Review

Cite This: Chem. Rev. 2018, 118, 10775−10839 pubs.acs.org/CR

Nanostructured Metal Hydrides for Hydrogen Storage

Andreas Schneemann,†,⊥ James L. White,†,⊥ ShinYoung Kang,‡ Sohee Jeong,§ Liwen F. Wan,‡
Eun Seon Cho,§,∥ Tae Wook Heo,‡ David Prendergast,§ Jeffrey J. Urban,§ Brandon C. Wood,‡
Mark D. Allendorf,† and Vitalie Stavila*,†
†
Sandia National Laboratories, Livermore, California 94551, United States
‡
Lawrence Livermore National Laboratory, Livermore, California 94550, United States
§
Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
∥
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon
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34141, Republic of Korea

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ABSTRACT: Knowledge and foundational understanding of phenomena associated

with the behavior of materials at the nanoscale is one of the key scientific challenges
toward a sustainable energy future. Size reduction from bulk to the nanoscale leads to a
variety of exciting and anomalous phenomena due to enhanced surface-to-volume ratio,
reduced transport length, and tunable nanointerfaces. Nanostructured metal hydrides
are an important class of materials with significant potential for energy storage
applications. Hydrogen storage in nanoscale metal hydrides has been recognized as a
potentially transformative technology, and the field is now growing steadily due to the
ability to tune the material properties more independently and drastically compared to
those of their bulk counterparts. The numerous advantages of nanostructured metal
hydrides compared to bulk include improved reversibility, altered heats of hydrogen
absorption/desorption, nanointerfacial reaction pathways with faster rates, and new
surface states capable of activating chemical bonds. This review aims to summarize the
progress to date in the area of nanostructured metal hydrides and intends to understand
and explain the underpinnings of the innovative concepts and strategies developed over the past decade to tune the
thermodynamics and kinetics of hydrogen storage reactions. These recent achievements have the potential to propel further the
prospects of tuning the hydride properties at nanoscale, with several promising directions and strategies that could lead to the
next generation of solid-state materials for hydrogen storage applications.

CONTENTS 4.1. Experimental Structural Analyses 10789

4.1.1. Transmission Electron Microscopy 10789
1. Introduction 10776 4.1.2. X-ray and Neutron Techniques 10789
2. Classes of Nanostructured Metal Hydrides 10779 4.1.3. Vibrational Spectroscopy 10790
2.1. Bonding in Metal Hydrides 10779 4.2. Theoretical Structural Determination 10790
2.2. Nanostructured Binary Hydrides 10780 4.2.1. Wulff Construction 10790
2.3. Nanostructured Intermetallic Hydrides 10781 4.2.2. Prototype Electrostatic Ground State
2.4. Nanostructured Complex Metal Hydrides 10782 Method 10790
3. Synthetic Routes 10783 4.2.3. Microstructure Modeling 10791
3.1. Ball Milling 10783 4.3. Thermodynamic and Kinetic Analysis 10791
3.2. Gas-Phase Synthesis 10784 4.3.1. Thermodynamic Measurements 10791
3.2.1. Gas-Phase Condensation 10785 4.3.2. Thin Film Hydrogen Content Measure-
3.2.2. Plasma Deposition 10785 ments 10792
3.2.3. Thin Film Syntheses 10786 4.3.3. Rate Analysis and Kinetic Models 10793
3.3. Reductive Methods 10786 4.3.4. Thermodynamic Models 10794
3.3.1. Chemical Reduction 10786 5. Effects of Morphology on Hydrogen Storage
3.3.2. Electrochemical Reduction 10787 Properties 10795
3.3.3. Thermal Decomposition 10787 5.1. Free-Standing Nanoparticles 10795
3.4. Nanoconfinement 10787 5.2. Thin Films 10797
3.4.1. Host Materials 10788 5.3. Nanoconfined Metal Hydrides 10800
3.4.2. Impregnation Methods 10788
3.4.3. Synthesis Inside the Pores 10789
4. Methods to Analyze Structure and Storage Received: May 17, 2018
Properties 10789 Published: October 2, 2018

© 2018 American Chemical Society 10775 DOI: 10.1021/acs.chemrev.8b00313

Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews Review

5.3.1. Confinement in Carbons 10800 world energy problems by delivering and storing energy using
5.3.2. Other Rigid Porous Hosts 10806 hydrogen. The Hydrogen Economy offers a potential solution
6. Mechanistic Effects of Nanosizing 10807 to satisfying global energy needs while reducing (with the
6.1. Effects of Surfaces 10811 ultimate goal of completely eliminating) carbon dioxide and
6.1.1. Effects on Reaction Enthalpy 10811 other greenhouse gas emissions and improving energy security.
6.1.2. Effects on Reaction Pathways 10812 Hydrogen storage is an essential component of a viable
6.1.3. Surface Entropy and Disorder 10812 hydrogen economy.4 Whether the application is stationary or
6.1.4. Chemical Kinetics at Defective Surfaces 10813 geared for the transportation sector, volumetric and
6.1.5. Chemical Impurities and Oxidation 10813 gravimetric efficiencies often dictate feasibility. The mobile
6.2. Effects of Internal Interfaces and Micro- vehicular application is one of the most challenging
structure 10814 applications, as it requires materials with very large gravimetric
6.2.1. Effects of Grain Boundaries 10815 and volumetric hydrogen capacities and also mandates other
6.2.2. Types of Interphase Boundaries 10815 stringent properties such as extended cycle-life, low impurity
6.2.3. Effects of Reactive Phase Boundaries 10817 levels, and fast kinetics of hydrogen uptake and release.
6.2.4. Effects of Nonreactive Phase Bounda- Hydrogen-powered fuel cell vehicles (HFCVs) are now
ries 10817 commercially available and store the fuel in fiber-reinforced
6.2.5. Nucleation and Phase Transformation tanks at 700 bar. Although sufficient to achieve reasonable
Mechanisms 10818 driving range (∼350−450 km), they still fall short of the
6.3. Other Size-Related Effects 10820 ultimate U.S. Department of Energy (DOE) capacity targets
6.3.1. Shortened Diffusion Pathways 10820 for on-board storage for light-duty vehicles (0.065 kg H2/kg
6.3.2. Altered Phase Coexistence Behavior 10820 system and 0.050 kg/L, Table 1). The resulting overall fuel
6.4. Metal Hydride-Host Interactions 10820
6.4.1. Physical Confinement Effects 10821 Table 1. Summary on the Targets for Hydrogen Storage
6.4.2. Electronic Coupling Effects 10821 Systems Set by the United States Department of Energy for
6.4.3. Chemical Interactions with the Host 10821 on-Board Vehicular Applications7
7. Conclusions 10822
storage parameter units 2020 2025 ultimate
Author Information 10823
Corresponding Author 10823 system gravimetric kWh kg−1 1.5 (4.5) 1.8 (5.5) 2.5 (6.5)
capacity: usable, (wt %)
ORCID 10823 specific-energy
Author Contributions 10823 from H2
Notes 10823 system volumetric kWh L−1 1.0 (0.03) 1.3 (0.04) 1.7 (0.05)
capacity: usable (kg H2 L−1)
Biographies 10823 energy density
Acknowledgments 10824 from H2
List of Abbreviations 10825 storage system cost $ kWh−1 net 10 (333) 9 (300) 8 (266)
References 10825 ($ kg−1 H2)
min/max delivery °C −40/85 −40/85 −40/85
temperature
cycle-life (uptake/ cycles 1500 1500 1500
1. INTRODUCTION release cycles)
The ever-growing fossil fuel-based economy has led to a minimum delivery bar (abs) 5 5 5
pressure
number of new challenges facing our civilization in the 21st
cycle life (1/4 tank cycles 1500 1500 1500
century, such as pollution and irreversible climate change due to full)
to excessive drilling, mining, and growing amounts of system fill time min 3−5 3−5 3−5
greenhouse gases. The dominance of fossil fuels as prevailing fuel purity (H2 % H2 99.97% 99.97% 99.97%
energy sources is clearly unsustainable in the long run because from storage)
the adverse impact of a single energy source is additive and
repetitive, and once the harmful consequences have accumu- cost is a significant additional concern, exceeding the target
lated beyond a critical threshold, permanent damage ensues.1,2 due to costs of the tank, compressor, and associated fueling
Diversification of energy sources and the development of station hardware. The ultimate hydrogen storage material
alternatives to fossil fuels such as hydrogen-powered and should have a high gravimetric capacity (≥10 wt % hydrogen),
electric vehicles are not only highly desirable, but some of have high reversibility (≥1500 cycles), and release hydrogen
them are currently technologically feasible and cost-compet- below 85 °C, which would allow the utilization of waste heat
itive. Advanced energy materials with improved properties are from a PEM fuel cell for desorption. The storage medium must
a prerequisite for most technological innovations and are also be “kinetically fast,” meaning that the material is capable of
mandatory to meet the increasing demands of a growing global releasing hydrogen at the demanded rate (up to 2 g H2 s−1)
population. As a consequence, it becomes apparent that and also can uptake hydrogen fast enough so the tank can be
alternative energy solutions and materials are critical for a refueled with hydrogen in the desired time (∼15 g H2 s−1).
sustainable future.1 Consequently, on-board storage remains a factor limiting the
Hydrogen is considered an attractive alternative fuel, or widespread adoption of HFCVs. Metal hydrides, which bind
more precisely an alternative energy carrier, particularly when hydrogen chemically, and sorbents, which store H2 through
used in hydrogen polymer electrolyte membrane (PEM) fuel physisorption, comprised of light elements could, in principle,
cells.3 The concept of an ecologically clean “Hydrogen meet the DOE storage targets, yet each of these two classes of
Economy” was first introduced in the mid-1970s and has materials has its own advantages and drawbacks. For instance,
been gaining momentum as a viable remedy for the growing materials such as 170 Mg(BH4)2 (14.9 wt %) and LiBH4 (18.5
10776 DOI: 10.1021/acs.chemrev.8b00313
Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews Review

Figure 1. Processes accompanying hydrogen storage reactions in bulk (a) and nanostructured (c) metal hydrides. Despite differences in chemical
properties, the local bonding (b) can be similar.

Figure 2. Examples of nanostructured metal hydrides, including NPs, core−shell structures, nanowires, nanotubes, thin films, and multilayers: (a)
palladium NPs (adapted with permission from ref 25. Copyright 2009 Elsevier), (b) Mg@MgO core−shell NPs (adapted with permission from ref
26. Copyright 2014 Elsevier), (c) magnesium nanowires (adapted from ref 23. Copyright 2007 American Chemical Society), (d) palladium
nanotubes (adapted with permission from ref 27. Copyright 2000 Elsevier), (e) Pd-capped Mg thin film (adapted with permission from ref 28.
Copyright 2008 Elsevier), and (f) Mg/Cr multilayer film (adapted with permission from ref 29. Copyright 2014 Elsevier).

