International Journal of Hydrogen Energy xxx (xxxx) xxx

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International Journal of Hydrogen Energy

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Unleashing the power of hydrogen: Challenges and solutions in

solid-state storage
Ya-Long Du a , Z.Y. Sun a,* , Bi’an Fu b, Qin Huang a
a
Hydrogen Energy and Space Propulsion Laboratory (HESPL), School of Mechanical, Electronic and Control Engineering, Beijing Jiaotong University, Beijing, 100044,
PR China
b
Chinese Academy of Macroeconomic Research, Beijing, 100038, PR China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Ibrahim Dincer Solid-state hydrogen storage presents a promising solution for achieving high-density, safe, and sustainable
hydrogen energy applications. This review systematically examines the performance optimization of hydrogen
Keywords: storage materials, focusing on enhancing storage capacity, improving operational conditions, and addressing
Hydrogen energy economic constraints. Notable progress has been achieved in physical adsorption materials, particularly in
Solid-state hydrogen storage
carbon-based materials and metal-organic frameworks (MOFs), with adsorption capacities reaching up to 7.5 wt
Physisorption and chemisorption
% at cryogenic conditions. Additionally, advancements in chemical absorption technologies, such as magnesium-
Hydrogen storage materials
Material optimization based hydrides with hydrogen capacities exceeding 7.6 wt%, have demonstrated improved dehydrogenation
kinetics through catalytic and structural modifications. The study further evaluates emerging quasi-molecular
hydrogen storage materials, such as lithium-decorated borospherene, achieving a maximum theoretical capac­
ity of 13.8 wt%. Strategies including catalyst incorporation, nanostructure engineering, and hybrid material
development are analyzed to enhance hydrogen storage performance under ambient conditions. The findings
contribute to advancing scalable hydrogen storage technologies, providing insights into future research di­
rections for achieving practical hydrogen energy solutions.

1. Introduction scenarios [10–12]. In contrast, liquid hydrogen storage can improve

hydrogen storage density by liquefying hydrogen gas at cryogenic
Hydrogen energy is increasingly acknowledged as a sustainable en­ temperatures (approximately − 253 ◦ C) [13]. However, maintaining
ergy source globally and is regarded as a viable solution for mitigating such ultra-low temperatures requires substantial energy, and these
climate change and its associated environmental repercussions [1]. It storage systems’ complexity and economic considerations increase the
has emerged as a significant alternative to conventional fossil fuels, technological barriers for implementation [14]. Furthermore, safety
enabling various nations to meet their decarbonization objectives and concerns associated with phenomena such as heat transfer and phase
adhere to the commitments outlined in the Paris Agreement. Hydrogen transitions during liquid hydrogen storage warrant thorough consider­
energy, functioning as an energy carrier, facilitates the storage of ation [15]. Technically, hydrogen can also be stored and transported in
renewable energy derived from wind and solar sources in the chemical solid state, using solid-state materials like carbon-based materials and
form of green hydrogen, which can be transported via freight and/or metal hydrides that adsorb hydrogen through physical and/or chemical
pipelines from the production sector to energy consumption points, as processes [6,16–18]. This method reduces energy losses typically asso­
illustrated in Fig. 1. ciated with high-pressure or cryogenic storage, enhances safety, allows
Hydrogen possess unique physical properties, a high susceptibility to long-term storage, and links large-scale liquid hydrogen storage and
embrittlement, and significant chemical reactivity, which create limited hydrogen requirements for terminal use. Furthermore, it enables
numerous challenges for storing and delivering hydrogen in gas-state. the dehydrogenation of hydrogen solely when required, presenting a
These challenges include lower hydrogen storage density [6], poten­ promising alternative for hydrogen storage and transportation.
tial leakage from embrittlement in storage tanks [7–9], and the risks of Numerous studies are currently being conducted on storing and
spontaneous combustion or explosive reactions in high-pressure leaks transporting hydrogen in solid-state. The predominant focus of these

* Corresponding author.
E-mail addresses: sunzy@[Link], [Link]@[Link] (Z.Y. Sun).

