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Advances and Outlook of Boron−Hydrogen Containing Materials for

Potential Clean Energy Applications: A Review
Haojie Li,* Bingke Yang, Xuetao Wang, Zhen Yao, and Yilin Zhu

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ABSTRACT: Hydrogen energy has characteristics of pollution-free,

high energy density, utilized in many forms, which is considered to be
the ideal energy to replace traditional fossil energy and the ultimate
Downloaded via HACETTEPE UNIV on February 11, 2024 at 22:45:06 (UTC).

energy source for human beings. However, how to store it efficiently and
safely remains a challenging problem, which limits its large-scale
application. The high hydrogen storage density and excellent
thermodynamic stability of boron−hydrogen materials make them
advantageous in storing hydrogen energy, which provides a good
solution to hydrogen storage issues. In addition, boron−hydrogen
materials have other potential applications in clean energy fields, and
these applications have not been summarized systematically. Therefore,
this Review summarizes the research progress of boron−hydrogen
materials in storing hydrogen energy, producing hydrogen, acting as a
reductant, rocket fuel, and fuel cells. The research progress and the problems faced in the large-scale application of boron−hydrogen
materials and future solutions are analyzed. The Review provides valuable insights and references for the potential application
research of boron−hydrogen materials.

1. INTRODUCTION with the above-mentioned hydrogen storage methods, borohy-

The shortage of fossil energy and the aggravation of environ-
mental pollution have made the renewable energy represented
by hydrogen energy gradually become a research hotspot.1 The
high energy density and absolute cleanness make hydrogen
energy to be the energy of the future. However, hydrogen is
difficult to store on a large scale; how to achieve safe and efficient
storage and conversion of hydrogen energy has become a major
technical challenge in its applications.2
Among the many hydrogen storage methods, the solid-state
hydrogen storage is considered to be the most promising
method for the future due to its high hydrogen storage density
and room-temperature storage. Currently, three types of solid-
state hydrogen storage materials are known: intermetallic
compounds (AmBn, A and B are metals), metal hydrides
(MgH2, AlH3, etc.), and coordination hydrides (NaAlH4,
Mg(AlH4)2, etc.). For AmBn, the lower mass storage density
and slower hydrogen uptake and release kinetics limit its
application.3 For metal hydrides, the hydrogen release of AlH3 is
exothermic, and the product is Al that cannot be rehydro-
genated, while MgH2 has a high enthalpy of hydrogen release
(75 kJ/mol) and slow reaction kinetics of hydrogen absorption
and release and is easily oxidized.4 For the coordination hydride,
only 3.5 wt % H2 is stored reversibly after 100 cycles of NaAlH4,
and the performance stability is poor. The release of hydrogen
from Mg(AlH4)2 is an exothermic reaction, and the product
cannot absorb hydrogen and cannot be recycled. Compared
drides (metal borohydrides, NH3BH3, N2H4BH3, etc.) hydro-
gen storage has the following advantages: high mass hydrogen
storage density, suitable thermodynamic kinetic properties, high
reversibility, diversification of modification methods, etc.
Therefore, many researchers5 consider borohydrides one of
the most promising materials for solid-state hydrogen storage.
Borohydrides is a kind of ionic compound with covalent bond,
its excellent characteristics of high stability at room temperature
and high hydrogen content have attracted much attention. For a
long time, borohydrides have been used as reducing agents in
chemical synthesis and solid rocket fuel.6 With further research,
it was found that borohydrides are also a good hydrogen carrier
and ionic conductor, and they have been widely used for solid
state hydrogen storage, hydrolysis, alcoholysis, and pyrolysis for
hydrogen production, fuel cells and several other fields.7−9 For
example, Xu et al.10 recently found that doping perovskite solar
cells (PSCs) materials with borohydrides can significantly
improve their photoelectric conversion efficiency and stability.
Received: April 21, 2023
Revised: July 10, 2023
Published: July 26, 2023

© 2023 American Chemical Society https://doi.org/10.1021/acs.energyfuels.3c01393

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Figure 1. (a) Molecular structure of hydrazine borane; (b) ammonia borane; (c) sodium borohydride; (d) lithium borohydride.
In addition, some researchers11,12 have found that borohydrides
can participate directly in the fuel cell reaction, which makes
hydrogen fuel cell vehicles safer and more reliable because it
avoids the hydrogen storage step. These studies indicate that the
borohydrides play a variety of functions as carriers in the process
of energy conversion and storage. In the current research, the
research on boron−hydrogen materials is mainly focused on
hydrogen storage, hydrogen production and fuel cells, and there
is little research on mild reductant and rocket fuel. In addition,
most of the available borohydride review articles are related to a
particular aspect (for example, focused on the catalyst), and
there is no complete review of the application of borohydrides in
various aspects; the guidance for the future application research
of borohydrides is slightly insufficient. Therefore, a complete
overview of boron−hydrogen material applications in clean
energy is necessary.
Further, with the advent of the hydrogen economy, as a high
hydrogen energy material with great application potential, it is
necessary to review the research progress of boron−hydrogen
materials in hydrogen storage, hydrogen production, mild
reductant, and rocket fuel and fuel cells, analyze the problems
and possible solutions for future applications, and provide
guidance and insight for the research of potential applications of
boron−hydrogen materials.
2. THE POTENTIAL APPLICATION FIELD
2.1. High Capacity Hydrogen Storage. The biggest
bottleneck in hydrogen utilization is storage and transportation
due to its small atoms, light and hard to liquefy. Therefore, how
to achieve efficient and secure storage and transport restricts its
large-scale application.13 The mainstream of the current high
pressure gaseous hydrogen storage and low temperature liquid
hydrogen storage, but both have technical flaws in safety and
cost. Solid hydrogen storage based on borohydrides has the
advantage of high hydrogen storage density, safety and
reliability, showing clear advantages over gaseous hydrogen
storage and cryogenic liquid hydrogen storage.14 Representative
borohydrides contain NH3BH3, N2H4BH3, NaBH4, Ca(BH4)2,
etc.15−17 Borohydrides are formed by the interaction of B−H
covalent bonds, B−N coordination bonds, or metal ion
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Review
bonds18−21 and have a high degree of thermodynamic stability
and controllability of chemical reactions. Figure 1 shows
common boro-hydrogen compounds, the nonmetallic borohy-
drides hydrazine borane (HB, Figure 1a) and ammonia borane
(AB, Figure 1b) and the metallic borohydrides sodium
borohydride (Figure 1c) and lithium borohydride (Figure 1d).
The high mass hydrogen storage density of borohydrides
makes them useful for a variety of energy storage applications.22
Table 1 shows several common borohydrides and their
Table 1. Hydrogen Storage Density of Some Common
Borohydrides
sample wt % sample wt %
NaBH4 10.8 Mg(BH4)2 14.9
Ca(BH4)2 11.6 KBH4 7.5
Al(BH4)3 16.9 Be(BH4)2 20.8
LiBH4 18.5 Ti(BH4)3 13.1
NH3BH3 19.6 N2H4BH3 15.4
theoretical hydrogen storage capacity. Among them, LiBH4,
NaBH4, and KBH4 have been industrially produced, and the
production costs are relatively low. The mass hydrogen storage
density of LiBH4 is up to 18.5 wt %, but the dehydrogenation
temperature above 400 °C and the reversible hydrogen release
condition are relatively harsh. The mass hydrogen storage
density of NaBH4 is 10.8 wt %, and the pyrolysis temperature
can reach more than 500 °C.23 Existing scientific research24 has
discovered that the electronegativity of an element affects the
stability of its compounds: the higher the electronegativity and
the stronger the stability, the more difficult the compound is to
decompose; its decomposition temperature is related to its
element electronegativity of the compounds. Therefore, it is
critical to counteract the effect of electronegativity to enable the
reversible hydrogen uptake/release of borohydrides under mild
conditions. In general, the methods to improve the hydrogen
storage and release properties of borohydrides mainly include
nanomodulation, composite systems, ion substitution,25 doping
modification,26 and so on. Among them, the composite system
and nano-modulation have great advantages in improving the
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Figure 2. (a) Mechanical mixture of NaBH4 and CoCl2·6H2O. (b) Tablets of solid NaBH4/Co composites. (c) Diffraction patterns of newly prepared
tablets. (d) Effect of pressing pressure on the hydrogen production rate of NaBH4/Co composites. (e) Effect of pressing pressure on the hydrogen
production rate for the preparation of the CoxB−Cl catalyst. Reproduced with permission from ref 28. Copyright 2019, Mdpist, Switzerland.