wt %) nominally can meet both the gravimetric and volumetric
targets.5 Unfortunately, other factors limit successful use of
hydrides as storage materials, and none currently can
simultaneously meet the DOE targets for minimum delivery
pressure, charging/discharging rates, and capacity. Sorbents, in
contrast, have rapid adsorption/desorption rates and are
readily reversible, but their capacities are very low except at
cryogenic temperatures, typically 77 K.6
The reasons for the inadequate performance of any given
hydride are complex, but in general these can be broken down
into thermodynamic and kinetic factors. Considering thermo-
dynamics, hydrogen storage materials (including both sorbents
and light metal hydrides) fall on either side of an ideal, but
effectively empty, range of hydrogen binding energies, with
sorbents binding H2 too weakly through physical adsorption
and hydrides binding it too strongly with chemical bonds.
Metal hydrides suffer additionally from slow H2 uptake and
release kinetics and limited reversibility, due in the case of
some complex hydrides to the intricate reaction pathways and
myriad intermediates involved. Many strategies have been
10777
considered for improving these properties with varying degrees
of success.5,8,9 These include entropic effects,10 altering the
morphology of hydride particles,11 mechanical strain,12 and
dopants or other chemical additives.13 Although one cannot
say that the potential of any of these has been exhaustively
evaluated, the improvements achieved so far are modest.
A promising approach that has garnered substantial
attention in the past decade is nanostructuring of the metal
hydrides. Many recent experiments and models that will be
described in this review suggest that nanostructured metal
hydrides have significantly, rather than incrementally, different
thermodynamics and kinetics than their bulk counterparts. For
example, a substantial decrease in the H2 desorption enthalpy
is predicted for very small MgH2 particles.14 Similarly, force
field modeling predicts a decrease in thermodynamic stability
of MgH2 as particle size decreases from 2.0 to 0.6 nm.15
Barriers for H2 desorption from NaAlH4 are also predicted and
experimentally found to depend on particle or cluster size.16−18
Nanoconfinement of Li3N was shown to fundamentally alter
both the hydrogenation and dehydrogenation reaction path-
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Chemical Reviews
ways as a direct consequence of solid−solid nanointerfaces
within the material.19 These are just a few examples to show
that there is ample evidence for altered physical and chemical
properties of nanostructured metal hydrides compared to bulk
(Figure 1).
Nanostructured materials have sizes intermediate between
molecules and microscopic structures. They can be a wide
variety of shapes and sizes (Figure 2), but they share the
characteristic of having at least one dimension be on the
nanoscale, which is typically defined as being between 1 and
100 nm (1 nm = 10−9 m). Nanoparticles (NPs), which have
three nanodimensions, are among the most common
nanostructures in materials science due to their relative ease
of synthesis, often through nucleation and restricted growth
processes, display large fraction of surface atoms, which makes
them attractive for numerous applications, particularly in
catalysis and energy-related applications.20 Some NPs are
composed of two different materials, either in a Janus structure,
in which each covers a portion of the exterior of the particle, or
a core−shell structure, with one of the materials completely
encapsulating the other (typically designated as core material@
shell material).21,22 Hollow nanotubes and solid nanorods
(also called nanowhiskers, nanowires, or nanopillars, often
depending on the aspect ratio of length to width) are elongated
in one dimension.23 Two-dimensional materials, which have
only one nanoscale dimension, include planar and sometimes
curved structures including nanosheets, nanoflakes, nanorib-
bons, and thin films.24 Some films that have been prepared
possess alternating layers of two or more discrete materials;
even though these multilayers may be grown thicker than 1
μm, the discrete layers typically are individually less than 100
nm and thus remain classified as nanostructured. A further
distinction among 2D materials is that thin films are generally
synthesized by deposition onto a flat (occasionally mono-
crystalline) substrate of another material, whereas nanosheets,
nanoflakes, and nanoribbons are usually prepared independ-
ently of a synthetic foundation.
Nanoconf inement (Figure 3) is a broad term that involves
either the formation of a nanostructured material inside a host
(nanoscaffolding) or the encapsulation or coating of a material
with a rigid matrix (nanoencapsulation). We define nano-
scaf folding as confinement of a material inside of a scaffold with
permanent porosity. The host material has nanoscale pores or
Figure 3. Schematic depicting the two major subclasses of
nanoconfinement discussed in this review: nanoscaffolding (left),
with the hydride inside a host with permanent porosity, and
nanoencapsulation (right) with the hydride wrapped by a nonporous
material, such as graphene.
10778
Review
recesses into which the confined material is introduced, bound,
and then restricted from movement or agglomeration with
other particles. The pores, therefore, determine the shape and
dimensionality of the nanoscale material. Nanoencapsulation is
defined here as incorporation of a nanoscale material inside a
secondary material which is not necessarily porous, named as
the matrix or shell (e.g., graphene,30−33 reduced graphene
oxide,34−36 and polymers22,37−39). Encapsulation can also
occur in core−shell NPs26,40,41 and multilayered thin
films29,42 and involves a preformed nanostructure that acts as
a barrier to particle/grain growth and serves as protection
against disruptive conditions that could cause agglomeration or
pulverization upon cycling.
Theory and modeling are playing a critical role in elucidating
nanoscale phenomena associated with thermodynamics and
kinetics of metal hydrides. The advances in computational
power and the emergence of supercomputers enabled quantum
mechanical, empirical, mesoscale, and continuum approaches
to modeling various phenomena in metal hydrides.43 Classical
molecular dynamics (MD) simulations are widely used to
discover mechanisms and diffusion pathways, examining
moderate-to-large sized systems (i.e., ∼103 to 106 atoms).
Density functional theory (DFT) calculations are used to
quantify energy barriers and end-state phase energies for
various phases and reactions. Combining MD and DFT
calculations enable direct simulations of time-evolution (pico-
to nanoseconds) to identify mobile species and energy barriers.
Kinetic Monte Carlo simulations can cover much longer time
scales (up to seconds), whereas continuum methods can, in
principle, cover time scales from seconds to hours.
Experimental confirmation of predictions is challenging for
several reasons, although there is abundant evidence indicating
that nanoscale metal hydrides have lower H2 desorption
temperature than bulk hydrides.24,44−49 First, the sizes
suggested by the calculations at which changes in properties
occur are much smaller than those produced by mechano-
chemical approaches, which are fraught with problems,
including the presence of impurities, lack of size control, and
poor reproducibility. Alternatively, bottom-up approaches to
nanoscaling, such as the formation of dendrimers, aerogels, and
inorganic templates (e.g., zeolites), are unsuitable due either to
the highly reactive nature of storage materials or the
substantially detrimental impact on gravimetric capacity.44−49
Second, tuning particle size can sometimes be difficult. Pores in
host materials are not always monodisperse, making it hard to
achieve uniform thermodynamic behavior and identify the
transition to nonbulk properties. For example, NaAlH4
particles supported on carbon nanofibers have broad size
ranges (e.g., 19−30 nm), resulting in hydrogen desorption
temperatures from 70 to 200 °C.50 Molten-metal infiltration of
carbon aerogels, which have a distribution of pore sizes, yields
2−5 nm Mg particles,51 but wetting agents (e.g., Ni) degrade
the scaffold, and blocking of the outermost pores appears to
limit infiltration. Third, the chemical environment surrounding
the particle may play an important role. For example, colloidal
stabilization of Mg particles yields 5 nm diameter particles that
desorb H2 as low as at 85 °C (>150 °C lower compared to
bulk).52
In general, the factors leading to improved properties at the
nanoscale are still poorly understood, however, and there are
numerous challenges to be resolved or overcome. Free NPs are
not stable, so some form of stabilization or hosting is required.
Unfortunately, nanoconfinement adds dead mass and volume
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Chemical Reviews
that reduces storage capacity. From a synthetic aspect, some
modeling suggests that nanoscale effects do not present
themselves until particles are one nanometer in size or even
smaller. Thin films lack capacity and the low-cost fabrication
techniques required for large-scale production. Core−shell
architectures may avoid this problem but are still very much at
the research stage. In nanoconfined materials, it is unclear
which is the critical factor: surface-to-volume ratio, particle-
host interaction energy, or cluster geometry (“magic number”
effects are observed when metals such as gold are nanoscaled,53
for example), though some scaffolds may also have catalytic
effects independent of the size of the hydride.54 Carbon,
probably the most economical nanoconfinement material, is
difficult to characterize in terms of its pore chemistry, and thus
it is problematic to control and synthesize reproducibly.
Nevertheless, nanoscaling is a promising synthetic strategy
that in recent years has attracted considerable atten-
tion.48,49,55−58 Several review articles with a narrower focus
were published in recent years.44,46−48,59−62 Given the renewed
interest in hydrogen storage in general and metal hydrides in
particular (for storage as well as other applications), a more
current and general review is warranted. In this article, we
review new experimental and theoretical approaches to
synthesizing nanostructured metal hydrides and probing their
hydrogen storage properties.
This review aims to describe, summarize, and analyze
reports in the scientific literature on nanostructured metal
hydrides, both simple and complex, and their use for hydrogen
storage, including their capacities and their thermodynamic
and kinetic properties in H2 uptake and release. Techniques for
making nanostructured metal hydrides will be presented, as
will computational methods for probing their properties.
Previous review articles and book chapters on metal hydrides
typically discuss nanostructuring only briefly and not as a
comprehensive study, and some have focused specifically on a
narrow class of nanostructured metal hy-
drides.8,24,44−46,55,56,58,60,61,63−69 In addition, the present re-
view covers the recently discovered novel classes of nano-
structured hydrogen storage materials, such as graphene-
encapsulated metal hydrides and core−shell nanostructures,
which present a major leap forward in improving both the
thermodynamics and kinetics of metal hydrides for hydrogen
storage applications.
2. CLASSES OF NANOSTRUCTURED METAL
HYDRIDES
Bulk metal hydrides have been known for more than two
centuries: Gay-Lussac and Thenard reported the synthesis of
potassium hydride by reaction of potassium metal and gaseous
hydrogen upon heating in 1811.70 In 1874, Hautefeuille and
Troost measured the equilibrium plateau pressures for the
reactions of metallic lithium, sodium, and potassium with
hydrogen.71,72 However, bulk metal hydrides started to be
considered as media for solid-state hydrogen storage in the
1960s, when several intermetallic hydrides (e.g., Mg2NiHx,
LaNi5Hx, and TiFeHx)73 were discovered and shown to absorb
and desorb hydrogen gas reversibly in a wide temperature
range (i.e., −50 to 400 °C). While many intermetallic hydrides
can absorb substantial quantities of hydrogen on a molar basis,
most of these alloys, composed of heavy rare-earth or
transition metals, have a maximum storage of about 1−2%
hydrogen by weight, with the exception of Mg alloys, which
have a capacity up to 7.6 wt % hydrogen.
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Review
Metal hydrides in general, and nanostructured metal
hydrides in particular, can be grouped into three large classes:
(1) binary hydrides MHx (M= main-group or transition metal,
such as in LiH, MgH2, PdH0.6, TiH2); (2) intermetallic
hydrides, ABxHy (A is typically the hydriding metal and B is
the nonhydriding metal, such as TiFeHx, TiMn2Hx, and
LaNi5Hx); and (3) complex metal hydrides, MEHx (E = boron
(borohydrides, e.g., LiBH4, Mg(BH4)2); nitrogen (amides, e.g.,
LiNH2, Mg(NH2)2), aluminum (alanates, e.g., NaAlH4,
Mg(AlH4)2)). In binary ionic hydrides such as NaH and
CaH2, hydrogen exists as the negatively charged hydride ion
(H−). In contrast, interstitial hydrides, such as palladium
hydride, are usually nonstoichiometric compounds, with
hydrogen existing as atoms dissolved in the lattice of host
metal atoms. Complex metal hydrides are compounds
composed of metal cations and polyatomic hydrogen-
containing anions such as alanates (AlH4−), borohydrides
(BH4−), and amides (NH2−). These compounds possess
hydrogen atoms covalently bound to aluminum, boron, or
nitrogen, with the hydrogen atoms having either δ+ or δ−
polarity.
2.1. Bonding in Metal Hydrides
Metal hydrides exhibit a great diversity of chemical bonds,
spanning from metallic bonding, as in interstitial hydrides such
as PdHx, ionic bonding in some binary and complex hydrides,
and partial or full covalent bonding as in the lightest binaries
(LiH and MgH2) and complex hydride anions (AlH4− and
BH4−). A detailed discussion of these is provided recently by
Jensen et al.74 However, to orient the reader we present a brief
summary here.
Extensive experimental thermodynamic data for metal
hydrides are available, typically including the enthalpy and
entropy of H2 desorption. Heats of formation for binary
hydrides of the alkali and alkaline earth metals and main-group
elements have also been measured; for example, see Bourgeois
et al. and references therein.75 Calorimetry and other
experimental techniques have been used to estimate M-H
bond dissociation enthalpy (BDE) in main group and
transition metal hydrides; the latter have received considerable
attention in this regard.76−81 For example, the “hydricity” of
transition metal complexes in solution, which is the energy
required to form a hydride ion (MH → H− + M+), has been
measured in a number of cases;81,82 these data are useful for
understanding chemical reactivity and bond-breaking events
within catalytic cycles. Critical assessments of the literature and
associated thermodynamic phase modeling (CALPHAD
method) have provided phase diagrams for a number of
hydrides,83 and these are a valuable tool for evaluating the
reactivity of these materials.
However, although thermodynamic data for H2 desorption
reactions are plentiful, they do not always constitute
dissociation energy (ΔH°BDE) for an individual M-H bond
but instead are the average bond energies relative to the
condensed-phase products. Consequently, one must turn to
other approaches, in particular theory, to obtain detailed
insight into the bonding of metal hydrides. In addition to
reaction energies, first-principles calculations can provide
densities of states, atomic charges, and orbital compositions
that reveal the underlying nature of the metal−hydrogen
interaction. The most common approach is DFT, which has
been applied to virtually all classes of metal hydrides of interest
for hydrogen storage75,84−92 and used to screen hydrides for
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Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews
Figure 4. Isothermal hydrogenation profiles of Pd octahedrons (red) and cubes (blue) at 303 K at a hydrogen pressure of 101.325 kPa (1.0 bar
H2). (b) Schematic potential energy diagrams of the Pd octahedrons (red) and cubes (blue). (Reproduced from ref 111. Copyright 2014 American
Chemical Society.)
specific applications.93−96 An important conclusion obtained
from these studies is that, for binary hydrides, the primary
factors influencing M-H BDE are (1) the difference in the
electronegativities of the metal and hydrogen79 and (2) the
cohesion energy of the metal relative to the energy cost for
lattice expansion upon formation of the hydride. 75,92
Consequently, the stability of binary hydrides from alkaline
metal hydrides through the early transition metals (Sc and Y)
is dominated by the charge transfer between the metal atom
and hydrogen.75 In the case of complex metal hydrides, the
bond energy of the M-H diatomic (M typically being B or Al)
is also an important parameter that can be used to characterize
the bonding.92
A few specific cases are illustrative. For two of the lightest
hydrides, LiH and MgH2, extensive charge transfer leads to
negative enthalpies of formation: −89.3 to 99.1 kJ mol−1 for
LiH97,98 and −76.2 to −77.0 kJ mol−1 for MgH2.99−104 The
bonds in these hydrides have mixed ionic−covalent character,
whereas in hydrides of the heavier elements, such as CaH2 and
SrH2, the bonding is primarily ionic.74 Proceeding down the
periodic table, hydride stability begins to decrease beyond the
early transition metals as a result of the competition between
metal cohesion energy and electronegativity difference. Miwa
and Fukumoto computed heats of formation for first-row
transition metal dihydrides and showed, consistent with
experimental results, that at Group 8 (Fe), both the metal
cohesion energy and the energetic penalty for the lattice
expansion upon M-H bond formation reach a maximum.
Beyond this point, the dihydrides become unstable.105 A
similar conclusion was reached in an earlier study by Smithson
et al.88 Deeper into the periodic table, the bonding eventually
becomes metallic, with hydrogen located at interstitial sites and
allowing variable compositions (effectively, solid solutions)
without a phase change. In this case, bonding is much weaker.
For example, experimental formation enthalpies for bulk PdHx
(x = 0.25, 0.75, and 0.8) are only −17.7 to 19.5 kJ mol−1.106,107
It should be noted that DFT calculations consistently
underestimate hydride formation enthalpies; the disagreement
with experiment is greatest for alkaline and alkaline earth
hydrides (as much as 20 kJ mol−1 for KH).75 Nevertheless,
correct trends are predicted, even for complex transition metal
hydrides.95
The picture does not change dramatically for complex main
group metal hydrides. Yoshino et al. performed a DFT study
for the hydrides LiBH4, LiAlH4, LiNH2, and NaAlH4.92 Their
analysis indicates that the factors controlling the bonding
trends in these hydrides are similar to those for metal
dihydrides, with the added factor that the hydride anion
10780
Review
(AlH4− and BH4−) is bound ionically to an alkali- or alkaline-
earth metal. The B−H and Al−H bonds have strong covalent
character,92 with X-H bond orders from 0.5 to 0.75 and similar
ionicities for the four hydrides. The predicted bond order, B−
H ≈ N−H > Al−H, indicates that B−H and N−H are more
covalent than Al−H. This is consistent with a later
investigation by Sholl and co-workers, who considered the
bonding in Mg(BH4)2 and Mg(AlH4)2 and concluded that B−
H bonds possess a significantly higher degree of covalency than
Al−H bonds.108 The B−H BDE predicted by molecular cluster
calculations is a high 384 kJ mol−1,86 which is consistent with
the higher thermal stability of the borohydrides. These
predictions are all consistent with what is known empirically
about the stability of these hydrides.
Overall, these results suggest that it may be difficult to
influence the thermodynamics of metal hydrides by nano-
structuring alone (i.e., steric effects that may alter the
arrangement of ions), particularly for strongly ionic hydrides
for which Coulombic forces may be difficult to alter.
Alternatively, the kinetics of hydrogen desorption and uptake
could be dramatically affected. As seen subsequently in this
article, however, such conclusions are overly simplistic and
other factors, such as surface energy, interactions with “non-
innocent” pore walls, internal nanointerfaces, and mechanical
strain can exert large effects that can change the behavior of
these materials.
2.2. Nanostructured Binary Hydrides
Most of the metals on the periodic table form stable binary
metal hydrides. When the surface of a metal, e.g., palladium, is
exposed to hydrogen gas, the hydrogen molecules are initially
adsorbed then split into hydrogen atoms, which diffuse on the
surface and into the bulk. The absorption and desorption of
hydrogen by Pd occurs via cycling between two phases; at low
hydrogen concentration, the α-Pd phase is stable, whereas at
higher hydrogen concentrations the β-Pd phase is the
dominant species. The effect of size on hydrogen storage
properties has been known for a while, and cycling under
hydrogen gas near the equilibrium pressures needed for the
formation of Pd hydrides was reported to change with particle
size.107,109,110 Recent work by Li et al. has demonstrated that
the morphology of Pd may play a critical role in the absorption
rates of hydrogen, and that temperature as well is critical for its
uptake, absorption, and diffusion. Figure 4 shows the
isothermal hydrogenation profiles of Pd octahedrons (red)
and cubes (blue) at 303 K, under a hydrogen pressure of
101.325 kPa (1.0 bar H2).111 In situ electron energy-loss
spectroscopy (EELS) on individual palladium nanocrystals
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revealed that palladium nanocrystals undergo dramatic changes
during the phase transition between the α and β phase, and
surface effects dictate the size dependence of hydrogen
absorption pressures.112
Among bulk noble metals, palladium is the only metal that
can absorb and desorb hydrogen at near-ambient conditions of
temperature and pressure. Downsizing metal particles to a few
nanometers changes the ratio of surface to bulk atoms and can
introduce fundamental changes in the thermodynamics of
hydrogen uptake. For example, bulk Ir and Rh form hydride
phases only at impractical H2 pressures in excess of 4 GPa.
Nanoscaling Ir and Rh to <10 nm particles results in hydrogen
being absorbed near or at room temperature to form the
corresponding hydride phases.113−117 These results indicate
that the thermodynamics of the Rh−H and Ir−H hydride
systems are highly dependent on the particle size and, at the
smallest size tested (1 to 2 nm), can result in 7 to 8 orders of
magnitude decreases in the equilibrium plateau pressure
required to form the hydride phase. For example, bulk Rh
absorbs hydrogen at 4 × 109 Pa, whereas 2.3 nm particles of
Rh have a midplateau pressure of only 30 Pa.
Magnesium hydride has been extensively studied as a
convenient model system to explore the effect of nano-
structuring on the thermodynamics and kinetics of hydrogen
storage reactions. Although many different synthetic ap-
proaches to Mg nanostructures have been proposed, synthesis
of pure Mg NPs is complicated by the high reactivity of Mg.
Polymer wrapping was proposed as an efficient way to reduce
the reactivity; for example, 5 nm Mg NPs coated with polymers
were produced in solution by Jeon et al.21 The authors used
poly(methyl methacrylate) (PMMA) as a capping ligand, with
bis(cyclopentadienyl)magnesium (Cp2Mg) as the magnesium
source. During the reduction of the organometallic precursor
by lithium naphthalide, burst-nucleation and growth processes
occur and PMMA-coated Mg nanocrystals are produced. The
valuable finding in this study is that PMMA acts not only
merely as a capping ligand but also as a gas-selective barrier.
Generally, Mg metal readily forms MgO and Mg(OH)2 layers
upon exposure to air or water, which consequently decreases
the hydrogen storage ability because those oxides are inactive
materials for storage and prevent the penetration of H atoms to
the remaining metal. PMMA prevented the oxidation of Mg
due to the higher H2/O2 permeability ratio of PMMA
compared to those of other polymers such as poly-
(dimethylsiloxane) and polycarbonate, which resulted in
enhanced air stability of PMMA-coated Mg NPs even after 3
days of air exposure.
Other synthetic methods such as mechanochemistry,118 gas-
phase condensation,119 and plasma-metal reactions120,121 (see
section 4) generally produce nano-MgH2 with a larger particle
size distribution. In addition to transmission electron
microscopy (TEM), powder X-ray diffraction (XRD), both
lab- and synchrotron-based, is often used to determine the
crystallite size in nano-MgH2 and shows significant broadening
for particles <50 nm. Dopants and additives are sometimes
incorporated into nano-MgH2 to enhance the kinetics; these
are typically transition metals or transition metal compounds.
It must be noted that the kinetics of MgH2 NPs and thin films
are improved even at particle/grain sizes of 50 nm or larger. In
contrast, thermodynamic improvements were only observed
for particle/cluster sizes of <10 nm (section 5).
Several other binary metal hydrides, particularly those of the
alkali and alkaline-earth metals, which bind hydride more
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ionically, are not of substantial interest for hydrogen storage.
While some, such as NaH, CaH2, and LiH, have fairly high
gravimetric hydrogen capacities (4.2, 4.8, and 12.5 wt %,
respectively), especially compared to the heavy metals, the
strength of the ionic bonds and the high energetic costs
associated with forming metallic sodium, calcium, or lithium
lead to desorption temperatures above 400 °C, significantly
greater than the desired release temperatures for near room
temperature applicaitons.5 However, these and other metal
hydrides are of significant interest for the development of high-
temperature thermochemical energy storage systems, for
instance, as storage media for concentrated solar thermal
applications.122−129
2.3. Nanostructured Intermetallic Hydrides
Intermetallic hydrides have found many applications, which in
addition to hydrogen storage systems include nickel metal
hydride (NiMH) battery electrodes, hydrogen purification
systems, hydrogen sensors and catalysts, heat pumps, and
cooling systems.68 Although metal hydrides composed of two
or more metals store relatively low quantities of hydrogen per
unit mass, the kinetics of hydrogen absorption and desorption
are relatively fast in those of them that store the hydrogen in
interstitial sites in the metal lattice. Most interstitial metal
hydrides are intermetallic metal hydrides of general formula
AmBnHx. The properties of these materials are largely
determined by the interaction between the interstitial hydro-
gen atoms and the metal atoms. However, not all intermetallic
hydrides store hydrogen interstitially. One notable exception is
Mg2NiH4, which is not an interstitial hydride but rather a
complex metal hydride with NiH44− ions; it does, however,
form the intermetallic compound Mg2Ni upon dehydrogen-
ation.130,131 The most important stoichiometries of interme-
tallic metal hydrides are AB5 (CaCu5 structural type), AB2
(Laves phase), AB (CsCl structural type), and A2B (AlB2
structural type). Less common intermetallic hydrides include
A2B17, A6B23, A2B7, AB3, and A3B stoichiometries.132 The first
intermetallic hydrides were reported in the early 1960s;
currently, several thousands of these materials are known. A
rather comprehensive list of intermetallic metal hydrides is
available as part of the Hydrogen Storage Materials Database,
http://hydrogenmaterialssearch.govtools.us/.133
Nanostructuring has been widely used to improve the
properties of intermetallic hydrides. For instance, the structural
and hydrogen storage properties of ball-milled nanostructured
TiFe0.5Ni0.5/graphite composite are significantly altered
compared to bulk. 134 Both bulk and nanostructured
TiFe0.5Ni0.5 materials crystallize in a cubic CsCl-type structure.
However, after hydrogenation, the formation of the hydrogen-
poor β phase is observed for the bulk compound, whereas the
nanostructured TiFe0.5Ni0.5/graphite composite forms the
hydrogen-rich γ phase with improved reversible hydrogen
capacity. Mössbauer spectroscopy on Fe centers indicate
significant changes in the isomer shift toward the γ phase,
which indicates a decrease of the s-electron density at the Fe
nuclei due to the charge transfer from the metal to the nearby
hydrogen atoms.134
TEM investigation of nanostructured Mg-10Ni-2Mm (Mm
= 99.7% lanthanum-rich mischmetal) showed a significant
reduction in grain size during ball-milling. Additionally,
nucleation of intermetallic MmMg12 at the grain boundaries
of Mg and Mg2Ni occurred. The interface between MmMg12
and Mg2Ni was semicoherent and features an ordered
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repetition of the consistent atomic arrangements.135 The
kinetics of H absorption and desorption are improved upon
ball-milling due to the fast hydrogen diffusion in the
nanograins, thus providing paths for fast H-exchange.
Pressure−composition−temperature (PCT) diagrams show
the presence of two plateaus, one each for the Mg + H2 ⇌
MgH2 and Mg2Ni + 2H2 ⇌ Mg2NiH4 reactions. The MgH2
plateau showed no hysteresis and practically no slope, while
the plateau for Mg2NiH4 exhibited both a pronounced
hysteresis and a slope, particularly for the nanocrystalline
sample.135 Other examples of microstructure refinement in
intermetallic hydrides can be found in a review by Varin et al.57
2.4. Nanostructured Complex Metal Hydrides
Complex metal hydrides consist of (predominantly alkaline
and alkaline earth) metal cations and “complex” hydrogen-
containing anions, for instance alanates (AlH 4 −) and
borohydrides (BH4−). The appeal of this class of hydrides
arises from their gigantic gravimetric hydrogen content, due to
their composition of mostly light elements (e.g., LiBH4 and
Mg(BH4)2 contain 18.4 and 14.9 wt % H2, respectively).
However, some drawbacks of these materials are the very
endothermic hydrogen release and the lack of reversibility.
Strategies are being successfully developed to overcome these
limitations, for example by catalyst doping or nanosizing and
confinement. A comprehensive review article by Orimo et al.5
discusses the general feasibility of complex hydrides for
hydrogen storage application in great detail. Within the next
few paragraphs, we will summarize the properties of some
prototypical complex hydrides, namely LiBH4, LiAlH4, Mg-
(BH4)2, and NaAlH4.
Table 2 summarizes some of the important dehydrogenation
properties of bulk complex metal hydride materials. Even
Table 2. Summary of Some Critical Values That Describe
the Dehydrogenation Properties of the Discussed Hydrides
H2 ΔH
hydride wt % Ea (kJ mol−1) Tdec (°C) (kJ mol−1 H2)
LiAlH4 10.6 82−115; 160; 180; −10; 25; 140b
86−90a 400b
NaAlH4 7.4 118, 120a 180; 190; 40.9; 15.6; 120b
400b
LiBH4 18.4 146a 483−492b 74d
Mg(BH4)2 14.9 310.7; 160.9c 320b 53b
a
Data from Christian and Aguey-Zinsou.136 bData from Klebanoff et
al.137 cData from Fichtner.66 dData from Mauron et al.138
though they feature very high gravimetric hydrogen contents,
their activation energies and decomposition temperatures
(Tdec) are unfeasible for practical use. Downsizing of the
hydrides through nanostructuring can reduce the enthalpy or
activation energy needed to desorb hydrogen, in some cases
rather dramatically, in part because the diffusion limitations
within bulky highly crystalline, covalent networks are over-
come,45 though a number of other reasons have been proposed
and will be discussed in section 6.
The confinement of hydrides in porous materials, e.g.,
aerogels, porous carbons, or metal−organic frameworks, not
only allows the stabilization of NPs and hinders their
recombination and agglomeration but also forces interactions
between the pore walls and the hydride particles. The effect of
confinement of four light-metal hydrides, LiAlH4, NaAlH4,
LiBH4, and Mg(BH4)2, is described, along with a short
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perspective on other promising materials and strategies. Figure
5 shows a schematic depiction of hydride confinement in three
Figure 5. Schematic representation of hydride confinement in three
classes of materials, namely, metal−organic frameworks (left), carbon
aerogels (center), and mesoporous carbons (right).
classes of materials, namely, carbon aerogels, mesoporous
carbons, and metal−organic frameworks. Apart from these,
other porous materials commonly used are carbon nanofibers
and porous oxides.
Lithium aluminum hydride (LiAlH4) has a high hydrogen
content of 10.6 wt %. The material releases H2 in a three-step
process, via the intermediates Li3AlH6 and LiH. The three
reaction steps take place at (1) 160−180 °C, (2) 180−225 °C,
and (3) above 400 °C, with enthalpies of −10, +25, and +140
kJ mol−1 H2, respectively.139 The last step of the reaction is
energetically unfeasible, lowering the effective capacity to only
about 7 wt %. Additionally, it was calculated by Jang et al. that
the rehydrogenation process to form LiAlH4 from Li3AlH6
requires high H2 pressures, above 1000 bar.140,141 However,
due to the excellent desorption properties of the bulk material,
a lot of work is still invested into preparing nanoscale or
nanoconfined LiAlH4.
Sodium aluminum hydride, also called sodium alanate, has a
slightly lower hydrogen capacity than LiAlH4, amounting to 7.4
wt % H. NaAlH4 decomposes to release hydrogen in three
steps according to the following reactions:
3NaAlH4 F Na3AlH6 + 2Al + 3H 2
Tdec = 180 − 190 °C; ΔH = 40.9 kJ mol−1 H 2 (1)
Na3AlH6 F 3NaH + Al + H 2
Tdec = 190 − 225 °C; ΔH = 15.6 kJ mol−1 H 2 (2)
NaH F Na + 1/2H 2
Tdec ≥ 400 °C; ΔH = 120 kJ mol−1 H 2 (3)
The last step occurs at very high temperatures (Tdec ≥ 400
°C), making it infeasible for practical use. A fundamental
breakthrough came with the discovery by Bogdanović and
Schwickardi that doping sodium aluminum hydride with
titanium not only improves the kinetics of dehydrogenation
reaction but also makes the reaction reversible.13 Since then,
the decomposition and reabsorption of hydrogen in the
NaAlH4 system has been one of the most intensively
investigated reactions in the field of solid hydrogen storage
materials.142−149 Much of this research has been devoted to the
confinement of this complex hydride in different host matrices,
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Figure 6. Reduction of (a) the crystallite size and (b) the breadth of the particle size distribution as a function of ball milling time of LiH.
(Reproduced with permission from ref 183. Copyright 2008 Elsevier.)
with some interesting effects which are discussed in the
following section.
LiBH4 attracts substantial research as a hydrogen storage
material, as it has one of the highest gravimetric hydrogen
content of any material, 18.4 wt %. Differential thermal analysis
(DTA) studies suggest very high dehydrogenation temper-
atures starting at 380 °C, with the majority of H2 released
above 420 °C.150−152 The dehydrogenation process is not yet
fully understood, and different proposed reaction routes
include intermediates such as LiB3H8153 and Li2B12H12.154,155
Hence, substantial research has been devoted into lowering the
dehydrogenation temperature by downscaling of the crystallite
size and embedding the material into nanoscaffolds.
Mg(BH4)2 has exceptional gravimetric hydrogen content of
14.9 wt %. The desorption onset of this material is very high,
and hydrogen release is usually observed at temperatures above
320 °C. The release of hydrogen most likely occurs in a 3-step
reaction cascade:
6Mg(BH4)2 F 5MgH2 + Mg(B12H12) + 13H 2 (4)
5MgH2 F 5Mg + 5H 2 (5)
5Mg + Mg(B12H12) F 6MgB2 + 6H 2 (6)
It must be noted that other reaction pathways have been
proposed and experimentally determined for bulk and
nanoscale Mg(BH4)2, as summarized in a recent review article
by Zavorotynska et al.156 The reversible hydrogen uptake by
MgB2 was demonstrated by Severa et al. under 950 bar H2
pressure at 400 °C.157 At the current research stage, this
material seems still very attractive, if the hydrogen absorption
and desorption properties can be enhanced.
3. SYNTHETIC ROUTES
The synthetic approaches toward nanostructured metal
hydrides can be divided into top-down and bottom-up
approaches. The top-down approach involves breaking down
bulk metal hydride particles until NPs or nanocrystallites are
formed, whereas bottom-up approaches involve building up
NPs from atoms, molecules, clusters, and other small structural
blocks. It is important to distinguish between methods that
create isolated NPs and methods which generate microscopic
powders composed of nanograins or nanocrystallites. Ball-
milling has been extensively explored for nanosizing and
nanostructuring, due to its relative simplicity and general
applicability of the process.118,158 Due to air- and water-
sensitivity of metals and metal hydrides, the milling is typically
performed under inert gas or under hydrogen. In addition to
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reducing the particle size, ball-milling is a versatile technique to
introduce dopants and catalysts.159−168 Plasma processing
techniques have been also applied to synthesize small hydride
NPs by using both hot and cold plasma techniques, but these
synthetic methods are less general and generally produce
samples that are inhomogeneous, poorly crystalline, and with
ill-defined particle size.169 Bottom-up synthetic approaches
were developed in recent years to overcome these limitations.
These approaches include gas-phase condensation,23 wet-
chemical synthesis,52 and nanoconfinement18 inside porous
scaffolds through liquid-phase infiltration. Although these
methods tend to offer better control over particle size, the
homogeneity and solvent contamination can be an issue.
3.1. Ball Milling
One of the most-used techniques to reduce the particle size in
metal hydrides is ball milling, which involves the mechanical
grinding of a solid sample with one or more inert and hard
balls (e.g., ceramic, flint, tungsten carbide, or stainless steel)
moving at a high speed and crushing the powder. Under
certain regimes, the resulting materials are mostly composed of
small NPs or nanocrystallites.170−180 The “NPs” derived from
mechanochemical processes are different compared to particles
formed via solvent-based chemistry approaches and tend to
contain gross internal grain boundaries, fractures, dislocations,
or internal disorder, whether the crystals they contain are
nanocrystalline or not. For brittle materials, particle fracture is
well-described by Griffith theory, which shows the relationship
between applied nominal stress and crack length at fracture.
The stress, σF, at which crack propagation leading to particle
fracture occurs is approximated by the following equation:
γE
σF ≈
c (7)
where c is the length of the crack (in m), E is the modulus of
elasticity (in N/m2), and γ is the surface energy of the milled
material (in J/m2).181 In ductile materials, a plastic zone
accompanies the tip of the crack, which leads to the energy
dissipation as heat. Therefore, additional energy is needed for
crack growth in ductile materials as compared to brittle
materials. In practice, as particles decrease in size upon ball
milling, a certain limit is reached beyond which no reduction in
size occurs.79,182,103 Typically, the grain size of metal hydrides
decreases from a few microns to a few nanometers (Figure 6).
Ç akmak et al. showed that mechanical milling of Mg with
10% Ti yields large Mg agglomerates up to 100 μm in size,
with embedded Ti fragments of micron and submicron size
distributed within the agglomerates.184 The Mg agglomerates
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are made of coherently diffracting crystallites, which can be as
small as 26 nm after 30 h of milling. Pang et al. developed a
mechanical-force-driven physical vapor deposition (PVD)
approach for the synthesis of 1D complex hydrides in which
Mg(AlH4)2 nanorods with diameters of 20−40 nm and 10−40
LiBH4 nanobelts were formed.185 The procedure involves
high-energy ball milling of ether precursors [Mg-
(AlH 4 ) 2 (Et 2 O)] n (where Et 2 O = diethyl ether) and
[LiBH4(MTBE)]n (MTBE = methyl tert-butyl ether) to form
the corresponding nanostructures (Figure 7). The final
Figure 7. (a) Mg(AlH4)2 nanorod synthesis procedure. SEM images
of (b) the Mg(AlH4)2 etherate precursor, (c) the as-deposited
Mg(AlH4)2 etherate precursor, and (d) as-synthesized Mg(AlH4)2.
The scale bar in panel b of 2 μm; the scale bar in panels c and d is 200
nm. (e) HRTEM image of the LiBH4 nanobelts. Scale bar: 10 nm. (f)
Selected-area electron diffraction pattern of region in panel e.
(Adapted with permission from ref 185. Copyright 2014 Springer
Nature.)
Mg(AlH4)2 nanorods and LiBH4 nanobelts are generated by
heat-treating the deposited material under vacuum. The 1D
Mg(AlH4)2 and LiBH4 nanostructures show superior hydrogen
storage properties compared to bulk counterparts.
Ball milling of MgCl2 and LiH mixtures results in MgH2 NPs
as small as 7 nm in size embedded in a LiCl matrix. In
comparison to bulk MgH2, the mechanochemically produced
MgH2 with the smallest particle size showed a 2.8 kJ mol−1 H2
decrease in the decomposition reaction enthalpy. However,
only a small reduction in the desorption temperature was
observed, as the decrease in ΔS partially counteracted the
effect from the change in ΔH.186 Ball milling is efficient in
reducing the activation energy of hydrogen absorption/
desorption from MgH2.174,187−189 However, this improvement
is not always due to the small particle size. For instance, ball
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milling partially hydrolyzed MgH2 for 25 h reduces the
activation energy of hydrogen desorption from 217 to 140 kJ
mol−1 due to removal of the oxide/hydroxide layer from the
surface of MgH2 particles.190
Vijay et al. employed reactive mechanical milling to
synthesize Mg−Ti−Fe nanocomposites, which can be hydro-
genated to form MgH2.191 The hydrogenation reaction starts at
80 °C, and the material absorbs 4 wt % H2 and desorbs 3.8 wt
% H2 at 300 °C. Wang et al. produced Mg−Ce alloys by
melting, which were further milled under hydrogen and finally
mixed with 10 nm Ni NPs.192 This treatment results in a
CeMg12 intermetallic, which can absorb 2.9 wt % H2 at 120 °C
within 30 min, and can desorb hydrogen as low as 180 °C. The
low desorption temperature of 180 °C reported for this
composite is puzzling, as the PCT results for the Mg−Ce/
nano-Ni composite indicate a plateau pressure of 1 atm
hydrogen at 280 °C. Milling the Mg/Mg2Ni0.8Cr0.2 with 40 nm
TiO2 NPs yields a material reported to desorb up to 4.2 wt %
H2 at 240 °C.193
Ball-milling complex metal hydrides is less efficient in
reducing the particle size, compared to doing so for binary and
intermetallic hydrides. Nevertheless, high-energy milling of
LiAlH4 was reported to produce grain sizes below 100
nm.194,195 For high-energy ball-milled LiAlH4, the activation
energy for hydrogen release to form Li3AlH6 and LiH is
reduced from 111 to 100 kJ mol−1.196 In addition, ball milling
is a convenient technique to introduce additives in complex
metal hydrides. For instance, ball milling was used to introduce
metal and metal halides additives to LiAlH4 and LiBH4,
significantly reducing the activation energy for hydrogen
release.163,195−201
However, despite significant progress, ball milling has
important limitations, such as yielding nonuniform particle
sizes and shapes as well as issues with contamination. The large
amount of strain developed in metal hydride particles during
the milling process makes it virtually impossible to obtain
defect-free crystals via this method. In addition, metal and
metal hydride ball milling is believed to create highly reactive
surfaces that readily react with oxygen, even residual oxygen
present on the surfaces of the milling balls and vessel. Although
the exact role of such oxide layers is not very well-understood,
excessive oxidation can cause capacity loss and create issues
with hydrogen diffusion. On the other hand, the resulting high
density of grain boundaries can, to some extent, facilitate
hydrogen diffusion and thus improve the overall kinetics.
Finally, even though the hydride particles are in the desired
nanoscale regime initially, the material can undergo significant
recrystallization and particle growth upon heating during
hydrogen absorption and desorption, eventually leading to
bulk-like behavior.
3.2. Gas-Phase Synthesis
Gas-phase synthesis is a bottom-up method for producing
metal and metal hydride NPs from individual atoms or
molecules. This method allows synthesis of complex,
sophisticated NPs, owing to the fast kinetics and non-
equilibrium processes it entails.202,203 Thus, control over the
composition and morphology can be achieved by growth
parameters such as pressure, cooling rate, NP drift velocity,
and aggregation zone length. Postsynthetic techniques
employed after NP growth, such as in situ mass filtration
and deposition temperature, offer additional possibilities for
the synthesis of tailored NPs. In the following sections, we
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Figure 8. (a) TEM image of Mg-TiH1.971 composite. HR-TEM images of (b) Mg particle and (c) TiH1.971 particle. (Adapted with permission from
ref 212. Copyright 2014 Elsevier.)
cover gas-phase condensation and plasma deposition techni-
ques for the synthesis of metal hydride NPs.
3.2.1. Gas-Phase Condensation. Gas-phase condensa-
tion is a variety of gas-phase synthesis that involves rapid
cooling of metal vapor to produce NPs. For instance,
magnesium nanocrystals of different sizes can be synthesized
by condensation under inert gas and then the surface
decorated with metallic nickel.204 Synchrotron radiation
powder X-ray diffraction and Sieverts measurements reveal
that Ni significantly improves the hydrogen release and uptake
kinetics of the NPs. The enhancement of hydrogen sorption
properties is believed to be due to the formation of Mg2Ni and
Mg2NiH4 phases in the nanocrystals.204 A similar approach was
used to isolate Mg−Pd composite NPs by inert gas
condensation of Mg vapors followed by vacuum evaporation
of Pd clusters. Irreversible formation of the Mg 6 Pd
intermetallic phase takes place upon vacuum annealing,
resulting in Mg/Mg6Pd composite NPs. At 573 K and 1
MPa hydrogen pressure, the metal-hydride transition leads to
the formation of Mg3Pd and Mg5Pd2, whereas at 5 MPa H2
pressure the Pd-richer MgPd intermetallic is obtained.205
Mg−Ti nanostructured samples were prepared via compac-
tion of NPs grown by inert gas condensation. The formation of
a solid solution of Ti in hexagonally close-packed (hcp) Mg
was detected up to 15 at. % Ti, while after in situ hydrogen
absorption, the alloy phase separates into MgH2 and TiH2.
When Ti content reaches 22 at. %, a metastable Mg−Ti−H
face-centered cubic (fcc) phase was observed after hydrogen
absorption. Although the enthalpy of hydride formation is
unchanged compared to bulk MgH2, the addition of Ti
enhances the kinetics with hydrogen absorption/desorption
times of only several minutes at 300 °C.206
Nanostructured metal hydrides of compositions Ti−H, Zr−
H, Ti−N−H, Zr−N−H, and Ti−Zr−N-H were synthesized
using combustion wave under hydrogen. The self-propagating
high-temperature reaction produced hydride nanograins as
small as 50 nm.207 They exhibited improved hydrogen storage
characteristics, including faster kinetics and longer cycle-life.
3.2.2. Plasma Deposition. Hot and cold plasma
processing techniques169,208 are suitable for both metal and
metal hydride nanoparticle synthesis, because plasma provides
distinctive advantages, including high enthalpy, fast response,
and high chemical reactivity. The arc plasma method for
nanoparticle synthesis achieves supersaturation of NPs by
vaporizing metals and metals by charging electrodes until the
breakdown voltage is reached. The arc of spark formed across
electrodes vaporizes the metal, which is transported to the tail
of the arc where the vapors fall into a highly supersaturated
state, which achieves effective formation of NPs by nucleation
and condensation. Hydrogen plasma metal reaction is a
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variation of the plasma processing techniques.209 The method
was initially developed by Ohno and Uda to produce metal
NPs in the presence of hydrogen and argon gas but was later
adapted to create metal hydride NPs.
Mg NPs decorated with nickel were isolated by arc plasma
evaporation of pure Mg followed by the electroless plating of
Ni on the Mg particles in a NiCl2 solution.41 The PCT
measurements indicate a hydrogenation enthalpy of the Mg−
Ni composite of −73.6 kJ mol−1 H2, similar to bulk Mg. Core−
shell structured binary Mg@Ti and ternary Mg@Ti@Ni core−
shell nanocomposites were synthesized using an arc plasma
method followed by electroless plating in solutions.41 The
hydrogenated composites with core−shell structures contain a
MgH2 core and Ti or Mg−Ni hydride shells. Based on PCT
measurements, the hydrogen absorption enthalpy (−67.1 kJ
mol−1 H2) of the ternary composite was slightly higher than
that of the binary composite (−77.2 kJ mol−1 H2). In addition,
both the binary and ternary hydride display lower activation
energies of H2 absorption than bulk MgH2.
The hydrogen plasma metal reaction (HPMR) method was
employed to synthesize various Mg-based nanocomposites.
Shao et al. reported hexagonal 50−500 nm Mg particles with
slightly improved hydrogen storage properties.210 By varying
the HPMR reaction conditions, Kooi et al. were able to further
reduce the Mg particle size to between 10 and 80 nm, leading
to a more significant improvement in kinetics of hydrogen
desorption.211 The HPMR method was used to generate a
Mg−Ti−H nanocomposite composed of 40−180 nm
hexagonal Mg NPs, with 13 nm spherical TiH1.971 NPs
uniformly dispersed on the surface of Mg particles (Figure
8).212 The presence of TiH1.971 on the surface seems to limit
the sintering upon cycling. Addition of TiF3 to MgH2 NPs
synthesized through the HPMR method showed a beneficial
effect on kinetics and hydrogen absorption capacity at low
temperatures but was found to have no effect on H2
desorption.120 Other nanostructured metal hydrides synthe-
sized using the HPMR method include Zr55V29Fe16Hx,213
Mg2NiH4,214−217 Mg2CoH5,214 Mg2FeH6,214 Mg2CuHx,218
TiFeHx,219 Mg−Al−H,220 Mg−Zn−H,221 and several Mg−
La-TM-H (TM = Ti, Fe, and Ni)222 nanocomposites.
Zhang et al. developed a similar method called acetylene
plasma metal reaction for the synthesis of 15−85 nm Mg
NPs.121 By using acetylene, the growth of large Mg particles is
limited by the formation of carbon on the metal surface from
the decomposition of acetylene. Some control over the Mg
particle size can be achieved by varying the amount of
acetylene in the plasma, with a clear decreasing trend with
increasing acetylene content. Figure 9 shows the samples
prepared by acetylene plasma metal reaction with 28%, 21.7%,
14.3%, and 5.3% concentrations of acetylene, respectively. The
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Figure 9. TEM images of Mg NPs prepared by the acetylene plasma
reaction with acetylene content of (a) 28%, (b) 21.7%, (c) 14.3%, (d)
5.3%, and (e) 0%, and (f) size distribution of Mg NPs synthesized
with 21.7% acetylene. (Reproduced with permission from ref 121.
Copyright 2010 Elsevier.)
optimized acetylene concentration of 21.7% yields Mg NPs
with particle sizes from 15 to 85 nm with an average size of
about 40 nm. The equilibrium plateau measurements reveal
anomalously low values for particles of this size ΔH and ΔS
values of hydrogen absorption of −65.5 kJ mol−1 H2 and 122.7
J mol−1 K−1, respectively.121
In addition to binary and intermetallic hydrides, complex
metal hydrides can also be synthesized using plasma
techniques. For instance, reactive plasma involving the
evaporation of lithium metal in an Ar/NH3 atmosphere leads
to hollow Li2NH nanospheres with particle sizes between 100
and 400 nm.223 A similar approach can be used to synthesize
Mg3N2 nanocubes, which can be converted into 100−200 nm
Mg(NH2)2 nanospheres.224
Despite significant progress, the practical fabrication of the
metal hydride NPs and other nanostructures by plasma
methods is a complicated phenomenon which involves close
interactions among the thermofluid field, the induced electro-
magnetic field, and the processed particle phases, with
numerous process variables that need to be optimized
independently. The plasma methods are in principle scalable,
but are currently limited to only a few examples of metal
hydride NPs, for which optimized synthesis conditions have
been established.
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3.2.3. Thin Film Syntheses. The vast majority of thin
films for hydrogen storage are prepared starting with the pure
metal, often in ultrahigh vacuum (UHV) conditions. Physical
vapor deposition (PVD) is the most common technique.
Different subcategories of PVD include vacuum thermal
evaporation,225 molecular beam epitaxy (MBE),226,227 elec-
tron-beam deposition,28,228,229 ion-beam sputtering (IBS),230
and magnetron sputtering.42,231−233 These methods are highly
conducive to making films composed of more than one metal
by adding additional sources. Co-deposited metals can be in
intimate contact with each other even when they are
immiscible on the bulk scale, and alloys and intermetallic
compounds can be formed by annealing miscible metals.
Layered films are also quite feasible, particularly with
immiscible metals, though the formation of intermetallics can
be limited even between alloying metals by avoiding or limiting
annealing, leading to distinct layers with minimal blending.
Wet chemical methods have also been employed, using
preformed NPs and casting them into a thin film.234 Metal
hydrides are too sensitive for the ablative techniques described
above, and they would decompose into hydrogen and the other
constituent elements instead. Therefore, hydrogen is intro-
duced to the metallic films after they are formed.
3.3. Reductive Methods
3.3.1. Chemical Reduction. Chemical reduction with
hydrogen or other reducing agents has been widely used to
synthesize NPs of inorganic materials.235−240 However, many
of the surfactant-based approaches developed for other
inorganic nanoclusters of NPs are not suitable for synthesizing
nanostructured metal hydrides due to their high reactivity with
various classes of organic molecules, including thiols, alcohols,
and amines. Organic ethers and hydrocarbons are usually the
solvents/surfactants of choice, as metals and metal hydrides are
relatively stable in these compounds. For instance, Mg
nanocrystals of controllable sizes can be prepared by chemical
reduction of bis(cyclopentadienyl)magnesium using a solution
of potassium with an aromatic hydrocarbon in glyme.
Depending on the aryl anion used, Mg nanocrystals of 25
nm (potassium biphenyl), 32 nm (potassium phenanthrene),
or 38 nm (potassium naphthalene) were isolated. The
hydrogen sorption kinetics were shown to be dramatically
faster for nanocrystals with smaller diameters (Figure 10),
although the activation energies calculated for hydrogen
absorption (115−122 kJ mol−1) and desorption (126−160 kJ
mol−1) were within previously measured values for bulk Mg.
This large rate enhancement cannot be explained by the
Figure 10. Left: Mg nanocrystals synthesized by
bis(cyclopentadienyl)magnesium reduction with potassium in aro-
matic solvents. Right: Kinetics of hydrogen uptake for 25 (black), 32
(red), and 38 nm (blue) Mg nanocrystals at 300 °C. (Reproduced
from ref 241. Copyright 2011 American Chemical Society.)
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decrease in particle size alone but is likely due to an increase in
the defect density present in smaller nanocrystals.241
Liu et al. reported the possibility of in situ catalytic doping of
Mg nanocomposites with Ni during chemical reduction with
lithium naphthalide in tetrahydrofuran (THF).242 The
approach generated small Ni NPs deposited on the surface
of 10−20 nm Mg NPs. Upon hydrogenation of the
nanocomposite at 225 °C, the γ-MgH2 phase appears. PCT
measurements reveal that the Mg−Ni nanocomposite has
superior hydrogen storage properties over the pure Mg
prepared using the same method. The Mg−Ni nanocomposite
can absorb 85% of its maximum hydrogen capacity within 45 s
at 125 °C, and a hydrogen capacity of 5.6 wt % can be
obtained within 10 h at room temperature. Through the use of
Ca as the reducing agent with di-n-butylmagnesium, the
formation of Mg nanofibers with a width of 40 nm and a length
of 0.4−4 μm was also reported when 1-dodecanethiol was used
as a surfactant.243
3.3.2. Electrochemical Reduction. Electrochemical re-
duction is a simple method for the preparation of nano-
structured metal hydrides. The electrodeposition process
involves the use of a two- or three-electrode cell system,
where the electrolyte generally serves both as the source of the
metal, often Pd or Mg, and as the conductive medium. By
controlling the potential or current density of an electro-
chemical cell, deposition occurs from an oxidized form in
solution to a metallic state at the surface. The most
straightforward is the synthesis of interstitial hydrides, such
as palladium hydride by using various electrochemical baths.244
The synthesis of Mg NPs has also been reported through the
electrochemical reduction of organomagnesium compounds.
Haas and Gedanken proposed a sono-electrochemical
synthetic approach to prepare 4 nm magnesium NPs deposited
at the tip of a sonicating probe with ethyl- and butylmagnesium
chloride as magnesium precursors.245 Mg nanowires (NWs)
were electrodeposited onto a Pt electrode with ethyl- or
methylmagnesium chloride as a precursor (Figure 11).246
Using magnesium acetate as a precursor and appropriate
modification of the electrochemical synthetic method by Reetz
and co-workers,247 Mg NPs of 5 nm were electrochemically
synthesized in THF with tetrabutylammonium bromide as a
stabilizer. In this process, the cationic surfactant adsorbed at
the counter electrode, where Mg2+ is reduced, prevents direct
adsorption of the Mg nuclei onto the electrode surface in favor
of the nucleation and growth of surfactant stabilized Mg NPs
in the electrolyte.248,249
Tarascon et al. studied the electrochemical reactivity of
MgH2 with Li and demonstrated a reversible capacity of 1,480
mAh g−1 at an average voltage of 0.5 V versus Li+/Li°. The
electrochemical reaction results in formation of a composite
containing Mg NPs embedded in a LiH matrix, which can be
converted electrochemically into MgH2 NPs of 10 to 40 nm.250
Lithium hydride NPs have also been synthesized electro-
chemically by reductive hydrogenation of metallic lithium
intercalated into graphite.251 TGA-MS measurements reveal
that the onset of hydrogen desorption for the sub-100 nm LiH
NPs is >500 °C lower compared to bulk LiH and starts at
around 200 °C.
3.3.3. Thermal Decomposition. Metal and metal hydride
NPs can also be synthesized via thermal decomposition of
metal salts and organometallic precursors. Thermal decom-
position of di-n-butylmagnesium leads to β-hydrogen elimi-
nation with formation of MgH2 and the corresponding alkene.
10787
Review
Figure 11. Scanning electron microscopy (SEM) images of Mg
nanowires electrodeposited from (a) methylmagnesium chloride and
(b) ethylmagnesium chloride. (c) Diameter size distribution of NWs
prepared from EtMgCl. (Adapted with permission from ref 246.
Copyight 2012 The Royal Society of Chemistry.)
Similarly, alkyl derivatives of Li, Na, and Al can be used to
generate nanoscale LiH, NaH, and AlH3. A variation of this
approach is to perform the reaction under hydrogen pressure;
Jensen and coauthors reported MgH2 NPs inside carbon
aerogels using this approach.252 Figure 12 shows a schematic of
the process, which initially involves MgBu2 (with Bu = n-butyl)
infusion into the aerogel scaffold using heptane as a solvent.
After solvent removal, the nanoconfined MgBu2 is thermally
decomposed at 170 °C under 55 bar H2, which simultaneously
hydrogenates the Mg to give scaffold-incorporated MgH2 NPs.
De Jongh and coauthors reported a direct synthesis of LiH
NPs confined inside meso- and macroporous carbon xerogel
pores using n-butyllithium as a precursor.253 Since the xerogel
contains both meso- and macropores, the resulting LiH
particles have a wide particle size distribution from a few
nanometers to a few microns. Nevertheless, the H2 desorption
kinetics are improved, with the onset of hydrogen release as
low as 100 °C. Organometallic precursors of other metals have
also been used, for example, organoaluminum compounds are
suitable for alane nanoparticle synthesis; however, under the
reaction conditions used, AlH3 is believed to decompose
quickly into Al and gaseous hydrogen.254 Hydrogenation of
Et3Al at 150 °C under 20 MPa H2 pressure in the presence of a
Mg catalyst results in 99% triethylaluminum conversion, but
metallic Al is isolated instead of AlH3.255 In contrast, Aguey-
Zinsou and co-workers found that carrying out the Et3Al
hydrogenation (10 MPa H2) in the presence of a Mg catalyst
and tetraoctylammonium bromide as a surfactant, NPs of α-
AlH3 could be produced.256
3.4. Nanoconfinement
Different approaches have been used to prepare nanosized
hydrides in porous host materials and the feasibility of different
methods depends on the nature of the host and the hydride.
Impregnation methods, commonly used for the preparation of
catalyst/support materials, are frequently also used for the
preparation of hydride@host composites. We will introduce
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Figure 12. Schematic of in-pore synthesis of MgH2 NPs via thermal decomposition of Mg(n-C4H9)2 under hydrogen gas.252

