metal hydride is an endothermic reaction. Moreover
the centre temperature drops down right after the desorption reaction occurs.
Figure 12. Pressure distribution of hydrogen from metal hydride at [0.08, 0.14] in simulation time 600s during desorp‐
tion.
3.2.3. Velocity time distribution during desorption
In Figure 13, the velocity of hydrogen released during desorption within MHHST is shown at
time interval of 600_s. At a point [0.08, 0.14] inside the MHHST, the velocity of hydrogen
increases with increasing simulation time due to endothermic nature of the reaction and tends
to decrease further as simulation time is increases. If the desorption temperature varies within
the bed and pressure is very low, the velocity of hydrogen increases.
Figure 13. Velocity distribution of hydrogen in metal hydride during desorption.
3.2.4. Concentration distribution
The concentration of hydrogen in metal hydride tank during reaction decreases rapidly with
time, as shown in Figure 14. There was a larger percentage of hydrogen in metal hydride
storage due to the cold nature of the wall and low heat transfer from the bed to the surrounding
cooling fluid, and this was due to low poor thermal conductivity of the metal hydride particles.
The concentration of hydrogen decreases as the time increases, and heat distribution within
the MHHST also increases. At higher temperature and higher heat transfer coefficient, the
concentration of hydrogen in metal hydride decreases with increasing simulation time.
3.2.5. Hydrogen flow rate
The rate of hydrogen desorption from metal hydride storage tank is shown in Figure 15. At
the start of the reaction, hydrogen desorption rate is very slow at 0_ s, but it increases gradually
with time as the tank is heated up at a temperature of 333K.more hydrogen was released from
metal hydride hydrogen storage tank. At simulation time of 600_s, larger percentage of
hydrogen was released from MHHST, and it is evidence that at increasing simulation time and
higher temperature, and low pressure, more hydrogen will be released.
Figure 14. Concentration of hydrogen in metal hydride during desorption at simulation time (600_s).
Figure 15. Hydrogen flow rate from metal hydride in simulation time 600s during desorption
3.2.6. Temperature distribution in the tank with fins
Figure 16 shows the temperature distribution within the MHHST during simulation of
hydrogen absorption and desorption at simulation time of 600_s.the temperature profile shows
two different temperature scales supplied to the system. The temperature supplied by the
copper plate to the system, which changes with time along the MHHST, the temperature
released by metal hydride when it absorbs/ desorbs hydrogen; it was observed that tempera‐
ture increases rapidly at different distances of the MHHST. The time taken for the temperature
to be released was 551.4_s.
Figure 16. Temperature pattern along the metal hydride hydrogen storage tank.
3.2.7. Pressure profile
Figure 17 shows the pressure distribution in MHHST during the simulation, there is an increase
in pressure along different distances within the computational domain of the tank. it was
observed that pressure increased rapidly from the equilibrium pressure to the set point
pressure of 40 bar at a temperature of 273_K within a simulation time of 600_s for absorption
process. In addition, for desorption process, the pressure decreases rapidly from the equili‐
brium pressure to set point pressure of 10bar at a temperature of 333_K within a simulation
time of 600s in the tank due to the endothermic nature of the reaction.
Figure 17. Pressure variation along metal hydride hydrogen storage tank.
4. Conclusions
The objectives of this research have been achieved, thus dynamic mathematical model for the
MHHST was developed. The following conclusions can be drawn;
1. In order to verify the model, the numerical model presented above was compared to
experimental results of Jemni et al, [3]. The influence of all the operating parameters
in the model such as temperature, pressure, density, velocity, and flow rate was
investigated. It was found that the pressure and temperature axial distribution in the
MHHST for absorption, are in good agreement with the measured experimental values
of Jemni et al. [3].
2. The simulations of heat and mass transfer for MHHST with different internal geometries
were done. Heat transfer, mass transfer and momentum transfer modules were effectively
incorporated in COMSOL Multiphysics 4.0a software. Geometry was built for the
problem, and boundary conditions were properly allocated to the each domain in the
model. The energy (convection and conduction), mass (diffusion), and momentum
(Darcy’s law) transport equations and some specific user – defined subroutines were
implemented in the software. It was discovered that the geometry with fins results in faster
absorption and desorption when compared with the geometry without fins, in which the
absorption/desorption rate is very slow and produce very negligible values for absorp‐