comprehensive performance of hydrogen storage and release some scholars30 have proposed that introduce a catalyst in the
from borohydrides. 2LiBH4−MgH2 system to improve the performance. Huang et
The composite hydrogen storage material consists of a al.31 prepared Ni@g-C3N4 catalysts from graphene, carbon
borohydride and a second phase compound. The second phase nitride (g-C3N4), and Ni, which exhibited excellent performance
compound can be a single element, a metal hydride, a metal in the 2LiBH4−MgH2 system, with reduced hydrogen release
fluoride, a borohydride, an amino complex, etc.3 Hydrogen temperature and reaction activation energy along with increased
storage performance is mainly improved in the following ways: hydrogen storage density.
more stable hydrogen release reaction products and lower
MgH2 Mg + H 2 (1)
enthalpy variations of the reaction in the composite. When
borohydrides are compounded with hydride, not only the
regulation of thermodynamic properties is achieved but also the 1 5 13
2LiBH4 Li 2B12H12 + LiH + H2
high hydrogen storage capacity is maintained. Future multi- 6 3 6 (2)
component composite hydrogen storage systems are the focus of
research; the attraction between H+ and H− between different 1 1 5
Li 2B12H12 LiH + 2B + H 2
hydrides can also be used to improve the hydrogen storage 6 3 6 (3)
properties of composites.27 The introduction of catalytic
performance materials into composites can also improve the Mg + 0.23LiH 1.23Mg 0.816Li 0.184 + 0.51H 2 (4)
hydrogen storage properties.28
Among them, the complexes of metal borohydrides and Mg(or Mg 0.816Li 0.184) + B MgB2 (5)
hydrides, namely reactive hydride composites (RHCs), have
been widely studied. Yan et al.29 studied the dehydrogenation 2LiBH4 + MgH2 2LiH + MgB2 + 4H 2 (6)
process of the 2LiBH4−MgH2 system in an inert atmosphere. As
the temperature increases, 2LiBH4−MgH2 undergoes a more NaBH4 composites also have excellent hydrogen storage
complex dehydrogenation process, which can be represented by properties. Netskina et al.28 mechanically mixed NaBH4 and
eqs 1−5, with eq 6 being the total reaction. Also, the formation CoCl2·6H2O (Figure 2a) to make tablets of NaBH4/Co
of the intermediate compound Li2B12H12 was observed (0−1 composites (Figure 2b), and the tablets were again subjected
MPa pressure), which affects the formation of MgB2 and has an to X-ray diffraction (XRD, Figure 2c). They then looked at how
inhibitory effect on the reversible hydrogen absorption process. the pressure affects the rate of hydrogen production from
Therefore, the generation of Li2B12H12 is usually suppressed by NaBH4/Co composites. The findings demonstrated that the
increasing the pressure (2 MPa), which can improve the solid-state NaBH4/Co composite’s hydrogen production rate
hydrogen storage performance of the system. In addition, to increased as the pressing pressure increased (Figure 2d). They
improve the hydrogen storage and release performance of the attribute this to the high pressure that causes the formation of a
2LiBH4−MgH2 system, some scholars have proposed nanoscale cobalt boride catalyst between NaBH4 and CoCl2, which
LiBH4 or MgH2, but the improvement is not obvious. Therefore, facilitates the reaction and thus increases the hydrogen
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Energy Fuels 2023, 37, 11584−11607
Energy & Fuels
Figure 3. (A) Hydrogen release of pure HB at (a) 65 °C, (b) 100 °C, (c) 140 °C, and (d) 150 °C. (B) Hydrogen release of HB/LiH at (a) 100 °C, (b)
130 °C, and (c) 150 °C. The horizontal line at 14.8 wt % (d) shows the theoretical amount of H2 that can be released from HB/LiH. Reproduced with
permission from ref 27. Copyright 2009, American Chemical Society.
production rate. This was successfully eliminated by preparing
the CoxB−Cl catalyst by reducing CoCl2 in NaBH4 solution, but
at this point the hydrogen production rate was reduced by a
factor of 2 (Figure 2e). The decreased activity of the CoxB−Cl
catalyst is caused by the air oxidizing its active component to
generate Co(OH)2; therefore, the use of the CoxB−Cl catalyst
in solid NaBH4/Co composites is not suitable.
Another kind is HB (N2H4BH3, 4H+, 3H−), which has a
hydrogen content of 15.4 wt % and is also an excellent hydrogen
storage material. During the experiments, it was found that the
hydrogen release rate of HB was slow; for this reason, Hugle et
al.27 proposed to improve the hydrogen release rate of HB by
mixing LiH and HB equimolarly 1:1. They obtained the HB/
LiH mixture (4H+,4H−) after mixing with a theoretical
hydrogen storage capacity of 14.8 wt %. After that, the hydrogen
release behaviors of HB and HB/LiH mixtures were investigated
at different temperatures, and the results showed that HB had a
theoretical hydrogen content of 15.4 wt % but released 6.5 wt %
of hydrogen in the experiment at 140 °C, while the HB/LiH
mixture had a theoretical hydrogen content of 14.8 wt % and
released 11.9 wt % of hydrogen in the experiment at 150 °C.
Figure 3A shows the hydrogen release for pure HB at various
temperatures, whereas Figure 3B shows the hydrogen release for
the HB/LiH composite at various temperatures. It can be seen
that the hydrogen release from the HB/LiH composite is better
than that from pure HB.
Nanomodulation exploits the size effect of nanostructures to
improve the hydrogen storage and release properties of
borohydrides.23,32 The specific operation is when the borohy-
drides are loaded in a suitable manner onto a porous carrier,33
which may be porous carbon, carbon nanotubes, mesoscopic
molecular sieves, etc. Nanosizing borohydrides allows for
shorter hydrogen diffusion paths, increases hydrogen uptake/
release reaction surfaces and specific surface areas, and provides
more hydrogen diffusion channels and active reaction sites.
Nanomodulation improves hydrogen storage properties
through the following mechanisms: interaction between nano-
particles (NPs) and nanoporous carrier surfaces,30 which
reduces the stability of NPs and facilitates their hydrogen
separation. The nanoconfinement domain allows the NPs to
grow in a defined framework, where the growth of the material is
inhibited and agglomeration is avoided, maintaining a stable
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nanostructure even after many cycles of hydrogen absorption/
exhaustion. Meanwhile, nanolimited domains reduce the
generation of intermediates with high thermodynamic stability
during cyclic hydrogen absorption/release. In addition, a carrier
with high thermal conductivity accelerates the heat transfer
properties during hydrogen absorption/release, thus improving
the hydrogen absorption/release performance of the material.
Shao et al.34 prepared nanoLiBH4@MC-NbF5 by mixing
LiBH4 with mesoporous carbon (MC) containing NbF5 NPs as
a basis to investigate the effect of synergistic interaction between
LiBH4 and Nb-based catalysis on the reversible hydrogen
storage performance of LiBH4. The experimental results showed
that the improvement of nano-LiBH4@MC-NbF5 was signifi-
cant compared to that of bulk LiBH4. The bulk LiBH4 starts
releasing hydrogen at 375 °C, while the LiBH4@MC-NbF5
nanocomposite starts releasing hydrogen at 150 °C, which is the
lowest hydrogen release temperature among the four materials.
Surprisingly, at 200 °C, there is no obvious desorption signal of
LiBH4 in the bulk (Figure 4a). Ball milling LiBH4−NbF5
releases a small amount of H2 (Figure 4b). LiBH4@MC releases
0.99 wt % H2 (Figure 4c), while LiBH4@MC-NbF5 releases
about 6.52 wt % H2 (Figure 4d). The above experiments
demonstrate that the synergistic effect can obviously improve
the borohydrides hydrogen absorption/release performance,
which has the possibility to be an important solution for
improving the performance of complex borohydrides.
Yang et al.35 successfully prepared Mg(BH4)2·6NH3@AC
nanocomposites using activated carbon and Mg(BH4)2·6NH3
by wet impregnation and a subsequent in situ ammonification
process (Figure 5a). The experimental findings demonstrated
that the dehydrogenation thermodynamics of Mg(BH4)2·
6NH3@AC composites were greatly improved by reducing the
weight ratio of Mg(BH4)2 and AC, and the dehydrogenation
temperature was also decreased. It can be observed that the
initial dehydrogenation temperature of all five composites is
lower than that of Mg(BH4)2·6NH3 (Figure 5d). Furthermore,
in the analysis of the high-speed spectrograms of the complete
decomposition of the Mg(BH4)2·6NH3@AC composites, for B
1s, 192.0 eV was considered as the BN compound signal, while
190.7 eV was considered as the new B-containing compound
signal (Figure 5b). In analysis of the spectrogram of N 1s, they
found amorphous BN at 398.5 eV and new nitrogen-containing
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Figure 4. (a) DSC-MS profiles of bulk LiBH4, (b) DSC-MS profiles of
LiBH4−NbF5, (c) DSC-MS profiles of LiBH4@MC, and (d) DSC-MS
profiles of LiBH4@MC-NbF5. DSC profiles and MS spectra (m/z = 2)
are shown as black and blue curves, respectively. Reproduced with
permission from ref 34. Copyright 2014, American Chemical Society.
compounds at 399.4 eV (Figure 5c). Combined with the analysis
of B 1s spectra, they suggested that new Mg−B−N compounds
might be formed after the decomposition of Mg(BH4)2·6NH3@
AC.
In exception to the light metal borohydrides mentioned
above, AB and HB are also widely used for solid hydrogen
storage.36−38 The former AB is a molecular crystal with one
molecule having one N−B coordination bond, three N−H
covalent bonds, and three B−H covalent bonds.39 For AB
(NH3BH3, 3H+, 3H−), it has a high hydrogen content of 19.6 wt
%, is nontoxic, and is highly stable under environmental
conditions.40,41
Nanosizing the AB can improve its hydrogen storage capacity.
To this end, Valero-Pedraza et al.42 added alkaline water
containing AB dropwise to cetyltrimethylammonium bromide
(CTAB, surfactant) and added the obtained aqueous AB and
CTAB solution dropwise to dodecane C12H26 (Figure 6a) and
successfully prepared two different diameter sizes of AB
nanospheres depending on the molar ratio AB/CTAB (Figure
6b). It is noteworthy that some mass loss was avoided because
no scaffold was used in the preparation process, and AB did not
undergo a hydrolysis reaction under alkaline conditions. No
signal generation was observed for δ ≥ 0 in BNMR experiments
under alkaline conditions (Figure 6c and d), which confirmed
the stable presence of AB and facilitated the preparation of AB
nanospheres. The experiments performed on the prepared AB
nanospheres showed better dehydrogenation properties.
Above all, the cyclic hydrogen storage and hydrogen release
properties of borohydrides still have great technical obstacles at
the present stage. For example, thermodynamic stability and
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reversibility or regenerative ability is currently the biggest
bottleneck of scale application.43,44 For the stability regulation of
borohydrides, it is difficult to achieve the expected effect only by
the composite system and nanomodulation, and the synergy
between several methods (nanomodulation, composite system,
ion replacement, and doping modification) is advantageous for
the stability regulation of borohydrides. But for the reversibility
of borohydrides, through the development of efficient catalysts,
the hydrogen-releasing property of metallic borohydrides and
nonmetallic borohydrides has reached an acceptable level, as the
2LiBH4−MgH2 system, but the regeneration of hydrogen-
releasing byproducts has not been fundamentally broken. The
main performance is that the regeneration procedure is
complicated, and the regeneration reaction efficiency is low,
which cannot be applied on a large scale due to high cost and
harsh reaction conditions.
2.2. Hydrogen Production via Hydrolysis, Alcoholysis,
and Themolysis. Hydrogen can be produced from borohy-
drides via the method of hydrolysis, alcoholysis and pyrolysis.
Hydrolysis occurs mainly through the reaction of borohydrides
with water to release hydrogen, with a relatively slow reaction
rate, it usually requiring a catalyst and produce a large number of
reaction byproducts. Hydrogen production by alcoholysis
mainly occurs through the reaction of borohydrides with
alcohol solutions (CH3OH, CH3CH2OH, etc.), which usually
also requires a catalyst, and a controlled hydrogen production
reaction can be achieved under suitable pH conditions and an
appropriate catalyst. Hydrogen production by pyrolysis, which
mainly involves the thermal decomposition of borohydrides
under heating conditions, it also produces impurity gases and
leads to impure hydrogen. Compared with borohydride
pyrolysis requires specific temperature conditions, the hydrol-
ysis and alcoholysis reaction can be carried out under mild
temperature conditions, which have attracted more attention
from researchers.
2.2.1. Application of Borohydrides Hydrolysis for Hydrogen
Production. Borohydrides hydrolysis is mainly through the
reaction of borohydrides with H2O to produce hydrogen gas.
The reaction process has to break through the energy barrier,
which belongs to irreversible reaction. The hydrogen production
materials mainly include coordination hydride and AB.45,46 For
example, NaBH4 has the superior properties of a high theoretical
amount of hydrogen storage (10.8 wt %), good stability in
alkaline solution and being nontoxic.47 Under the action of a
catalyst, NaBH4 hydrolysis can occur at room temperature to
produce high purity hydrogen.48 The hydrolysis of NaBH4 to
produce hydrogen follows the procedure described in eq 7.
However, the actual hydrogen production efficiency is not high
because of its low solubility in water, about 0.15 g·g−1. In the
NaBH4 hydrolysis reaction, NaBH4 is only partially soluble in
the solution, which leads to the hydrogen production efficiency
being too low to meet the demand of industrial applications.49
NaBH4 + (2 + x)H 2O
catalyst,ambient conditions
NaBO2 ·x H 2O + 4H 2 (7)
The key to improving the industrial application of hydrogen
storage materials is improving the efficiency of hydrogen release
and regeneration. For the NaHB4, it is important to improve the
hydrolysis efficiency and byproducts’ (NaBO2·4H2O or NaBO2·
2H2O) regeneration of NaBH4 in future research. The
development of accelerators is the most effective way to
improve the efficiency of the hydrolytic hydrogen production of
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Figure 5. (a) Preparation process of Mg(BH4)2·6NH3@AC. (b) 0.2:1 Mg(BH4)2·6NH3@AC nanocomposites fully decomposed B 1s high-resolution
spectra. (c) 0.2:1 Mg(BH4)2·6NH3@AC nanocomposites fully decomposed N 1s high-resolution spectra. (d) TPD-MS profiles of bulk Mg(BH4)2·
6NH3 and prepared Mg(BH4)2·6NH3@AC nanocomposites. Reproduced with permission from ref 35. Copyright 2015, Royal Society of Chemistry.