the commonly used host materials and discuss typical methods

for incorporating the hydrides into the systems.
3.4.1. Host Materials. There are few prerequisites for
materials to be suitable host materials for confining hydride
NPs, apart from being stable and nonreactive toward the
hydride NPs and the hydrogenation/dehydrogenation pro-
cesses. Furthermore, for potential real-world applications,
having a low density for high gravimetric and volumetric
loading is advantageous. The most commonly used materials
for these stabilizations are usually carbon-based scaffolds with
an inherent porosity. Quite often, aerogels prepared by the
polymerization and carbonization of resorcinol and form-
aldehyde are used. Their pore sizes are determined by the pH
of the solution from which they are synthesized,257 and surface
areas and pore volumes can also be modulated by
postsynthetic treatments, such as carbon dioxide activa-
tion.16,258 Additionally, monolithic, rather than powdered,
aerogels can be mechanically abraded if a portion of the
hydride material meant for infiltration adheres, typically as bulk
hydride rather than nanoscale, to the exterior, allowing for
more accurate assessment of solely the nanoconfined
hydride.252,259 Another frequently used carbon material is
CMK-3,260 which is prepared by polymerization of carbon
sources (e.g., sugars) inside the pores of the ordered Figure 13. TEM micrographs (a,b) and electron diffraction pattern
(c) of Mg encapsulated in a poly(methyl methacrylate) nanowrapper.
mesoporous silica template SBA-15.261 The large surface area
(Adapted with permission from ref 21. Copyright 2011 Nature
and pore volume, which allow the deposition of a large volume Publishing Group.)
ratio of hydride in this material, make it a frequent choice.
Apart from that, the tunability of the pore space and the
possibility to dope the host structure with heteroatoms also 3.4.2. Impregnation Methods. Impregnation methods
make this particular material highly interesting for the comprise two major synthetic approaches of hydride confine-
controlled inclusion of hydrides. The use of high surface area ment. On the one hand, there are solvent impregnation
graphite (HSAG) is also very common, since the material itself methods that rely on the solubility of the hydride in an organic
is commercially available. More exotic materials include, for solvent. Second, there are melt infiltration methods, which
require the hydride to have a melting point under reasonable
instance, metal−organic frameworks, which consist of metal-
conditions (i.e., LiBH4 and NaAlH4 melt at 268 and 183 °C,
containing building blocks bridged by organic ligands.262 The
respectively, under ambient conditions).137 However, mixtures
tunability of this class of materials makes them interesting
of two or more hydrides can form eutectics, which have lower
hosts by allowing discrete tuning of pore geometry and melting points than the constituent components and can thus
functionality. However, the weak metal−ligand coordination also be melt-infiltrated into host materials.61,263 Several binary
bonds and the high weight penalty from the different inorganic borohydride eutectics have been confined and examined in this
clusters are considerable drawbacks to employment as stable way.264−268 Importantly, melt infiltrations are often carried out
and high-capacity hosts. under hydrogen backpressure to avoid desorption during the
More and more commonly, materials without any inherent process. Mg(BH4)2 decomposes prior to melting even at
porosity are used for the encapsulation of hydrides; in some typical H2 pressures employed (up to 200 bar).269,270
cases these hosts are also referred to as nanowrappers (Figure In general, melt infiltration is a method that achieves very
13).21,30,34 Materials that have been used for the nano- high loadings. The porous host is usually ground with the
encapsulation of particles are graphene, graphene oxide, and hydride to ensure good mixing and afterward put in a tube
poly(methyl methacrylate) polymers.21 Essentially, hydrogen furnace with H2 gas overpressure. De Jongh and co-workers
has a small enough kinetic diameter to diffuse through these additionally pressed the hydride/porous host mixture (MgH2
wrappers, while other gases are blocked out. These wrappers and carbon), in order to get the two compounds into more
protect the materials from external contamination, stabilize intimate contact, and they ended up with loadings of 15−
small particles, and tune the hydrogenation and desorption 20%.51 For hydrides such as MgH2, LiBH4, and NaAlH4, there
behavior. are numerous reports describing loadings of up to 50−65%. In
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one of these, at 60% loading, the average NaAlH4 crystallite
size was found to be greater than the average pore diameter of
the aerogel hosts, suggesting that larger pores fill first or more
readily during melt infiltration than smaller pores.257
In the case of solvent impregnation, the host material is
soaked by a solution of the precursors. For hydrides, the most
common solvents are ethers, such as (methyl tert-butyl ether
(MTBE), diethyl ether, or THF. In the case of NH3BH3,
MeOH is also a frequently used solvent. The loadings achieved
by this technique are often not as high as for melt infiltration,
even though in the case of NH3BH3 there are several reports
highlighting over 50 wt % of hydride loading.271 However,
repeated instances of solvent impregnation can be employed to
enhance hydride infiltration. For instance, Zheng and co-
workers used multiple soaking steps with a 1 wt % NaAlH4
solution to impregnate SBA-15 and achieved an actual loading
of 20 wt %.272
3.4.3. Synthesis Inside the Pores. There have been
several reports highlighting the possibility of hydride synthesis
inside the pores. In order to realize this, the host must be stable
against the very reactive precursor molecules, e.g., Mg(Bu)2.
There are several reports on carrying out the synthesis of
MgH2 inside the pore space of different host materials. Usually,
the host is exposed to a solution of Mg(Bu)2 in heptane at low
temperatures. The solvent is then removed with vacuum,
creating finely dispersed Mg(Bu)2, which is converted into
MgH2 and butane gas by hydrogenation.273 In this study, 22 wt
% of MgH2 were generated inside carbon nanofibers. Nielsen
and co-workers were able to incorporate 18.2 wt % inside a
carbon aerogel by this method.259 However, potentially higher
loading could have been achieved, as the used carbon aerogel
was a single monolith and excess MgBu2 that crystallized on
the outside surface was removed mechanically. The highest
reported value for MgH2 loading by this method was achieved
by Jia and co-workers, amounting to 37.5 wt %. In their study,
doped CMK-3 frameworks were exposed to Mg(Bu2) and
afterward dried over several days.274 The hydrogenation step
was realized inside of a PCT instrument. In the literature, the
in-pore synthesis has not been limited to MgH2; Mg(BH4)2
was synthesized inside the pore of a carbon aerogel by Züttel et
al.275 They first melt-infiltrated the aerogel with MgH2 and
afterward ball milled the MgH2-containing aerogel in a B2H6/
H2 atmosphere for 3 days, yielding Mg(BH4)2 in carbon
aerogel.
4. METHODS TO ANALYZE STRUCTURE AND
STORAGE PROPERTIES
For optimization of hydrogen storage properties of nano-
structured metal hydrides, it is critical to establish a
quantitative feedback loop concerning particle size, shape,
composition, internal structure, and their relationship to the
myriad of synthetic variables. Without a tight feedback loop
between the structure and function, the synthetic effort is
random with respect to whether changes in synthetic protocol
are improving the final material. Unfortunately, extending
standard analytic methods to determine the structure of
nanoscale metal hydrides is not straightforward, as these
materials are composed of light elements and pose all sort of
issues related to sample reactivity and sensitivity to X-rays and/
or high-energy electrons. Experimental methods to determine
the structure of nanostructured metal hydrides are mainly
based on X-ray, neutron, and electron microscopy
tools.23−25,33−42,276
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4.1. Experimental Structural Analyses
4.1.1. Transmission Electron Microscopy. Transmission
electron microscopy is one of the most used techniques to
characterize nanostructured metal hy-
drides.23−25,33−42,146,164,277−279 One of the most important
recent developments is the spherical aberration correctors for
both conventional TEM and scanning TEM (STEM) modes,
enabling atomic scale imaging and chemical analyses of hydride
samples.280 A critical requirement is making the sample
thickness below about 500 nm in order to have a sufficient
fraction of the electron beam transmitted through the sample.
The typical resolution of an image in contemporary TEM
instruments is in the range of 0.2 nm without using a spherical
aberration corrector, and one can achieve a resolution of 0.05
nm by employing various corrections. Metal hydride samples
are typically beam sensitive; that is, they decompose to
hydrogen and the metal under the high flux and energy of the
standard electron beam, and they typically require cryogenic
conditions and low-dose or low-energy electron beams to
maintain their original structure.
4.1.2. X-ray and Neutron Techniques. X-ray and
neutron techniques can provide detailed information about
the structure and dynamics of nanostructured metal hydrides.
The sensitivity of a material to X-rays depends on the number
of electrons and thus the atomic number of its constituent
elements; as such, hydrogen is undetectable. However, the
interactions of neutrons with nuclei is not proportional to the
number of nucleons; thus, hydrogen is readily measured, and
protium and deuterium can even be distinguished.281 Current
efforts are focused on developing new beams and optics to
produce appropriate and tunable wavelengths/energies and
detecting their interactions with materials. This is particularly
helpful to ascertain the arrangements, both physical and
chemical, of atoms and to track their movements or
rearrangements during hydrogen storage reactions.23−25,33−42
The arrangement of atoms inside nanoscale metal hydrides
can be determined using several techniques based on
scattering, diffraction, spectroscopy, and imaging. Since both
X-rays and neutrons are in principle nondestructive, such
techniques can be used for in situ studies of nanostructured
metal hydrides during hydrogen absorption and desorption. X-
ray diffraction is one of the most common analytical methods,
though neutron diffraction has also occasionally been
employed in hydrogen storage materials.282 Small-angle
scattering measurements, with both X-rays (SAXS) and
neutrons (SANS), are highly useful in analyzing nanoscale
materials, especially those that are nanoconfined.283−288
Synchrotron radiation techniques have proved versatile in
elucidating the mechanisms of hydrogen storage reactions,
with techniques involving “soft” X-ray (∼0.1 keV, correspond-
ing to a wavelength of 12.4 nm) to “hard” X-rays (∼100 keV,
or a wavelength of 0.0124 nm). For many of the experimental
methods mentioned above, the primary advantages of
synchrotron X-ray sources are the high intensities and energies
accessible, allowing for rapid sampling with high signal-to-noise
and measurements under non-UHV conditions, as in ambient-
pressure XPS (APXPS). X-ray diffraction, in particular, benefits
from the large penetration depth of short wavelength photons,
which permits high pressure and high temperature operations,
including for the in situ measurement of hydrogen absorption
and desorption in hydrides.289 However, some important
techniques also exploit the tunability of synchrotron radiation.
X-ray absorption spectroscopy (XAS), which can be divided
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into X-ray absorption near edge structure (XANES) and
extended X-ray absorption fine structure (EXAFS), involves
the excitation of a core electron of a particular element that is
dependent on the oxidation state and the coordination
environment of atoms in the sample.290 EXAFS in particular
extends its reach beyond the first coordination sphere to more
distant neighbors, allowing a more extensive structural analysis
of which atoms are near each other in the material, such as
which sites hydrogen occupies in a Pd−Rh nanoalloy.291
Modeling of XAS spectra of pure materials has proven useful,
particularly in metal hydrides, which oxidize readily even in
low oxygen environments and for which the presence of oxide
phases may distort accurate analysis.36,292 In situ XAS, with
both heating and hydrogen pressure, has been employed to
probe the hydrogenation and dehydrogenation of rGO-
wrapped Ni-doped Mg NPs.35 Scanning transmission X-ray
microscopy (STXM) is an application of XAS in which an
absorption image is obtained at varying photon energies,
resulting in a spectrum for every pixel. The resulting set of
images can be deconvoluted into component phases based on
known XAS spectra, yielding a compositional map of the
material.293
4.1.3. Vibrational Spectroscopy. While X-ray methods
can investigate the oxidation states of elements, vibrational
spectroscopy is able to study the bonding among atoms,
especially in the polyatomic anions of complex metal hydrides.
Infrared (IR) spectroscopy can readily assess the presence of,
for example, aluminum−hydrogen,294 boron−hydrogen,292,295
and nitrogen−hydrogen bonds, and the changes between
hydrogenated and dehydrogenated states are apparent. Diffuse
reflectance infrared Fourier-transform spectroscopy (DRIFTS)
in particular has been employed for in situ desorption
measurements, using heating capabilities.296 Raman spectros-
copy has also been employed to detect vibrational modes in
complex hydrides, both ex situ and in situ.297,298 Using X-ray
Raman spectroscopy (XRS), a synchrotron technique,
Miedema et al. monitored the in situ dehydrogenation and
rehydrogenation of nanoconfined LiBH4 in carbon, since the
high-energy X-rays permit the use of elevated pressures of
hydrogen.299 Neutron vibrational spectroscopy (NVS), which
is very sensitive to hydrogen-containing species, has been
measured for both bulk300 and nanoconfined19 complex metal
hydrides. A disadvantage to NVS is that 10B absorbs neutrons
well and drastically decreases the signal in B−H-containing
materials; however, the use of 11B-enriched samples overcomes
this problem.300
4.2. Theoretical Structural Determination
4.2.1. Wulff Construction. Theoretical modeling is a key
component of understanding the structural features of
nanostructured metal hydrides. DFT is the technique of
choice to predict the crystal structures and atomic arrange-
ments in metal hydride NPs and nanoclusters. Johnson and
Sholl introduced a “top-down” approach to predicting the
shape and surface energy of metal and metal hydride
nanoclusters.301 The crystal structure of each nanocluster is
assumed to be identical to the bulk crystal, aside from
relaxation of the atoms in the first few layers near the surface.
For each surface exposed on a nanocluster, the energy
difference between edge and bulk atoms is characterized by a
surface energy. The equilibrium crystal shape of a material can
be then predicted using the calculated surface energies and the
Wulff construction. The Wulff construction is a method to
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determine the shape of a crystal by performing energy
minimizations to identify the preferred crystal planes.302 The
Wulff construction, coupled with Gibbs energy minimizations,
can then be used to gain insights into thermodynamic stability
of metal and metal hydride nanoclusters.
4.2.2. Prototype Electrostatic Ground State Method.
Another powerful tool to predict the structures of both bulk
and nanoscale complex metal hydrides, called the prototype
electrostatic ground state (PEGS), was introduced by Majzoub
and Ozoliņs.̌ 303 This Monte Carlo approach identifies ground
state structures by minimizing the electrostatic energy of a
system of spherical cations and geometrically complex anions,
subject to constraints of interatomic distances. The energy
functional used this Monte Carlo approach is given by the
following equation:
Q iQ j ϵss
Etot = ∑ + ∑
i>j
R ij i>j
R ij12 (8)
where Etot is the total energy of the system. The first
summation is the Coulombic energy, with Qi and Qj denoting
the ionic charges and Rij is the interion distance, whereas the
second term, in which ϵss is the soft-sphere interaction
potential, is taken from the repulsive part of the Lennard-
Jones potential, which only contributes to the overall energy
when the ions physically overlap. Both sums involve all ions in
the material, including both the metal cations and the rigid
complex anions. The main advantage of the PEGS approach is
that it can generate crystal structures quickly, without the need
for the extremely time-consuming development of interatomic
potentials. In addition to accurately predicting the crystal
structures of a number of bulk alanates and borohy-
drides,304−309 the nano-PEGS variation of the code was used
to generate ground-state structures for NaAlH4 and LiBH4
nanoclusters.144,310,311 The model takes advantage of the ionic
nature of metal hydrides by fixing the local arrangement of
complex anion groups, for example, the BH4− anion in LiBH4.
Not only does the PEGS method accurately predict many
known crystal structures, but it can also predict the structure of
unknown materials. The predicted structure can then be
refined using more accurate DFT calculations to establish the
atomic coordinates of all atoms, including hydrogen.
Majzoub et al. used the predicted nano-PEGS structures to
evaluate the thermodynamic stability of LiBH 4310 and
NaAlH4144 nanoclusters via the grand-canonical free-energy
minimization approach based on total energies and vibrational
frequencies obtained from DFT calculations. Nanoclusters of
LiBH4 containing fewer than 12 formula units are predicted to
dehydrogenate through intermediates of the form LinBnHm (m
≤ 4n) into (LiB)n clusters (Figure 14). In the sodium
aluminum hydride system, the stability of NaAlH4 and AlH3
clusters increases as cluster size shrinks. Interestingly, AlH63−
nanoclusters are unstable due to a Jahn−Teller distortion
arising from degenerate highest occupied molecular orbitals,
leading to decomposition of the normally octahedral species.
This instability of the dehydrogenation intermediate Na3AlH6
yields a one-step decomposition in nanoscale NaAlH4. The
calculated PCT isotherms for both LiBH4 and NaAlH4 exhibit
sloping plateaus due to finite size effects, and the
decomposition temperatures of free-standing clusters are
found to decrease slightly with size due to thermodynamic
destabilization of reaction products.
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boundary effects,327 and elastic inhomogeneous effects328,329 in

particles and polycrystals. The method has been actively
utilized to study phase evolution in materials for electrical
energy storage,330−332 but has only recently been applied to
hydrogen storage materials. Voskuilen et al.333 developed a
phase-field model for describing hydrogen transport and
operating reactions for hydriding LaNi5 and TiCrMn. In
addition, Ulvestad et al.334,335 employed the steady-state phase-
field calculations to analyze the internal strain field and
hydriding phase morphology in Pd NPs. Further development
of phase field-models for hydrogen storage will provide a
means of more systematically exploring the interplay between
microstructure and reaction kinetics.
4.3. Thermodynamic and Kinetic Analysis
Accurate determination of the thermodynamics and kinetics of
metal hydrides is critical to ascertaining the effect of structural
nanoscaling on the hydrogen storage properties. Many of the
Figure 14. Atomic geometries of various B−H clusters determined experimental techniques employed for bulk hydrides are the
from nano-PEGS and first principle calculations. (Reproduced from same for nanostructured materials and are described below.
ref 306. Copyright 2012 American Chemical Society.) Computational models used to deconvolute energetic con-
tributions from various size-related properties are discussed in
section 6.
Since the PEGS approach uses a simple energy model 4.3.1. Thermodynamic Measurements. The general
consisting of purely electrostatic interactions, it has some reaction involving reversible hydrogen storage in metal
limitations in predicting the structures of metal hydrides with a hydrides can be written as
high-degree of covalent character. Other methods, such as x
constrained evolutionary algorithms,69,312−316 have been ABHx(s) F AB(s) + H 2(g)
2 (9)
proposed for the prediction of metal hydride crystal structures
consisting of well-defined molecular units. In this approach, The equilibrium state of this reaction can be described in terms
each structural unit is treated as a rigid body with fixed bond of the equilibrium constant K and enthalpy change by the van’t
lengths, and then the positions of preformed molecules are Hoff equation:
found through constrained global optimization, a process of
finding the most stable crystal packing given a fixed bond d ln K ΔH 0
=
connectivity. This evolutionary approach to structure deter- dT RT 2 (10)
mination has been successfully implemented in the USPEX Since
(Universal Structure Predictor: Evolutionary Xtallography)
code.317−322 However, despite progress, prediction of com- ΔG 0 = −RT ln K (11)
pounds with large unit cells is still challenging. For instance, and
none of the existing theory methods are able to accurately
predict the structure of γ-Mg(BH4)2 with the P61 symmetry, ΔG0 = ΔH 0 − T ΔS 0 (12)
which has as many as 330 atoms in the unit cell.323 and, because the gaseous hydrogen is the only species with an
4.2.3. Microstructure Modeling. Beyond the crystal activity not equal to one, eq 10 can also be represented as
structure and nanoscale geometry of the particles, modeling
the impact of microstructural features on hydrogen storage at d ln peq ΔH 0
=
the nanoscale is likewise important. Nevertheless, there have dT RT 2 (13)
been relatively few attempts to directly model the micro-
or
structure in hydrogen storage materials. One example can be
found in the work of Michel and Ozoliņs,̌ who investigated ΔH 0 ΔS 0
microstructural effects on diffusion kinetics in the bulk Na− ln peq = − −
RT R (14)
Al−H system by considering different model arrangements of
NaAlH4, Na3AlH6, and Al.169 Another example comes from the where p is the equilibrium pressure for reaction 1; ΔH , ΔS0,
eq 0