tion/desorption rate.
3. Temperature, pressure and density non-steady distributions inside the metal hydride
porous bed were revealed. It was found that absorption occurs faster at a lower temper‐
ature and higher pressure because absorption process is exothermic reaction, and
desorption occurs at higher temperature and lower pressure due to the endothermic
nature of desorption process. Concentration increases with absorption of hydrogen and
decreases with desorption of hydrogen.
5. Abbreviations
2D; Two-Dimensional
PDE; Partial differential Equations
MHHST; Metal hydride hydrogen storage tank
USDE; United States Department of Energy
CFD; Computational Fluid Dynamic
DOE; Department of Energy
PEMFC; Proton exchange membrane fuel cell
ODEs; Ordinary differential equations
HHV; Higher heating value
LHV; Lower heating value
SPEFC; Solid polymer electrolyte fuel cell
MFPM Multi; facilitated proton membrane
DFAFC; Direct formic acid fuel cell
Acknowledgements
The authors will like to express their sincere gratitude to the faculty of Engineering and built
environment, Tshwane University of Technology Pretoria South Africa for her financial
assistance.
Author details
Olaitan Akanji* and Andrei Kolesnikov
Department of Chemical, Metallurgical & Materials Engineering, Tshwane University of
Technology, Pretoria, South Africa
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Section 4
Hydrogen Utilization
Chapter 5
Treatment of Hydrogen Bonds in Protein Simulations
Ya Gao, Ye Mei and John Z. H. Zhang
Abstract
The hydrogen bond plays an essential role in maintaining the secondary structures of
protein, and an accurate description of hydrogen bond interaction is critical in protein
folding simulation. Modern classical force fields treat hydrogen bonding as nonbond‐
ed interaction, which is dominated by electrostatic interaction. However, in the widely
used nonpolarizable force fields, atomic charges are fixed and are determined in a
mean-field fashion. Applying nonpolarizable AMBER force field in the folding
simulations of some short peptides, the native structure cannot be well populated.
When polarization effect is introduced into the simulation by utilizing either the on-
the-fly charge fitting or the polarizable hydrogen bond model, the native structure
becomes prominent in the free energy landscape. These studies highlight the necessity
of electrostatic polarization effect in protein simulation.
Keywords: hydrogen bond, quantum mechanics, molecular mechanics
1. Introduction
The function and chemical properties of protein are determined by its three-dimensional
structure.[1, 3] The native structure of protein at physiological temperature and solvent
condition, which is located at a free energy minimum, is a result of delicate balance between
many competing interactions, including van der Waals forces, hydrophobic interaction, and
electrostatic interaction, such as salt bridge and hydrogen bond (H-bond).[4, 5] During folding
process, the unfolded structure collapses first to minimize the area of hydrophobic surface that
is exposed to the solvent and hydrogen bonds begin to form. Hydrogen bonds, providing most
of the directional interactions, are the dominant feature in the formation of protein secondary
or tertiary structures. They play an indispensable role in the stabilization of the native structure
of a protein. α helix and pleated β -sheet were predicted in 1951 by Linus Pauling and Robert
Corey on the basis of hydrogen bonding and cooperative criteria.[6] Therefore, correctly
describing the thermodynamic properties of inter/intra-protein hydrogen bonds is essential.
Hydrogen bond is formed when an electronegative atom (H-bond acceptor, A) approaches a
hydrogen atom bonded to another electronegative atom (H-bond donor, D). There exist many
hydrogen bond donors and acceptors in proteins, such as the amide and carbonyl groups of
the backbone, as well as the polar functional groups (amides, carboxyl groups, hydroxyl
groups, and amines) in the side chains of some amino acids.
Different parameters can shed light on the different aspects of the nature of H-bonds estab‐
lished for a given system. The interaction energy is the best indicator of H-bond strength. The
geometry of the H-bond complex, and in particular, the distance and angle around the H-bond
also provide a very good indication of such interaction. When a hydrogen bond is formed, the
distance between the H and the acceptor (A) atoms has to be smaller than the sum of their
corresponding van der Waals radii. Furthermore, the D–H–A angle should be close to 180º. In
practice, a cutoff of 120 or 90º is employed. Now, it is well accepted that, in neutral systems,
H-bonds formed between O, N, or O/N pairs of atoms are very strong, whereas those formed
between C-H and a π system are weak. The formation of an H-bond can usually cause red shift
of IR spectroscopic bands, even though improper blue shifts have been also detected.
2. Computational studies of hydrogen bonds
2.1. Quantum chemistry method