NaBH4. Currently known effective accelerators are acids (HCl,
CH3COOH, etc.) and metals (Pt, Ru, Ni, Cu).50 Among them,
metal catalysts have high catalytic activity, chemical stability and
controllability and have become the focus of future research.
Li et al.,51 through ethylenediamine tetra-acetic acid (EDTA)
derivatives of carbide with a core−shell structure, synthesized
nitrogen doped MC graphite encapsulated cobalt NPs (Co@
NMGC; Figure 7a) and used them to catalyze the NaBH4
hydrolysis reaction. The experimental results show that the
cobalt-based complex catalyst has the best catalytic activity at
500 °C. Its maximum hydrogen production rate is about 3 times
that of the pure cobalt catalyst, and the former catalytic effect is
significantly better. According to the Arrhenius formula, the
activation energy of the Co@NMGC catalyst is 35.2 kJ·mol−1,
which is lower than that of most catalysts (see Table 2). High
activity, stability, and low cost are the characteristics of an
excellent catalyst.
The stability of the catalyst is important for catalytic reaction.
Figure 7b shows the hydrogen production rate of the Co@
NMGC catalyst during 20 cycles of catalysis. It can be seen that
the hydrogen production rate decreases, possibly due to the
reduction of active sites caused by the byproducts adhering to
the catalyst particle surface, or possibly the active material on the
catalyst surface is oxygenated but still maintains 83% of the
initial activity. This is higher than the Co−Ce−B/Chi-C
catalyst52 (80% initial activity maintained after 10 cycles, Figure
7c) and the Co−Fe3O4−CNT catalyst53 (67% initial activity
maintained after eight cycles, Figure 7d). Low-cost catalysts are
important for hydrogen production through hydrolysis.
Compared with noble metal catalysts such as the Ru/ZIF-67
catalyst54 and Pd(0)/GO-ILCS catalyst,55 the cost of Co@
11589
NMGC catalysts is very low, and the activation energy difference
between the three in the reaction is not significant. Low-cost,
high-activity catalysts tend to attract more attention.
Although the research on the hydrolysis of sodium
borohydride has made great progress, the high cost of synthesis
leads to limitations of its application. Therefore, the low-cost
synthesis of sodium borohydride has become a key issue.
Sodium borohydride is synthesized by the following methods:
industrial synthesis, direct reduction, high-energy ball milling,
and electrochemical reduction. Among them, the high-energy
ball milling method is a one-step regeneration of NaBH4 from
NaBO2·xH2O (hydrolysis byproduct), which is widely used with
the advantages of a simple process, low cost, and mild reaction
conditions.
Zhong et al.61 synthesized NaBH4 from Mg2Si and NaBO2·
2H2O using a high-energy ball milling method at 1000 r/min
under an argon atmosphere. Then, the effect of different molar
ratios (Mg2Si/NaBO2·2H2O, ball milling for 20 h) on the
product yields was investigated. It was found that at a molar ratio
of 3:1, the product yield reached as high as 78%. Qin et al.62
successfully regenerated NaBH4 using a high-energy ball milling
method using magnesium alloy (Mg17Al12) and hydrolysis
byproducts NaBO2·2H2O and NaH as raw materials. NaH can
accelerate the reaction and increase the NaBH4 production rate.
In their ball milling experiments, they found that the yield was
only 23% when no NaH was added; 30% when 1 wt % was
added; 51% when 5 wt % was added; and 57% when 10 wt % was
added, and the addition of NaH obviously promoted the
reaction. Moreover, in the experiments, the formation of
MgAl2O4 was observed when 5 or 10 wt % NaH was added
(Figure 8b and c), but this phenomenon was not observed when
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Figure 6. (a) Schematized process for nanosizing AB at room temperature. The first step (i) is the dropwise addition of an aqueous alkaline solution of
AB into the CTAB aqueous solution. The second step (ii) is the dropwise addition of the as-obtained aqueous solution of AB and CTAB into
dodecane. (b) Two specimens, 1 and 2, were prepared according to the molar ratio of AB/CTAB. (c) B NMR image of liquid phase specimen 1. (d) B
NMR image of liquid phase specimen 2. Reproduced with permission from ref 42. Copyright 2019, American Chemical Society.

Figure 7. (a) Schematic diagram of Co@NMGC catalyst preparation. (b) Hydrogen generation rate versus a number of cycles for Co@NMGC
catalyst after 20 cycle tests. (c) Hydrogen production rate versus the number of cycles for the Co−Ce−B/Chi-C catalyst after 10 cycle tests. (d)
Hydrogen production rate versus the number of cycles for Co−Fe3O4−CNT catalyst after eight cycle tests. Panels a and b reproduced with permission
from ref 51. Copyright 2020, Elsevier. Panel c reproduced with permission from ref 52. Copyright 2018, Elsevier. Panel d reproduced with permission
from ref 53. Copyright 2017, Elsevier.