work of Wood et al., who considered the thermodynamics of a
few different model microstructures in the nanoscale Li−N−H
system.19 Although illustrative, these attempts have relied on
static models without explicitly considering how the micro-
structure evolves during the reaction.
The phase-field method has emerged as one of the most
powerful methods for mesoscale modeling of material
microstructural evolution.324 This method is based on the
diffuse-interface description that naturally connects the
essential thermodynamic and kinetic ingredients of relevant
chemical and materials processes.325 Recent advances have
extended the method to account for surface effects,326 grain
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and ΔG0 are the standard enthalpy, entropy, and Gibbs free
energy change of the reaction; T is the absolute temperature;
and R is the universal gas constant.
Equation 14 indicates that a plot of ln peq vs 1/T has a slope
of −ΔH0/R and an intercept of ΔS0/R. For an equilibrium
pressure of 1 bar, the decomposition temperature Tdec is
ΔH 0
Tdec =
ΔS 0 (15)
For a typical standard entropy change of a metal hydride of
120 J K−1 mol−1 H2, at 350 K ΔH0 = 30 kJ mol−1 H2. ΔH0
values of ∼30 ± 10 kJ mol−1 H2 are considered within the
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Figure 15. Changes in the rates of absorption (a,d) and desorption (b,e) and the activation energy (c,f) as functions of the hydrogen content in Ni-
doped (a−c) and undoped (d−f) rGO-Mg composites. (Adapted with permission from ref 35. Copyright 2017 John Wiley and Sons.)
range of interest for near-ambient temperature reversible
hydrogen storage applications. For a hydride with an
equilibrium pressure of 1 bar, a 10 kJ mol−1 H2 variation in
ΔH0 results in about 80 K change in the decomposition
temperature.
The thermodynamics, particularly the equilibrium pressure
peq, are typically measured using a volumetric Sieverts-type
instrument. A sample of known initial mass and composition,
either with or without hydrogen, is loaded into a pressure
vessel, and the volume of the sample holder is calibrated using
a typically inert gas and the calibrated volumes and pressure
transducers inside the instrument. The two calibrated volumes,
both that exclusively within the instrument manifold and the
total volume including the pressure vessel, are utilized to
determine the amounts of hydrogen dosed and the final
remaining gas not adsorbed or absorbed by the sample,
respectively. Frequently, numerous measurements are obtained
at a variety of pressures and, often, temperatures to sample a
representative portion of the pressure−composition−temper-
ature space. In general, the pressure is modulated sequentially,
gradually adding more or removing more hydrogen from the
system to shift the composition, while remaining at constant
temperature, and several such isotherms are measured to yield
the van’t Hoff plot. Gravimetric instruments yield identical
information as volumetric setups, but the compositional shifts
are determined by changes in the measured mass of the
material, rather than from differences in the dosed and final
hydrogen amounts, as it absorbs and desorbs H2.
In a simple interstitial hydride such as Pd, a flat plateau in a
pressure−composition isotherm is established, with little
pressure change corresponding to a substantial change in the
hydrogen content in the material as the solid solution of α and
β phases evolves from mostly α to mostly β.336 The midpoint
of this plateau, as long as it remains at constant composition, is
typically chosen as the value of peq. In more complex systems,
however, a sloping, rather than flat, plateau is obtained; the
slope may result from atomic disorder, such as defects or
noncrystallinity, or from nonequilibirium processes, as found in
irreversible reactions.337 Some hydride systems completely lack
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any semblance of a plateau if the disorder is particularly
substantial, as found in amorphous and some nanostructured
materials.338 If a material has a multistep (de)hydrogenation
reaction, as in NaAlH4/Na3AlH6, or contains two hydrides in a
mixture, such as MgH2 and Mg2NiH4, multiple plateaus,
corresponding to each reaction, will be present in the PCT
curves.
4.3.2. Thin Film Hydrogen Content Measurements. In
general, the total mass of a deposited film is very small and
below the threshold for gravimetric or volumetric measure-
ments described above that are commonly used in determining
hydrogen uptake.230 Therefore, alternative analysis methods
must be employed to gain insight into the hydrogen content of
thin films.339 Nuclear reaction analysis (NRA) bombards the
sample with 15N ions at different energies to sample different
depths, and emitted γ rays, which are proportional to the
hydrogen concentration at each depth, are detected. Elastic
recoil detection analysis (ERDA) employs heavy ions, such as
Cl7+ or Ag9+, to obtain depth profile concentrations of all
elements, including H.232,340 Neutron reflectometry or
reflectivity relies in part on the large neutron cross-section of
hydrogen and measures the scattering angle of neutrons by a
sample based on the scattering lengths of the pure metal
compared to that of the metal with hydrogen.341
In addition to the more direct measurements of the presence
of hydrogen, other techniques have been developed that sense
changes in the parent material as the hydrogen content evolves.
In hydrogenography, visible light is used on materials that
transition from reflective metals to opaque or transparent
hydrides upon hydrogenation, utilizing a property that also has
applications in switchable mirrors and windows.342,343 IR
emission also has been employed, monitoring changes in
intensity over time and even over area as a material is cycled.28
The IR emissivity depends on the electrical resistivity, which
decreases as a metal is hydrogenated to a semiconducting or
insulating hydride, and is itself often used as a measure of
uptake.230,234 XRD is another commonplace indirect analysis
method and is sensitive to both small changes in lattice
parameter, at low hydrogen contents, to complete structural
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Figure 16. (a) Computed activation barrier for early hydrogenation of MgB2 from Arrhenius analysis. (b) Reaction energy landscape for the two-
step mechanism of dissociation and diffusive adsorption, with adsorption energies derived from ab initio calculations. (c) Experimental and
simulated uptake curves showing the change in rate-limiting step. (d) Schematic of the proposed mechanism. (Reproduced with permission from
ref 292. Copyright 2017 The PCCP Owner Societies.)
transformations from the metal crystal structure to that of the
hydride. For thin films, grazing angle, also known as glancing
incidence, XRD is employed so that the X-ray beam samples
the film preferentially, rather than the substrate.
4.3.3. Rate Analysis and Kinetic Models. Kinetic
modeling and analysis of hydrogen storage materials is critical
to developing an understanding of rate-limiting processes
during (re/de)hydrogenation. In many instances, kinetic
insights can be obtained by fitting time-dependent reaction
data to well-known models of (de)hydrogenation that exhibit
characteristic uptake behavior.344 Dominant rate-limiting
mechanisms can then be straightforwardly identified from
model parameters derived from the fit.345 Alternatively, more
complex mechanisms may require advanced approaches that
directly extract activation energies for relevant kinetic
processes. One way to obtain kinetic data for a metal hydride
is to measure the time-dependence of the hydrogen uptake or
desorption during acquisition of a PCT isotherm. Small
perturbations in the dosed gas pressure, generally though not
necessarily while on the equilibrium plateau, lead to recovery
over time toward the initial sample pressure, as the stored
capacity and gaseous H2 content shift relative to each other,
restoring equilibrium according to Le Chatelier’s principle.337
The rate of this restorational change can then be used, along
with those measured at other temperatures, to fit the Arrhenius
eq 16, in which k is the rate constant, A is the pre-exponential
factor, and Ea is the activation energy.346,347 The activation
energy for the (de)hydrogenation reaction can thus be
extracted from the slope of the plot of the natural logarithm
of the rate (or rate constant) vs the reciprocal absolute
temperature. In principle, this process can be extended across
the entire range of (de)hydrogenation, yielding Arrhenius-
derived activation barriers for each degree of hydrogen content
in the metal hydride. The activation energy as a function of
reaction progress can then be utilized to analyze dynamic
changes in rate-limiting processes and/or to inform the more
detailed kinetic models. For example, Cho et al. applied this
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method to analyzing multiple isothermal data for rGO-
encapsulated Ni-doped Mg NPs to extract the activation
energy.36 By interrogating the varying activation energy with
the extent of the hydrogen absorption/desorption reactions
(see Figure 15), they could identify the rate-limiting
mechanisms for different reaction stages of (de/re)-
hydrogenation.
Ea ij 1 yz
jj zz + ln(A)
R kT {
ln(k) = −
(16)
Another common approach to obtaining Ea is the Kissinger
method.348 This method is usually used to determine the
activation energy from nonisothermal (de)hydrogenation
reaction data with different heating rates, typically using
differential scanning calorimetry (DSC) systems, and has been
widely used in hydrogen storage research.173,176,194,294,344,349
The linearized Kissinger eq 17, in which A is a constant,
assumes a constant heating rate, β, leading to a temperature at
which the maximum rate occurs, Tm, seen as a peak in a DSC
curve which shifts to higher values as β increases. Kissinger
analysis has the advantage of requiring fewer measurements
overall. However, it assumes only a single rate-limiting process,
so the composition range of interest must be chosen carefully if
multiple processes are kinetically competitive. Though many
standard DSC instruments operate at ambient pressure with
gas flow, high-pressure variants are available to maintain a H2
overpressure and thus interrogate compositional spaces
otherwise inaccessible.
ij β yz ij AR yz E ij 1 yz
lnjjj 2 zzz = lnjjj zzz − a jjj zzz
jT z
k m {
j Ea z
k { R jk Tm z{
(17)
Kinetic models and analyses have been applied to analyze a
wide scope of kinetic processes ranging from the surface-
related initial stage of (re/de)hydrogenation to the deeper
hydriding/dehydriding phase transformations. For deeper
hydrogenation processes, one of the most common approaches
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applies the Johnson-Mehl-Avrami−Kolmogorov (JMAK)
model, which describes the hydrogenation process as a phase
transition operated by simultaneous nucleation, growth, and
impingement of a new phase inside the parent phase.344 A
recent review article by Pang and Li documented the JMAK
model, as well as a number of other predefined kinetic models,
such as geometrical contraction models for interface- or
diffusion-controlled processes.344 Their review also provides a
comprehensive overview of the assumptions and derivations of
these kinetic models, as well as several examples of application
to hydrogen storage.
Within certain reaction regimes, it may be difficult to
identify the specific rate-limiting steps. One example is the
earliest stages of (de)hydrogenation, in which governing
processes may differ significantly from later stages dominated
by diffusion, nucleation, and/or growth. A recent example of
this can be found in the work of Ray et al.292 They employed a
multiscale approach that combines quantum-mechanical
calculations, the Arrhenius analysis method, and a kinetic
model to verify the relevant heterogeneous multistep chemical
and materials processes during the initial stages of hydro-
genation of MgB2. In their integrated model, the energy
landscape for the entire process (Figure 16b) was constructed
by combining the hydrogen binding energetics from DFT
calculations and the activation energies (Figure 16a) from the
Arrhenius analysis of isothermal hydrogen uptake curves for
three different temperatures. The energy landscape para-
metrized the corresponding kinetic model consisting of
coupled differential equations that describe coevolving kinetic
processes, which verified the rate-limiting processes (Figure
16c).
4.3.4. Thermodynamic Models. Fundamental phase
diagrams for several metal−hydrogen systems have been
constructed by conventional CALculation of PHAse Diagrams
(CALPHAD) modeling method,83,350,351 which relies on
inputs from experimental measurements and ab initio
calculations of thermodynamic quantities. Other similar
techniques informed by DFT enthalpy calculations have also
been proposed for computing thermodynamic or thermochem-
ical equilibria of multicomponent hydrogen storage materials.
Kim et al. demonstrated a thermochemical equilibrium
calculation approach using data obtained from DFT
computations.352 They investigated the thermodynamically
stable solid and gas phases of LiNH2, LiBH4, Mg(BH4)2, as
well as their mixtures with destabilizing compounds.
Akbarzadeh et al. determined the hydride phase diagrams of
the Li−Mg−N−H system353 by combining DFT calculations
with the grand canonical linear programming (GCLP) method,
which determines phase expression by minimizing the grand-
canonical Gibbs free energy across several simultaneous
competing reactions.354 This method was also used to
investigate the phase equilibria of the Li−Ca−B−N−H
system.355 Wood et al. introduced an extension of the GCLP
method that further incorporates phase coexistence by
considering the entropy of mixing within an ideal mixing
model.
Within DFT, the temperature dependency of the Gibbs free
energy is usually included by employing the quasi-harmonic
approximation, which extrapolates thermal effects from zero-
temperature phonon frequencies.306,353,356 This approximation
is well suited for considering thermal effects of high-frequency
modes such as bond stretching; however, it has been suggested
that inaccurate results may be produced for complex hydrides
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if rotational modes associated with molecular anions are
sufficiently anharmonic at operating temperatures. Indeed, in
NPs, the larger free volume associated with surfaces, interfaces,
and grain boundaries is likely to exacerbate anharmonic effects.
Zarkevich et al.357,358 considered the anharmonic contributions
to the enthalpies of phase transformations and hydrogen
storage reactions in LiBH4. By computing the degrees of
freedom originating from anharmonic motion using ab initio
molecular dynamics and classical statistical mechanics, they
showed that including these effects brought phase transition
temperatures and melting enthalpies into better agreement
with experiments.
DFT methods for computing enthalpy and entropy can be
extended to predict the thermodynamic stability of NPs by
combining calculations of bulk and surface regions. The most
straightforward method involves determining the effective
surface energy of the particle by considering the surface
energies of various individual orientations and terminations,
then weighting them relative to their expression within an
equilibrium Wulff shape. The effective surface energy is then
scaled according to the surface area and combined with the
bulk energy to estimate the Gibbs free energy of the particle.19
Note that this approach assumes that the particle assumes an
ideal Wulff shape with well-defined facets, and that the core
region behaves like the perfect bulk material. As a result, it is
likely better suited for larger NPs than for smaller NPs, of
which disordered surface regions comprise a larger fraction of
the material and core regions are difficult to delineate.
Recognizing this difficulty, a number of authors have turned
to explicit modeling of cluster geometries within DFT.
For clusters, the size-dependent particle geometry of
nanoscale metal hydrides has been predicted by a variety of
methods, including molecular dynamics simulations,15 cluster
expansion,359 and PEGS combined with a genetic algorithm.310
For example, using cluster expansion on NaAlH4, Mueller et al.
proved that particles larger than 5 nm in diameter expose
prominent low energy surfaces, as expected, but surface facets
and structures become less clear in smaller particles.359
In addition to surface energies, the energy of internal
interfaces and grain boundaries can contribute meaningfully to
the thermodynamics of metal hydride NPs, particularly when
phases coexist during (de)hydrogenation. Interface energies
can be computed by explicitly attaching two phases within
periodic boundary conditions in DFT360−362 or by using
appropriately parametrized classical force fields. However,
because determining lattice commensurability and preferred
interface orientation can be difficult, this approach is best
suited for simpler intermetallic and binary hydrides. For
complex hydrides and other systems featuring highly
disordered interfaces, the chemical composition and structure
of the phase boundaries can be difficult to model explicitly (see
section 6.2). To this end, Wood et al. introduced a simpler
method for approximating the internal interface energetic
penalty in the Li−N−H system as a weighted sum of surface
energies of involved phases.19 Because the weights of
individual surface energies were difficult to discern a priori,
the authors instead employed a statistical sensitivity analysis to
determine the likelihood of phase expression as a function of
the weighting factor. From this analysis, it was possible to
demonstrate the critical roles of internal nanointerfaces in
determining the (de)hydrogenation reaction pathways of the
Li−N−H system. Further developments in accurate modeling
of interface energetics are recommended.
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Figure 17. Illustration of supporting materials for nanoconfinement: (a) porous host matrix (porous carbon, silica, MOF, carbon fiber, and
aerogel), (b) ligands (surfactants and polymers), (c) wrapping carbon (graphene and graphene oxide) and synthetic methods for producing
nanomaterials: melt infiltration, solvent impregnation, and solution-based synthesis.
5. EFFECTS OF MORPHOLOGY ON HYDROGEN
STORAGE PROPERTIES
For nanostructured materials, morphology has special sig-
nificance since it dictates observed physical and chemical
properties. Morphology is attained during particle growth
through a self-assembling process dictated by the interplay of
size and molecular interactions.363 Deviations from bulk
properties become prominent as the sizes of nanomaterials
start to be comparable to the size of constituent blocks.
Properties of metal hydride nanocomposites are controlled not
only by morphology of individual nanomaterials, but also by
the nature of interactions, which, in turn, are determined by
the distribution of the nanomaterials in the hydride matrix.
Reducing the particle size of metal hydrides to nanoscale
dimensions offers new possibilities to optimize the perform-
ance of hydrogen storage. Ball milling, one method of
nanoscaling, yields freshly prepared surfaces that are highly
unstable, such that the newly created NPs (10−50 nm or
larger) can easily aggregate into much larger particles (200−
300 nm).11 An alternative approach to creating stable NPs is to
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use supporting materials, which can stabilize NPs to <10 nm.
Various supporting materials such as porous matrices, ligands,
and wrapping carbon materials have been proposed, and
different synthetic routes to create these supported metal
hydride nanomaterials have been experimentally studied
(Figure 17). In the following section, we will discuss the
most common morphologies found in nanoscale metal
hydrides.
5.1. Free-Standing Nanoparticles
Isolated metal hydride NPs are difficult to synthesize, and most
of the work so far has been focused on metals, which can form
metal hydride NPs upon exposure to hydrogen. Metal hydride
NPs are convenient model systems to investigate the effect of
size on reaction pathways, reversibility, as well as the
thermodynamics and kinetics of the process. Polymer-coated
Pd NPs with diameters of 2.6 ± 0.4 and 7.0 ± 0.9 nm were
investigated by PCT and show a narrowing of the two-phase
regions of solid-solution and hydride phases. The smaller
nanoparticles exhibited a smaller ΔH, indicating the weakening
of the Pd−H bond as size decreases.107 However, it was found
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that the hydrogen binding energy differs for Pd atoms on the
surface compared to those in the core. Kitagawa et al.
investigated the Pd/Pt core/shell-type bimetallic NPs and
found a new hydrogen absorption site in the nanointerface
between the Pd core and Pt shell.364
Yamauchi et al. observed the size dependencies of the
hydrogen-storage properties of coated Pd NPs with diameters
of 2.6 ± 0.4 and 7.0 ± 0.9 nm.107 The authors chose poly(N-
vinyl-2-pyrrolidone) (PVP) to passivate the Pd NPs because it
binds well to metal surfaces. The carbonyl groups of PVP
partly coordinated to the surface Pd, which limited the growth
of the Pd NPs. As a result, the particle size of Pd increased as
the amount of PVP decreased. The Pd NPs showed
significantly different isotherms from those of Pd bulk; the
NPs displayed higher hydrogen uptake at low pressure and a
smaller change in enthalpy (Figure 18).
Figure 18. TEM images of Pd NPs with diameters of (a) 2.6 ± 0.4
nm (Pd−S) and (b) 7.0 ± 0.9 nm (Pd-L). (c) Absorption pressure−
composition isotherms of the Pd−S (red), Pd-L (blue), and bulk Pd
black (black) at different temperatures from 303 to 393 K. (Adapted
with permission from ref 107. Copyright 2008 American Chemical
Society.)
Magnesium hydride has been studied extensively as it has
one of the highest capacities of all binary metal hydrides. NPs
of MgH2 typically display accelerated kinetics of hydrogen
release and/or uptake.23,121,21,365,241 Liu et al. isolated 8−25
nm Mg NPs using an electroless approach and found that the
thermodynamics significantly deviate from that of bulk MgH2
with a significant decrease of both enthalpy (63.5 kJ mol−1 H2)
and entropy (118.4 J K−1 mol−1 H2) for particle sizes below 25
nm.366 Experiments by Paskevicius et al. on MgH2 NPs
embedded in a LiCl matrix show that the enthalpy decreases
by 2.8 kJ mol−1 H2, coupled with an entropy decrease of 3.8 J
K−1 mol−1 H2.186
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Nanowires or NPs of Mg with diameters >50 nm23 and
hexagonal 50−500 nm Mg particles210 show no change in
thermodynamic properties, but dramatic improvements in the
kinetics, with activation energies being decreased from 120 to
38 kJ mol−1 H2.23 Urban et al. reported air-stable 5 nm Mg
NPs with reduced activation energies for hydrogen absorption
(25 kJ mol−1) and desorption (79 kJ mol−1), and a cycling
temperature of 200 °C.21 Sub-10 nm Mg NPs show an even
more dramatic improvement in H2 storage properties, with fast
kinetics and improved thermodynamics which lead to
hydrogen cycling below 120 °C.52,367 Aguey-Zinsou reported
that LaNi5 NPs of about 26 ± 8 nm have an enthalpy decrease
of 5 kJ mol−1 H2 for absorption and 8 kJ mol−1 H2 for
desorption, while the entropy decreased by 15 J K−1 mol−1 H2
for absorption and 19 J K−1 mol−1 H2 for desorption.368
Methods to synthesize free-standing NPs of complex metal
hydrides are scarce and have only been demonstrated for a few
materials. Varin and Parviz explored the influence of the
addition of TiN, TiC, and ZrC NPs on the activation energy of
LiAlH4 dehyrogenation.369 LiAlH4 was mixed with separately 5
wt % of each of the compounds in a high impact ball mill.
Interestingly, the activation energies for the first dehydrogen-
ation step are not strongly influenced and remain in the known
range for the bulk material, amounting to 87.7, 89.5, and 96.4
kJ mol−1 H2 for the composites containing TiN, TiC, and ZrC,
respectively. However, a drastic decrease is observed for the
second dehydrogenation step, with activation energies of 76.6,
79.5, and 63.4 kJ mol−1 H2 for the TiN-, TiC-, and ZrC-
containing composites, respectively. Liu et al. studied the effect
of doping LiAlH4 with micro- and nanosized TiH2.370 The
doping was achieved by ball milling and resulted in a marked
decrease of the activation energy by 20 and 24 kJ mol−1 for the
micro- and nano-TiH2 doped LiAlH4, respectively.
Christian and Aguey-Zinsou used an antisolvent approach to
synthesize NPs of sodium borohydride coated with a shell of
nickel.371 In contrast to bulk NaBH4 which releases hydrogen
>500 °C, the NaBH4/Ni nanocomposite can be cycled as low
as 350 °C with a 5 wt % capacity; 80% of hydrogen can be
desorbed and absorbed in less than 60 min, and full capacity is
reached within 5 h. A similar approach used to LiH/Ni core−
shell particles resulted in a dramatic improvement in the
kinetics of hydrogen desorption with about 10 wt % hydrogen
being absorbed and desorbed at 350 °C, a significant
improvement compared to bulk LiH (700 °C). Pang et al.
developed a mechanochemistry/PVD approach for the syn-
thesis of 20−40 nm Mg(AlH4)2 nanorods and 10−40 nm
LiBH4 nanobelts185 with improved kinetics of hydrogen
desorption; importantly, the morphology of the Mg(AlH4)2
nanorods persisted after hydriding/dehydriding cycles.
Li2NH hollow nanospheres prepared by plasma metal
reaction of lithium with ammonia show a surface area of 79
m2 g−1. The porosity coupled with particle morphology leads
to enhanced hydrogen storage kinetics. The Li2NH hollow
nanospheres absorb 6.0 wt % hydrogen in 1 min at 200 °C; in
addition, the desorption temperature is decreased by about 115
°C compared with the bulk sample (Figure 19).223 The same
group reported nanocubes of Mg3N2 which can be converted
to Mg(NH2)2 hollow nanospheres by reacting with ammonia
gas.224 The Mg(NH2)2 nanospheres milled with MgH2 release
about 6.5 wt % hydrogen be heating to 400 °C, with the initial
2.5 wt % hydrogen released between about 75 and 225 °C.
Table 3 summarizes the synthesis and hydrogen storage
properties of numerous freestanding metal hydride NPs.
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Figure 19. (a) Hydrogen sorption curves of Li2NH hollow nanospheres (marked by N) and micron-sized particles (marked by M). (b) TEM
image of the as-prepared hollow nanospheres. (Adapted from ref 223. Copyright 2008 American Chemical Society.)
5.2. Thin Films
Thin films differ from NPs in both the synthetic methods and
the resulting structure, necessitating unique analytical methods
for determining hydrogen sorption properties. Unlike free NPs,
though similar to confined or encapsulated particles, thin films
have a rigid substrate upon which they are deposited.
Additionally, films have two macroscopic dimensions, with
only the thickness being on the nanoscale. These materials,
therefore, are dominated by the surface facing away from the
substrate, leading to highly anisotropic communication with
the gas phase. However, thin films are rarely monocrystalline
but instead typically highly textured, with small crystallites,
numerous grain boundaries, and occasionally even some
porosity, depending on deposition conditions and method.
A wide variety of metals have been formed as thin films for
numerous different hydrogen-based applications, including
hydrogen-switchable windows and mirrors339,372−374 and
metal-hydride batteries.375 While these are intriguing fields,
these properties are not germane to this review, which instead
will focus on the changes in H2 sorption relevant to hydrogen
storage, particularly in lighter materials that are of potential
interest for on-board vehicular storage.
Palladium has often been studied due to its simplicity, fast
kinetics, and isostructural hydride. Di Vece et al. prepared
MBE and nanocluster Pd films on glass and investigated their
behavior with both extended X-ray absorption fine structure
(EXAFS) and optical transmission spectroscopy to determine
the effect of hydrogen cycling.226,227 The authors found that
hydrogenation led to Ostwald ripening, even at ambient
temperature, due to reduction of the binding energy in the
hydride compared to the metal. Additionally, the smaller
nanoclusters lacked the miscibility gap, evidenced by a plateau
in the pressure as H content changes, between the α and β
Pd−H phases that was evident for the MBE film and is more
typical of the bulk material. Similarly sized films electron-beam
deposited on quartz showed a narrowing of the plateau,
particularly for 10 nm thick films, due to the induced stress
from clamping of the film to the substrate.376 Khanuja et al.
compared both thin films and layers of discrete NPs, deposited
on Al on glass, to investigate differences in resistivity
changes.377 Hydrogenation was slowed in the films due to
in-plane strain and clamping effects that were absent in the NP
layers which had interparticle gaps. Using sub-10 nm Pd NPs
synthesized by reduction from PdCl42− with ethylene glycol
and dropcast onto glass, Gupta et al. found that the change in
resistivity was dominated by the geometric effect of the Pd
particles expanding to form the hydride, which has a larger
10797
Review
lattice parameter, and the electronic effect of making them less
metallic had a lesser absolute effect.234
Several other transition metals have been investigated in thin
film format. Palladium is often used as a capping layer in these
systems because it facilitates hydrogen activation from the gas
phase and protects the highly oxophilic metals against
oxidation from oxygen and moisture. Iron−titanium was
evaporated onto silicon and covered with 20 nm of Pd.228
The resulting material was partially amorphous and could be
charged to 0.35 H per metal atom, with a discharge down to
0.12 H/M, indicating deep trapping sites. In addition, it was
possible to charge the amorphous film with hydrogen at higher
temperatures and lower pressures than microcrystalline films
due to the high disorder. Zirconium was cosputtered with Ni,
Co, Fe, and Cu onto glass and cycled from vacuum to 1 bar.230
The change in electrical resistance upon hydrogenation was
most pronounced in the Ni-containing samples, and higher
desorption temperatures restored the low resistivity better due
to increased ripening and growth of the grain sizes. Hamm et
al. aimed to destabilize metal hydrides using the clamping
stress from the substrate (estimated to be −1.1 kJ mol−1 H
GPa−1) but needed the strong adhesion of niobium on
sapphire Al2O3 to prevent delamination and dislocation
formation.378 Only films thinner than 6 nm were able to
avoid plastic deformation and achieve the high stress desired
up to 1 H/M, though 10 nm films could deform elastically after
an initial plastic deformation cycle due to hardening from
interactions of dislocations.
Magnesium has received much attention in thin film
research because of its lightweight and high gravimetric
capacity (7.6 wt % H); it also absorbs hydrogen very poorly
in the bulk due in part to the slow H diffusivity in Mg, making
research into nanostructured magnesium especially rele-
vant.67,379−381 Dura et al. prepared 100 nm Mg thin films
with 50 nm of Pd as a cap on monocrystalline Al2O3 and
found, using both scanning electron microscopy (SEM) and
the scattering length from neutron reflectivity, that the porosity
increased from 4% to 25% upon cycling.382 Gautam et al.
sputtered rather thick films (500 and 1000 nm) of Mg capped
with Pd.231,232 They found that the γ-MgH2 phase forms as a
result of compressive stresses while annealing and that the
absorption amount, mean crystallite size, and number of
defects all increase with absorption temperature in the 150 to
250 °C range. A significant drawback to the capping of Mg
with palladium is the formation of a variety of intermetallic
species at the interface between the two.
Transition metals have been added into thin films of
magnesium to act as catalysts as well, either codeposited or in
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Chemical Reviews Review

Table 3. Hydrogen Storage Properties of Freestanding Metal Hydride NPs

Ea |ΔH| |ΔS|
material size (nm) shape synthesis method H2 wt % (kJ mol−1) (kJ mol−1)a (J mol−1 K−1)a ref
Pd 2.6 sphere solution-based chemistry/PVP ∼0.4 35b 83b 107
Pd 7.0 sphere solution-based chemistry/PVP ∼0.5 31b 67b 107
Pd 14 cube solution-based chemistry/CTAB 18.0b 27.4b 61.5b 109
47.1c 33.4c 75.8c
Pd 32 cube solution-based chemistry/CTAB 20.2b 28.5b 66.9b 109
50.6c 35.5c 82.3c
Pd 65 cube solution-based chemistry/CTAB 22.6b 29.9b 72.6b 109
54.4c 37.6c 88.2c
Pd 110 cube solution-based chemistry/CTAB 25.3b 35.4b 82.4b 109
60.5c 40.9c 94.4c
Pd 18 cube solution-based chemistry 28−36b 64−86b 418
Pd 24 cube solution-based chemistry 27−32b 61−78b 418
Pd 30 cube solution-based chemistry 32−36b 79−90b 418
Pd 32 cube solution-based chemistry 31−37b 74−94b 418
Pd 40 cube solution-based chemistry 30−35b 74−86b 418
Pd 42 cube solution-based chemistry 31−35b 75−87b 418
Pd 43 cube solution-based chemistry 29−32b 70−80b 418
Pd 45 cube Solution-based chemistry 28−34b 65−85b 418
Pd 54 cube solution-based chemistry 32−36b 79−92b 418
Pd 60 cube solution-based chemistry 35−41b 88−107b 418
Pd 63 cube solution-based chemistry 33−42b 83−108b 418
Pd 85 octahedron solution-based chemistry 27−31b 62−75b 418
Pd 85 octahedron solution-based chemistry 30−38b 71−96b 418
Pd 85 octahedron solution-based chemistry 29−32b 68−78b 418
Pd 38 × 137 nanorod solution-based chemistry 33−38b 81−96b 418
Pd 38 × 215 nanorod solution-based chemistry 34−38b 84−98b 418
Pd 47 × 185 nanorod solution-based chemistry 33−39b 78−97b 418
Rh 2.3 irregular solution-based chemistry ∼0.15 113
Rh 2.4−7.1 irregular ∼0.1 114
Rh 7.1−10.5 irregular ∼0.1 115
Ir 1.5 irregular solution-based chemistry, PVP ∼0.09 116
Ir 1.5 irregular solution-based chemistry ∼0.09 117
Li 4 spherical solution-based chemistry 2.0 419
Mg 2−7 sphere ball milling in LiCl 71.2b 129.6b 186
Mg 15 irregular electroless reduction 142.8c 63.5b 118.4b 273
Mg 30−50 nanowire gas phase condensation 33.5b 65.3c 23
38.8c
Mg 80−100 nanowire gas phase condensation 38.7b 65.9c 23
46.5c
Mg 150−170 nanowire gas phase condensation 70.3b 67.2c 23
81.1c
Mg 6.0 irregular Mg(n-Bu)2 hydrogenation 5.7 64.8c 420
Mg 40 hexagon acetylene plasma metal reaction 5.5 61.6b 65.5c 122.7 121
114.0c
Mg 5 sphere Cp2Mg reduction with Li-naphthalide in 5.97 25b 21
PPMA 79c
Mg 7−15 irregular spark discharge 4.2 60−120b 365
Mg 25 irregular Cp2Mg reduction with potassium 6.7 122b 241
126c
Mg 32 irregular Cp2Mg reduction with potassium 6.6 118b 241
131c
Mg 38 irregular Cp2Mg reduction with potassium 6.1 115b 241
160c
Mg 8−25 spherical electroless reduction ∼6.2 63.5 118.4 366
MgH2 11−20 fibers stabilization with azide-terminated poly ∼2.6 421
(styrene)
Ni-doped 5.4 irregular Mg(n-Bu)2 hydrogenation 5.4 22.7b 62.1b 420
MgH2 64.7c
Mg/Ti 10−20 irregular gas phase condensation 68.1 119 119
Mg/Ti 12 irregular spark discharge 4.0 45 84 422

10798 DOI: 10.1021/acs.chemrev.8b00313

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Chemical Reviews Review

Table 3. continued
Ea |ΔH| |ΔS|
material size (nm) shape synthesis method H2 wt % (kJ mol−1) (kJ mol−1)a (J mol−1 K−1)a ref
Mg/Ti 50 irregular spark discharge 4.0 170.9c 73.0b 130.9b 423
75.8c 134.8c
Mg/V 50−150 hexagons hydrogen plasma metal reaction 5.2 71.2b 74.3b 155.8b 424
119.4c 74.4c 152.9c
Mg/Co 50−150 hexagons hydrogen plasma metal reaction 4.9 82.3c 138.8c 425
Mg/Ti/Pd 60 nanodots molecular beam epitaxy 70 129 426
Mg/Ni 10−20 irregular chemical reduction 6.0 139.1c 70.0b 242
57.4b 70.7c
Mg@Ni hexagons arc plasma 5.1−6.1 88.9b 73.7b 105.5b 427
81.3c 104.5b
Mg/Ti,Fe,Ni irregular mechanical milling 4.2 45.7 428
MgH2/TiH2 5−10 irregular mechanical milling 4.6 16.4 429
MgH2/TiH2 5−10 irregular mechanical milling 6.1 68.2c 127c 430
MgH2/Nb2O5 irregular mechanical milling 6.3 431
Mg2FeH6 100 irregular reduction of precursor 4.95 89c 145c 432
Mg2FeH6 100 irregular sintering Mg/Fe NPs 5.0 165.7c 82.4c 140.2c 433
Li/Mg 8−40 irregular chemical reduction 159b 66.9 122.1 434
Na/Mg 7−52 irregular chemical reduction 148b 71.1 130.9 434
K/Mg 8−32 irregular chemical reduction 134b 63.2 117.8 434
LiAlH4 2−16 spherical stabilization with 1-dodecanethiol 5.7 417
Mg(AlH4)2 20−40 nanorods physical vapor deposition 9.0 97.3c 185
Mg(NH2)2/ 100 hollow plasma metal reaction 6.5 224
MgH2 nanospheres
Li2NH 100 hollow plasma metal reaction 6.0 223
nanospheres
MgB2 irregular milling under H2 4.0 435
LiBH4 10−40 nanobelts physical vapor deposition 185
LiBH4 30−50 spherical stabilization with PMMA 436
NaBH4 50−120 spherical stabilization with PMMA 436
Ca(BH4)2 100−300 hollow stabilization with PMMA 436
nanospheres
NaBH4/Ni 10−30 spherical solvent precipitation 5.0 371
a
The absolute magnitude of ΔH and ΔS. bValue obtained from absorption measurements. cValue obtained from desorption measurements.