Quantum chemistry method is an ideal approach to calculate the energy of a hydrogen bonded
system since all electronic and steric effects are fully taken into account. Molecular orbital
methods, especially the post Hartree–Fock (HF) methods, are capable of providing an accurate
description of systems containing hydrogen bonds. Thus, Møller–Plesset methods such as
MP2[7] can be considered ideal for the study of hydrogen bonds. However, even a single point
calculation at MP2 level of medium-sized hydrogen bond systems can be very demanding.
Density functional theory (DFT) methods such as B3LYP[8, 9] is becoming more and more
popular these days. It has been shown that B3LYP calculation provides very good description
of strong H-bond systems, comparing with the experimental data or MP2 results. However,
Kim et al. have shown that in the case of some systems with weak H-bond such as C-H π or
O-H π , B3LYP does not offer the same level of reliability as MP2.[10]
The basis set superposition error (BSSE) is another issue to be considered in the computation
of H-bond complexes, which arises because of the incompleteness of the basis set functions.
Applying the basis set of the complex to each molecule will yield a lower energy than that from
the calculation with the basis set for the monomer itself. Therefore, BSSE introduces a non‐
physical attraction between the two monomers. It has been shown that the BSSE correction of
the potential energy surface leads to sizeable differences in the H-bond lengths for correlated
calculations using split-valence basis sets with polarization and diffuse functions.
Treatment of Hydrogen Bonds in Protein Simulations 123
Although much progress has been made for investigating the nature of H-bonds utilizing
quantum chemistry methods, few ab initio calculations have been carried out on the calculation
of dynamic properties of hydrogen bond interaction for biomolecules due to relatively large
size of systems. Thus, a more efficient computational method is desired.
2.2. Molecular mechanics method