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Table 2. Comparison of Activation Energies (Ea) for NaBH4 NaBO2·xH2O solution reacted with CO2 and was dried, and the
Hydrolysis Using Various Catalystsa product was collected. The reaction products Na2B4O7·xH2O
and Na2CO3 were mixed with Mg, and NaBH4 was obtained
catalyst sample Ea (kJ·mol−1) ref
after ball milling in a yield of 78.9%. H− in NaBH4 is converted
Co3O4 macrocubes 48 56 from H+ in ligand water.65 The reaction mechanism was
Co−Fe3O4−CNT 42.79 53 investigated using XRD and FTIR, as shown in Figure 9C and D,
NiCo2O4 hollow 52.2 57 respectively. Observing Figure 9C, the diffraction of Na2B4O7·
furrow-like Co−Ni−B 42.8 58 5H2O was enhanced after 10 min of ball milling, and only MgO
Co−Ce−B/Chi-C 33.1 52 was observed at 30 min. The diffraction of NaBH4 was not
Co−P/CNTs-Ni foam 49.94 59 obvious at 5 h. Na 2 B 4 O 7 ·10H 2 O can be regarded as
Ru/ZIF-67 36.4 54 Na 2 B 4 O 5 (OH) 4 ·8H 2 O. 66 The BO3 3− and BO4 5− in
CoB/ZIF-8 57.72 60 [B4O5(OH)4]2− and the CO32− absorption bands in Na2CO3
Pd(0)/GO-ILCS 38 55 are observed to get weaker until they disappear completely in
Co@NMGC 35.2 51 Figure 9D, while the B−H absorption bands in NaBH4 are
a
Adapted with permission from ref 51. Copyright 2020, Elsevier. getting stronger. Therefore, the regeneration mechanism can be
expressed as in eqs 12−16. Equation 17 is the total reaction.
1 wt % was added (Figure 8a), probably due to the weak Na 2B4O7 ·10H 2O Na 2B4O7 ·5H 2O + 5H 2O (12)
promotion effect of low NaH concentration.
Ouyang et al.63 mixed Mg with NaBO2·2H2O (molar ratio 2H 2O + Mg Mg(OH)2 + H 2 (13)
5:1) and ball-milled it for 15 h at a BPR of 50:1. XRD
characterization of the products suggests that reaction 7 should
occur (NaBH4 and MgO are generated), but this is not rigorous. Mg + Mg(OH)2 2MgO + H 2 (14)
To investigate the reaction mechanism of NaBH4 regeneration,
XRD and Fourier Transform Infrared Spectroscopy (FTIR) H 2 + Mg MgH2 (15)
were used to characterize the substances during the experiment,
as shown in Figure 9A and B, respectively. As shown in Figure Na 2B4O7 ·5H 2O + Na 2CO3 + 15MgH2
9A, only Mg and NaB(OH)4 diffraction peaks can be seen at 10
min ball milling. A large amount of Mg(OH)2 is generated at 1 h, 4NaBH4 + 15MgO + CH4 + 10H 2 (16)
and a large amount of Mg is decreased. Only MgO and NaBH4
diffraction peaks can be seen at 10 h. Observing Figure 9B, the Na 2B4O7 ·10H 2O + Na 2CO3 + 20Mg
B−O and B−O−H in NaB(OH)4 become weaker until they 4NaBH4 + 20MgO + CH4 (17)
disappear completely, while the B−H in NaBH4 is vibrating. In
the experiment, NaBO2·2H2O is equivalent to NaB(OH)4. For another common nonmetallic borohydride, NH3BH3,
Thus, the regeneration mechanism can be considered as the there are three main ways of dehydrogenation of AB, namely
process of progressive substitution of the OH− group in pyrolysis and hydrolysis and alcoholysis. Among them, the
NaB(OH)4 by the H− ligand of intermediate product MgH2. pyrolysis method is not suitable because of its slower kinetics of
The relevant responses are as follows; eq 11 is the total reaction. hydrogen release, and it also requires a higher reaction
2MgH2 + NaB(OH)4 2Mg(OH)2 + NaBH4 temperature. Both hydrolysis and alcoholysis can release large
(8) amounts of hydrogen under modest conditions. The alcoholysis
method usually requires the addition of methanol as fuel, which
2Mg(OH)2 + 2Mg 4MgO + 2H 2 (9) is more costly and therefore also less suitable for large-scale
2H 2 + 2Mg 2MgH2 applications. Hydrolysis is usually catalyzed by catalysts to
(10) release hydrogen rapidly, and some nonprecious metal catalysts
NaBO2 ·2H 2O + 4Mg NaBH4 + 4MgO are less costly and more stable. Therefore, hydrogen production
(11)
by hydrolysis under nonprecious metal catalysts should be the
In order to reduce the reaction cost, a new method to focus of future development. AB hydrolysis usually follows
regenerate NaBH4 was proposed by Zhu et al.64 First, the reaction 18.

Figure 8. XRD patterns of the products from ball milling Mg17Al12 and NaBO2·2H2O and adding (a) 1 wt % NaH, (b) 5 wt % NaH, and (c) 10 wt %
NaH after different reaction times. Reproduced with permission from ref 61. Copyright 2019, Elsevier.

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Figure 9. (A) XRD patterns of products after ball milling Mg and NaBO2·2H2O mixtures for different durations. (B) FTIR spectra of (a) raw NaBO2·
2H2O; products after ball milling Mg and NaBO2·2H2O and mixtures for different durations. (C) XRD patterns and (D) FTIR spectra of commercial
Na2B4O7·10H2O and products obtained after ball-milling Mg, Na2B4O7·10H2O, and Na2CO3 mixtures at 1200 CPM for different durations. Panels A
and B reproduced from ref 63. Copyright 2017, John Wiley and Sons. Panels C and D reproduced from ref 64. Copyright 2020, John Wiley and Sons.

catalyst researchers68,69 show that the mechanism of AB hydrolysis is

NH3BH3 + 2H 2O NH+4 + BO2 + 3H 2 (18)
Zhou et al.67 applied nanoporous ruthenium (NP-Ru)
catalysts to the hydrogen production by hydrolysis of AB.
They prepared Ru20Al80 alloy by melting Ru and Al in a furnace
under the protection of argon gas. Then, NP-Ru was prepared
under a temperature of 50 °C and selective etching of HCl. The
catalytic effect of NP-Ru on AB hydrolysis was investigated at
different reaction temperatures, and it was found that the
catalytic effect increased with increasing temperature (Figure
10a). The activation energy of related reactions was also
calculated (Figure 10b). The k is the rate constant and is taken
from the straight part of the curve in Figure 10a. After that, the
image (Figure 10b) was made according to the relationship
between ln k and 1/T at different reaction temperatures, and the
slope of the image was marked as M, which was calculated as M =
−7998k. According to the Arrhenius formula, Ea was calculated:
Ea = 66.5 kJ·mol−1. Comparison was made of the activation
energies of AB hydrolysis catalyzed by different Ru-containing
catalysts at room temperature (see Table 3). The stability of NP-
Ru was also studied, and it was found that 67% of its initial
catalytic activity was retained after five experiments (Figure
10c). SEM image analysis of the postexperimental NP-Ru
showed that the ligaments connecting adjacent holes thickened
but did not aggregate, which contributed to the stabilization of
the nanostructures. In addition, they found that the catalyst
concentration was related to the reaction rate as a first-order
reaction. In conclusion, the current studies by some
11592
still unclear and needs to be studied; the catalytic mechanism of
the catalyst is not yet generally accepted. In addition, a series of
problems such as the high cost of AB synthesis, the development
of nonprecious metal catalysts, and the recovery and purification
of hydrogen gas need to be solved.
Furthermore, the catalytic performance of different catalysts is
compared, and the influence factors are analyzed. Comparing
them with Ru@MWCNT70 (Ru loaded with multiwalled carbon
nanotubes), Ru@Al2O371 (Ru nanoparticles loaded with
Al2O3), and Ru/graphene NPs72 (Ru nanoparticles loaded
with graphene) catalysts, it can be seen that the higher catalytic
turnover frequency (TOF) and higher activation energy of
carbon carriers can be attributed to their domain-limited effect
on metal nanoparticles, which can effectively limit the
agglomerative growth of metal particles. Comparing them with
Ru@SiO273 (Ru nanoparticles loaded on SiO2), RuNi/TiO2
P2574 (RuNi bimetallic nanoparticles loaded on TiO2), RuNi/
Ti3C2X275 (RuNi bimetallic nanoparticles loaded on Ti3C2X2, X
= OH and/or F), and Pt-CoCu@SiO276 (Pt-decorated CoCu
bimetallic nanoparticles loaded on SiO2) catalysts, it can be seen
that the synergistic effect of multimetals will improve the
catalytic activity; the large specific surface area of the carriers
facilitates the exposure of more active centers, which will also
improve the catalytic activity. The high price of precious metals
is a big problem, and enhanced atomic utilization of precious
metals or the development of low-content-precious−nonpre-
cious metal catalysts may be a solution.
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Figure 10. (a) The plot of moles of H2 per mole of AB versus time in the catalytic hydrolysis in the presence of NP-Ru at various temperatures. (b) Plot
of ln k versus 1/T in a log−log scale, Ea = 66.5 kJ·mol−1. (c) The plot of moles of H2 per mole of AB versus time toward catalytic dehydrogenation of AB
in the presence of NP-Ru. (d) Plots of moles of H2/moles of N2H4BH3 versus time for the catalytic hydrolysis of HB using RhCl3, Rh/Al2O3,
Rh(0)NPs@FAU, RuCl3, Ru/Al2O3, and Ru(0)NPs@FAU as catalysts at room temperature. Panels a, b, and c reproduced with permission from ref
67. Copyright 2016, Elsevier. Panel d reproduced with permission from ref 78. Copyright 2011, Elsevier.