discrete layers. Nickel forms Mg2Ni, which can be hydro-
genated to Mg2NiH4. Oguchi et al. synthesized 100 nm thick
combinatorial Mg1−xNix thin films capped with Pd.28 The
compositions with more Mg showed greater hydrogenation via
IR emission imaging, and using XRD, the authors found that a
nickel-stabilized fcc Mg phase enabled faster kinetics and a
lower temperature of reaction by transforming to a similarly
structured fluorite-type hydride. Fry et al. made a multibilayer
film, capped with Pd, with 150 pairs of 16.5 nm Mg and 2.5 nm
Ni−Fe−Cr (predominantly nickel).42 PCT measurements,
made possible by the large amount of material, showed faster
hydrogenation than ball-milled Mg and two different plateaus:
one for MgH2 and one for Mg2NiH4, indicating mixing
between the layers. After cycling, the delaminated films broke
down into powder containing Fe NPs as well as Mg−Ni and
Mg−Pd intermetallics. A 4% Fe-doped Mg thin film was
deposited on silicon in a wedge shape to study the effect of film
thickness on hydrogenation.229 The rate of hydrogenation, as
determined from IR emissivity, was limited by the diffusion of
hydrogen through MgH2; however, PCT and van’t Hoff studies
showed that the enthalpy and entropy for the reaction were
less than those for pure magnesium films.
A pair of multilayered Mg/FeTi thin films with different
layer thicknesses retained the intact FeTi layers upon cycling,
while the Mg layers formed NPs confined between the
sandwiching layers.383 The thinner layers had more stable
10799
kinetics and capacity under cycling because the Mg/MgH2
particles could not grow as large and limit the transport of
hydrogen. Ti, like Fe, is immiscible with Mg and, like Pd, has
been used to protect the Mg and dissociate H2, while forming
TiH2. Baldi et al. made films with layers of 10 nm Ti and 20
nm Mg, capped with Pd, on glass.343,384 Magnesium
sandwiched between two layers of titanium absorbed H2 at
lower pressures than Mg between Ti and Pd (Figure 20),
which they explained as due to clamping stress and alloying
with the palladium. Mooij and Dam conducted follow-up
experiments, again with Ti-sandwiched Mg, that showed that,
in a 10 nm Mg film, the hydride phase nucleates in the same
locations repeatedly, but upon dehydrogenation, the metallic
phase has no visibly obvious nucleation points but appears to
fade in because the barrier to Mg nucleation is small and thus
the number of nuclei is large.385,386 Bannenberg et al.
continued the study with neutron reflectivity and hydro-
genography measurements on deuterated Ti−Mg films,
showing that the nucleated β-MgH2 regions grow at a constant
radial rate, with plastic deformation of the encompassing Ti
and Pd layers to fit the larger phase.341 As in the study by Dura
et al., the Mg layer was thicker after dehydrogenation,
indicating increased porosity and enabling faster rehydrogena-
tion kinetics. An X-ray photoelectron and Auger spectroscopy
investigation on cosputtered Mg−Ti films was conducted by
Jensen et al. and found, in addition to some partially oxidized
DOI: 10.1021/acs.chemrev.8b00313
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Chemical Reviews
Figure 20. Mg sample deposited on a glass wafer and partially covered
with a 2 nm thin Ti layer. (a) Sketch of the sample architecture. (b)
Pressure−temperature isotherms (PTIs) measured during loading at
333 K. (Reprinted with permission from ref 384. Copyright 2009 AIP
Publishing.)
Mg, the presence of H atoms trapped in interstitial sites
between Ti atomic clusters and the Mg matrix.233
Multilayers of 18 nm magnesium with 1 nm chromium or
vanadium as catalysts showed different mechanisms from each
other, though the two activation energies were similar.29 Both
catalyzed systems were much faster than the Mg control, but
the thermodynamics were comparable. A set of Mg2Si−Mg
thin films, each capped with palladium, was prepared by
sputtering to determine the limitations on hydrogenation of
Mg2Si, especially compared to ball-milled particles.387
Adsorbed hydrogen diffused through Mg2Si and reacted with
metallic Mg without substantially hydrogenating the silicide;
only regions immediately proximal to either the Mg or Pd were
affected, so very small particles (<2 unit cells) would be
required for full conversion to MgH2 and Si.
While thin films are of interest in fundamental research on
nanostructuring in controlled and tunable ways, they have
some drawbacks as well. The total hydrogen capacity of a thin
film is minuscule due to the small area typically employed for
deposition; this limitation significantly curtails the use of thin
films in practical applications and restricts their utility to more
fundamental research into the effects of nanostructuring. In
addition, some films are prone to either Ostwald ripening or
pulverization upon cycling, breaking down the original
nanostructures and limiting the clamping effects from the
substrate, further diminishing the possibility of their long-term
deployment. Table 4 contains details about synthesis and
hydrogen storage properties of nanostructured thin films.
5.3. Nanoconfined Metal Hydrides
The limitation of metal hydride nanoparticle growth by a
physical barrier that controls the ultimate nanocrystal size is a
robust strategy that has been demonstrated in a number of
studies.45,46 A wide variety of metal hydride nanostructures
have been synthesized via these approaches. Porous matrixes
such as porous carbons, carbon fibers, aerogels, silicas, and
MOFs have been utilized as supporting materials because the
pore sizes are readily modulated, thus providing more
homogeneous size distributions and fewer aggregations of
metal hydride nanomaterials.
5.3.1. Confinement in Carbons. Activated nanoporous
carbons (ACs) and carbon nanofibers (CNFs) are two of the
most commonly used templates in the synthesis of metal
hydride nanomaterials due to their excellent accessibility and
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Review
ultrasmall pore size (from 2 to 0.5 nm) that can be achieved
via various synthetic methods.50,51,349,388−393 De Jongh et al.
have prepared high-purity and oxygen- or nitrogen-modified
ACs in order to synthesize Mg/C nanomaterials.51 The high-
purity carbon support has a nonpolar nature, which might
impede the infiltration of molten magnesium into the pores.
To improve the wetting on the surface of the porous carbon,
nitrogen, or oxygen was introduced. Mg nanomaterials were
prepared by melt infiltration, and the average size of Mg
decreased from a few nanometers for hierarchical micro and
mesoporous AC with ∼10 at. % O), to ∼2 nm for high surface
area graphite with mainly 2−3 nm pores to less than 1−2 nm
for microporous AC-based samples (Figure 21a). It is
demonstrated that AC is able to mechanically confine Mg
nanomaterials inside the pores and prevent oxidation of Mg
shortly after preparation (Figure 21b).
The use of AC as a confinement medium has been extended
to other materials, such as metal alanates and borohy-
drides.349,388−391,394 Nanosized NaAlH4 materials in high-
purity porous carbon HSAG-500 with relatively small pores
(mainly 2−3 nm) were prepared by the melt infiltration
method.388 After melt infiltration, the NaAlH4/C nano-
composites were examined by physisorption measurements
because the metal alanate and borohydride materials
decompose under the electron beam in TEM. The
Brunauer−Emmett−Teller (BET) surface area and the
Barrett−Joyner−Halenda (BJH) total pore volume decreased
from 500 to 156 m2/g and from 0.57 to 0.32 cm3/g,
respectively, after infiltration, indicating that the NaAlH4
efficiently filled (or blocked) most of the pores. In a follow-
up study by the group of de Jongh, the possibility of changing
the reaction pathway by nanosizing it in HSAG and AC was
presented.395 In addition, NaBH4 and LiBH4 nanostructures
were also confined in HSAG-500, which was confirmed by
broadening and reduction in the intensity of XRD peaks and
the decrease in the total pore volume of the carbon, which is in
good agreement with the materials completely filling in the
carbon pores.389,390 By modifying a conventional method
through changing the pH of the initial solution, Nielsen et al.
produced several distinct nanoscale pore dimensions in carbon
aerogels, which distinctly influenced hydrogen release and
uptake properties in the NaAlH4 system.257
Nielsen et al. explored the influence of the pore size of
resorcinol-formaldehyde carbon aerogels on the hydrogen
desorption kinetics of nanoconfined NaAlH4.16 With increas-
ing pore size of the NaAlH4-loaded scaffold, the onset
temperature increases, linking the desorption kinetics to the
particle size, which, in turn, is controlled by the pore size.
Stephens et al. were able to alter the hydrogen desorption
temperature of NaAlH4 by melt-infiltrating the hydride into an
aerogel with 13 nm pores.396 Dehydrogenation to NaH was
achieved at 150 °C with reasonable kinetics. Additionally, it
was possible to rehydrogenate the material fully at 160 °C
under 100 bar H2 pressure. Jensen et al. infiltrated a TiCl3-
doped resorcinol-formaldehyde aerogel with NaAlH4 via melt
infiltration.397 The resulting nanocomposite hosted NaAlH4
particles with a size of 37 nm.
Gross and co-workers described the synthesis of LiBH4
inside pyrolyzed resorcinol-formaldehyde aerogels with varying
pore size (13 and 25 nm) by melt intrusion.398 The activation
energy was lowered to 103 and 111 kJ mol−1 for the 13 and 25
nm LiBH4-loaded aerogels, respectively. In comparison, the
activation energy for bulk LiBH4 amounts to 146 kJ mol−1.
DOI: 10.1021/acs.chemrev.8b00313
Chem. Rev. 2018, 118, 10775−10839
 Table 4. Hydrogen Storage Properties of Metal Hydride Thin Films
H2 |ΔS|
metal(s)a thickness (nm)b substrate synthesis method wt % Ea (kJ mol−1) |ΔH| (kJ mol−1) (J mol−1 K−1) ref
Pd 10 glass vacuum evaporation 377
Pd 60 glass vacuum evaporation 377
Pd 16 Si/SiO2 laser vaporization 226
Chemical Reviews

Pd 50 Si/SiO2 MBE 226

Pd 2.5 15 nm Au, 2.5 nm Cr on laser vaporization 39c 227
glass
Pd 4 15 nm Au, 2.5 nm Cr on MBE 53.4c 227
glass
Pd 10 quartz e-beam evaporation 376
Pd 15 quartz e-beam evaporation 376
Pd 20 quartz e-beam evaporation 376
Pd 10 glass nanoparticle 234
deposition
Pd/C 300 Al2O3 PVD 437
Pd/C 300 SiO2 PVD 438
FeTi+Pd 100 + 20 Si e-beam evaporation 228
Zr+Co 100 + 50 glass ion-beam sputtering 230
Zr+Cu 100 + 50 glass ion-beam sputtering 230
Zr+Fe 100 + 50 glass ion-beam sputtering 230
Zr+Ni 100 + 50 glass ion-beam sputtering 230
Nb+Pd 5 + 20 Al2O3 (112̅0) cathode beam 378

10801
sputtering
Nb+Pd 10 + 20 Al2O3 (112̅0) cathode beam 378
sputtering
Nb+Pd 40 + 20 Al2O3 (112̅0) cathode beam 378
sputtering
Mg+Pd 400 + 25 Si magnetron sputtering 387
Mg+Pd 100 + 50 Al2O3 sputtering 382
Mg+Pd 500 + 80 glass magnetron sputtering 231
Mg+Pd 1020 + 10 glass magnetron sputtering 232
Mg+Pd 100 + 5 Si(100) magnetron sputtering 233
Mg+Pd 200 + 1.5 Si(100) magnetron sputtering 233
Mg+Pd 3000 + 14 glass PVD 5.4 141.6d 73.9d 134.8d 29
Pd+Mg+Pd 20 + 2000 + 20 Si PLD 68c 439
Mg+Pd NPs 25 + 2.5 Si magnetron sputtering 440
Mg+Pd NPs 25 + 5 Si magnetron sputtering 440
Mg+Pd 400 + 25 glass magnetron sputtering 441
Mg+Pd 400 + 25 Al2O3 magnetron sputtering 441
Mg+Pd 400 + 25 LiGaO2 magnetron sputtering 441
Cr+Mg+Pd 6 + 160 + 30 Si magnetron sputtering 61 (1st cycle),d 77 (2nd 442
cycle)d
Mg+Al 1500 + 100 quartz magnetron sputtering 340
Mg+Ti 1500 + 100 quartz magnetron sputtering 340
Review

Mg/NiFeCr+Pd 150×(16.5 + 2.5)+15 glass PVD 4.6 71.6d 80.5d, 66.6d 142d, 123d 42

Chem. Rev. 2018, 118, 10775−10839

DOI: 10.1021/acs.chemrev.8b00313
 Table 4. continued
H2 |ΔS|
metal(s)a thickness (nm)b substrate synthesis method wt % Ea (kJ mol−1) |ΔH| (kJ mol−1) (J mol−1 K−1) ref
Mg8.5Cu1.5+Ta+Pd 1500 + 7.5 + 7.5 Si magnetron sputtering 443
Mg8.5Ni1.5+Ta+Pd 1500 + 7.5 + 7.5 Si magnetron sputtering 3.5 79.6 (MgH2)d, 78.6 147.8 443
(Mg2NiH4)d (Mg2NiH4)
Chemical Reviews

Mg8.5Ni1Cu0.5+Ta+Pd 1500 + 7.5 + 7.5 Si magnetron sputtering 3.5 443

MgxNi+Al 1500 + 100 quartz magnetron sputtering 340
MgxNi+Ti 1500 + 100 quartz magnetron sputtering 340
MgxNi1‑x+Pd (0.4 < x < 0.9) 100 + 5 oxidized Si(100) e-beam evaporation 28
Mg2.9Ni 1160 Si(001) magnetron sputtering 4.45 59.5 (Mg2NiH4),c 444
69.5 (MgH2)c
Mg6Ni 30−40 Si magnetron sputtering 280
Mg9.6Fe0.4+Pd (0−500)+6 Al2O3 (0001), Si (001) e-beam evaporation 229
Mg9.6Fe0.4+Pd 600 + 6 Si(001) e-beam evaporation 42.7,c 66.9d 86,c 102d 229
Mg/FeTi+Ta+Pd 15×(85 + 15)+7.5 + 7.5 Si magnetron sputtering 4 383
Mg/FeTi+Ta+Pd 45×(28 + 5)+7.5 + 7.5 Si magnetron sputtering 4.5 79d 140d 383
Ti+Mg+Nb+Pd 10 + 20 + 10 + 10 glass, quartz magnetron sputtering 343
Ti+Mg+Ni+Pd 10 + 20 + 10 + 10 glass, quartz magnetron sputtering 343
Ti+Mg+Pd 10 + 20 + 20 glass, quartz magnetron sputtering 343
Ti+Mg+Pd 10 + 10 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Pd 10 + 20 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Pd 10 + 30 + 40 glass, quartz magnetron sputtering 384

10802
Ti+Mg+Pd 10 + 40 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Ti+Mg+Pd 10 + 20 + 10 + 20 + 10 glass, quartz magnetron sputtering 343
Ti+Mg+Ti+Pd 10 + 20 + 10 + 10 glass, quartz magnetron sputtering 343
Ti+Mg+Ti+Pd 10 + 10 + 10 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Ti+Pd 10 + 20 + 10 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Ti+Pd 10 + 30 + 10 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Ti+Pd 10 + 40 + 10 + 40 glass, quartz magnetron sputtering 384
Ti+Mg+Ti+Pd 10 + 10 + 10 + 10 quartz magnetron sputtering 386
Ti+Mg+Ti+Pd 10 + 10 + 10 + 10 quartz magnetron sputtering 341
Ti+Mg+V+Pd 10 + 20 + 10 + 10 glass, quartz magnetron sputtering 343
Mg+Ti+Pd 1500 + 7.5 + 7.5 Si(100) magnetron sputtering 445
Mg+Fe+Pd 1500 + 7.5 + 7.5 Si(100) magnetron sputtering 445
Mg+Nb+Pd 1500 + 7.5 + 7.5 Si(100) magnetron sputtering 445
Mg+Ta+Pd 1500 + 7.5 + 7.5 Si(100) magnetron sputtering 445
Mg80Ti20+Pd 100 + 5 Si(100) magnetron sputtering 233
Mg80Ti20+Pd 200 + 1.5 Si(100) magnetron sputtering 233
Mg/Cr+Pd 150×(18 + 0.8)+14 glass PVD 6.1 65.7d 73.6d 133.7d 29
Mg/V+Pd 150×(17 + 1.2)+14 glass PVD 5.4 67.6d 73.3d 133.4d 29
Mg+Mg2Si+Pd 200 + 100 + 25 Si magnetron sputtering 387
Mg2Si/Mg+Pd 50×(3 + 5)+25 Si magnetron sputtering 387
Mg2Si/Mg+Pd 25×(6 + 5)+25 Si magnetron sputtering 387
Mg2Si/Mg+Pd 16×(9 + 5)+25 Si magnetron sputtering 387
Review

Chem. Rev. 2018, 118, 10775−10839

DOI: 10.1021/acs.chemrev.8b00313
Mg2Si/Mg+Pd 12×(12 + 5)+25 Si magnetron sputtering 387
Chemical Reviews Review

Metals are listed in order of deposition, with those closest to the substrate first. Alternating layers in a multilayer are denoted with a slash (/), whereas a subsequent layer is denoted with a plus sign (+).
Thickness values correspond to the listed order of metals, separated with a plus sign. Multilayers with alternating compositions have the number of bilayers first, multiplied by the two component
387
387
387
446
ref
(J mol−1 K−1)
|ΔS|

117c

thicknesses in parentheses. A range of thicknesses is denoted with a dash (−). cValue obtained from absorption measurements. dValue obtained from desorption measurements.
|ΔH| (kJ mol−1)

Figure 21. (a) Dark-field mode transmission electron micrographs for

Mg/activated carbon nanocomposites. (b) Energy-dispersive X-ray
spectroscopy (EDX) results for and Mg/activated carbon samples.
(Reprinted from ref 51. Copyright 2007 American Chemical Society.)

Furthermore, the kinetics of the hydrogen release are strongly

influenced by the pore size and thus the final LiBH4 particle
53c

size. The H2 release rate at 300 °C was determined to be 12.5

wt % h−1 for the aerogel with smaller pores compared to 7.8 wt
% h−1 for the aerogel with 25 nm pores (Figure 22). Yan et al.
wt %Ea (kJ mol−1)
H2

4.5
sputtering
sputtering
sputtering
sputtering
synthesis method
magnetron
magnetron
magnetron
magnetron

Figure 22. TGA curves at 10 °C min−1 and dehydrogenation

temperatures for LiBH4 (a) with nonporous graphite (453 °C), (b) in
2 nm activated carbon (375 °C), (c) in 13 nm carbon aerogel (381
°C), and (d) in 25 nm carbon aerogel (390 °C). (Reproduced from
ref 398. Copyright 2008 American Chemical Society.)
substrate

were able to prepare a Mg(BH4)2@aerogel (resorcinol-

formaldehyde) nanocomposite by ball milling a nanocompo-
site of MgH2@aerogel in an B2H6/H2 atmosphere.275 It was
possible to lower the activation energy of the first dehydrogen-
Si
Si
Si
Si

ation step even further to 102 kJ mol−1. The hydrogen

7.5 + 7.5 + 1500 + 7.5 + 7.5

desorption peaked at 160 °C, which is also significantly lower

than that of the bulk material.
thickness (nm)b

Zhang et al. reported the synthesis of LiBH4 NPs deposited

15×(7.5 + 10)+25

in an amorphous mesoporous carbon.399 They achieved 5 nm

100 + 100 + 25

LiBH4 particles homogeneously distributed throughout the

carbon by ball milling of commercially available LiBH4 with
72 + 25

CMK-3. The ordered structure of CMK-3, originally formed by

templating with the SBA-15 silica, was destroyed by the ball
milling process. The final product showed a hydrogen uptake
Pd+Nb+Mg0.75Nb0.25+Nb+Pd

of 16 wt % (in relation to the metal hydride) and a

rehydrogenation capacity of 6 wt %. Furthermore, this
Table 4. continued

approach leads to a decrease in the enthalpy of hydrogen

metal(s)a

desorption by 27 kJ mol−1 H2. Using CMK-3 as a host, Cahen

Mg2Si+Mg+Pd

et al. were able to stabilize 5 nm LiBH4 particles by incipient

Mg2Si/Pd+Pd

solvent impregnation.400 The confinement had a striking effect

Mg2Si+Pd

on the dehydrogenation properties, lowering the desorption

enthalpy to 54.9 kJ mol−1. The combination of nanoconfine-
ment and a catalyst was studied by Shao et al.401 The porous
a
b

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Chemical Reviews
Figure 23. Temperature-programmed desorption of (a) bulk NaAlH4, LiAlH4, and LiBH4 and (b) their composites after wet impregnation.
(Reproduced with permission from ref 136. Copyright 2010 The Royal Society of Chemistry.)
carbon CMK-3 was first loaded with NbF5 and afterward melt
infiltrated by LiBH4. This combination reduced the onset
temperature of hydrogen desorption to 150 °C (compared to
375 °C for bulk LiBH4) and the activation energy is reduced to
97.8 kJ mol−1. Moreover, the material can be rehydrogenated
at 200 °C under 60 bar of H2 pressure. These findings were
ascribed to the particle size and to the presence of active Nb-
containing species.
Liu et al. showed the effect of nanoconfinement in porous
carbons (4.4 nm pores) on the hydrogen release of
Li4BN3H10.402 The bulk material has a hydrogen content of
approximately 11 wt %; however, it also possesses some
significant drawbacks, such as the irreversibility of the reaction
and the release of NH3 and B2H6 which accompanies
dehydrogenation. It was shown that confining this material
in a nanoporous carbon host drastically alters the decom-
position pathway from a three-step to a two-step mechanism.
The onset temperature of dehydrogenation was lowered by
more than 160 °C and furthermore, the NH3 and B2H6
emission was reduced immensely. Another rising star among
storage materials is Li3N, which hydrogenates by a two-step
reaction via Li2NH + LiH to LiNH2 + 2 LiH. The theoretical
hydrogen content amounts to 10.4 wt % and the initial
hydrogen release has its onset at 150 °C. However, the very
stable intermediates LiH and Li2NH do not proceed to release
hydrogen until a temperature of 430 °C is reached, rendering
this class of material unfeasible. Interestingly, Wood and co-
workers were able to prepare LiH/LiNH2 in situ in the pores
of an amorphous nanoporous carbon by infiltration with
metallic Li dissolved in liquid NH3.19 This confinement had a
profound impact on the hydrogen release properties, making
the whole reaction fully reversible at 250 °C. Furthermore,
DSC data of the nanohydride revealed a single-step reaction
pathway.
Another interesting strategy was shown by Majzoub’s group,
reversing the concept of lowering the dehydrogenation
temperature and presenting a system which actually increases
the stability of the hydride.403 In their study, nanoporous
carbons doped with pyridinic nitrogen were prepared and
infiltrated with LiBH4. The NPs formed a BH3 capping layer,
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mediated by the Lewis donor nitrogen in the porous host,
which increased the dehydrogenation temperature by 25 °C.
Metal borohydrides can also be incorporated into porous
carbons through solvent impregnation.267,349,394 For instance,
Fichtner et al. demonstrated the use of solvent impregnation to
synthesize unsolvated Mg(BH4)2 NPs inside the pores of AC.
The nanoscaling of the hydride by confinement led to a
decrease of the desorption onset temperature. Furthermore,
distinct changes of the activation energy of the two-step
desorption process were observed. The first step shows a
striking decrease of the activation energy from 310.7 kJ mol−1
H2 for bulk Mg(BH4)2, to 176.2 kJ mol−1 H2 for Mg(BH4)2
confined in the activated carbon. In contrast, an increase of the
activation energy was observed for the second dehydrogen-
ation step and a value of 189.5 kJ mol−1 H2 was determined for
the nanocomposite, while the bulk material had an activation
energy of 160.9 kJ mol−1 H2. Comănescu et al. used a similar
approach for creating Ca(BH4)2 nanostructures with the
surface area and pore size of the carbon supports further
optimized through a chemical activation and a heat treatment
step.391 A new activator, KOH, was used instead of the
traditional chemical activator, CO2, because physical activation
of CO2 was shown to randomly expand the pores resulting in a
heterogeneous structure with various pore sizes.404,405
Carbon nanotubes have also been the subject of some
nanoconfinement studies. Christian et al. were able to stabilize
LiAlH4 NPs of roughly 10−20 nm in size by encapsulating
them in carbon nanotubes via wet impregnation with a
precursor solution.136 The encapsulation had a marked effect
on the hydrogen release properties, lowering the release
temperature to 120 °C (Figure 23). Furthermore, the reaction
pathway was altered by this method to a single step of
hydrogen release, decreasing the activation energy to 64 kJ
mol−1 (instead of 82−115 kJ mol−1 H2 and 86−90 kJ mol−1 H2
for the first and second dehydrogenation steps, respectively).
In the same study, sodium alanate NPs and LiBH4 particles
were deposited on carbon nanotubes, resulting in a strong
decrease of the dehydrogenation activation energy to 88 kJ
mol−1 for LiBH4.136 The resulting NaAlH 4 NPs had
dimensions of 10 × 20 nm on average. The encapsulation
caused a marked decrease of the activation energies for the
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Chemical Reviews
two-step dehydrogenation from NaAlH4 via Na3AlH6 to NaH.
The resulting values for the first and second step were 45 and
122 kJ mol−1, respectively.
Tan et al. revealed the positive effect of Pd and Pt doped
multiwalled carbon nanotubes (MWCNTs) on the dehydro-
genation properties of LiAlH4.406 By adding 20 wt % of Pd- or
Pt-doped MWCNTs, the dehydrogenation temperature was
lowered by 28 and 15 °C, respectively, while the amount of
hydrogen released (per LiAlH4 unit) was not affected. At
temperatures above 300 °C, when the third dehydrogenation
step takes place, the formation of Li5PtH3 was observed via in
situ powder X-ray diffraction (PXRD), confirming an alteration
in the high temperature dehydrogenation pathway.
Activated carbon nanofibers are also versatile hosts
successfully used to confine metal hydrides. Using the melt
infiltration method, Lohstroh et al. successfully embedded
NaAlH4 NPs into the pores of CNFs (pore size ranging from
0.5 to 4 nm) under high hydrogen pressure.392 After the
insertion of NaAlH4, the surface area of CNFs was reduced
from 1815 to 242 m2/g and the pore volume decreased from
0.66 to 0.09 cm3/g. To produce different sizes of infiltrated
nanomaterials, Baldé et al. used different drying temperature
conditions and metal hydride loading.50 By decreasing the
drying temperature and initial loading of NaAlH4, the size of
NaAlH4 particles decreased from 1 to 10 μm to 19−30 and 2−
10 nm (Figure 24). The particle growth can be limited by
Figure 24. Kissinger plots for NaAlH4-impregnated CNFs with
particles of three different sizes. (Reprinted from ref 50. Copyright
2008 American Chemical Society.)
using a lower concentration, and the viscosity of the solvent
increases at lower temperatures, which yields a greater
dispersion. de Jongh and co-workers showed the possibility
of substantially lowering the desorption temperatures by
impregnation of CNFs with well dispersed, nanosized
NaAlH4 (9 wt % hydride on carbon).407 Remarkably, it was
possible to render the process reversible, something that was
not observed before for bulk alanates in the absence of
additives. The sample reabsorbed 26% of its initial hydrogen
content after treatment for 48 h under 90 bar H2.
A continuing effort in the development of new nanoparticle
systems has employed graphene and its derivatives as
encapsulating materials. The developments have in turn been
driven by the distinct advantages of graphene because it avoids
some of the inevitable disadvantages of other approaches for
hydrogen storage. Graphene, consisting of a single atomic layer
of carbon, has a large surface area and a lightweight and open
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structure, which provides the optimum environment for
hydride encapsulation, i.e., high potential loading of nanoma-
terials and small dead mass (i.e., inactive material mass).
Moreover, graphene-based nanomaterials have shown high
catalytic activity, stability, thermal and electrical conductivity.
Chong et al. successfully demonstrated NaBH4 encapsula-
tion inside graphene using a solution of NaBH4 in n-
propylamine sonicated with graphene.30 The system demon-
strates good reversibility and rapid uptake and release, albeit at
relatively high temperatures. Figure 25 shows TEM images of
Figure 25. TEM images of (a) as-synthesized and (b) dehydro-
genated NaBH4@GNs. Low (c) and high (d) magnification images of
rehydrogenated NaBH4@GNs. (Adapted from ref 30. Copyright 2015
John Wiley and Sons.)
NaBH4 NPs with diameters of 2 to 16 nm well-dispersed
throughout the entire graphene host, both before and after
dehydrogenation and rehydrogenation. Dehydrogenated mate-
rials show similar sizes as that of the as-synthesized one;
however, the average size of the rehydrogenated one was
increased to 45 nm. Even though the initial morphology of
NaBH4 nanomaterials is not well retained by graphene, this
approach shows that nanoconfinement with graphene is able to
realize improved hydrogen sorption performance. NaBH4
nanostructured with graphitic nanosheets (NaBH4@GNs)
has also been prepared from the mechanical milling method
by Li et al.408 The nanostructure exhibits exceptional stability,
in which the size and morphology are well sustained even after
5 cycles of uptake/release. However, residual contaminants
such as LiCl produced during the synthesis hamper the
hydrogen storage ability. Stable LiH was generated during the
dehydrogenation and consequently decreased the H2 capacity
and disrupted reversibility. In order to restrict the generation
of stable LiH, MgH2 was added to react with LiCl
subsequently produce Li3Mg12. Ultimately, a high cyclic
capacity is exhibited in the new NaBH4@GNs. Graphene is
a promising candidate for the wrapping matrix with reducing
the size of metal hydride materials in nanoscale as proven in
the experimental results.
Gasnier et al. used entangled graphenes, which are prepared
via pyrolysis of a graphene hydrogel.409 The porous graphene
aerogels was melt infiltrated with LiBH4 at 300 °C under 30
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Chemical Reviews
bar H2. The pore size, ranging from 6.1 to 26 nm, was
controlled by the precursor concentration, and the total pore
volume increased by incorporating graphene rather than
carbonizing precursors, which resulted in the higher loading
of LiBH4 nanomaterials in the pores. A similar wrapping
material for the nanoencapsulation of metal hydrides is the
functionalized graphene called graphene oxide (GO), which
contains oxygen moieties (carboxyl and hydroxyl groups) or
reduced graphene oxide (rGO). Cho et al. first reported the
facile solution-based coreduction method for Mg NPs
encapsulated by rGO nanosheets using Cp2Mg and GO
precursors in THF.34 The TEM analysis showed monodisperse
Mg NPs with diameters of 3.25 ± 0.87 nm. rGO-Mg
multilaminates exhibit high hydrogen storage capacity and
cyclability because Mg NPs were well-encapsulated by rGO
and consequently protected from oxidation. In addition, Pd/
rGO nanocomposites have also been prepared via a solution-
based method and electrochemical method from the reduction
of the GO and Pd precursors as well.410
Carbon-based porous matrices confining nanomaterials have
improved the performance of hydrogen sorption because they
are lightweight and act as catalysts. However, inhomogeneous
pore sizes with irregular morphologies in carbon-based porous
matrixes have inspired the creation of hosts with well-defined
pores with narrow size distributions.
5.3.2. Other Rigid Porous Hosts. In addition to pure
carbon materials, MOFs and silicas have seen increasing use in
the nanoconfinement of hydride materials. MOFs are attractive
porous supports for the synthesis of metal hydride nanoma-
terials because their well-ordered crystalline structure and
monodisperse pore dimensions provide a highly controlled
cavity size and chemical functionality. Fischer et al. were the
first to prepare transition-metal nanoclusters inside MOFs by
employing organometallic precursors.411 This approach was
extended to the preparation of metal hydrides with dimensions
of a few nanometers.18,412,413 Bhakta et al. were first to
infiltrate NaAlH4 inside the pores of the MOF HKUST-1
(Cu3BTC2 with BTC3− = benzenetricarboxylate).413 Remark-
ably, the dehydrogenation temperature was substantially
lowered, and hydrogen evolution from the sample was
observed starting at 70 °C. In a follow up study, the kinetics
and thermodynamics, as well as the pathway of the
dehydrogenation process for these nanoconfined hydrides
were unveiled.17 Notably, the two-step reaction from NaAlH4
to NaH showed enthalpies of 47.3 kJ mol−1 H2 and 45.6 kJ
mol−1 H2 for the nanoconfined hydride, compared to 40.9 and
15.6 kJ mol−1 H2 for the bulk material. The activation energy
for this process amounted to 53 kJ mol−1 (compared to 118
and 120 kJ mol−1 for the individual reaction steps of the bulk
material).
Stavila et al. investigated the infiltration into another
framework, namely CPO-27(Mg) (also known as MOF-
74(Mg), Mg2(dobdc) with dobdc4− = 2,5-dioxido-1,4-
benzenedicarboxylate) in the presence of catalytic amounts
of titanium chloride.18 The framework possesses 1D channels
lined with open metal sites that are capable of stabilizing the
titanium catalyst. After loading the pores with NaAlH4 by melt
infiltration, 1.2 nm metal hydride particles are obtained. The
activation energy of the dehydrogenation is lowered to 57.4 kJ
mol−1 and the desorption onset was already observed at 50 °C.
Remarkably, it is possible to rehydrogenate the material under
mild conditions (10.4 MPa H2 , 160 °C); after four
dehydrogenation/rehydrogenation cycles, a 15% loss in
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reversible capacity is observed. Nanoconfinement of NaAlH4
leads to an alteration of the reaction pathway, resulting in a
one-step dehydrogenation process, suppressing the formation
of the Na3AlH6 intermediate. More recently, other MOF
structures, including MIL-100(Al), have also been used in
confining a metal hydride for yielding well-defined NPs with
improved H2 sorption properties.412,413
Silica can also serve as a nanoscale template which allows
well-tailored size and shape of metal hydride nanomateri-
als.272,414,415 Metal hydrides, such as NaBH4, NaAlH4, and
LiBH4, infiltrated into the nanoscale channels of mesoporous
silica SBA-15 show improved desorption properties through
destabilization.414,415 However, the presence of silanol (Si−
OH) groups in the pore channels of SBA-15 caused the metal
hydride to be partially oxidized during the infiltration process.
To prevent oxidation, Zheng et al. utilized SBA-15 function-
alized with methyl groups, which shows the enhanced
hydrogen storage ability of NaAlH4 (Figure 26).272
Figure 26. (a) High resolution TEM micrograph of NaAlH4/OMS
(ordered mesoporous silica). (b) Dehydrogenation over time for
pristine NaAlH4 (black) and for the NaAlH4/OMS composite (blue)
at 150 and 180 °C. (Adapted with permission from ref 272. Copyright
2008 American Chemical Society.)
Core−shell architectures have also been used to encapsulate
complex metal hydrides. Preparation of these systems is more
complicated because of the extreme reactivity of metal
borohydrides, amides, and alanates. Christian et al. first used
the liquid-phase method for the synthesis of core−shell NaBH4
NPs, with the Ni shell acting as both a stabilizer and a
catalyst.371 In addition, the Ni shell prevents agglomeration of
NaBH4 NPs and evaporation of Na or NaH during the
desorption step. As a result, the core−shell system shows
reversibility under relatively mild conditions and a stable core−
shell structure up to 350 °C. However, at high desorption
temperatures (>350 °C), a distinct change in morphology was
observed due to sintering of the Ni shell. Various other metals
can be used as a shell (Co, Cu, Fe, Ni, and Sn) in order to
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Chemical Reviews
retain the shape of NaBH4 core during desorption.416 The Sn
shell (melting point = 232 °C) fell apart at 300 °C, the Ni shell
was unstable at 600 °C, and the remaining three metals
maintained their structures even at the higher temperature
(Figure 27). Wang et al. expanded this approach to LiAlH4@Ti
and showed significant improvements in hydrogen storage
properties of LiAlH4.417
Figure 27. TEM micrographs of the core−shell structures in the as-
synthesized (left), 300 °C annealed (center), and 600 °C annealed
(right) particles: (a) NaBH4@Co, (b) NaBH4@Cu, (c) NaBH4@Fe,
(d) NaBH4@Ni, and (e) NaBH4@Sn. (f) Temperature-programmed
desorption of the core−shell NPs at a rate of 10 °C min−1 monitored
by mass spectrometry. (Adapted with permission from ref 416.
Copyright 2013 Royal Society of Chemistry.)
These porous matrixes are able to decrease the particle size
of metal hydrides to less than 10 nm and prohibit the
aggregation into larger particles. However, there are a few
disadvantages, including the decrease in gravimetric and
volumetric hydrogen densities, because this approach has
thus far exhibited only limited loading of metal hydride into
the dead weight of inert supports. Thus, the development of
new synthetic methods diminishing the usage of supports for
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preparation of nanomaterials has been also studied. Table 5
contains details about synthesis and hydrogen storage
properties of nanoscaffolded and nanoencapsulated metal
hydride NPs.
6. MECHANISTIC EFFECTS OF NANOSIZING
Across a vast range of applications, nanomaterials exhibit their
own unique chemical and physical properties compared to
their bulk counterparts.469 It is well known that various kinds
of physicochemical properties can be tuned by manipulating
material dimensions. As to metal hydrides for hydrogen
storage, many studies have reported that their thermodynamics
and kinetics can be improved via nanostructuring. Nanoscale
metal hydrides possess high surface areas, leading to an
increased surface energy, which is expected to improve
hydrogen sorption thermodynamic and kinetic characteristics.
Also, nanostructuring plays a key role in generating and
enhancing the effects of controlled interfaces between different
material phases, which can induce certain forms of lattice
deformation or distortion that can be beneficial for cycling.
Furthermore, confinement effects can fundamentally alter
materials properties, either through chemical or electronic
interactions with the confining medium or else through
mechanical confinement stress.
Potential effects of nanostructuring or nanoconfinement on
the thermodynamics of metal hydrides are usually represented
in terms of the enthalpy change upon cycling. For most metal
hydrides, ΔH is negative (exothermic) upon hydrogenation,
indicating the relative stability of the hydrided form, with the
notable exception being AlH3. Furthermore, in complex metal
hydrides and most light metal hydrides, the magnitude of the
reaction enthalpy tends to be too large, which in turn signifies
impractically high operating temperatures. This fundamentally
originates from the high lattice enthalpy and strong ionic and
covalent bonding that characterizes these materials classes.14
Accordingly, one of the primary goals of nanosizing and
nanoconfinement is to destabilize the hydride, thereby
reducing the magnitude of the reaction enthalpy and
facilitating practical use within a reasonable range of operating
temperature. For complex metal hydrides, the reaction entropy
may be altered in addition to the reaction enthalpy, providing a
second avenue for thermodynamic tuning.
Likewise problematic are the often sluggish hydrogenation
and dehydrogenation kinetics of metal hydrides. Poor kinetics
may be associated with slow diffusion, chemical bond
activation, nucleation of reaction products, or formation of
stable intermediate phases in multistage reactions. As a result,
cycling of metal hydrides often requires hydrogen release
temperatures and uptake pressures far in excess of what is
predicted thermodynamically. Nanoscale and nanoconfined
metal hydrides can offer significant advantages in this regard by
reducing diffusion lengths, facilitating chemical kinetics and
nucleation or altering reaction pathways.
Review articles by Berube et al.,11 Pundt and Kirchheim,470
Pundt,471 de Jongh and Adelhelm,45 Vajo,47 and Wang472
systematically surveyed earlier efforts exploring the effects of
nanosizing, nanoconfinement, and microstructure on the
interactions between hydrogen and solid-state materials.
These articles comprehensively documented various effects of
surfaces, phase boundaries, grain boundaries, dislocations,
vacancies, and other structural defects at the nanoscale. In the
following sections, we review some of their conclusions, while
focusing heavily on more recently reported/proposed mech-
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 Table 5. Hydrogen Storage Properties of Nanoconfined Metal Hydrides
Vtot Ea |ΔH| |ΔS|
hydride porous host Davg (nm) (cm3 g−1) infiltration method solvent or atmosphere loading/wt % H2 wt % (kJ mol−1) (kJ mol−1) (J mol−1 K−1) ref
PdHx CMK-3-template 3.5 1.14 reduction of PdCl4 500 °C, Ar or 300 °C, H2/Ar 10 2.8−3 447
PdHx CMK-3-CVD 6 1.13 reduction of PdCl4 500 °C, Ar or 300 °C, H2/Ar 10 1.4−1.6 447
PdHx CMK-3 1.1 solvent impregnation 300 °C, H2, Ar 17.2 1.45 448
Chemical Reviews