Molecular mechanics is a popular computational method, in which the electronic degrees of
freedom of the molecules are ignored, and only motions of the nuclei are calculated. The
fundamental assumption underlying all molecular mechanics methodologies is the Born–
Oppenheimer approximation, which allows separated motions for nuclear and electrons.
In molecular mechanics methods, the molecule of interest and surrounding solvent are
typically treated as classical particles interacting through an empirically derived and compu‐
tationally tractable potential energy function (“force field”). Molecular dynamics or Monte
Carlo simulations can provide wealth of information to interpret, complement and design
experiments. Most force fields were developed in the early 1980s, such as AMBER, CHARMM,
and OPLS. In the first-generation AMBER force field, hydrogen bond energy is explicitly
Cij Dij
expressed as a 10–12 function as Rij12
− Rij10
. The inclusion of the first term is to prevent the
occurrence of unrealistically short H-bonds and the second term is to “fine tune” the H-bond
distances and energies to desired values.
This kind of potential function had not been changed until AMBER94 force field was proposed.
In AMBER94, hydrogen bond is incorporated into electrostatics interaction due to the im‐
proved performance of the new RESP charge model and new van der Waals parameters.
Current AMBER force fields, following the potential energy functional form of AMBER94,
comprise bonded (bond, angle, and dihedral) and nonbonded terms (van der Waals and
electrostatic interaction), which are parameterized against gas phase quantum chemical
calculations, spectroscopic, and thermodynamics experimental data of small model molecules.
The potential energy function has the following form.
å K (b - b ) å Kq (q - q )
2 2
V=
(r ) b 0
+ 0
bonds angles
+ å Aij / r
nonbij
( 12
ij ) - (B ij
/r 6
ij ) + (q qi j
/ rij )
+ å (V
dihedrals
n (
/ 2 ) 1 + cos éënf - d ùû )
3. Treatment of hydrogen bond in protein simulations
3.1. Deficiency in the treatment of hydrogen bond