Table 3. Comparison of the Catalytic AB Hydrolysis Activity conducive to the purification of H2 and should be avoided as
of Different Metal Catalysts at Room Temperature much as possible. Currently, rhodium-based catalysts are more
effective in catalyzing hydrogen production from HB hydrolysis.
catalyst sample TOF (min−1) Ea (kJ·mol−1) ref
To this end, Karahan et al.78 first reported the hydrolysis of HB
Ru@MWCNT 329 33 ± 2 70 catalyzed by a metal catalyst at room temperature. They
Ru@Al2O3 39.6 48 71 experimented with different catalysts, and the results showed
Ru/graphene NPs 100 11.7 72 that rhodium(III) chloride had the highest catalytic activity in
RuNi/TiO2 P25 914 28.1 74 the reaction. The amount of H2 gas produced by hydrolyzing HB
RuNi/Ti3C2X2 824.7 25.7 75 under different catalysts is shown in Figure 10d. When the
Pt-CoCu@SiO2 272.8 51.01 76 solution contains rhodium(III) chloride, the reaction occurs
Ru@SiO2 200 38.2 73 completely regardless of how the solution is mixed with solid
NP-Ru 26.7 66.5 67 HB. This catalytic approach has some potential for applications
such as small, portable fuel cells. Although the above methods
are amazing, rhodium-based catalysts are expensive due to their
For HB, a white solid that is stable in argon at room high precious metal content. Therefore, a balance of high
temperature and has a hydrogen content of up to 15.4 wt %, it is selectivity, high activity, and low cost has become the
a relatively excellent hydrogen carrier material.77 The selective development direction for HB hydrolysis catalysts.79
and fast catalytic dehydrogenation of HB is the key to its 2.2.2. Application of Borohydrides Alcoholysis for Hydro-
application in hydrogen production, so the preparation of a fast gen Production. In addition to hydrogen production by
and selective catalyst has become the key. There are three main hydrolysis, hydrogen production by alcoholysis was also
reactions in the hydrolysis of HB, and the reaction formula is as discussed. The alcoholysis method has the following advan-
follows: tages.80,81 The relatively few reaction steps allow for better
N2H4BH3(S) + 3H 2O N2H4 + H3BO3 + 3H 2(g) control of the reaction rate, and the solute can even be
regenerated, allowing the reaction to proceed in cycles. For
(19)
example, the reaction equation for the alcoholysis of NaBH4 and
N2H4 N2(g) + 2H 2(g) (20) its regeneration is as follows:
catalyst
3N2H4 4NH3(g) + N2(g) (21) NaBH4 + 4CH3OH NaB(OCH3)4 + 4H 2 (22)
According to the above three formulas, in order to maximize NaB(OCH3)4 + 4NaH NaBH4 + 4NaOCH3 (23)
the preparation of hydrogen, we should select a suitable catalyst
to perform the hydrolysis of the BH3 group (see eq 19) stored in The effects of solvent amount, substrate concentration,
N2H4BH3 and the selective breakdown of the N2H4 group (see temperature, and catalyst on the reaction of NaBH4 and
eq 20). Reaction 21 will produce impurity gas NH3, which is not CH3OH were investigated experimentally by Ramya et al.82 The
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Figure 11. (a) Effect of solvent dosage on the amount of hydrogen production. (b) Effect of substrate concentration on the amount of hydrogen
produced. (c) Effect of catalyst type on the amount of hydrogen produced. Reproduced with permission from ref 82. Copyright 2013, John Wiley and
Sons.

Figure 12. (a) Flowchart of the reaction of AB and methanol to produce hydrogen and the regeneration of AB using alcoholysis byproducts. (b)
Turnover frequency of rhodium(0) NPs supported on the surface of oxide nanopowders for the evolution of H2 gas from the methanolysis of AB at 25
°C. Reproduced with permission from ref 84. Copyright 2019, Elsevier.

experimental results showed that the reaction rate was catalyst

independent of the addition of solvent (Figure 11a); the
reaction rate was proportional to the concentration of the
substrate (Figure 11b), which was a primary reaction. The
reaction rate could be accelerated by increasing the temperature,
and the reaction rate would be further increased by the
exothermic alcoholysis reaction. In addition, when studying the
effect of catalyst on the reaction rate, it can be found that
different catalysts affect the reaction rate differently, among
which NiCl2, Ni2B, and RuCl3 can promote the reaction very
rapidly (Figure 11c). In conclusion, the reaction rate is affected
by various factors, among which the substrate concentration and
reaction temperature are relatively well controlled, but the
selection of a suitable catalyst is a very difficult issue, which is
also a difficult problem limiting the hydrogen production by
alcoholysis.
AB alcoholysis at an appreciable rate only in the presence of an
effective catalyst releasing 3.0 equiv of H2 per mole of AB at
ambient temperature, as shown in eq 24.83 AB and methanol are
mixed and reacted under a suitable catalyst to produce hydrogen
(Figure 12a), and the byproduct is used to regenerate AB (see eq
25).
11594
NH3BH3 + 4CH3OH NH4B(OCH3)4 + 3H 2
(24)
NH4B(OCH3)4 + LiAlH4 + NH4Cl
THF,0°C to RT,3 8 h
NH3BH3 + LiAl(OCH3)4 + NH3
+ H 2 + HCl
(25)
The selection of suitable catalysts is of great importance for
AB alcoholysis. Ö zkar84 conducted a study on metal catalyst-
catalyzed hydrogen production from AB methanol. They loaded
metal NPs onto oxide nanopowders as a way to improve their
catalytic activity and lifetime and thus prepared four composite
catalysts. In the AB alcoholysis experiments, the four catalysts
showed different catalytic activities, with Rh(0)/nanoAl2O3
having the highest TOF of over 200 min−1, followed by
Rh(0)/nanoSiO2 at about 160 min−1, and the remaining two
catalysts having approximately the same activity of about 150
min−1 (Figure 12b). In addition, if bimetallic nanoparticle
catalysts are prepared using synergistic effects, an overall
increase in catalytic activity may be achieved, and the economic
benefits may be further enhanced if nonprecious metals are
included.
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Figure 13. SEM images of various SiO2 catalysts and AB-SiO2 composites before and after thermolysis. Reproduced with permission from ref 85.
Copyright 2020, Elsevier.

2.2.3. Application of Borohydrides Pyrolysis in Hydrogen

Production. The following describes the application of
borohydride pyrolysis for hydrogen production and the
challenges it has to face. Shin et al.85 investigated the thermal
dehydrogenation process of AB. They prepared AB-SiO2
nanocomposites via a mixing and pressing process, in which
SiO2 plays a catalytic role. They classified AB-SiO2 into four
categories according to the size of the SiO2 diameter, and their
SEM images before and after thermal cracking are shown in
Figure 13. It can be seen that the range of 5−15 nm shows a
blocky structure, while 12 nm, 20−30 nm, and 60−70 nm show
a cotton-like structure. The postexperimental images show that,
in the AB-SiO2 composite, the AB thermal decomposition
disappears, leaving only the cotton-like structure of the SiO2
catalyst. In addition, their study showed that for AB-SiO2 (85 wt
% AB, SiO2 size of 12 nm) composites, the reaction can be
completed in 1 min at 85 °C to produce 11.2 wt % H2. The above
experiments suggest that nanosized AB loaded on a carrier and Figure 14. Thermal decomposition of HB followed by in situ XRD (λ =
then pyrolyzed to produce hydrogen may be a feasible approach. 0.69405 Å). Reproduced with permission from ref 86. Copyright 2016,
Moury et al.86 investigated the thermal decomposition Elsevier.
process of HB by in situ XRD, as shown in Figure 14. As can
be seen from the graph, HB crystals melt slowly at 37 °C, melt
rapidly at 37−44 °C, melt completely in liquid phase above 44 detected NH3. It is worth noting that the former N2H4 is a toxic
°C, start to decompose at 65 °C, reach a maximum at 71 °C, and and explosive compound, while the latter NH3 is harmful to
then start to decline and become constant at 174 °C. Other gases humans. Some researchers89 also nanosized HB to inhibit the
are produced by the pyrolysis of HB, and to determine the generation of N2H4 and NH3 during its pyrolysis dehydrogen-
composition of these gases, they are dissolved in toluene after ation. The experimental results were not ideal, and N2H4 and
the reaction, and the solution is analyzed by H NMR. Although NH3 were still generated in large quantities. Therefore, the
the characteristic signals of NH3 and N2H4 overlap, Hannauer et pyrolysis of HB for hydrogen production has certain dangers,
al.87 detected the evolution of N2H4 in them, while Mebs et al.88 which limit its large-scale application.
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Figure 15. UV−vis spectra for Ru@rGO catalyzed reduction of aqueous in the presence of (a) AB, (b) MeAB, and (c) DMAB. Reproduced with
permission from ref 93. Copyright 2020, John Wiley and Sons.