PdHx MIL-100(Al) 0.87 0.65 solvent impregnation 280 °C, H2, Ar 10 3.1b 412
PdHx MIL-101(Cr) 1.2−1.6 1.64 solvent impregnation pentane/H2O 20 449
PdHx COF-102 1.2 1.35 chemical vapor infiltration Ar 9.5 0.4b 450
Mg6Pd HSAG 2−3 0.69 solvent impregnation/Melt 650 °C, Ar 18.5 1.7 451
infiltration
MgH2 Ni-CMK-3 2−3 0.66 MgBu2 infiltration 200 °C, 80 bar H2 37.5 107.6 274
MgH2 RF-aerogel 22 1.27 MgBu2 170−200 °C, 50−78 bar H2, 18.2 1.14 259
Ar, heptane
MgH2 RF-aerogel 7 0.65 MgBu2 170−200 °C, 50−78 bar H2, 10 0.62 259
Ar, heptane
MgH2 RF-aerogel 13 0.8 MgBu2 Ar 14.8 252
MgH2 activated carbon 0.5−3 0.79 MgBu2 Ar 22 142.8 63.8 117.2 273
fiber
MgH2 RF-aerogel(Ni) 13 0.8 melt infiltration Ar 9.6 452
MgH2 RF-aerogel(Cu) 13 0.8 melt infiltration Ar 12.7 452
MgH2 RF-aerogel 13 0.8 melt infiltration Ar 3.6 452
MgH2 HSAG 2−3 0.65 melt infiltration 625 °C, H2, Ar 10−15 51
MgH2 activated carbon <2 0.45 melt infiltration 625 °C, H2, Ar 15−20 51

10808
MgH2 SNU-90 1.3 1.64 chemical vapor infiltration 30 bar H2 200 °C 10.5 0.71b 453
MgH2 RF-Aerogel 16.6 1.32 MgBu2 150 °C, 150 bar H2 24.8 1.8 454
MgH2 RF-Aerogel 27.1 1.32 MgBu2 150 °C, 150 bar H2 24.3 1.3 454
MgH2 RF-Aerogel 14.7 1.85 MgBu2 150 °C, 150 bar H2 37.1 3.1 454
MgH2 RF-Aerogel 25 1.89 MgBu2 150 °C, 150 bar H2 40.2 2.2 454
MgH2 Ni nanobelt MgBu2 100 °C, 60 bar H2 32 34.4 76.9 69.2 455
MgH2 Ni-doped hollow 3.4 1.53 MgBu2 NH2NH2·H2O 60 6.63 46.9,c 264
carbon −49.1
AlH3 HSAG 2−3 0.66 solvent impregnation Et2O 14.4 0.25 61
LiBH4MgH2 0.13 TiCl/RF- 26 1.3 grinding/melt infiltration 310 °C, 60 bar H2 33.3 3.6 456
aerogel
LiBH4MgH2 RF-Aerogel 2.2 1.27 melt infiltration 50 bar H2,heptane, Ar 35 11.5a 397
LiBH4 CMK-3 4.5 1.3 ball milling 3 bar H2 “50” 14 40 399
LiBH4 pyrolyzed aerogel 13 0.8 melt infiltration 280−300 °C, Ar 25−30 12.5 103 398
LiBH4 pyrolyzed aerogel 25 1.38 melt infiltration 280−300 °C, Ar 45−50 7.8 111 398
LiBH4 CMK-3 4.5 1.3 solvent impregnation MTBE 33 3.4 400
LiBH4 HSAG 2−3 0.65 melt infiltration 295 °C, H2 150 bar 25 1.45 390
LiBH4−Ca(BH4)2 RF-aerogel 30 1.21 melt infiltration 210 °C, 110−130 bar H2 38.4 6.23 156 268
LiBH4−Ca(BH4)2 RF-aerogel 30 3.13 melt infiltration 210 °C, 110−130 bar H2 64.9 7.34 130 268
LiBH4 Activated carbon 1.75−3.2 0.87 solvent impregnation THF 28.4−30 9 457
LiBH4 NbOF5−CMK-3 3.8 1.25 melt infiltration 300 °C, 140 bar H2 6.52a 97.8 401
LiBH4 CNT solvent impregnation THF 1.5 0.27 88 136
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HSAG 2−3 0.66 melt infiltration 30 18.1a 458

Chem. Rev. 2018, 118, 10775−10839

DOI: 10.1021/acs.chemrev.8b00313
LiBH4 295 °C, 100 bar H2
 Table 5. continued
Vtot Ea |ΔH| |ΔS|
hydride porous host Davg (nm) (cm3 g−1) infiltration method solvent or atmosphere loading/wt % H2 wt % (kJ mol−1) (kJ mol−1) (J mol−1 K−1) ref
LiBH4 SBA-15 4.7−6.5 0.35−0.83 solvent impregnation MTBE 33−50 414
LiBH4Ca(BH4)2 CMK-3 3.5 1.63 ball milling + melt infiltration 200 °C, 3 bar H2 11a 265
2LiBH4−NaAlH4 RF-Aerogel 30 1.21 melt infiltration 310 °C, 110 bar H2 25.3 9.52a 459
Chemical Reviews

LiBH4−LiAlH4 carbon nanofiber 3 1.2 sequential solvent impregnation/ Et2O/310 °C, 110 bar H2 66 6.8a 117 266
melt infiltration
Li/LiH/LiBH4 HSAG 2−3 0.65 melt infiltration 200 °C, 100 bar H2 20 460
LiAlH4 CNT solvent impregnation THF 1.2 0.19 64 136
LiAlH4 HSAG 2−3 0.66 solvent impregnation THF 10a 458
LiAlH4 HSAG 2−3 0.66 solvent impregnation THF 18.9 0.6 461
LiAlH4 TiO2/Porous 4.55 0.28 solvent impregnation THF 37 6.2 47.1 462
carbon
NaH HSAG 2−3 0.66 physical mixing Ar 33 3.8−4.4a 463
NaBH4 graphite (300 ball milling LiBH4, NaCl 6.8 408
mesh)
NaBH4 HSAG 2−3 0.66 solvent impregnation H2O 25 6.7a 389
NaBH4 HSAG 2−3 0.66 melt infiltration 520 °C, 5 bar H2 25 7.9a 389
NaAlH4 RF-aerogel 13 0.8 melt infiltration 189 °C, 183 bar H2 48.6 5.5 396
NaAlH4 HSAG 2−3 0.65 melt infiltration H2 20 7.4a 388
NaAlH4 RF-aerogel 10 0.91 melt infiltration 189 °C, 210 bar H2 34.1 1.3 16
NaAlH4 RF-aerogel 11 1.3 melt infiltration 189 °C, 210 bar H2 41.5 1.9 16
NaAlH4 RF-aerogel 10 2.21 melt infiltration 189 °C, 210 bar H2 51.3 2.4 16

10809
NaAlH4 RF-aerogel 8 2.11 melt infiltration 189 °C, 210 bar H2 56.5 2.7 16
NaAlH4 TiCl3/RF-aerogel 8 1.93 melt infiltration 189 °C, 210 bar H2 48.6 2.1 16
NaAlH4 HSAG 2−3 0.65 melt infiltration H2, 180−190 bar, 180 °C 5−80 6.3 395
NaAlH4 carbon nanofiber 0.36 solvent impregnation THF 9 2.84 407
NaAlH4 carbon nanofiber 0.36 solvent impregnation THF 2 58 50
NaAlH4 RF-aerogel 4 0.36 melt infiltration 189 °C, 210 bar H2 12.8 257
NaAlH4 RF-aerogel 7 0.69 melt infiltration 189 °C, 210 bar H2 27.3 257
NaAlH4 RF-aerogel 10 0.91 melt infiltration 189 °C, 210 bar H2 34.1 257
NaAlH4 RF-aerogel 13 0.86 melt infiltration 189 °C, 210 bar H2 31.8 257
NaAlH4 RF-aerogel 19 1.33 melt infiltration 189 °C, 210 bar H2 41.9 257
NaAlH4 RF-aerogel 22 1.39 melt infiltration 189 °C, 210 bar H2 43 257
NaAlH4 RF-aerogel 26 1.3 melt infiltration 189 °C, 210 bar H2 41.4 257
NaAlH4 RF-aerogel 39 1.09 melt infiltration 189 °C, 210 bar H2 37.2 257
NaAlH4 RF-aerogel >100 0.26 melt infiltration 189 °C, 210 bar H2 32 257
NaAlH4 CNT solvent impregnation THF 5.68 0.45 45 136
NaAlH4 Ti/Carbon 0.36 solvent impregnation THF 8 145
nanofiber
NaAlH4 HKUST-1 1.07 0.41 solvent impregnation THF 4 413
NaAlH4 HKUST-1 1.07 0.41 solvent impregnation THF 4 53 47.3 17
NaAlH4 MOF-74(Mg) 1.2 0.593 melt infiltration 195 °C, 250 barH2 21 4.5a 57.4 18
NaAlH4 SBA-15 10 solvent impregnation THF 20 4.8 272
Review

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 Table 5. continued
Vtot Ea |ΔH| |ΔS|
hydride porous host Davg (nm) (cm3 g−1) infiltration method solvent or atmosphere loading/wt % H2 wt % (kJ mol−1) (kJ mol−1) (J mol−1 K−1) ref
Na/NaH/ HSAG 2−3 0.65 melt infiltration 180 °C, 120 bar H2 20 460
NaAlH4
Mg(BH4)2 activated carbon 0.61 solvent impregnation Et2O 44 176.2; 349
189.5c
Chemical Reviews

Mg(BH4)2 RF-aerogel 10 0.52 ball milling B2H6/H2 6 (27% 102 275

MgB12H12)
Mg(BH4)2 Ni-RF-Aerogel 9 0.5 melt infiltration (MgH2) 120 °C, B2H6/H2 10 464
Mg(BH4)2 Ni-CMK-1 4.80 0.86 solvent impregnation THF 7.21a 21.3 465
Mg(BH4)2 Cu2S hollow 20 0.128 solvent impregnation THF 289
spheres
Ca(BH4)2 Cu2S hollow 20 0.128 solvent impregnation THF 289
spheres
Mg(BH4)2 • 6 activated carbon 2 1.1 solvent impregnation NH3 50 9.3 466
NH3 (Mg(BH4)2·Et2O))
NH3BH3 CMK-3 4.5 1.29 solvent impregnation MeOH 50 2.1 467
NH3BH3 CMK-3-Li 4.5 1.29 solvent impregnation MeOH 50 3.5 98 467
NH3BH3 RF-carbon-cryogel 9 0.7 solvent impregnation THF 24 9a 120 468
NH3BH3 MCM-41 4 solvent impregnation THF 33−75 468
NH3BH3 SBA-15 7.5 1.2 solvent impregnation MeOH 50 67 271
a
Hydrogen desorption values are normalized as weight percent of the infiltrated hydride. bHydrogen content is determined by absorption measurements on the corresponding metal/host complex.
c
Enthalpies for two consecutive reaction steps occurring at different temperatures.