Utilizing molecular dynamics simulations to investigate the structural properties of proteins
has been an important tool in biological science for decades. With continuous advancing of
computer technology, the difficulty in time scale for protein simulation is lessened signifi‐
cantly. For example, D. E. Shaw utilized a specialized supercomputer, Anton, to investigate
the folding mechanism of a series of proteins, and the simulation time was extended to
microseconds.[11] A 58-residue protein BPTI conducted by Shaw also reached one millisecond.
[12] However, successful application of computer simulation is impeded by the accuracy of
force field employed. Defects in the potential energy could strongly bias the simulation results
toward incorrect conformations.
An important deficiency that exists in current pairwise force fields is lack of polarization.[13,
16] When an isolated molecule interacts with another molecule, or is placed in an external
electric field, its charge distribution will be distorted due to polarization effect. Current force
fields are amino-acid specific or mean-field like and, therefore, fail to give accurate represen‐
tation of the electrostatics of the specific protein environment, which is highly inhomogeneous
and protein specific. In a previous work of Zhang et al.,[17] a short α -helix cannot fold to its
native structure with AMBER03 [18] force field, despite that this force field has been proved
to bias helical conformation.[19] In the past two decades, many attempts have been made to
explicitly incorporate polarization effects into molecular modeling,[20] such as the fluctuating
charge model,[21, 22] Drude oscillator,[23, 24] induced multipole,[25, 29] and quantum
mechanical treatment.[30, 33]
3.2. Improvement in the treatment of hydrogen bonds

Based on a recently proposed fragment-based scheme (molecular fractionation with conjugate
caps, MFCC), a new scheme termed polarized protein-specific charge (PPC) model has been
proposed for protein dynamics.[34] PPC is derived from first principle quantum calculation
and therefore can correctly represent the electronically polarized state of the protein. It has
been proven that the polarization effect plays an important role in pKa shifts for ionizable
residues,[34] hydrogen bond stability,[35, 40] protein folding, and native structure stabiliza‐
tion,[17, 41, 45] dynamic properties of proteins,[46, 48] protein–ligand binding affinity,[47, 49,
51] and protein–protein recognition specificity.[52] The polarization of backbone hydrogen
bonding is found critical to the success of folding simulation of proteins. In those works, the
polarization of hydrogen bonds is included in the simulations by performing on-the-fly
quantum mechanical calculations to generate dynamically updated atomic charges. However,
on-the-fly charge fitting is computationally expensive, in which quantum mechanical calcu‐
lations must be periodically carried out to obtain new atomic charges for residues involved in
hydrogen bond formation or cleavage. It is desirable to employ a simpler but effective method
to include polarization of hydrogen bond for protein simulation. Thus, a new polarization
model for the main chain hydrogen bond based on an analytical fitting of atomic charges was
proposed, which is computationally more efficient.[53]
In the fitting, a pair of alanine dipeptides with a backbone hydrogen bond was utilized as the
model system, which is shown in Figure 1.
Atomic charges are calculated by a restrained fitting to the electrostatic potential generated
from quantum chemistry calculation.[54, 56] By varying the donor–acceptor distance but
keeping the other degree of freedom fixed, the charge variation of atom N and O with respect
Figure 1. Left: model system used in fitting the atomic charge polarization as function of donor–acceptor distance in
hydrogen bond pair. The charge transfer is only allowed between N and H, and between C and O as dipeptide in the
ellipses. Right: amount of charge transfer as a function of donor–acceptor distance of atoms O (top) and N (bottom).
to their asymptotic values are shown in Figure 1, both of which can be fitted to a single
exponential function. In this approach, charge transfer between residues is not allowed and
only the atomic charges of the N, H, C, and O atoms in the hydrogen bond can vary. Thus, the
amounts of charge transferred for H and C atoms are exactly the negative of that for N and O
atoms, respectively. The fitted functional forms for N and O atoms are
-0.493 ´ exp ( -0.455 R ) ,