In short, in the application of hydrogen production by DMAB, respectively. The final experimental results showed that
borohydrides hydrolysis, a breakthrough has been made in the AB reduction was the fastest (Figure 15a), MeAB was the second
development of high-efficiency catalysts to achieve low-cost and fastest (Figure 15b), and DMAB was the slowest (Figure 15c),
controllable hydrogen production, and the current research which was consistent with the amount of H2 produced by their
focus is on the reversible regeneration of byproducts. In the hydrolysis catalyzed by Ru@rGO. This shows that our
study of hydrogen production by alcoholysis, different temper- speculation is correct. In addition, they found that when AB
atures, substrate concentrations and catalyst types can influence was used as the reducing agent, the initial turnover frequency of
the reaction effect. Influenced by realistic conditions, the this reaction system was 7.6 mol Cr2O72−/mol Ru·min, which
selection of a suitable catalyst for the reaction purpose has was higher than most of the reaction systems, and Ru@rGO was
become the mainstream approach. Therefore, the preparation of also stable in the reaction, maintaining 80% of its initial activity
highly selective and active catalysts has become a hot research at a conversion of 90% at the fifth reuse.
topic. In the study of hydrogen production from borohydrides AB can be used as a reducing agent to prepare catalysts. Yang
pyrolysis, there is a big problem to be faced: the purity of H2 and et al.94 synthesized dispersed, magnetically recoverable CoNi/
unwanted byproducts, such as borazine. Therefore, borohy- RGO catalysts by reducing aqueous solutions of cobalt(II)
drides pyrolysis for hydrogen production is not desirable, and chloride, nickel(II) chloride, and graphite oxide at room
there are still some challenges to be solved. temperature in which AB acted as a reducing agent. The
2.3. Application of Reducing Agents and Rocket Fuels. CoNi/RGO catalyst can also be applied to the hydrolysis of AB
2.3.1. Application of Borohydrides in Reducing Agent Field. and showed excellent catalytic activity. It can be seen from Table
Borohydrides not only are used as a hydrogen storage material to 4 that the activity of the CoNi/RGO catalyst is better than that
produce hydrogen but also have applications in other fields. One of monometallic catalysts such as Ru/γ-Al2O3, Pd/RGO, Ni/γ-
of the uses is as a reducing agent,90,91 which can reduce high- Al2O3, and Co/γ-Al2O3, which may be due to the effect of
valent cations to low-valent cations under mild conditions and bimetallic synergistic catalysis. Meanwhile, the activity of CoNi/
can also be used to make catalysts. In the following, we will RGO catalysts is higher than those of Ag@Ni/graphene and
describe the application of borohydrides in terms of their Co0.32Pt0.68/C catalysts but lower than those of Ag@Co/
reducing properties. Cr(VI) is a harmful substance for
humans,92 while Cr(III) is an essential trace element for Table 4. Catalytic Activities of Different Catalysts Used for
humans. Yurderi et al.93 successfully prepared graphene oxide the Hydrolytic Dehydrogenation of ABa
(Ru@rGO) loaded with ruthenium NPs as a catalyst for the first
time by a two-solvent wet chemical reduction method. After TOF (mol H2·mol catalyst−1· Ea
catalyst min−1) (kJ·mol−1) ref
that, they chose three reducing agents (NH3BH3, CH3NH2BH3
(MeAB), and (CH3)2NHBH3 (DMAB)) to reduce Cr(VI) to Ru/γ-Al2O3 23.05 67 95
Cr(III) under the reduction of reducing agents and catalysis by Ag@CoNi/ 15.89 47 96
graphene
Ru@rGO, and the relevant reaction equations are as follows: Au@Co 13.64 97
H3NBH3 + 2H 2O NH4BO2 + 3H 2 (26) Co0.32Pt0.68/C 10.99 41.5 98
Ag@Co/graphene 10.24 20.03 99
CH3NH 2BH3 + 2H 2O CH3NH3BO2 + 3H 2 (27) Cu@Co/graphene 8.36 51.3 100
Ag@Ni/graphene 7.7 49.56 99
(CH3)2 NHBH3 + 2H 2O (CH3)2 NH 2BO2 + 3H 2 Co0.75B0.25 7.24 40.85 101
(28) Pd/RGO 6.25 51 ± 1 102
Ag/C/Ni 5.32 38.91 103
+
Cr2O27 + 8H+ + 3H 2 2Cr 3 + 7H 2O (29) RuCo/γ-Al2O3 3.64 47 104
Ni/γ-Al2O3 2.45 105
According to the above equation, it can be seen that the Co/γ-Al2O3 2.27 62 105
reducing properties of the three reducing agents come from H2 CoNi/RGO 19.54 39.89 94
produced by their hydrolysis. Therefore, it can be speculated
a
that the more H2 produced, the more reductive the Ru@rGO Adapted with permission from ref 94. Copyright 2014, Hindawi Ltd.,
catalyst is, when it catalyzes the hydrolysis of AB, MeAB, and Adam House.

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Figure 16. (a) Test setup for atmospheric combustion test. (b) Representative image of HSF ignitor. (c) Hot fire test of H2O2/PE hybrid rocket with
HSF igniter ignition +1.1 s. (d) Hot fire test of H2O2/PE hybrid rocket with HSF igniter ignition +3.0 s. Panels a, c, and d are reproduced with
permission from ref 109. Copyright 2022, Elsevier.

Figure 17. (a) IDTs of 25 wt % AB containing paraffin wax with various additives. (b) Change in the concentration of AB vs IDT of HSFs. (c) Change
in concentration of Pd−C in HSFs vs IDT. Reproduced with permission from ref 110. Copyright 2021, Elsevier.

graphene and Ag/C/Ni catalysts, which is due to the different
compositions of the catalysts. In addition, the cycle durability of
the catalyst is also a point to be considered.
2.3.2. Application of Borohydrides in Rocket Fuel Field.
Among hybrid rocket propellants, hypergolic solid fuel (HSF)
has a great advantage because it ignites in contact with an
oxidizer without the need for additional ignition,106−108 which
simplifies the system. Finding an additive for HSF that can react
with H2O2 is crucial. Metal hydride additives, such as NaBH4,
require dehumidification and isolation from air due to their high
hygroscopicity and have unstable combustion or frequent hard
starts in the hot-fire test (HFT), whereas AB performs well in
HFT with shorter startup times. Therefore, we focus on the
recent research progress of AB in HSF; for example, the
preparation and ignition characteristics of new HSF, the
influencing factors of self-ignition ignition, the application of
high-speed multispectral techniques in self-ignition ignition, and
the study of delayed ignition characteristics of self-ignition.
For this purpose, Jeong et al.109 investigated the performance
of the new HSF during combustion by hot fire tests and
atmospheric combustion tests. The relevant experimental setups
11597
are represented by Figure 16a, c, and d. The new HSF consists of
AB and other materials, and a total of four different sizes of HSF
have been prepared, one of which is HSF-1 (Figure 16b). The
final experimental results showed that AB burned stably for a
long time at different mass flow rates of oxidant and achieved the
transition from HSF to polyethylene at a certain oxidant mass
flow rate. Thus, this new HSF can be used as a disposable self-
igniting igniter for hybrid fuel rockets or as an alternative fuel.
The study of the factors affecting spontaneous ignition of AB
is important for its use as a rocket fuel. To this end, the effect of
variation of AB and Pd−C weight percentages on the
spontaneous ignition of HSF was investigated by Jeong et
al.110 HSF consists of 25 wt % AB, 1 wt % additives (carbon
black, MnO2−C, Pt−Ru−C, and Pd−C), and 74 wt % paraffin.
The spontaneous ignition experiment was carried out by
contacting the HSF of different components with H2O2. It was
found that the ignition delay times (IDTs) decrease as the AB wt
% increases. It was also observed that different additives have
different effects on the ignition delay time, and the IDTs of Pt−
Ru−C and Pd−C additives are 2.0 and 1.2 ms (Figure 17a),
respectively. We chose the Pd−C additive considering the cost.
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Figure 18. (a) BO2, HBO2, BO, and AB emission intensity of AB particles burning in air as a function of height. (b) AB-representative image of the air
diffusion flame; the white line represents the pixels used for the intensity profile. Reproduced with permission from ref 111. Copyright 2020, Elsevier.

Figure 19. (a) Hypergolic drop test setup of ignition delay measurement. (b) High-speed camera ignition sequence images of the 40% AB-paraffin
blend. Reproduced with permission from ref 112. Copyright 2019, Elsevier.