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Chemical Reviews
anisms by which thermodynamics and kinetics are altered
upon nanosizing or nanoconfinement of metal hydrides.
We begin by discussing the effects of surfaces, which play an
increasingly dominant role for nanoscale systems. Next, we
give an overview of effects associated with internal interfaces in
metal hydride NPs and nanostructures, including the roles of
grain boundaries and internal phase boundaries. Third, we
introduce some additional effects of nanosizing on kinetics,
including diffusion and plateau pressure behavior. Finally, we
discuss potential effects associated with the confining medium,
including hydride-host interactions. Particular emphasis is
given to experimental and theoretical studies designed to probe
specific mechanisms associated with nanosizing and nano-
confinement.
6.1. Effects of Surfaces
Among the most obvious thermodynamic implications of
particle size is the high surface energy introduced by
unsatisfied chemical bonds. At the nanoscale, the relative
contribution of surface energies to the reaction enthalpy
becomes increasingly large due to the high surface-to-volume
ratio.
6.1.1. Effects on Reaction Enthalpy. Certain simple
binary metal hydrides have higher surface energies than their
dehydrided phases, which allows some portion of the enthalpy
of formation to be stored as an excess surface energy and
contributes to decreasing the magnitude of ΔH. Kim et al. used
DFT to compute the reaction enthalpy for NPs of several
archetypical binary metal hydrides.301 The authors mixed bulk
enthalpy calculations with surface energies, invoking a Wulff
construction to generate realistic nanoparticle shapes and
properly weight energies of different surfaces. Among their
tested binary simple metal hydrides (VH2, LiH, ScH2, TiH2,
AlH3, MgH2, and NaH), only MgH2 and NaH exhibited a
reduction in the magnitude of the reaction enthalpy upon
nanosizing (Figure 28). In all other cases, the dehydrided
phases had higher surface energies and led to significant
increases in the magnitude of the reaction enthalpy.
Perhaps for this reason, much of the effort in surface-
induced hydride destabilization has focused on MgH2, which
has an average surface energy of 2.08 J m−2 compared with
Figure 28. Variation in the enthalpy of the metal/metal hydride
reaction as a function of metal particle size for seven different metal
hydrides. (Reproduced with permission from ref 301. Copyright 2009
IOP Publishing.)
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0.55 J m−2 for Mg.473 Wagemans et al. studied the surface-
induced destabilization effect in MgH2 using DFT calculations
on clusters, predicting a significant reduction of reaction
enthalpy (>10%) for clusters below 2 nm in size due to surface
effects alone.14 These results generally agreed with the later
DFT calculations of Kim et al.,301 as well as direct
hydrogenation simulations by Cheung et al. using the ReaxFF
method.15 Experimentally reported values for reaction enthalpy
reduction in MgH2 upon nanosizing show a somewhat greater
variation. Paskevicius et al. reported a reduction of <4% for
MgH2 particles of ∼7 nm, similar to the predicted value for
that size.186 However, experiments performed by Zhao-Karger
et al. on nanconfined MgH2 particles with <3 nm diameter
found much greater reductions, up to twice the predicted value
based on surface effects alone.273 A possible explanation for
this discrepancy may lie in additional enthalpic contributions
from internal interfaces or confinement stress, as discussed in
sections 6.2 and 6.4.
It is important to note that surface-induced thermodynamic
changes can be activated only if very small particles are
produced without agglomeration, which tends to reduce
surface area during synthesis and cycling. Even within a
confining medium, particles are likely to interact with one
another, particularly as they undergo dramatic changes in
volume and morphology during cycling. Likewise, catalyst
additives or synthesis byproducts (e.g., solvents) may also alter
effective surface energies via additive-particle interactions.
Berube et al.473 explored the reduction of effective surface
areas due to agglomeration by considering the van der Waals
interactions between MgH2 NPs. In noninteracting ideal MgH2
particles, the reaction enthalpy shift increases monotonically
with smaller particle size, exceeding 5 kJ mol−1 for particles
smaller than ∼15 nm radius (compared with the 75 kJ mol−1
reaction enthalpy of bulk MgH2). However, at the same time,
the authors suggested that the effective surface area
exponentially decreases with smaller particle sizes due to van
der Waals-induced particle clustering. Considering these two
competing factors, the enthalpy shift due to surface energies
has a maximum at ∼7 nm radius, and never exceeds 4 kJ mol−1.
It is worth noting that not only is there an optimum particle
size to achieve the maximal enthalpy shift, but the magnitude
of energy contribution by particle surface energies is also
constrained to <5−6% of the total reaction enthalpy. Such a
small contribution indicates that even for cases like MgH2 for
which the surface energy ordering favors hydride destabiliza-
tion at the nanoscale, this factor alone may not appreciably
manipulate the hydrogen storage thermodynamics. Never-
theless, it may be possible to mitigate particle clustering within
a properly structured confining medium.
In contrast to MgH2, most complex metal hydrides are
loosely packed molecular salts. These compounds typically
have rather low surface energies, often far below that of their
denser dehydrogenation products. For instance, the average
surface energy of NaAlH4 is only 0.06−0.15 J m−2, far lower
than those of the dehydrogenated products NaH and Al
(∼0.20 and 0.74 J m−2, respectively).359,474,475 This implies
that surface energy contributions within nanoscale NaAlH4
should increase the equilibrium desorption temperature for the
full reaction, contrary to the preferred outcome.
Such undesirable surface energy effects on enthalpy have
been generalized to other complex metal hydrides. Hazrati et
al.476 computed the energy of (LiBH4)n, (Li)n, (B)n, (LiB)n,
and (LiH)n (n = 2 to 12) nanoclusters using ab initio
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Chemical Reviews
calculations and found that the total energies of the fully
hydrided (LiBH4)n nanoclusters are less influenced by the
particle size n compared to the other phases. In fact, the
stability of (LiBH4)n nanoclusters was comparable to the bulk
material, inferring a relatively low cohesive energy and a
negligible surface energy penalty associated with cluster size.
The lower surface energies of complex metal hydrides relative
to their binary metal hydride counterparts likely complicates
strategies for nanoconfinement-induced destabilization of such
materials via surface energy effects alone.
Another factor that must be considered in determining the
impact of surface energy penalties on reaction enthalpy is
possible competition from other polymorphs of the hydrided
or dehydrided phase. An example of this phenomenon is the
stabilization of β-Li3N over the more common α-Li3N variant
at the nanoscale, which has been attributed to different surface
energy contributions for the two phases.19 Such competition
between polymorphs in complex metal hydrides will generally
tend to mitigate changes in reaction enthalpy.
6.1.2. Effects on Reaction Pathways. Surface energies
can also alter the relative stability of various intermediate
phases that appear during cycling of nanoscale particles. Such
intermediates play an especially critical role in the kinetics of
many complex metal hydrides, which often feature multistage
decomposition pathways. Stable intermediates can be
thermodynamic sinks, making further reaction difficult except
under the most extreme driving forces. Likewise, nucleation of
intermediates can incur unacceptable kinetic penalties.
Under the most favorable circumstances, surface effects can
destabilize otherwise stable intermediates to the point that they
will no longer form at all. In this event, the reaction pathway is
fundamentally altered, often with significant enhancements in
the overall reaction kinetics. Mueller and Ceder used DFT
calculations and a cluster expansion model to show that surface
effects in nanoscale NaAlH4 could alter the dehydrogenation
reaction pathway from two-stage decomposition to single-stage
decomposition, bypassing formation of the Na3AlH6 inter-
mediate phase altogether for particles <52 nm in diameter
(Figure 29).359 At the same time, they predicted that the
Figure 29. Phase diagram of the NaAlH4 (region A)-Na3AlH6+Al
(region B)-NaH+Al (region C) system as a function of NaAlH4
particle size and temperature, showing the possibility of direct
conversion from NaAlH4 to NaH+Al at sizes smaller than ∼50 nm.
(Reproduced from ref 359. Copyright 2010 American Chemical
Society.)
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equilibrium temperature required to achieve full dehydrogen-
ation could be reduced to as low as 65 °C for these particles by
eliminating Na3AlH6 as a thermodynamic sink. Their argument
was based upon comparing the enthalpy of NPs of each
isolated phase for different particle sizes and considering the
thermodynamically preferred products at different temper-
atures.
Experimentally, Gao et al. also concluded that nanoconfine-
ment induced apparent single-stage decomposition in
NaAlH4.395 Using thermogravimetric analysis (TGA), they
found only a single desorption feature in the uncatalyzed
material when confined within 2−3 nm pores. To confirm the
thermodynamic origin of the behavior, they further hydro-
genated the samples under conditions that were within the
expected stability range of the Na3AlH6 intermediate, based on
the thermodynamic equilibrium of the bulk material. The
nanoconfined samples were than analyzed with 27Al NMR,
which confirmed the lack of any Na3AlH6-like species. Work by
Lohstroh et al. likewise found possible evidence of nano-
confinement-induced single-stage decomposition from PCT
analysis of NaAlH4 decomposition in 4−5 nm pores.392 In
addition, several authors observed suppression of solid−solid
phase transitions and melting of LiBH4 when confined in
nanopores.136,477 These studies also found that the undesirable
evolution of B2H6 was curtailed. Similar transitions to single-
stage pathways upon nanoconfinement have been observed in
other metal hydride systems, including LiBH4/MgH2 mix-
tures.47
6.1.3. Surface Entropy and Disorder. Unlike their
influence on the enthalpy of nanoscale hydrides and
intermediates, the impact of surfaces on entropy has been far
less explored. Nevertheless, it is reasonable that the additional
disorder, dynamics, and free volume introduced within surface
regions may provide a significant entropic gain compared to
bulk regions. Indeed, there is some evidence to suggest that
nanosizing can alter the reaction entropy. Using van’t Hoff
analysis, Zhao-Karger et al. determined that the decomposition
of MgH2 in <3 nm pores exhibited a reduction in the reaction
entropy with respect to the bulk by 19 J mol−1 K−1.273 Another
study by Paskevicius et al. on ∼7 nm MgH2 nanocrystals
reported a similar effect, with a more modest entropic
reduction of around 4 J mol−1 K−1.186 Analysis by Cho et al.
showed a reduction of 4−13 J mol−1 K−1 for MgH2 in 3−4 nm
pores in reduced graphene oxide.35 In each of these instances,
size reduction also resulted in reaction entropy decrease, with
the largest reductions for the smallest particles. As a result,
these studies had the unintended effect of further stabilizing
rather than destabilizing the hydrided form. Although the
authors did not identify the origin of entropy changes, surface
dynamics and disorder are some of the likely causes. If
nanosizing is to be used as a practical avenue for reducing the
reaction enthalpy of metal hydrides, any accompanying
reduction in entropy should also be curtailed.
In complex metal hydrides, reorientation of molecular ions
can provide an additional potential entropic contribu-
tion.300,478,479 These reorientations are often quite hindered
in the bulk, but are likely to be much freer at surfaces. Beyond
the thermodynamic implications, the dynamical disorder may
aid kinetic processes, including mass transport, chemical bond-
breaking, and phase decomposition kinetics. Using ab initio
molecular dynamics simulations, Wood and Marzari reported a
phase transition in (001) surface slabs of NaAlH4 from the
conventional tetragonal phase to a new orthorhombic phase
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Chemical Reviews
above 320 K.143 The authors concluded that this new phase is
stabilized by entropic contributions from rotationally disor-
dered AlH4− polyhedra. They further suggested that, because
the transition is accompanied by a significant volume
expansion to facilitate AlH4− rotation, it may be difficult to
nucleate in the bulk but should be more easily accommodated
at surfaces. The new orthorhombic phase was also determined
to have a lower surface energy than the conventional tetragonal
phase, suggesting preferential formation in nanoscale systems.
It was subsequently determined that the larger volume also
significantly lowers the barrier for defect mobility, implying it
may be relevant for facilitating hydrogen diffusion kinetics
during dehydrogenation.480
Additional work by Majzoub et al.304 based on the prototype
electrostatic ground state method303 demonstrated that the
orthorhombic phase found by Wood and Marzari is only one
example of several competing NaAlH4 polymorphs with very
similar free energies of formation. The authors concluded that
many of these phases are likewise stabilized by entropic factors
associated with rotation of AlH4− polyhedra.
Another example of the possible role of surfaces in
enhancing the rotational mobility of nanoscale complex
hydrides is found in the work of Shane et al., who studied
LiBH4 confined in carbon aerogels using hydrogen NMR.481
Based on an analysis of NMR line widths, they concluded that
dynamical motion of hydrogen persisted across a wide
temperature range. The intensity of this feature was larger
for smaller particles, leading the authors to conclude that its
contribution was associated with surface regions and grain
boundaries rather than bulk-like regions (additional kinetic
aspects of grain boundaries in metal hydride NPs are covered
in Section 6.2.1).
6.1.4. Chemical Kinetics at Defective Surfaces. In
surface regions, additional disorder and looser packing, as well
as undercoordination, may alter the kinetics of other chemical
processes, including hydrogen dissociation/recombination and
chemical bond activation. In this regard, it can be expected that
the higher concentration of surface atoms in nanoscale metal
hydrides should be advantageous for enhancing the overall
rates of all surface-active chemical processes. Likewise, NPs
express proportionately higher concentrations of corners and
edges, where atoms are typically even further undercoordi-
nated and therefore likely exhibit additional reactivity.
The relevance of undercoordinated surface atoms for H2
dissociation is suggested in DFT calculations by Vegge, who
showed that the NaAlH4 (110) surface, which is more open
and has lower coordination than the more common (001)
surface, exhibits a 0.9 eV lower H2 dissociation barrier.475
Based on these calculations, Baldé et al. reasoned that higher
dissociation activity at open surfaces, corners, and edges could
partially explain the dramatic reduction in decomposition
temperature they observed for 2−10 nm NaAlH4 particles
supported by carbon nanofibers.50 Similar undercoordination
arguments have been invoked to explain predictions of
improved desorption thermodynamics in MgH2 nano-
wires.482,483
The additional concentration of surface atoms in nanoscale
particles may also alter the nucleation kinetics of the hydrided
or dehydrided phases. Bardhan et al. explored this effect
systematically for Pd NPs.109 They employed a novel optical
technique based on probing luminescence during hydriding
and dehydriding of an ensemble of Pd nanocubes with exposed
(100) facets. By controlling the size distribution, they were
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able to investigate phase transformations in individual cubes of
particular sizes. In conjunction with statistical mechanical
simulations based on an Ising model, the authors claimed to
isolate the intrinsic size scaling laws on the thermodynamics
and kinetics of hydriding and dehydriding phase trans-
formations in NPs. This size scaling behavior was suggested
to arise from the thermal fluctuation-driven hydride nucleation
that preferentially occurs at the particle surfaces. As a result,
decreasing nanocrystal size and increasing temperature would
diminish the nucleation barrier, leading to the reduction of
hysteresis of plateau pressures and enhanced phase trans-
formation kinetics.
Beyond atomic rearrangement, surfaces can also facilitate the
creation of vacancies, which act as another source of
undercoordination that can facilitate chemical bond breaking.
Theoretical work by Du et al. showed that the B−H bonds
within the BH4− unit next to a Li monovacancy or divacancy
on the LiBH4 (010) surface become elongated due to charge
renormalization.484 Based on a nudged elastic band calculation,
they found that the energy barrier for H2 release is reduced
from 3.64 eV for the pristine LiBH4 (010) surface to 1.53 and
0.23 eV when the surface is defected by a Li monovacancy and
divacancy, respectively. The same group also studied hydrogen
desorption from the NaAlH4 (001) surface and claimed that
the process is “vacancy-mediated”.485 The authors performed
static and dynamic ab initio calculations to examine the
hydrogen recombination process on the NaAlH4 (001) surface
in the presence of a neutral Na vacancy. Their ab initio
molecular dynamics simulation showed spontaneous release of
hydrogen molecular on the picosecond time scale at 300 K.
Although the formation energy to create such a metal vacancy
is relatively high, it was suggested that dopants and impurities
such as TiCl3 might stabilize vacancy formation.
Possible surface defect-mediated kinetic improvements in
the decomposition of LiNH2 and LiNH2+LiH mixtures with
decreasing particle size were discussed by Hoang et al.486,487
They proposed two distinct mechanisms based on systematic
DFT calculations of formation energies and migration barriers
for native defects and defect complexes. For both mechanisms,
highly mobile interstitial and vacancy defects (Lii+,VLi−) on the
Li sublattice create vacancy (VH−) or interstitial (Hi+) defects
in the hydrogen sublattice. In the first mechanism, the
formation of Frenkel pairs (Hi+,VH−), the separation of the
defect species in the pairs, and the migration of Hi+ occur in
the bulk interior of LiNH2. In the second mechanism, the
formation of VH− occurs predominantly at the surface, where
activation energy barriers are lowered with respect to the bulk.
The authors claimed that the relative contributions of these
bulk and surface mechanisms may vary with the particle size,
which successfully explains the reduction of experimental
activation energies for the kinetic processes with increasing ball
milling time.
6.1.5. Chemical Impurities and Oxidation. When
additional chemical impurities are present in the metal hydride,
they are often more easily accommodated by surfaces than by
the bulk material. This is because surfaces already contain a
degree of structural and/or chemical inhomogeneity. The
relative prevalence of surfaces in nanoscale metal hydrides may
therefore lead to complete segregation of impurity atoms to
the surface regions, which can carry additional consequences
for hydrogenation and dehydrogenation kinetics. One example
can be found in the work of Cho et al., who reported the
kinetic enhancement of reduced graphene oxide-encapsulated
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Mg NPs by Ni doping.36 They observed the formation of Mg−
Ni nanoalloy clusters populated preferentially in the surface
regions. The authors proposed that these clusters create
stresses and local disorder that eliminate or reduce surface
reaction and hydrogen diffusion barriers, thereby aiding
hydrogenation.
The high concentration of undercoordinated atoms at the
surfaces of nanoscale metal hydrides also makes them more
susceptible to side reactions, such as oxidation. In the past, the
presence of a surface oxide has been considered as one of the
main factors that contribute to slow hydrogenation/dehydro-
genation kinetics, since it acts as a diffusion barrier between the
metal hydride and its environment. Multiple strategies have
been applied toward the mitigation of oxidation. In Mg metal,
annealing and high-temperature cycling have been used to
crack or destroy these surface oxides.488 For nanoscale
hydrides, embedding the metal or metal hydride into a
carbon-based host material can, to some extent, prevent the
formation of unwanted oxides and therefore improve the
overall kinetics.489 In this regard, a solution-based synthetic
approach may show an advantage over the ball-milling
technique because it can limit the access of active material to
air and moisture.
A few recent studies have indicated that the presence of a
properly controlled surface oxide need not necessarily inhibit
reaction kinetics and may even lead to select enhancements.
For example, Zhang et al. demonstrated that deliberate
formation of an MgO layer atop Mg2NiH4 NPs dispersed on
graphene was successful in keeping the particles from
agglomerating.33 They further showed that the oxide layer
exhibited selective gas permeability to H2, leading to enhanced
kinetics and stability. Nielsen and Jensen showed that the
Nb2O5 additive, which improves the completeness of H2
release and absorption in MgH2, forms the ternary oxide
MgxNb1−xO (0.2 ≤ x ≤ 0.6).462 This oxide, which has a larger
structure than either of the two binary oxides MgO and NbO,
serves to break up thick MgO and permit H2 diffusion out of
the hydride.
Wan et al. showed that when Mg is wrapped in a reduced
graphene oxide encapsulant the nanocomposite prevents the
formation of bulk-like MgO but allows for the presence of a
thin surface oxide layer.36 Surface-sensitive X-ray photo-
electron spectroscopy (XPS) and X-ray absorption spectros-
copy (XAS) techniques were combined with first-principles
simulations to prove the existence of a thin suboxide on the
metal surface and show that it does not necessarily hinder the
hydrogen dissociation kinetics. In addition, the authors showed
that formation of this thin interfacial suboxide can be beneficial
toward enhancing the mechanical stability and cyclability of
the nanocomposite due to stronger charge transfer observed
between the reduced graphene oxide and the slightly oxidized
Mg. The unique properties of the suboxide were attributed to
its lattice structure, which results from controlled or limited
oxidation of Mg. We emphasize here the distinction between
extensive oxidation and controlled or limited oxidation, which
can lead to very different surface structures and local oxygen
coordination environments. Thus, it may be difficult to ascribe
a single functionality to a surface oxide without knowledge of
composition or morphology.
Apart from simple metals, positive effects of surface
oxidation have also been proposed in the context of the
complex metal hydrides NaAlH4 and LiBH4. Using in situ XPS,
Delmelle et al. examined the formation and evolution of
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surface oxides on NaAlH4 during dehydrogenation.148 They
identified the formation of Al 2 O 3 and Ti 2 O 3 during
decomposition of TiCl3-doped NaAlH4 and attributed the
enhanced dehydrogenation kinetics to the high hydrogen
mobility within these oxides species near the surface. Kato et
al. and Carrillo-Bucio et al. both found that partial oxidation of
milled LiBH4, either with oxygen or oxide additives and limited
to the surface, reduced the activation barrier for dehydrogen-
ation, lowering the observed Tdec.490,491 The oxidized samples
exhibited additional Li2O by XPS following segregation of
lithium to the surface, which helped to destabilize LiBH4 for
hydrogen desorption and not release of diborane. These
studies suggest that the role of surface oxidation on metal
hydride hydrogenation and dehydrogenation kinetics may be
far more subtle and complex than has generally been supposed.
A better understanding of these effects may illuminate
additional avenues for improved kinetics of nanoscale hydrides
via control of surface chemistry.
6.2. Effects of Internal Interfaces and Microstructure
In metal hydrides, hydrogen uptake and release kinetics are
typically determined by a collective combination of solid-state
mass transport, structural modifications, and chemical
reactivity. These processes are in turn often associated with
complicated interactions at internal interfaces. For instance,
the presence of grain boundaries or internal phase boundaries
can affect hydrogen diffusion, which must take place through
or across such boundaries. Likewise, the relevant chemical
reactions tend to take place at interphase regions between
hydrided and dehydrided domains created by a structural
transformation. The presence of these interphase regions can
also alter the mechanical properties of the material, impacting
cycling behavior.
At the nanoscale, the energetic contributions of these
internal interfaces become increasingly important, maximizing
their impact on the overall reaction thermodynamics. Similarly,
many kinetic processes associated with these interfaces
increase in prominence as competing bulk processes, such as
diffusion, become less accessible. Beyond their effect on the
energy landscape, interfaces may themselves provide additional
storage sites for hydrogen atoms. Accordingly, understanding
the nature of these interfaces and their potential impacts on the
phase evolution pathway in nanoscale metal hydrides could
facilitate new strategies for enhancing hydrogen storage
performance.
In metal hydride systems, two major classes of internal
interfaces exist: grain boundaries and phase boundaries. The
former class refers to interfaces between two otherwise
identical crystal domains with different orientations. Indeed,
it can be assumed that under operating conditions, most metal
hydrides form polycrystals consisting of multiple grains
separated by grain boundaries. Examples include twin
boundaries and generic high-angle grain boundaries in
Pd.492,493 The latter class refers to interfaces between different
phases or crystal compositions. Such interfaces necessarily
form as intermediates and products coevolve during the course
of the hydriding/dehydriding reaction. Examples include the
well-defined α/β phase boundary in PdHx, as well as more
disordered interfaces such as those between reactants,
intermediates, and products in many complex hydrides.5,46
We begin by outlining different classes of internal interfaces
present in nanoscale metal hydrides. Next, we explore the
effects of grain boundaries on the thermodynamics and kinetics
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of hydrogenation and dehydrogenation, followed by a similar
discussion of the effects of interphase boundaries.
6.2.1. Effects of Grain Boundaries. Metal hydrides are
generally polycrystalline, particularly upon cycling as multiple
product-phase nuclei form. Moreover, these materials are often
treated via high-energy mechanical milling processes, which
disturb crystalline regions. This prompts a discussion of
possible impacts that grain boundaries and polycrystallinity
could have on thermodynamics or kinetics. Indeed, for
nanoscale metal hydrides with sufficiently small grains, atoms
in boundary regions can comprise a nonnegligible fraction of
the overall atoms.
A theoretical investigation into the possible role of grain
boundaries on the thermodynamics of nanoscale metal
hydrides was performed by Berube et al.10,473,494 Using a
simple model approximating a grain boundary as two surfaces
of spherical particles, the authors found that the presence of
7−9 nm grains in nanoscale MgH2 could reduce the reaction
enthalpy by up to 9−10 kJ mol−1.473 However, they concluded
that the real value is likely smaller, since the two-surface model
places an upper limit on the real grain boundary energy. The
same authors also explored the effects of excess volume, which
is relevant for high-angle grain boundaries or for similarly
structured interparticle regions in agglomerated particles. Such
regions may be introduced during high-energy mechanical
milling processes. Their model used a general equation of state
to consider the effects of excess volume and tensile stress on
both the enthalpy and entropy. In MgH2 NPs, this enthalpy
was found to be similar in magnitude to the grain boundary
energy computed from the two-surface approximation (Figure
30).473 More generally, the authors further postulated that
entropy of disordered excess volume regions could be a
significant factor in stabilizing many metal hydrides.10
Figure 30. Comparison of the reduction of the enthalpy of formation
of MgH2 predicted by the four different mechanisms described in the
legend. (Reproduced with permission from ref 473. Copyright 2008
Elsevier.)
Additional efforts to elucidate the roles of grain boundaries
have focused on their contribution to hydrogen solubility in
nanosized simple hydrides.470 For example, Mutschele and
Kirchheim experimentally investigated the hydrogen sorption
and solubility in nanocrystalline Pd.493 They observed the
increased and reduced solubility limits of the hydrogen-poor α
and hydrogen-rich β phases, respectively, resulting in a
narrowed miscibility gap. They explained this behavior based
on a theoretical model incorporating the difference in local
solubility between grain interiors and boundaries, as well as the
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assumption of solid-solution characteristics of grain bounda-
ries. Weissmuller and Lemier also reported solubility variations
in nanograin interiors in Pd, which they attributed to the
mechanical stress generated by grain boundary segregation of
hydrogen.495
Compared with simple hydrides, the effects of grain
boundaries in complex hydrides have received considerably
less attention. This may be because the structure and
composition of grain boundaries in these materials are
particularly difficult to ascertain. However, the far lower
surface energy of most complex hydrides with respect to simple
hydrides (section 6.1.1) suggests that the thermodynamic
implications of grain boundaries may be comparatively minor.
Instead, the most significant effects may be on kinetics. One
example can be found in the recent work by Ray et al., which
focused on the chemical impact of grain boundaries on the
initial hydrogenation reaction pathways of MgB2 by combining
spectroscopic characterization with multiscale modeling.292 By
comparing reference calculations against spectroscopic meas-
urements, they identified that high-energy edge B−B bonds at
grain boundaries provide reaction sites for hydrogenation
according to a two-step mechanism (H2 dissociation and
“diffusive adsorption”), leading to the direct production of
Mg(BH4)2-like units without other persistent intermediate
chemical species. They suggested that a high density of
chemically reactive grain boundaries for nanoscale particles
may alter the hydrogenation reaction pathways and enhance
kinetics. Similarly, an NMR study by Shane et al. hinted at the
possible role of grain boundaries for enhancing hydrogen
dynamics in LiBH4.481
6.2.2. Types of Interphase Boundaries. In addition to
grain boundaries, metal hydrides at intermediate stages of
hydrogenation and dehydrogenation necessarily include
boundaries between different phases. A broad classification of
these interphase boundaries is shown in Table 6. The type of
boundary differs according to whether (de)hydriding is
predominantly a diffusive process or whether it involves
breaking and forming of chemical (i.e., ionic or covalent)
bonds.
The phase evolution of most complex hydrides (e.g., Mg−
B−H, Li−N−H, and Na−Al−H) involves reactive phase
boundaries, in which the formation of chemically and
structurally distinct phases occurs via interfacial cleavage and
formation of bonds with hydrogen. On the other hand, the
phase evolution of simple hydrides, which encompass metallic
(interstitial) hydrides such as PdHx as well as ionic hydrides
such as MgH2, involves nonreactive phase boundaries. In these
systems, hydrogen is incorporated into interstitial sites of the
host lattice through an intercalation-type process. The
resulting hydrided phase may or may not inherit the structural
characteristics of its dehydrided parent.
Broadly speaking, the interfacial energies associated with
reactive and nonreactive phase boundaries arise from different
dominant factors. Reactive phase boundaries usually feature
adjoining phases with little or no commonality in structural
and chemical features. In this case, the lattice continuity is not
likely to be maintained, and the phase boundaries become
incoherent. In this case, the coherency strain energy associated
with lattice commensurability can safely be neglected, and the
phase boundary propagation and corresponding phase
evolution instead become governed by interfacial rearrange-
ments of chemical bonding and mixing of molecular species. It
is worth emphasizing that not all complex hydride phase
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Table 6. Categorization of Internal Phase Boundaries in Metal Hydrides

Figure 31. (a) Free energy difference between α- and β-Li3N as a function of particle size. (b) Predicted Li2NH mole fraction after hydrogenation
at 100 bar H2 (red) and dehydrogenation at 1 bar (blue) as a function of particle size, with dashed lines representing the results when interfacial
free energy contributions are neglected. (c) Mole fractions of phases in the Li−N−H system as functions of pressure for bulk (left), 10 nm
(center), and 3.2 nm diameter particles (right). (Reproduced with permission from ref 19. Copyright John Wiley and Sons.)

boundaries fall within this category; for example, David et al.
suggested that the lattice similarity between LiNH2 and Li2NH
may preserve coherency at the interface between these two
materials.496 Nevertheless, as a general rule, it can be assumed
that most complex metal hydrides will tend to form incoherent
interfaces.
For nonreactive phase boundaries, the intercalation-type
hydriding process usually implies similarity in lattice features.
In this case, some degree of coherency of the lattice planes at
the interface can be assumed. The lattice mismatch between
the constituent phases, which arises from expansion upon
incorporation of hydrogen, then becomes the most significant
contributor to the interfacial energy. The resulting long-range
elastic field can extend well into the bulk interior, influencing
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the overall thermodynamics and kinetics. The exact degree of
coherency is usually determined by the volumetric and
structural disparity between the transforming phases. For
example, the hydrogen-poor and hydrogen-rich phases in the
Pd−H system (a nonreactive metallic hydride) share the same
fcc-based crystal structure, so the corresponding interfaces may
maintain interfacial coherency to a large degree at the
nanoscale.110 On the other hand, the hydrogen-poor and
hydrogen-rich phases in the Mg−H system (a nonreactive
ionic hydride) have different crystal structures (hcp Mg versus
body-centered tetragonal (bct) MgH2) and different volumes
(∼30% difference). Accordingly, it is highly likely that
interfacial dislocations or defects are introduced in such
systems in order to reduce the coherency strain energy
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resulting from the extreme lattice mismatch, forming a
semicoherent interface.497 Some of the key differences between
the subcategories of the interphase boundaries are also
summarized in Table 6.
6.2.3. Effects of Reactive Phase Boundaries. As particle
size decreases, it is natural to assume that the increase in the
ratio of interface-to-bulk atoms enhances the energetic
contribution of internal interphase boundaries to the overall
enthalpy. However, because reactive interfaces within complex
metal hydrides are exceedingly difficult to observe or to model
explicitly, there is very little information about the specific
impact of these interfaces on reaction thermodynamics or
pathways.
One such study recently performed by Wood et al. used a
combined experiment-theory approach to examine the possible
effect of internal interphase boundaries (“nanointerfaces”) and
microstructure on the reaction pathways of the Li3N/
[LiNH2+2LiH] hydrogen storage system upon nanoconfine-
ment.19 Their experiments determined that the Li2NH phase,
which exists as an intermediate in the decomposition pathway
of the bulk material, is suppressed upon cycling of ∼3 nm NPs.
The elimination of this intermediate enabled a single-step
decomposition pathway, leading to enhanced overall kinetics
and better reversibility. Their computational investigation
found that surface energy effects could not account for the
destabilization of Li2NH. Instead, they proposed that the
behavior was driven by the interfacial energy penalties incurred
in nanoscale particles. By accounting for the approximate
interfacial energy within a microstructural model, they verified
that thermodynamic penalties associated with interfacial
energies could indeed become catastrophic for small NPs,
altering the reaction pathways in agreement with observations
(Figure 31).
The thermodynamic calculations of Wood et al.19 also
provide insight into other possible nanointerface-driven kinetic
enhancements. First, the predicted equilibrium phase fractions
transitioned much more abruptly with pressure for Li3N NPs
than for the bulk material, suggesting a stronger driving force
for phase growth or depletion. Second, the authors concluded
that the elimination of the undesirable intermediate (Li2NH)
as a solid phase necessarily increases the nonstoichiometry of
the product phase (LiNH2) during intermediate reaction
stages, which they reasoned would lead to likely enhancements
in mass transport kinetics.
Although not directly applied to nanoscale systems, other
studies have attempted to unravel the effects of phase
boundaries and their microstructural arrangements on kinetics
and reaction pathways. Michel and Ozoliņs ̌ studied the effect
of the microstructural arrangement of NaAlH4, Na3AlH6, and
Al directly affects the diffusional fluxes of relevant defects in
these phases, which in turn modifies the overall (de)-
hydrogenation kinetics.498 Microstructure-dependent reaction
pathways for the dehydrogenation of (LiNH2+LiH) mixtures
have also been explored.486,487 Hoang et al. reasoned that, if
LiNH2 and LiH are in intimate contact in a particle, the
dehydrogenation reaction occurs without forming NH3, since
hydrogen atoms from LiNH2 can be recombined with
hydrogen atoms from LiH at the LiNH2/LiH interface. On
the other hand, if these phases are not in intimate contact, the
dehydrogenation reaction is dominated by the decomposition
of LiNH2, which generates NH3 as an intermediate species. In
nanoscale particles, microstructure may differ from the bulk,
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and the effects of interfaces become increasingly important,
magnifying the relevance of these conclusions.
6.2.4. Effects of Nonreactive Phase Boundaries. For
nonreactive interfaces, the interfacial energies are likely to be
dominated by mechanical effects associated with coherency
strain. Beyond the higher overall proportion of interfacial
atoms found in nanoscale systems, the degree of coherency
strain due to lattice mismatch between dehydrided and
hydrided phases can itself become size dependent. Although
widely studied in the context of other energy storage
materials,499 detailed studies of the effects of interfacial
coherency strain on reaction thermodynamics and kinetics in
hydrogen storage materials have appeared only recently.
One way to establish the relevance of coherency strain in
nanoscale systems has been to employ thin films.343,500,501
Baldi et al. reported experimental results for stacks of thin films
containing two Mg layers under different mechanical
constraints defined by the neighboring layers.343 In their
experiment, one Mg layer was sandwiched between Ti layers.
This had the effect of isolating Mg elastically, since the
immiscibility of Mg (or MgH2) and Ti (or TiH2) leads to a
fully incoherent interface. The other Mg layer was bound to
Pd, which alloys with Mg at the interface. This clamps Mg
elastically, since the Mg/Pd interface becomes fully coherent
(see the inset of Figure 32). Experiments and corresponding
Figure 32. Pressure-transmission isotherm measured by optical
hydrogenography on a multilayer thin film sample shown schemati-
cally in the inset. (Reproduced with permission from ref 343.
Copyright 2009 American Physical Society.)
elasticity modeling results indicated that the elastically clamped
Mg layer exhibited a higher plateau pressure, implying that this
layer was destabilized by the elastic strain contribution from
the mechanical constraint (Figure 32). These results explicitly
demonstrate the significant impact that internal strain can have
on the hydrogen storage thermodynamics. They also imply
that the local thermodynamics of nanoscale particles may be
controlled by the coherency of the phase boundary, which
determines the relative strain energy contribution.
The theoretical foundations for the thermodynamics of open
two-phase systems with coherent interfaces were established by
Schwarz and Khachaturyan, who subsequently applied the
methodology to understand phase transformations in metal
hydrides.502,503 Their model considered the absorption/
desorption of interstitial atoms by a solid crystalline host
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with a coherent mixture of the two phases. They identified that
the coherency strain associated with lattice mismatch produces
a macroscopic energy barrier between transforming phases,
which connects the system thermodynamics to the phase
transformation kinetics. They also reasoned that this energy
barrier is proportional to the macroscopic volume, which
means that it cannot be easily surmounted by thermally
assisted processes. Instead, the phase transformation occurs
once the external gas pressure surpasses a critical point, beyond
which the free energy of the entire system can be decreased by
the transformation because the barrier vanishes. In this regime,
the two transforming phases cannot coexist at equilibrium. The
authors also claimed that the barrier associated with the
coherency strain is the thermodynamic origin of the hysteresis
in plateau pressures between hydriding and dehydriding phase
transformations. Within their model, the shift in plateau
pressures could be directly quantified in terms of elastic
parameters of the constituent phases.
Recently, experimental efforts to verify the role and
magnitude of coherency strain have benefited significantly
from advanced characterization techniques. These have
enabled more systematic exploration of thermodynamic and
kinetic impacts of intrinsic particle size, shape, and internal
defects on the phase behaviors of hydriding and dehydriding of
nanoscale metal hydrides. These studies have focused on
simple metals that form semicoherent or coherent interfaces
upon hydriding, including Pd and Mg. The use of these simple
model systems allows for unbiased decoupling of mechanical
strain effects from more complex chemical factors.
Baldi et al. successfully observed the phase changes during
hydrogen absorption/desorption of a single isolated (100)-
terminated Pd nanocrystal utilizing in situ EELS in an
environmental transmission electron microscope.112 Exploiting
differences in the plasmon resonances between the hydrogen-
poor α and hydrogen-rich β phases of PdHx for phase
identification, they characterized a sharp α-to-β transition and
a large hysteresis in the accompanying uptake and release
isotherms of small particles. They found that the results
followed the coherent thermodynamic theory of Schwarz and
Khachaturyan,502,503 suggesting coherency is maintained
during the phase transformation for their particle sizes. The
authors also observed a positive correlation between the
hydrogen loading pressure and particle size. This effect was
attributed to the stress generated by excess hydrogen
concentration near the surface. They argued that because the
surface region forms a coherent interface with the particle
interior, the hydrogen-rich outer region exerts a hydrostatic
tensile stress on the particle core. This stress modifies the
equilibrium chemical potential of the particle interior. Broadly
consistent results were found by Syrenova et al., who used
plasmonic nanospectroscopy to study the hydride formation
thermodynamics of single-nanoparticle Pd for a variety of
particle sizes and shapes.418
Further evidence for interfacial coherency in nanoscale Pd
was established by Narayan et al. using in situ environmental
STEM and EELS during hydriding of Pd nanocubes.504 They
found that (100) phase boundaries, which minimize the elastic
energy, are always established regardless of the initially formed
phase boundary orientation. Because loss of interfacial
coherency would be expected to express different phase
boundaries, the conclusion was that interfacial coherency is
maintained in nanosized Pd crystals.
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Griessen et al. comprehensively compared existing thermo-
dynamic data for hydrogen absorption and desorption in Pd
NPs to those of a freestanding thin film and the bulk
material.110 Their results were used to obtain a general
thermodynamic principle of nanosizing effects (Figure 33).
Figure 33. Plateau pressures for hydrogenation of Pd NPs of varying
sizes. Experimental data from various sources are shown in green and
blue: Bardhan et al.109 (dots), Wadell et al.505 (triangles), Yamauchi
et al.107 (inverted triangles), Züttel et al.506 (half-shaded triangles),
Sachs et al.507 (diamonds), Syrenova et al.418 (squares), Lässer and
Klatt508 (stars), and Baldi et al.112 (half-shaded circles). Red squares
represent the upper spinodal pressure, pink circles the lower spinodal
pressure, and orange triangles the midpressure, all calculated with a
mean-field model. (Reproduced with permission from ref 110.
Copyright 2016 Springer Nature.)
Comparing against a thermodynamic model, they also
concluded that hydrogen absorption of NPs follows a coherent
interface phase transformation model. However, they also
asserted that desorption takes place fully coherently only for
small NPs (<50 nm). For larger particles, hydrogen desorption
occurs as some degree of coherency is released. These results
demonstrate that particle size affects the structure of the
interface.
6.2.5. Nucleation and Phase Transformation Mecha-
nisms. A number of modern in situ techniques have emerged
that allow direct imaging of the hydriding mechanisms of
nanoscale metal hydrides, including product nucleation
mechanisms and growth modes. To date, these have chiefly
been applied to Pd, which has sufficiently fast kinetics, is
resistant to beam damage, and can be made into single crystals
with a high degree of control. One example is the work of
Narayan et al., who used dark field imaging and selected-area
electron diffraction (SAED) to identify reaction intermediates
within in situ STEM and EELS measurements of PdHx.504
They explicitly verified that a nucleation-and-growth mecha-
nism dominates, with phase transformations originating from
(111) facets at the corners of the cube. Their imaging was able
to directly capture a dynamic two-phase coexistence
throughout the process (Figure 34). This nucleation behavior
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and surfaces are under tensile strain, whereas the particle

center is compressively strained.510
Ulvestad et al. also carried out a single-particle experiment
employing the coherent X-ray diffractive imaging (CXDI)
technique.334 The authors investigated the hydriding phase
transformation dynamics of Pd nanocubes with (100) facets
containing no dislocations by tracking the lattice constant
variation. Similar to the experimental result of Narayan et
al.,504 they observed the α-to-β phase transformation via a
nucleation-and-growth mechanism initiated from the cube
corners. They combined their experiments with steady-state
phase-field modeling to characterize the strain field distribution
across the nanocubes. Within the hydrogen-poor α phase, the
strain distribution was found to be dominated by the
hydrogen-rich surface layer. On the other hand, the strain
distribution of the hydrogen-rich β phase within the nanocube
was primarily dominated by elastic effects with small
compositional inhomogeneity, which tend to minimize the
surface area.
In another paper, Ulvestad et al. successfully characterized
the structural defects and their impact within hydriding Pd
nanocrystals utilizing Bragg coherent diffraction imaging
(BCDI; Figure 35).335 For particles with 150−300 nm sizes,

Figure 34. SEM brightfield images (left) and phase transformations

monitored by STEM (right) of Pd NPs of (a) 20 nm, (b) 36 nm, and
(c) 43 nm, with the scale bar being 25 nm in each image.
(Reproduced with permission from ref 504. Used under the CC BY
4.0 license.)