DqN =
and
DqO= 0.743 ´ exp ( -0.466 R ) ,
in which R is the donor–acceptor distance in angstroms. As shown in Figure 1, at the normal

hydrogen bond length (∼3 Å), the transferred charge is only about 0.1 e and 0.13 e for N and
O atoms, respectively. In the charge fitting procedure, mutual polarization was included.
Specifically, in the calculation of one dipeptide, the other one was taken as background charges
centered at atomic positions. The calculation was iterated until convergence was reached.
When the two dipeptides are infinitely separated, the residues are given the corresponding
AMBER charges. Thus, the charge variation can be determined by hydrogen bond length alone.
Compared with PPC model, this polarized hydrogen bond (PHB) charge model is more
efficient. In the current approach, only the main chain hydrogen bonds are considered.
Hydrogen bonds involving side chain atoms, as well as salt bridges, also have strong electro‐
static polarization effect, which may be taken into consideration by refined versions of this
approach.
4. Applications
4.1. Folding of a short helix under the PPC model
Electrostatic polarization and charge transfer play important roles in protein folding.[57, 58]
However, the fixed PPC from a prefixed structure cannot present the dynamic properties of
protein accurately, which undergoes a large conformational change in folding. A straightfor‐
ward method is performing on-the-fly quantum calculation to generate dynamically updated
atomic charge at each step of the molecular dynamics simulations. However, the computa‐
tional demanding is too expensive. A good approximation is implementing polarization into
molecular simulations when hydrogen bonds form or break, which is a good indicator of
secondary structure. During simulations, only residues involved in the formation or breaking
of hydrogen bonds are subjected to quantum calculation to refit atomic charges, while charges
of the rest residues are kept to their previous values.
The folding of a short α -helix 2I9M,[59] which is a “de novo”-designed 17-residue peptide,
was investigated by employing the dynamic PPC model in molecular dynamics simulations.
For comparison, REMD simulation under AMBER03 force field is also performed. Starting
from a linear structure, the peptide was successfully folded to its native state with the low
backbone root mean square deviation (RMSD) under PPC model. In contrast, due to the lack
of polarization effect, the hydrogen bonds of the peptide are too “loose” to form stable
secondary structure under AMBER03 force field, as shown in Figure 2.
Figure 2. Snapshots of the intermediate structures of peptide 2I9M in simulations using AMBER (upper) and dynami‐
cally polarized charge (lower). α -helix, purple; coil, white; turn, cyan. Reprinted with permission from ref. 17. Copy‐
right 2010, American Chemical Society.
Thus, polarized protein-specific charge, especially polarized hydrogen bond charge, plays a
critical role in the formation of secondary structures.
4.2. The thermal stability of a short helix under the PHB model
REMD simulations with 12 replicas (temperatures 267, 283, 300, 328, 353, 380, 409, 439, 471,
506, 542, and 577 K) were also performed for investigating the impact of H-bonds on the
thermal stability of the peptide. Comparing with standard molecular dynamics simulation at
room temperature, the energy barrier can be surmounted much more easily at high-tempera‐
ture replicas.[60] Two sets of MD simulations were performed using, respectively, the standard
AMBER03 and the PHB model. In the PHB model, only atomic charges of donors and acceptors
in hydrogen bonds are different, whereas other force field parameters were taken from the
AMBER03 force field. The starting conformation was a linear structure generated using LEaP
module in AmberTools and relaxed using energy minimization. The relaxed structure was
heated to its target temperature for each replica in 100 ps. The solvation effect was modeled
using the generalized Born (GB) model developed by Onufriev et al.[61] MD simulations were
extended to 120 ns for each replica.
The structure with RMSD from NMR structure below 2 Å was classified as the folded state.
The populations of the folded structure in two REMD simulations show a clear difference, as
shown in Figure 3.
Figure 3. Fraction of folded structure defined by root-mean-square deviation from the NMR structure below 2 as a
function of temperature in the simulations utilizing AMBER03 charge (black) and PHB charge (red). Reprinted with
permission from ref. 53. Copyright 2012, American Chemical Society.
At the lowest temperature (267 K), the percentage of folded structure using PHB charge model
was nearly 30% higher than that in AMBER03 force field. At NMR experimental temperature
(283 K), the fraction of folded structure in the PHB model is over 50%, whereas that in
AMBER03 force field is only about 35%, despite the overestimated helical propensity of
AMBER03 force field.
The melting temperature is defined as the temperature at which the free energies of the native
and unfolded states are equal, indicating the equal population (50% each) of folded and
unfolded states. In Figure 3, the melting temperature under AMBER03 force field is well below
the NMR temperature of 283 K, which is obviously inconsistent with the experimental
observation, suggesting 2I9M is thermally unstable. While under PHB model, the melting
temperature is about 286 K, which is in agreement with the experiment. This result shows that
hydrogen bond polarization is critical to the thermal stability of the helical structure of 2I9M.
The distribution of the peptide structure from the REMD simulation is determined by the free
energy distribution, which is calculated by Weighted Histogram Analysis Method (WHAM)
[62, 63] using density of states. Figure 4 plots the free energy changes along the RMSD at 267,
283, and 300 K using both the AMBER03 and PHB model.
Figure 4. Free energy curves as a function of the RMSD from the NMR structure in simulation utilizing AMBER03
charge (black) and PHB charge (red) at (top) 267 K, (middle) 283 K, and (bottom) 300 K. Reprinted with permission
from ref. 53. Copyright 2012, American Chemical Society.
The free energy curve under AMBER03 force field is first examined. At 267 K (top figure), the
free energy curve has a global minimum at RMSD around 1.6 Å and also a local minimum at
an RMSD value around 4 Å (unfolded state). The energy difference between the global
minimum and the local minimum is only 0.5 kcal/mol, indicating comparable populations of
structures are distributed at these two geometries. While the free energy curve under the PHB
model displays two nearly degenerate minima at RMSD near 1.25 and 1.6 Å, both representing
the folded structures. The free energy is essentially flat between the two minima. While at
RMSD = 3.5 Å, the free energy curve shows a very shallow local minimum, which is about 1