In addition, the effect of AB wt % in HSF containing 1 wt % of
Pd−C on IDTs was investigated, and the shortest IDTs of 0.9 ms
were found for 10 wt % AB (Figure 17b). Finally, the effect of
Pd−C wt % on IDTs in HSF containing 10 wt % AB was
investigated, and it was found that the shortest IDTs were 0.9 ms
for 1 wt % Pd−C (Figure 17c). At the same time, it was noted
that when 0.5 wt % Pd−C was added, the IDTs became 1.9 ms,
which was not possible by changing the same AB wt %,
indicating that Pd−C wt % has a higher priority than AB wt %.
High-speed multispectral imaging techniques can be used to
study the spontaneous ignition of AB. Therefore, Baier et al.111
used visible and infrared multispectral imaging to study the
process of AB spontaneous ignition with WFNA acting as an
oxidant. In the experiment, they selected optical filters
corresponding to the wavelength of the spectrum to observe
the initial gas evolution and the flame propagation process.
Subsequently, the formation of HBO2 was observed prior to
ignition, which may result from the decomposition of HNO3. It
can be seen from the emission intensity curve after combustion
that HBO2 is consumed to a certain extent at the flame front, as
shown in Figure 18a, and the pixel diagram is shown in Figure
18b, which is contradictory to what is known and may indicate
that boron in AB is burned more fully.
The ignition delay characteristics of HSF were investigated by
Bhosale et al.112 A 40% AB-paraffin mixture solid fuel was
prepared using a casting method with 95% H2O2 as an oxidant,
and the experimental setup is shown in Figure 19a. A green flame
can be observed in the experiment, which is caused by the
11598
presence of elemental boron, and the ignition delay time is 9.7
ms (Figure 19b), which is closer to that of pure AB (8.1 ms).
Baier et al.113 studied the spontaneous ignition delay time of AB
(synthesized by a novel water-promoted process) with WFNA
as the oxidant. It was found that the ignition delay time was
related to the size of AB particles, and the finer the AB particles
(D < 45 μm) and the shorter the delay time, the easier it was to
ignite. Subsequently, AB particles were loaded onto Sylgard-184
to construct the novel self-igniting solid fuel Sylgard-184-AB and
tested for self-ignition delay. Experimental results show that the
average ignition delay time of Sylgard-184-AB fuel is less than 50
ms and more than 30 ms when WFNA is used as oxidizer, but
still larger than that of pure AB fuel. This suggests that the
ignition delay time could be altered by changing the
composition of the solid fuel, which could be used in the future
to develop more efficient rocket fuel formulations.
2.4. Solar Energy Cell and Fuel Cell. When sunlight hits a
semiconductor material, it causes excess electrons in the n-zone
to move to the p-zone, resulting in electric potential and current,
which is also known as the photovoltaic effect.114 In addition to
the common semiconductor material silicon, PSC materials are
now gaining a lot of attention.115 Perovskite titanite solar cells,
because of their high photoelectric conversion efficiency, ease of
synthesis, and low price, are considered the most promising new
generation of solar cell materials.116 According to the present
study, the practical application of PSCs is influenced by their
internal structural stability. Existing studies have shown that a
large number of vacancy defects exist in perovskite crystal films
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Energy Fuels 2023, 37, 11584−11607
Energy & Fuels
Figure 20. (a) Inverted PSC structure diagram. (b) Inverted PSC energy level matching diagram. (c) J−V curve of inverted PSCs based on
PEDOT:PSS and 1-NaBH4−PEDOT:PSS films. Reproduced with permission from ref 119. Copyright 2022, John Wiley and Sons.
because of the low energy of formation of organic cations and
halide anions during the fabrication of perovskite crystal
films.117,118 Therefore, it becomes critical to reduce ionic
vacancies and avoid the volatilization of organic cations, which is
very important to enhancing the stability of PSCs.
To this end, Wu et al.119 used NaBH4 as an interfacial modifier
between poly(3,4-ethylenedioxythiophene):poly styrene-sulfo-
nate (PEDOT: PSS) and MAPbI3−xClx, where PEDOT:PSS
acts as the hole transport layer (Figure 20a). NaBH4 adsorbs
Pb2+ onto the PEDOT:PSS surface, which promotes perovskite
crystal formation and thus modifies interfacial defects,
improving the stability and photovoltaic conversion of PSCs.
By comparing the experimental results of both doped and
undoped NaBH4, we found that the former is better than the
latter in various aspects such as energy level arrangement (Figure
20b) and best performance J−V curves (Figure 20c). It was also
found that the performance of inverted PSCs was influenced by
the NaBH4 concentration, with enhanced performance param-
eters for inverted PSCs containing a 0.5−10 mg·mL−1 NaBH4
concentration compared to those without NaBH4. The above
approach provides an idea to explore new semiconductor
materials for the design of high-performance PSCs.
In the current energy context, traditional fuel cars have started
to be phased out gradually due to their environmental hazards
and nonrenewable energy. Hydrogen fuel cell vehicles have been
proposed, but they often need to be equipped with a hydrogen
storage tank, which takes up a large part of the space and is also
unsafe (high pressure, flammable, and explosive). Currently, the
main storage methods for hydrogen are gaseous, liquid, and
solid. Gaseous hydrogen storage is the most common and well-
established hydrogen storage method, which has a low hydrogen
storage density and a general hydrogen storage pressure of 35
and 70 MPa, and requires high requirements for the hydrogen
tank material. Liquid hydrogen storage is the process of
liquefying hydrogen at low temperature and high pressure and
storing it in a special container that is adiabatic and pressure-
resistant. The density of hydrogen storage is high, and high
energy is consumed in the process of hydrogen liquefaction,
which requires a very high amount of material for hydrogen
storage tanks. Compared with gaseous and liquid hydrogen
storage, solid-state hydrogen storage has advantages such as high
hydrogen storage density, low operating pressure, good safety,
and low cost. With the need to use hydrogen storage materials,
the more mature hydrogen storage materials are hydrogen
storage alloys (ABx). The A metal (Ti, Mg, etc.) has better
affinity with hydrogen and controls the amount of hydrogen
storage; the B metal (Fe, Ni, etc.) is a non-hydrogen absorbing
element and controls the release of hydrogen. Absorption/
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release of the hydrogen reaction is a reversible process, resulting
in a hydrogen storage alloy that can be recycled. Magnesium
alloys are currently the most studied hydrogen storage materials
and are considered as one of the most promising solid-state
hydrogen storage materials for industrial development due to
their high hydrogen storage density, abundant raw materials, low
price and high purity of hydrogen release. The direct ammonia
borane fuel cell (DABFC) uses a different type of hydrogen
storage than the method described above. DABFC is a hydrogen
carrier120,121 that indirectly powers the fuel cell through an
oxidation reaction at the anode in the presence of a catalyst.122
At present, some researchers have investigated the reaction
mechanism of the AB anode, which theoretically occurs as
follows.
NH3BH3 + 6OH = NH4+ + BO2 + 4H 2O + 6e
(30)
Based on current research results, most researchers believe
that ABOR is a chemical-electrochemical process with the
following reactions:
NH3BH3 + OH = NH3 + BH3(OH) (31)
BH3(OH) + 6OH = B(OH)4 + 6e + 3H 2O (32)
However, many researchers have different research views on
eq 32 of the electrochemical oxidation reaction process. Nagle et
al.123 studied ABOR in NaOH solution, in their experiments
they concluded that two electrochemical oxidation reactions
occurred with the following reaction equation:
BH3(OH) + 3OH = BH 2(OH) + 3e + H 2O (33)
BH 2(OH)3 + 3OH = B(OH)4 + 3e + 2H 2O
(34)
or
BH3(OH) + 3OH = BH(OH)2 + 3e + 2H 2O (35)
BH(OH)2 + 3OH = B(OH)4 + 3e + H 2O (36)
Later, as their research progressed, they generalized the
electrochemical oxidation reaction to eq 37. The number of
transferred electrons n in the equation depends on the degree of
hydrolysis of BH3(OH)−.
BH3(OH) + nOH
= B(OH)4 + ne + (3 0.5n)H 2 + (n 3)H 2O
(37)
11599 https://doi.org/10.1021/acs.energyfuels.3c01393
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Energy & Fuels
The oxidation reaction of AB on gold electrodes was also
studied under alkaline conditions by Belén et al.124 in their
experiments, they divided the electrochemical oxidation
reaction of ABOR into the following processes according to
the voltage range of the reversible hydrogen electrode (RHE) in
ABOR. The s in the following equation denotes the active site on
the electrode surface.
0 300 mV vs RHE: BH3(OH) + s + OH = BH 2OHad
+ 2e + H 2O
(38)
300 800 mV vs RHE: BH 2OHad + 5OH = BO2 + 4e
+ 4H 2O + s
(39)
Beyond 800 mV vs RHE: BH3(OH) + 6OH = BO2
+ 6e + 5H 2O
(40)
125
Wu et al., study of the catalytic performance of nonprecious
metal catalysts for ABOR, found that the Cu-doped Ni1−xCuxO
catalyst reduced the relative energy of each intermediate state of
the reaction compared to the NiO catalyst, where * denotes the
active site of the catalyst. The reaction equations for each step of
ABOR, as shown in Figure 21a, and the electrochemical
reactions of H* are shown in Figure 21b. The relative energy of
each intermediate state is shown in Figure 22.
Figure 21. (a) The reaction equation for each step of ABOR under
alkaline conditions. (b) In ABOR, the H* electrochemical reaction
equation.
In conclusion, the mechanism of ABOR is becoming clearer,
but its catalytic mechanism at different active sites remains to be
investigated, especially for nonprecious metal catalyst applica-
tions. Therefore, we review the progress in the study of
nonprecious metal catalysts in ABOR. Wu et al.125 prepared
porous Ni1−xCuxO catalysts grown on carbon fiber paper via a
hydrothermal-pyrolysis method and applied them to ABOR.
According to the experimental findings, the reaction had a
favorable starting potential of −0.316 VRHE, which is lower than
that of several noble metal catalysts. In addition, they also
calculated the formation energies of Ni1−xCuxO and NiO on
(100) (Figure 22a and b) and (111) (Figure 22c and d),
respectively. According to Figure 22a and c, it can be seen that
the doping of Cu greatly reduces the formation energy of each
reaction step, which is due to the catalytic effect of electronic
coupling between Ni and Cu, the coupling process of which is
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shown in Figure 22e. This also demonstrates the importance of
bimetallic catalytic synergies in catalyst development and
facilitates the application of AB in DABFC.
Due to their inexpensive price, nonprecious metal catalysts are
becoming more popular. Thus, the catalytic performance of
Ni3M/C (M = Pd, Ag, Co), a nickel-based carbon-loaded
electrocatalyst doped with nonprecious Co and precious metals
Pd and Ag, was tested by Zadick et al.126 They compared the
catalytic activity exhibited by Ni3M/C catalysts in catalyzing
ABOR in alkaline electrolytes. The experimental results showed
that all three catalysts exhibited good catalytic performance, with
the maximum catalytic current density of 4.5 mA·cm−2 for
Ni3Pd/C, 3 mA·cm−2 for Ni3Ag/C, and 2.5 mA·cm−2 for
Ni3Co/C (Figure 23a). In addition, they have studied the
stability of the nonprecious metal catalyst Ni3Co/C by
comparing identical-location transmission electron microscopy
(ILTEM) images before and after the reaction, as shown in
Figure 23b. The images show no degradation of the Ni3Co/C
catalyst in any form before and after the reaction, which confirms
the excellent catalytic stability of the Ni3Co/C catalyst. In the
above experiments, the nonprecious metal catalyst Ni3Co/C not
only has certain activity but also has very good stability, it
demonstrates the usefulness of cobalt in the realm of
nonprecious metal catalysts and paves the way for the direct
use of borohydride fuels in fuel cells.
In conclusion, based on the principle that AB can be
electrooxidized at appropriate electrodes under alkaline
conditions, some researchers127−129 have reported novel direct
ammonia borane fuel cells that use ammonia-borane as a direct
fuel, the total reaction and released energy of which is described
in Figure 24b. The schematic of the DABFC is shown in Figure
24a. By adjusting the molecular structure of the catalyst, such as
cationic doping, the redistribution of electrons in the substrate
material can be optimized to improve the electrocatalytic activity
of ABOR. Although AB-fueled fuel cells have made great
progress in terms of catalysts and applications, it has not yet
reached the standard for commercial use. In addition, there are
some challenges in the application of DABFC, such as
competing hydrolysis reactions, which can reduce the efficiency
of AB utilization and generate some impurities. Another
significant obstacle that hinders the advancement of DABFC
is the crossing of ions and neutral molecules between the anode
and cathode.
3. CHALLENGES AND PERSPECTIVES
The excellent properties of boron−hydrogen containing
materials, which make them widely used in the future energy
field, especially in the field of hydrogen energy applications,
many applications have been carried out in the field of hydrogen
energy storage and conversion, including hydrogen storage and
production, special type fuels, and direct fuel cells. In this review,
the hydrogen storage properties of borohydrides, different
hydrogen production methods, and their future development
trends are discussed, the applications in mild reducing agents,
rocket fuels and fuel cells are described in detail. In addition,
although the progress in borohydride research is impressive,
many key bottleneck problems remain to be overcome. In order
to achieve safe and efficient energy storage and utilization,
promote the large-scale use process, and further broaden its
application field, it can be considered in the following ways for
application in the energy field:
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Energy & Fuels pubs.acs.org/EF Review