was thought to originate from both mechanical and chemical

properties of the corners. The corners could be under tensile
strain, which may lower the enthalpy of the hydriding reaction
in these regions. At the same time, (111) surfaces may have
enhanced chemical reactivity, resulting in faster hydrogen
absorption. The morphology of nucleating phases was found to
follow a spherical cap model509 rather than a spherical shell
mechanism.112 The authors also concluded that the phase
transformation is limited by the motion of the phase boundary
rather than the surface reaction or bulk hydrogen diffusion.
A separate study by Narayan et al. reported in situ
characterization of the spatial distribution of hydride phases
within individual Pd nanocrystals with different structural
features (cube, pyramid, and multiply twinned icosahe-
dron).492 Employing plasmon EELS mapping, SAED, and Figure 35. Changes in displacement field and Bragg electron density
centered dark-field imaging techniques, they reconstructed the of PdHx during hydrogen exposure, demonstrating stress evolution
α and β phase distributions to evaluate the impact of structural and defect formation within the particle. (Reproduced with
defects and internal strain on the phase transformation permission from ref 335. Copyright 2017 Springer Nature.)
thermodynamics. Single crystalline cubes and pyramids of Pd
exhibited abrupt α-to-β phase transformation behaviors, with the relationship between equilibrium transformation and
fully hydrogenated and dehydrogenated crystals exhibiting particle size was found to be consistent with a coherent
homogeneous compositions. On the other hand, multiply interface mean-field theory model.110 In contrast, for particles
twinned icosahedral NPs, which contained twin planes and larger than 300 nm, they imaged dislocation nucleation near
defects, exhibited qualitatively different behavior. These the phase boundary during hydriding. Based on these results,
particles contained both α and β phases when hydrogenated, they estimated the critical particle size above which dislocation
with the former preferentially located near the center and the nucleation might theoretically occur due to coherency strain
latter at the edges. The authors claimed that this inhomoge- energy effects. Their measured critical size (∼300 nm) was a
neous spatial distribution of the phases could be explained in factor of 7−10 larger than the predictions, which were based
terms of a nonuniform internal strain field arising from on a core−shell microstructure model. They attributed this
structural defects and crystallite domain boundaries: the edges discrepancy to differences between the model and the actual
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hydriding phase morphology. Their experimental character-
ization instead suggested that the hydrogen-rich phase exhibits
a spherical cap geometry on the hydrogen-poor phase,
consistent with the phase morphology determined by Narayan
et al.504 With additional evidence from a phase-field micro-
elasticity calculation, they explained that the spherical cap
geometry produces less interfacial coherency strain energy than
the conventionally assumed core−shell geometry. These more
coherent interfaces raise the threshold particle size for
necessary dislocation formation.
6.3. Other Size-Related Effects
6.3.1. Shortened Diffusion Pathways. Arguably the
most oft-referenced effect of nanosizing on kinetics involves
shortening of the diffusion pathways, since the diffusion time, t,
is related to the distance the diffusing species must travel, l, and
the diffusion coefficient, D (eq 18). In metal hydrides for
which solid-state diffusion is rate limiting, shorter pathways
may lead to faster uptake or a transition to a different rate-
limiting process altogether. Despite this conventional wisdom,
systematic studies of size-dependent diffusion kinetics in metal
hydrides have been rare.
l2
t≈
2D (18)
One such study was performed by Yao et al., who
parametrized a core−shell model of Mg/MgH2 particles (or
grains) using experimentally derived diffusion coefficients.511
Their model assumed that hydride formation kinetics are
determined exclusively by diffusion kinetics and that rate
limitations in hydrogen diffusion are associated exclusively with
MgH2 rather than Mg. The authors predicted a substantial
effect on the overall kinetics of hydrogenation upon reduction
of particle/grain sizes, with 3 nm particles exhibiting ∼10×
faster hydrogenation than 30 nm particles at 100 °C.
6.3.2. Altered Phase Coexistence Behavior. Another
common feature of nanoscale metal hydrides is the
introduction of sloping behavior in the pressure plateau region
in the PCT analysis (see Figure 18). This is directly analogous
to the behavior exhibited by many nanoscale Li battery
electrodes upon electrochemical voltammetry cycling.512 Such
behavior has been observed in NPs of NaAlH4392 and
PdHx,107,492 for example. Whereas a flat plateau indicates
idealized two-phase thermodynamic coexistence and an abrupt
transformation between phases, as is generally observed for
bulk metal hydrides, there is no single definitive origin for a
sloping plateau. Instead, at least three mechanisms may be
invoked to explain the behavior in nanoscale metal hydrides.
6.3.2.1. Solid-Solution Mechanism. The most straightfor-
ward explanation for the sloping plateau involves stabilization
of solid-solution behavior, which is associated with higher
solubility of hydrogen in the dehydrided phase and vacancies
in the hydrided phase. Such behavior tends to be more
prevalent at surfaces, interfaces, and grain boundary regions
due to the higher degree of disorder.493,513 Furthermore, the
energetic penalty associated with the interfacial regions
becomes more significant at the nanoscale,499 which can
favor a single-phase solid solution in order to minimize the
presence of sharp interfaces. Another important factor is the
enhanced interfacial coherency (discussed further in section
6.2), which generates long-ranged stress fields that can
stabilizes solid solutions.514−516 In the limit that the critical
temperature falls below the experimental operating temper-
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ature, phase mixing will occur spontaneously, stabilizing a
solid-solution regime that exhibits PCT sloping behavior.
6.3.2.2. Particle-to-Particle Mechanism. Another possible
explanation assumes that phase segregation is maintained and
that phase transformations occur abruptly within individual
particles or grains but that the sloping plateau instead arises
from an ensemble of nonuniform particles or grains exhibiting
a dispersion of equilibrium pressures. For reasons discussed in
sections 6.1 and 6.2, the equilibrium pressure often varies with
particle size. Therefore, if the ensemble incorporates a broad
range of particles/grain sizes, sloping behavior will occur due
to the different equilibrium pressures as larger particles are
continuously activated. This mechanism was invoked by
Bardhan et al. to account for the PCT behavior of nanoscale
PdHx with a distribution of particle sizes.109
6.3.2.3. Defect-Mediated Mechanism. Sloping behavior
may also arise from the introduction of additional defects in
nanoscale particles. For instance, the introduction of
dislocations or twin boundaries can perturb the stress
distributions within the particle. For small particles or grains,
differences in the stress distributions may become more
pronounced rather than averaging out, as would be expected
for larger particles. The resulting inhomogeneous stress
distributions will result in a dispersion of pressure responses,
which can generate a sloped pressure plateau. This explanation
was favored by Narayan et al. in the interpretation of their in
situ results of the hydriding kinetics of different Pd
nanoparticle morphologies.492 The authors observed sequen-
tial mosaic-style loading behavior of the individual crystallites
within an icosahedral particle over a range of pressures. They
argued that the different equilibrium pressures of small regions
(i.e., crystallites) within the particle can be traced to different
degrees of strain modulated by different defect densities.
However, it is worth noting that, in explaining the sloped
plateau pressure in their measured isotherms, they could not
exclude the possibility of a continuous solid-solution
mechanism associated with the smallest tetrahedral crystallites
(∼10 nm). For these domains, the critical temperature could
be lower than their experimental operating temperature.
Alternatively, buildup of dislocations or structural defects in
nanoscale particles may arrest or pin the phase boundary
motion, slowing the relaxation kinetics and leading to
deviations from equilibrium. For reasonable cycling rates,
these deviations may manifest as sloping plateau behavior.
These explanations are broadly consistent with observations of
the phase transformation behavior of Pd NPs by Ulvestad et
al.335 They reported that, in small particles containing
dislocations, full transformation to the hydrogen-rich β phase
was not observed. The authors attributed this to two factors:
first, coherency loss due to dislocations and, second, inhibition
of phase boundary migration due to the interaction with
dislocations. Within this interpretation, a dispersion of
dislocation densities would translate to a dispersion of
equilibrium compositions and pressures, as well as phase
transformation rates, resulting in sloping plateau behavior.
6.4. Metal Hydride-Host Interactions
Although technical challenges may exist to stabilize NPs
smaller than 10 nm, recent studies show that by incorporating
hydrides into certain porous media or polymer based host
materials, the particle size of metal hydrides can be stabilized
to 5 nm or smaller.34,517 Carbon-based materials are of
particular interest as a choice of host material, because they are
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lightweight, relatively cheap, and abundant. Most carbon-based
materials are also good thermal conductors,518,519 which can
improve heat exchange during (de)hydrogenation of metal
hydrides. In general, the hydride−host interaction is expected
to be mostly physical, with the host material acting as passive
medium for enforcing small particle size. However, in some
cases, there is evidence that the host matrix can instead interact
directly with the active storage material and change its
properties. In the following sections, we discuss physical,
electronic, and chemical aspects of the metal hydride−host
interaction and address the potential impact of host materials
on the hydrogen storage performance of the nanocomposite.
6.4.1. Physical Confinement Effects. A host material is
generally expected to bring structural stabilization to hydride
NPs to avoid agglomeration or to help retain high energy
surfaces/phases that might be beneficial to (de)hydrogenation.
Numerous studies have demonstrated the ability to stabilize
hydride NPs to 1−3 nm in selected carbon matrix materials,
resulting in substantially enhanced (de)hydrogenation kinetics
and shifts in thermodynamic equilibria.11,34
One advantage of using these nongraphitic carbons as host
materials is their ability to change volume. Metal hydrides
generally experience significant volume change during (de)-
hydrogenation; for instance, converting Mg into MgH2 leads to
a volume expansion of ∼30%, with complex hydrides often
exhibiting far larger expansion.5 The structural flexibility of
carbon hosts allows them to accommodate the dramatic
volume change of hydrides, extending cycle life. Nevertheless,
expansion may accrue some residual stress exerted by the
confining medium at the interface with the hydride. Among
other effects, this confinement stress can alter the morphology
of the confined material. For instance, Chong et al. showed
that the NaBH4 nanoparticle encapsulated in a “graphene
wrapper” can maintain a spherical shape after cycling, whereas
a composite created by ball milling a mixture of NaBH4 and
graphene (NaBH4+graphene) shows an irregular shape of
NaBH4 distributed within flake-like graphene layers.30
Confinement stress can also affect the (de)hydrogenation
thermodynamics and kinetics. As discussed in section 6.1, the
reaction enthalpy and the pathways should be re-evaluated
when a change of surface energy is expected for the hydride
experiencing surface strain. The possibility of using volumetric
stress to alter hydrogen desorption properties was explored by
Ham et al.520 Using a thin film of a metastable phase of MgH2,
they measured stress-dependent hydrogen desorption thermo-
dynamics. The authors showed that stressed thin films can
release hydrogen at lower temperatures than stress-free MgH2,
suggesting mechanically induced destabilization.
A number of first-principles studies have also examined the
strain effect on (de)hydrogenation kinetics of metal hydrides.
Lei et al. computed the adsorption and dissociation energy of
H2 on Mg (0001) surface as a function of biaxial strain.521
Zhang et al. studied the dehydrogenation properties of MgH2
under biaxial strain and found that both tensile and
compressive strain lowers the activation energy for hydrogen
diffusion.522 Similarly, Benzidi et al. showed that under
compression, the energy barrier for hydrogen diffusion in
LiBH4 can be reduced from ∼93 to ∼86 kJ mol−1.12 The
elastic constraint placed by the host material may also assist the
buildup of internal strain energy at grain boundaries or
interphase boundaries, which might otherwise be easily
released for unconfined particles. This buildup could lead to
the creation or elimination of new metastable intermediate
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phases during cycling. A more detailed discussion regarding the
effect of mechanical stresses in the interior of confined NPs can
be found in section 6.2.
In addition to the potential confinement stress/strain
imposed by the host material, the carbon matrix can also
physically block certain intermediates from vaporization. For
example, Zhao-Karger et al. demonstrated that by infiltrating
LiBH4−Mg(BH4)2 into porous carbon, the toxic intermediate
B2H6 can be effectively retained in the composite.523
6.4.2. Electronic Coupling Effects. Beyond physical
confinement effects, host materials can also affect the behavior
of hydrogen storage materials by inducing electronic charge
transfer. Graphene-based carbon nanostructures in particular
have been extensively studied for their interactions with metals.
For example, graphene is considered as chemisorbed on
transition metals such as Co, Ni, Pd, and Ti due to strong
charge transfer between the metal and the graphene sheet.524
For weaker binding observed for graphene on Al, Cu, Ag, Au,
and Pt, the electronic coupling is still large enough to tune the
electronic structure of graphene such that the graphene sheet
may be considered as either hole doped or electron doped.524
Even for nanocomposites made of graphene and large band
gap semiconductors, such as TiO2, interfacial charge transfer is
still expected.525 However, most studies of graphene
interactions with other materials have focused on how the
electronic properties of graphene are modified. Here, we focus
instead on how electronic coupling at the graphene−hydride
interface may affect the (de)hydrogenation processes of the
hydride.
Berseth et al. used C60 fullerenes, carbon nanotubes, and
graphene as models of zero, one, and two-dimensional carbon
nanostructures and studied their interactions with NaAlH4.526
They found that these carbon nanomaterials are catalytic
toward hydrogen uptake and release in NaAlH4. To be able to
manipulate the electron localization in these carbon materials
and compare their electronic interactions with NaAlH4, they
synthesized carbon nanotubes with varying diameters
(curvature) using a solution-based preparation technique to
avoid potential metal and carbon contamination. Upon cycling
the nanocomposite, they found C60 had the best performance
to catalyze NaAlH4. This was attributed to the ability of C60 to
restrict electron donation from Na to AlH4, thereby weakening
the Al−H bond. From first-principles simulations, they
correlated the hydrogen removal energy to the electron
affinities of the carbon nanomaterials, which in turn are
related to local curvature. As the curvature increases, stronger
charge transfer occurs at the interface, which affects charge
partitioning within the hydride and influences (de)-
hydrogenation performance.
Nitrogen-doped porous carbons, NCMK-3 and NNPC, were
used by Carr et al. to confine LiBH4 and NaAlH4.403,527 The
pyridinic nitrogen atoms acted as Lewis bases on the complex
hydride anions, greatly increasing the desorption activation
energy of confined LiBH4 and, while decreasing the activation
energy of confined NaAlH4, increasing the temperature at
which maximum desorption from the alanate occurred (Figure
36).
6.4.3. Chemical Interactions with the Host. For
nanostructures based on carbon scaffolds or encapsulants,
carbon may also interact directly with hydrides to influence
their (de)hydrogenation performance.49,58 It has been shown
experimentally that, by adding carbon materials, the hydro-
genation kinetics of Mg metal can be greatly improved.528 DFT
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Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews
Figure 36. (a) Arrhenius plots of NaAlH4 confined in two undoped
carbons (NPC and CMK-3) and two N-doped carbons (NNPC and
NCMK-3) and of unconfined bulk NaAlH4 from isothermal
desorption. (b) Ramped-temperature hydrogen desorption from the
NaAlH4-infiltrated composites, with the black dashes representing the
temperature profile. (Adapted with permission from ref 527.
Copyright 2018 American Chemical Society.)
work also predicts that interstitial C in the Mg lattice can
simultaneously lower the activation energy for H2 dissociation
(by 0.16 eV) and improve atomic hydrogen diffusion through
the subsurfaces (by 0.33 eV or more).529 In other systems, de/
rehydrogenation may involve carbide formation, indicating a
direct reaction with the confining medium. For example,
Zhang et al. showed reversible appearance of Li2C2 phase in
the XRD patterns during de/rehydrogenation of nano-LiBH4
confined within mesoporous carbon.399 Miyaoka et al., based
on a Li−C−H system composed of hydrogenated graphite and
LiH, demonstrated the formation of both Li2C2 and CH4.530
Although reasonable cycling temperature (350 °C) was
achieved, the system suffered from low rehydrogenation
capacity due to the formation of CH4. Residual oxygen in
the carbon host, present as CO or CO species, can also
react with hydrides or their dehydrogenated forms. It has been
suggested that magnesium, which is very oxophilic, readily
scavenges oxygen from its confining scaffold and forms MgO,
which no longer participates in hydrogen cycling and decreases
the overall capacity over time.454
7. CONCLUSIONS
It is abundantly clear from the foregoing discussion that
research and development of nanoscale metal hydrides is a
vigorous field. In this review, we considered only work in
roughly the past two decades, which still accounts for more
than five hundred cited papers. These materials are no longer a
laboratory curiosity but are a growing subclass with potential
applications not only for hydrogen storage, as discussed herein,
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Review
but also for batteries, portable power, and solid electro-
lytes.46,63 There is now overwhelming evidence that nanosizing
affects the reaction pathways, kinetics, and thermodynamics,
with several theoretical and experimental investigations
suggesting that both the enthalpy and entropy of hydrogen
desorption can be altered. Synthetic approaches, both top-
down and bottom-up, are now available for all classes of metal
hydrides that can be used to produce both free-standing and
supported NPs or clusters, thin films, and nanowires, as well as
more complex shapes such as core−shell particles and
multilayers (e.g., Figures 2, 5, and 17).
Control over the nanohydride properties, in particular,
composition, size, and purity, is far greater than what was
previously achieved using conventional mechanical milling.
Supporting these experimental developments is the vast
increase in computing power and theoretical method
innovations that are making structure and property prediction
faster and more reliable. As a result, the fundamental
understanding of nanoscale properties has improved dramat-
ically in the past ten years, such that basic design principles are
beginning to emerge. On the most basic level, particle size
appears to be an almost universal property for predicting the
extent of nanoscale effects. Although this varies from one
material to another, recent investigations in which a high
degree of particle size control and uniformity was achieved
indicate that the most dramatic effects occur when the critical
dimension is 10 nm or less.
The preponderance of the available data indicates that
nanoscaling leads to significant improvements in the kinetics of
hydrogen uptake and desorption. However, it has yet to be
determined conclusively as to whether such dramatic effects on
the thermodynamics can be achieved. Theory suggests that it is
possible, but the most significant impacts from surface energies
are predicted for very small particle dimensions (a few
nanometers). Mechanical stresses due to volume expansion
upon hydrogenation also merit further theoretical and
experimental investigation, since stress effects on both kinetics
and thermodynamics have been proposed. These factors could
contribute to changes in reaction pathways, such as those
observed in NaAlH4, LiNH2, and LiBH4 for which the number
of reaction steps is reduced upon nanoscaling. Although theory
generally supports the conclusion that these are thermody-
namically driven, it cannot be ruled out that they may instead
result from lowering of a particular activation barrier to enable
the reaction to proceed through a different pathway. Indeed,
distinguishing between thermodynamic and kinetic effects can
be difficult, in part because thermodynamic data for the bulk
material are not always well established. More advanced kinetic
models that account for the diversity of physicochemical
processes that govern (de)hydrogenation may help to elucidate
which factors control the reaction pathway.
Rationalizing the observed improvements in hydride proper-
ties remains a matter of debate, as a number of factors that can
affect the metal hydrides at nanoscale, including surface area,
defects, nanointerfaces, and strain, are difficult to control. The
rather simplistic interpretation of the transport phenomena,
based solely on shorter diffusion times and lengths, occurring
during H2 absorption/desorption is appealing, but, in fact,
several other factors can affect the kinetics of nanoscale metal
hydrides. Examples include hydride−hydride and hydride−
scaffold nanointerfaces, where lattice mismatches and defects
sites are also likely to occur. Likewise, the effects of surface and
interface heterogeneity and disorder have not been studied in
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Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews
sufficient detail, nor has the evolution of internal micro-
structure. Consequently, understanding of the phenomena
controlling nanohydride properties remains incomplete.
In spite of this rapid progress, important challenges remain
regarding both fundamental understanding and practical
implementation of nanohydrides. Since most of these materials
are stabilized within some kind of host or shell, understanding
how the host/shell material affects properties is essential. The
presence of reactive sites within a nanoscaffold, such as open
metal sites in MOFs or Lewis acid or base sites in porous
carbons, make the host “non-innocent,” in the sense that
chemical interactions would be expected to be stronger than
weak van der Waals forces. Moreover, there is evidence that
even hosts that might otherwise be considered “passive” may
affect properties through the creation of solid−solid inter-
faces.60 Focused efforts employing both theory and experi-
ments are needed to provide insights for selecting and
designing host materials to achieve specific properties.
Similarly, there is evidence that solid−solid interfaces within
the nanoparticle itself that form during uptake or release of H2
can dramatically influence kinetics, as is the case of Li3N.19
Further investigation into the role of solid−solid interfaces and
material-host interactions for other metal hydrides is
recommended; this may necessitate additional developments
in theoretical modeling of interfaces.
The interest in using nanostructured metal hydrides for
hydrogen storage applications has prompted the need for more
accurate measurement of hydrogen capacity, thermodynamics,
and kinetics. The complex nature of the samples (particles of
various sizes, presence of porous hosts, impurities) have
presented new challenges for traditional hydrogen measure-
ment techniques. Several factors can affect the accuracy of the
measurements, including sample size, temperature gradients,
types of valves used, leak rates, and must be carefully
considered.531−533 In addition, many of the materials studied
are porous (e.g., gamma-Mg(BH4)2)323 and can adsorb helium,
which has typically been considered as a nonadsorbing species
for free space determination. Helium adsorption has been
shown to impact skeletal density measurements in porous
samples.531,532 The U.S. Department of Energy Fuel Cell
Technologies Office provided a comprehensive overview of the
recommended best practices in making measurements of the
hydrogen storage properties on their Web site.337 Finally, it is
critical for the community to report not only the hydrogen
capacity or the rate of hydrogen release and uptake but also
thermodynamic and kinetic data, such as enthalpy, entropy,
and activation energy (e.g., Tables 3−5). These values may all
change over the course of multiple dehydrogenation/
rehydrogenation cycles, so the stability of the storage materials
must be assessed, as has been done for some, but not many,
systems.
From a practical perspective, it should be noted that that
there are significant (∼20−30%) gravimetric and volumetric
penalties associated with using even optimized nanoscaffolds,44
which make it challenging to consider them for optimal
hydrogen storage systems. Ideally, a synthetic route to
nanoscale particles in the 1 to 20 nm range would be highly
desirable, producing NPs with enhanced kinetic behavior but
without the gravimetric and volumetric penalties associated
with scaffold use. A promising new direction is nano-
encapsulation of metal hydride NPs inside graphene and
reduced graphene oxide sheets. In selected cases, the
gravimetric penalty does not exceed 10%, compared to 50%
10823
Review
or more penalties typically observed for other carbon-based
nanoconfinement media, such as templated porous carbons or
carbon aerogels. Reduced graphene oxide is an excellent
encapsulating layer for wrapping Mg34 and Ni-doped Mg36
nanocrystals for hydrogen storage. In addition to high
gravimetric and volumetric hydrogen capacities, the materials
display enhanced air-stability, due to the rGO protecting layer.
In summary, the rapid progress made in the past decade has
created exciting new opportunities for synthesizing nano-
hydrides with properties tailored for specific applications.
Although nanoscale phenomena may seem quite distant from
large-scale applications such as vehicular hydrogen storage, the
recent advances are so significant that it is not difficult to
envision progress toward materials that could ultimately meet
some of the most challenging DOE technical targets. Proving
this true is a worthy scientific goal with profound implications
for future energy storage systems and, more broadly, for
countering the effects of climate change.
AUTHOR INFORMATION
Corresponding Author
*E-mail: vnstavi@sandia.gov.
ORCID
Andreas Schneemann: 0000-0001-6801-2735
James L. White: 0000-0002-8216-7212
Liwen F. Wan: 0000-0002-5391-0804
Eun Seon Cho: 0000-0001-9428-1269
Jeffrey J. Urban: 0000-0002-6520-830X
Brandon C. Wood: 0000-0002-1450-9719
Mark D. Allendorf: 0000-0001-5645-8246
Vitalie Stavila: 0000-0003-0981-0432
Author Contributions
⊥
A.S. and J.L.W. contributed equally to this work.
Notes
The authors declare no competing financial interest.
Biographies
Andreas Schneemann originates from Sprockhövel, Germany. He
obtained his M.Sc. and Ph.D. at the Ruhr University Bochum under
the guidance of Prof. Roland A. Fischer, working on metal−organic
frameworks. He was a visiting scholar in the laboratories of Ian A.
Fallis (Cardiff University), Seth M. Cohen (University of California,
San Diego), and Shin-ichiro Noro (Hokkaido University). After a
short stay as a scientific staff member at Technical University Munich
he joined the group of Mark D. Allendorf at Sandia National
Laboratories in Livermore, California on a German Research
Foundation (Deutsche Forschungsgemeinschaft) Fellowship. His
current research interests revolve around hydrogen storage materials,
particularly metal hydrides confined in porous matrices.
James L. White, a native of Pennsylvania, earned his Ph.D. in
chemistry and materials from Princeton University in 2016, working
under Prof. Andrew B. Bocarsly investigating electrocatalytic carbon
dioxide reduction. Prior to that, he obtained his honors B.S. degree in
chemistry with minors in biochemistry, mathematics, and economics
from the University of Delaware in 2011, where he did undergraduate
research on solid oxide fuel cell electrolytes with Prof. Joshua L.
Hertz. He is currently a postdoctoral fellow at Sandia National
Laboratories, where he has been studying complex metal hydrides,
their reactivity under extreme conditions, and their mechanisms, as
DOI: 10.1021/acs.chemrev.8b00313
Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews
part of the Hydrogen Materials−Advanced Research Consortium
(HyMARC).
ShinYoung Kang is a postdoctoral researcher at Lawrence Livermore
National Laboratory in Livermore, CA. She received her Ph.D. in
Materials Science and Engineering at Massachusetts Institute of
Technology in 2014. Her primary research focus is to understand
fundamental processes occurring in clean energy technology,
including hydrogen storage, batteries, and solar cells, and to provide
design insights using atomistic simulations.
Sohee Jeong earned her Ph.D. in Chemistry at Yonsei University in
2016. She is currently a postdoctoral fellow in Jeffrey Urban’s research
group at Lawrence Berkeley National Lab. Her research interests
include the development of new metal hydride complexes for gas
storage and the rational design of nanocrystals, with an emphasis on
transition metal dichalcogenide 2D materials.
Liwen Wan is currently a postdoctoral researcher at Lawrence
Livermore National Laboratory. She received her Ph.D. in Material
Sciences and Engineering in 2013 from Iowa State University and
then worked as a postdoctoral research fellow at Lawrence Berkeley
National Laboratory. Her research focuses on using theoretical
methods to study and probe chemical reactions and processes across
solid−liquid and solid−solid interfaces for energy storage and
conversion applications.
Eun Seon Cho is an Assistant Professor of Chemical and
Biomolecular Engineering at Korea Advanced Institute of Science
and Technology (KAIST). She received her Ph.D. in Materials
Science and Engineering in 2013 from Massachusetts Institute of
Technology. Her works in the area of hydrogen storage focus on the
development of nanostructured metal hydrides to enhance the
hydrogen release and absorption properties. Her major research
interests include the design and synthesis of functional hybrid
nanomaterials with organic and inorganic building blocks for energy
and environmental applications.
Tae Wook Heo is a Staff Scientist at Lawrence Livermore National
Laboratory. He earned his Ph.D. in Materials Science and Engineering
in 2012 from The Pennsylvania State University. He specializes in
mesoscale modeling of complex phase microstructures of various
classes of materials including hydrogen storage materials, battery
electrodes/electrolytes, and metallic alloys. Within the hydrogen
storage research program, his effort is mainly focused on mass
transport and phase transformations coupled to mechanical stress and
interfacial chemical reactions. He is actively involved in multiscale
integration connecting atomistic simulations with mesoscale formal-
isms, as well as code development for phase-field modeling of simple
and complex metal hydrides.
David Prendergast is a Senior Staff Scientist at Lawrence Berkeley
National Laboratory, working in its Energy Sciences Area. He is the
Facility Director for Theory at The Molecular Foundry, a National
User Facility for Nanoscience, serving academic, government, and
industrial research. He has a Ph.D. in Physics from University College
Cork, Ireland (2002). His research focuses on developments and
applications of first-principles electronic structure theory and
molecular dynamics in the context of energy-relevant phenomena in
chemistry and materials, from molecules to condensed phases. He has
particular expertise in the simulation and interpretation of
synchrotron X-ray spectroscopy measurements as a means of
connecting characterization of complex and dynamic homogeneous
or interfacial systems to atomistic or molecular-scale mechanistic
models and the development of the necessary computational methods
to derive such connections efficiently.
10824
Review
Jeffrey J. Urban is a Staff Scientist and Facility Director at the
Molecular Foundry located in Lawrence Berkeley National Labo-
ratories in Berkeley, CA. He earned his Ph.D. in physics and
chemistry in 2004 from Harvard University. His projects in the area of
hydrogen storage focus on the development of new approaches to
nanoscale metal hydrides and metal hydride hybrid materials
complexed with organic frameworks and graphene-based materials.
He has also studied the fundamental size-dependence of hydriding
phase transitions in metal hydrides, establishing the first general
model of confinement in these systems. A central theme in Dr.
Urban’s research is revealing the fundamental physical origins of
transport and phase transformation in hydrogen storage materials.
Brandon Wood is currently a Staff Scientist in the Materials Science
Division at Lawrence Livermore National Laboratory, U.S.A. He
received his Ph.D. in Materials Science and Engineering from MIT in
2007. His research activities lie in the application of ab initio and
mesoscale simulation techniques to materials for energy storage and
conversion, with particular emphasis on the use of high-performance
computing to understand complex interfaces. He is the Theory
Director for the U.S. Department of Energy Hydrogen Storage
Materials--Advanced Research Consortium (HyMARC), for which he
leads the development and application of multiscale computational
methods for probing kinetics and thermodynamics of metal hydrides
and sorbents. He has (co)authored more than 60 peer-reviewed
publications and two patents.
Mark Allendorf is Director of the Hydrogen Materials−Advanced
Research Consortium (HyMARC) and a senior scientist at Sandia
National Laboratories. He received an AB degree in chemistry from
Washington University in St. Louis and a Ph.D. degree in chemistry
from Stanford University. His research focuses on the fundamental
science and applications of metal−organic frameworks and related
materials. His work has been published in more than 170 publications,
including more than 130 journal articles. He is President Emeritus
and Fellow of The Electrochemical Society.
Vitalie Stavila is a Principal Member of Technical Staff at Sandia
National Laboratories in Livermore, CA. He earned his Ph.D. in
inorganic chemistry in 2002 from State University of Moldova. His
projects in the area of hydrogen storage focus on the development of
metal hydrides and sorbents with improved kinetics and thermody-
namics of hydrogen release and absorption. A central theme in Dr.
Stavila’s research is the rational design of new materials by changing
the chemical composition, the arrangement of the atoms or molecules
in crystalline or amorphous configurations, and the size, shape, and
orientation of nano- or macroscopic objects. Dr. Stavila coauthored
more than 110 journal articles and nine patents.
ACKNOWLEDGMENTS
Sandia National Laboratories is a multimission laboratory
managed and operated by National Technology and Engineer-
ing Solutions of Sandia, LLC., a wholly owned subsidiary of
Honeywell International, Inc., for the U.S. Department of
Energy’s National Nuclear Security Administration under
contract DE-NA-0003525. This work was performed in part
under the auspices of DOE by Lawrence Livermore National
Laboratory under Contract DE-AC52-07NA27344. Lawrence
Berkeley National Laboratory efforts were supported by the
Office of Science of the U.S. Department of Energy under
Contract No. DE-AC02-05CH11231. The authors gratefully
acknowledge research support from the U.S. Department of
Energy, Office of Energy Efficiency and Renewable Energy,
Fuel Cell Technologies Office through the Hydrogen Storage
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Chem. Rev. 2018, 118, 10775−10839
Chemical Reviews Review

Materials Advanced Research Consortium (HyMARC). A.S. NVS neutron vibrational spectroscopy
gratefully acknowledges the German Research Foundation NW nanowire
(Deutsche Forschungsgemeinschaft) for a Postdoctoral OMS ordered mesoporous silica
Fellowship (SCHN 1539/1-1). E.S.C. is grateful for financial PCT pressure−composition−temperature (measure-
support by International Energy Joint R&D Program of the ment)
Korea Institute of Energy Technology Evaluation and Planning PEGS prototype electrostatic ground state
(KETEP), granted financial resource from the Ministry of PEM polymer electrolyte membrane
Trade, Industry & Energy, Republic of Korea (No. PMMA poly(methyl methacrylate)
20188520000570). This paper describes objective technical PTI pressure−temperature isotherm
results and analysis. Any subjective views or opinions that PVD physical vapor deposition
might be expressed in the paper do not necessarily represent PVP poly(N-vinyl-2-pyrrolidone)
the views of the U.S. Department of Energy or the United PXRD powder X-ray diffraction
States Government. rGO reduced graphene oxide
SAED selected-area electron diffraction
LIST OF ABBREVIATIONS SANS small-angle neutron scattering
APXPS ambient pressure X-ray photoelectron spectros- SAXS small-angle X-ray scattering
copy SEM scanning electron microscopy
BCDI Bragg coherent diffraction imaging STEM scanning transmission electron microscopy
bct body-centered tetragonal STXM scanning transmission X-ray microscopy
BDE bond dissociation enthalpy Tdec decomposition temperature
BET Brunauer−Emmet−Teller surface area measure- TEM transmission electron microscopy
ment TGA thermogravimetric analysis
BJH Barrett−Joyner−Halenda pore volume analysis THF tetrahydrofuran
BTC benzenetricarboxylate UHV ultrahigh vacuum
Bu butyl (typically n-butyl) XANES X-ray absorption near edge structure
CALPHAD calculation of phase diagrams XAS X-ray absorption spectroscopy
CNF carbon nanofiber XPS X-ray photoelectron spectroscopy
CNT carbon nanotube XRD X-ray diffraction/diffractometry
Cp cyclopentadienyl XRS X-ray Raman spectroscopy
CXDI coherent X-ray diffractive imaging
DFT density-functional theory
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10839 DOI: 10.1021/acs.chemrev.8b00313

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