kcal/mol higher than the global minimum. This free energy curve explains why the helix is
thermally more stable under the PHB model. By increasing temperatures, the free energy curve
becomes flatter and the minimum at 1.25 Å gradually disappears but the minimum at 1.6 Å
remains, as shown in the middle and bottom figures of Figure 4. While under AMBER03 force
field, comparing the free energy curves at 283 and 300 K with those at 267 K, we observe that
the free energy difference between the folded and the unfolded states gradually diminished.
The above analysis implies the importance of polarization of backbone hydrogen bonding to
the helix formation and the thermal stability of the helix, which is consistent with the observed
effect of hydrogen bond cooperativity.[64, 67] The distributions of the number of hydrogen
bonds at 267, 283, and 300 K in both REMD simulations are plotted in Figure 5. The number
of hydrogen bond is counted using a sigmoidal function of the donor–acceptor distance d as
related to the strength of hydrogen bonds. It shows that the peak shifts from 3.8 under the
AMBER03 charge to 5.0 under the PHB model at 283 K, indicating that hydrogen bonds are
strengthened by including the polarization effect. Decreasing the temperature to 267 K, the
difference between the AMBER03 charge and PHB model becomes more remarkable, whereas
increasing the temperature to 300 K does the opposite.
Figure 5. Distribution of native hydrogen bonds population in 267, 283, and 300 K trajectories utilizing the AMBER03
charge (top) and PHB model (bottom). Reprinted with permission from ref. 53. Copyright 2012, American Chemical
Society.
4.3. Folding of a long helix under the PHB model
2KHK is a 53 amino acid straight long helix belonging to b30 to 82 domain of F1Fo adenosine-5-
triphosphate synthesis in Escherichia coli. In order to minimize the overall size of the water box
in MD simulations with explicit water, a 10-ns MD simulation with implicit water was
performed first. The last snapshot from this short MD simulation was extracted as the initial
structure (shown in Figure 6) for explicit water simulation. Simulations were performed using
both the standard AMBER03 force field and the PHB model, respectively.
Figure 6. The last snapshots of implicit water simulations (a) under AMBER03 force field and (b) PHB model. Reprint‐
ed with permission from ref. 45. Copyright 2013, AIP Publishing LLC.
The variations of RMSD from the native structure and radius of gyration (Rg) along the
simulation time are shown in Figure 7.
Figure 7. Backbone RMSD from the native structure and radius of gyration as a function of simulation time using AM‐
BER03 charge (black) and the PHB (red) model in explicit water. The representative structures and their relative distri‐
butions from these two simulations are also plotted (right panels). Reprinted with permission from ref. 45. Copyright
2013, AIP Publishing LLC.
The overall fluctuations of RMSD and Rg using AMBER03 charges are both larger than those
using PHB model. The most populated state under PHB model has an RMSD of 2.1 Å, while
under standard AMBER simulation, it is as large as 4.0 Å. The result indicates that hydrogen
bond polarization helps the folding of long helix, which is also reflected from the fluctuation
of Rg along the simulation time. Under PHB simulation, initially the peptide adopts a more
compact structure than the native structure. After 75 ns, the Rg wanders around the experi‐
mental value with small fluctuation. While under AMBER03 force field, Rg gradually deviated
from the native state. Snapshots of the intermediate states along the simulation time under
PHB model are plotted in Figure 8.
Figure 8. Snapshots of intermediate structures of the peptide at different simulation time under PHB model (compared
to the NMR structure). The C-terminal is always on the top. Reprinted with permission from ref. 45. Copyright 2013,
AIP Publishing LLC.
It is noted that although the structure near the N-terminal of the peptide is flexible, the helix
in the middle region is becoming more and more stable as simulation goes on.
The two-dimensional free energy landscapes from MD simulations under both AMBER03
force field and PHB model are shown in Figure 9, using the RMSD and Rg of the backbone as
the reaction coordinates.
Figure 9. Free energy landscapes at 288 K mapped to RMSD from the native structure and radius of gyration obtained
from simulations employing (top) AMBER 03 charge and (bottom) PHB model. The representative structures are also
shown in the figure. Reprinted with permission from ref. 45. Copyright 2013, AIP Publishing LLC.
Under AMBER03 force fields, due to the lack of polarization effect, enthalpy change may not
be enough to compensate for the entropy loss in the formation of secondary structure. The
global minimum located at RMSD of around 4.1 Å and Rg around 17.2 Å (versus 20.3 Å
calculated from the nuclear magnetic resonance (NMR) structure). The representative struc‐
ture is obviously twisted from the middle of the peptide as shown in Figure 9 (top panel).
Therefore, no stable native structure is founded in standard AMBER simulation. For compar‐
ison, the free energy landscape under the PHB model displays a global minimum at RMSD
around 2.0 Å (folded state), as shown in Figure 9 (bottom panel). The global minimum obtained
in the PHB model has an Rg value of about 20.0 Å, which is very close to the NMR value of
20.3 Å. There is also a local minimum at RMSD around 3.1 Å, which is a partially unfolded
state. At this local minimum, the N terminal of the peptide is unfolded, but the middle helical
fragment is almost intact. This free energy analysis shows that the helix is thermally more
stable under the PHB model.
5. Summary
Among many factors that are important to protein stability, hydrogen bonds are found to
correlate highly with the thermal stability. They are the dominant feature in protein secondary
structures of α helices and β sheets. Recent theoretical studies demonstrated that the strength
of hydrogen bonds from simulations under standard nonpolarizable force fields is underesti‐
mated due to the lack of polarization effect.
In this chapter, we present an accurate and efficient polarizable hydrogen bond model that
can be implemented in molecular dynamics simulations. By investigating the thermal stability
of a short α helical peptide and the folding of a long α helical peptide, it shows that including
polarization effect is very important in maintaining the hydrogen bonds, stabilizing the
structure, and folding protein to its native conformation. It also should be noted that folding
simulations of peptides with β sheets or mixed helix-sheet structures are still very challenging.
The difficulty lies in not only the lack of polarization effect but also the unbalanced secondary
structure propensity in used force fields.
Author details
Ya Gao1, Ye Mei2,3* and John Z. H. Zhang2,3
1 College of Fundamental Studies, Shanghai University of Engineering Science, Shanghai,