Figure 22. (a) Energy distribution of Ni1−xCuxO and NiO (100) structures at each step in ABOR. (b) Energy distribution of Ni1−xCuxO and NiO
(100) structures in the H* reaction step in ABOR. (c) Energy distribution of Ni1−xCuxO and NiO (111) structures at each step in ABOR. (d) Energy
distribution of Ni1−xCuxO and NiO (111) structures in the H* reaction step in ABOR. (e) Schematic diagram of the electronic coupling between Ni
and Cu, the electronic structure, and the charge transfer process of Ni1−xCuxO, with the transferred electrons in the process indicated by black
rectangles. Reproduced with permission from ref 125. Copyright 2019, American Chemical Society.

Figure 23. (a) Comparison of the activity of Ni3Ag/C, Ni3Pd/C, and Ni3Co/C catalysts for the electrocatalytic oxidation of AB under the same
experimental conditions. (b) ILTEM images of the Ni3Co/C catalyst obtained before (top three) and after (bottom three) the reaction. Reproduced
with permission from ref 126. Copyright 2017, Elsevier.

11601 https://doi.org/10.1021/acs.energyfuels.3c01393
Energy Fuels 2023, 37, 11584−11607
Energy & Fuels
Figure 24. (a) The schematic diagram of DABFC. (b) DABFC reaction equation and its release voltage, energy density, and capacity density.
(1) The cyclic hydrogen storage/release of borohydrides still
faces great technical obstacles at this stage, mainly
including complex reactions in the process of reversible
hydrogen absorption, a low hydrogen absorption rate,
harsh conditions, and high cost in the preparation of
borohydrides with superior performance, In addition, it is
difficult for a single modification method to effectively
improve the hydrogen storage/release properties of
borohydrides, the combination and coordination of
multiple methods (composite systems, nanomodulation,
ion substitution, doping modification) to jointly optimize
the thermodynamic and kinetic properties of the materials
will be a focus of future research.
(2) For the hydrogen production from borohydrides, there
are two major technical challenges that need to be
addressed: one is the reversible regeneration of
borohydrides, which is currently limited by low
regeneration efficiency and high regeneration cost, the
other is the development of high performance catalysts. It
is necessary to develop a catalyst with both high activity
and low cost. Currently, regulating and controlling the
catalyst composition and optimizing the suitable carrier
are the most commonly used methods for the develop-
ment of efficient catalysts. In addition, the magnetic
recyclable catalysts are also an important development
direction.
(3) The integration of energy materials development with
modern network database technology can reduce the
development cycle and improve research efficiency.
Machine learning theory is a good way to guide the
design and tuning of borohydride materials, for example,
the design of new borohydride materials with excellent
functionality by the screening and derivation of a material
structure database, including the characteristics of high
energy density or good hydrogen storage and release
properties, modification of borohydrides with customized
reducibility for use in different reduction reactions,
synthesis of new boro-hydrogen fuel with shorter ignition
delays (IDs) and a higher specific impulse by physical or
chemical methods to improve the performance of solid
rockets, and so on.
(4) The current challenge limiting the research and
application of borohydrides is their high cost, which
pubs.acs.org/EF Review
often discourages their scale application. Therefore, it is
important to develop large-scale synthesis techniques for
borohydrides that will not only drive their large-scale
application but also facilitate iterative upgrades across the
energy industry.
4. CONCLUSIONS
With the advantages of high hydrogen storage density,
reversibility and diverse modification methods, borohydrides
have various applications in the clean energy field. Therefore,
this paper reviews the applications of borohydrides in hydrogen
storage, hydrogen production, mild reductants, rocket fuel and
fuel cells and provides an outlook on the challenges in the
development and application process. For hydrogen storage, we
analyzed the improvement of borohydride hydrogen storage
performance in terms of composite systems and nano-
modulation, and concluded that the main difficulties faced by
RHC systems are the efficiency and cost of reversible hydrogen
uptake, while nano-modulation can improve the hydrogen
storage performance, but the actual capacity and the cycling
stability need further improvement. The improvement of
hydrogen storage performance by a single measure is limited,
and the combination and coordination of multiple methods
(composite systems, nanomodulation, ion substitution, and
doping modification) has greater competitiveness in optimizing
the material hydrogen storage performance.
The hydrolysis, alcoholysis and pyrolysis for hydrogen
production from borohydrides are discussed in this review.
For hydrogen production by hydrolysis and alcoholysis, the
hydrogen production performance of borohydrides with
different catalysts and their reversible regeneration are
investigated. The catalyst with high activity, low cost and
recyclable performance are the future research directions, and
the efficiency and cost of the reversible regeneration limit its
scale application. For hydrogen production by pyrolysis, the
byproducts are generated in the hydrogen production process,
such as borazine, which leads to H2 impurity. Borohydrides can
also be used as reducing agents and used in the field of
environmental governance and catalysis, which can reduce
harmful high-valent Cr6+ to harmless low-valent Cr3+ and reduce
metal ions to metal monomers to prepare nanoscale active metal
catalysts. For applications in HSF, much research has been
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Energy Fuels 2023, 37, 11584−11607
Energy & Fuels
focused on the synthesis of fuels with shorter ignition delays
(IDs) and higher specific impulses by physical or chemical
methods. In addition, some kinds of borohydrides can be used
directly as an anode fuel for fuel cells and indirectly to power
vehicles through oxidation reactions. Compared to regular
hydrogen fuel cell vehicles, the hydrogen storage tank is omitted,
which reduces the storage space and increases safety. In
conclusion, with the gradual deepening of research and the
maturity of related technologies, borohydrides will be an
excellent class of hydrogen storage materials with wide
application in clean energy.
■ AUTHOR INFORMATION
Corresponding Author
Haojie Li − Department of Energy and Power Engineering,
Henan University of Science and Technology, Luoyang
471003, China; Longmen Laboratory, Luoyang 471000,
China; Moganshan Institute ZJUT, Deqing 313200, China;
orcid.org/0000-0002-6115-2409; Email: haojl1221@
haust.edu.cn
Authors
Bingke Yang − Department of Energy and Power Engineering,
Henan University of Science and Technology, Luoyang
471003, China
Xuetao Wang − Department of Energy and Power Engineering,
Henan University of Science and Technology, Luoyang
471003, China; Longmen Laboratory, Luoyang 471000,
China
Zhen Yao − Department of Energy and Power Engineering,
Henan University of Science and Technology, Luoyang
471003, China
Yilin Zhu − Institute of Engineering Thermophysic, Chinese
Academy of Science, Beijing 100190, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.energyfuels.3c01393
Notes
The authors declare no competing financial interest.
Biographies
Haojie Li received his Ph.D. at Chongqing University. He is a Lecturer
of Henan University of Science and Technology and a researcher at
Moganshan Research Institute of ZJUT (Zhejiang University of
Technology), mainly focusing on the preparation of hydrogen energy
and hydrogen fuel cells.
Bingke Yang is a Postgraduate of Henan University of Science and
Technology and mainly studies the preparation of hydrogen.
Xuetao Wang is a Professor of Henan University of Science and
Technology, mainly focused on new energy and clean utilization of
fossil energy.
Zhen Yao is a Postgraduate of Henan University of Science and
Technology and mainly studies the preparation of hydrogen.
Yilin Zhu is an Assistant Research Fellow of the Institute of Engineering
Thermophysics, Chinese Academy of Science, mainly focusing on new
energy and energy system optimization.
■ ACKNOWLEDGMENTS
The authors gratefully acknowledged financial project supported
by Key Scientific and Technological Projects in Henan Province
(232102240067); Key Scientific Research Projects of Colleges
and Universities in Henan Province in 2023 (23A480002); and
pubs.acs.org/EF Review
Frontier Exploration Project of Longmen Laboratory
(LMQYTSKT015).
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