China
2 Center for Laser and Computational Biophysics, State Key Laboratory of Precision Spec‐
troscopy, Department of Physics and Institute of Theoretical and Computational Science,
East China Normal University, Shanghai, China
3 NYU-ECNU Center for Computational Chemistry at NYU Shanghai, Shanghai, China

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Hydrogen, as an energy carrier, is widely regarded as a potential cost-effective,

renewable, and clean energy alternative to fossil fuels in order to mitigate the energy
shortage and environmental pollution that are currently being faced. The rapid
development of advanced materials in hydrogen production, storage, and utilization
has opened up a new avenue for the conversion and utilization of hydrogen energy.
This book summarizes the current research progress in these areas and is expected
to aid in the development and design of advanced materials to improve hydrogen
production, storage, and utilization.
ISBN
ISBN978-953-51-6642-9
978-953-51-2219-7
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Advanced Materials For Hydrogen Production

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Advanced Materials For Hydrogen Production

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Advanced Materials for

Edited by Jianjun Liu

© The Editor(s) and the Author(s) 2015

First published in Croatia, 2015 by INTECH d.o.o.

Legal deposit, Croatia: National and University Library in Zagreb

Additional hard and PDF copies can be obtained from [email protected]

Advanced Materials for Renewable Hydrogen Production, Storage and Utilization

3,800+ 116,000+ 120M+

Our authors are among the

Selection of our books indexed in the Book Citation Index

Interested in publishing with us?

Professor Jianjun Liu received his Ph.D. in physical

Chapter 1 Introductory Chapter 3

Section 2 Hydrogen Production 9

Chapter 2 Characterization and Optical Properties of Layered InSe and

Section 3 Hydrogen Storage 51

Chapter 3 Metal Amidoboranes and Their Derivatives for

Chapter 4 Modeling of Hydrogen Absorption/Desorption in a Metal

Section 4 Hydrogen Utilization 119

Chapter 5 Treatment of Hydrogen Bonds in Protein Simulations 121

There is a tremendous lack of public appreciation of scientific and technological difficulties

Additional information is available at the end of the chapter

1.1. Importance of developing hydrogen energy

2. Advanced materials in hydrogen production, storage, and utilization

Nano-photocatalysts for hydrogen production plays an important role in enhancing conver‐

3. Outline of the book

Chapter 2 presents electron-microscopic, energy-dispersion, and optical (IR-absorption and

As an example for hydrogen storage, hydrogen desorption/adsorption processes in a metal

Address all correspondence to: [email protected]

[2] S. S. Mao, S. Chen, International Journal of Energy Research 31 (2007) 619–636.

[6] S. Shen, S. S. Mao, Nanophotonics 1 (2012) 31–50.

[8] N. L. Rosi, J. Eckert, M. Eddaoudi, D. T. Vodak, J. Kim, M. O’Keeffe, O. M. Yaghi,

[9] S. S. Han, H. Furukawa, O. M. Yaghi, W. A. Goddard, Journal of the American Chemical

[10] A. Fujishima, K. Honda, Nature 238 (1972) 37–38.

[11] S. U. M. Khan, M. Al-Shahry, W. B. Ingler Jr., Science 297 (2002) 2243–2245.

[12] A. I. Hochbaum, P. Yang, Chemical Reviews 110 (2010) 527–546.

Characterization and Optical Properties of Layered InSe

Yuriy Zhirko, Vasiliy Grekhov, Nikolay Skubenko,

Additional information is available at the end of the chapter

Keywords: Layered crystals, intercalation, SEM, EDX, photoluminescence

Unique chemical bonds—strong ion-covalent hybrids-p3-bonds inside crystalline layers and

Section 5 of the work describes the results of low-temperature investigations aimed at

Undoubtedly, the unique properties of this class of semiconductor compounds, in particular,

2.1. The method of electrochemical intercalation

2.2. Natural intercalation of InSe and GaSe single crystals

ambient atmosphere. To perform physicochemical investigations of naturally intercalated

Hydrogen deintercalation from electrochemically intercalated layered HХInSe and HХGaSe

3. Physical properties of InSe and GaSe crystals intercalated with hydrogen

3.1. Crystals intercalated with hydrogen-containing molecules

To study the influence of intercalation with hydrogen-containing molecules (HCM) of water,

Figure 8. SEM LYRA 3, magnification 5,000. Scale—20 mkm.

Element Series Unn. C norm. C Atom C Error (1 Sigma)

Carbon K-series 0.00 0.00 0.00 0.00

Oxygen K-series 6.16 9.52 33.15 1.03

Gallium K-series 20.63 31.86 25.46 0.63

Selenium K-series 37.96 58.62 41.38 1.23

Total : 64.75 100.00 100.00

Carbon K-series 0.00 0.00 0.00 0.00