[Link]
Received 18 December 2024; Received in revised form 9 February 2025; Accepted 27 February 2025
0360-3199/© 2025 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and
similar technologies.

Please cite this article as: Ya-Long Du et al., International Journal of Hydrogen Energy, [Link]
Y.-L. Du et al. International Journal of Hydrogen Energy xxx (xxxx) xxx

two categories: physical adsorption and chemical absorption, of which

the comparison of the principles is illustrated through the image infor­
mation in Fig. 2.
Physical adsorption is characterized by the adherence of hydrogen
molecules to the surfaces of porous materials with a high specific surface
area, facilitated by weak van der Waals forces. Carbon nanotubes are an
exemplary choice for hydrogen storage materials that rely on physical
adsorption due to their exceptionally high specific surface area and
substantial adsorption capacity [33,34]. Furthermore, advances in the
research of metal-organic frameworks (MOFs) have unveiled numerous
prospects for hydrogen storage through physical adsorption; however,
persistent limitations arise from the required conditions of low tem­
perature and high pressure, restricting their practical application [35,
36]. Conversely, chemical adsorption involves the formation of strong
chemical bonds between hydrogen and the constituent atoms (particu­
larly metal atoms) within the material. This reaction is typically seen
between hydrogen and metal hydrides, leading to the formation of these
hydrides. Frequently used chemisorbed hydrogen storage materials
include magnesium-based hydrides, titanium-based hydrides, and
sodium-based hydrides [37–40]. During the adsorption process,
hydrogen molecules dissociate and then recombine with metal atoms on
the material’s surface to create stable hydrides. However, the chemical
reactions that control hydrogen storage and release may impose ther­
modynamic limitations, thus restricting the effectiveness of this method
in real-world applications.
Fig. 1. Hydrogen as green energy and hydrogen storage [2–5]. (For interpre­ In addition to the previously mentioned solid-state hydrogen storage
tation of the references to colour in this figure legend, the reader is referred to principles, current research has explored the potential applications of
the Web version of this article.) hydrogen storage through quasi-molecular bonds [31,41]. Excimer bond
hydrogen storage represents a mechanism that lies between physical and
investigations is on enhancing the storage capacity, absorption and chemical adsorption. During the adsorption or absorption of hydrogen,
release rates, and long-term stability of hydrogen storage systems the bonds between hydrogen molecules remain intact but are weakened,
through material advancements [19–22]. Additionally, some research preventing the dissociation of these molecules. As a result, the interac­
efforts are directed toward improving the stability of the overarching tion strength between hydrogen storage materials and hydrogen falls
solid-state hydrogen storage and transportation system [23,24]. Despite within a spectrum that bridges physical and chemical adsorption,
the many studies undertaken in recent years, significant challenges still characterized by the excimer bond. Empirical studies suggest that
need to be addressed before the large-scale application of solid-state
hydrogen storage and transportation can be fully realized. This article
aims to provide a comprehensive summary of the current development
status in solid-state hydrogen storage and transportation. It will also
investigate this domain’s critical technical challenges and prospective
research directions.
This study systematically analyzes solid-state hydrogen storage ma­
terials, focusing on identifying the key challenges that impede their
practical applications. Unlike previous reviews that concentrated solely
on physical or chemical adsorption, this research offers an integrated
perspective, comparing the performance of various hydrogen storage
strategies across different operating conditions. Additionally, it explores
the emerging field of hydrogen storage through quasi-molecular
bonding, which represents a midpoint between physical and chemical
adsorption and shows promise for high hydrogen storage capacity and
reversible utilization under environmental conditions. By synthesizing
current research advancements and pinpointing significant performance
bottlenecks, this study outlines future research directions aimed at
accelerating the development of efficient and scalable hydrogen storage
technologies.

2. Principles and materials of solid-state hydrogen storage

Solid-state hydrogen storage represents a pioneering approach to

hydrogen storage by utilizing solid materials, contrasting with the
conventional methodologies of storing hydrogen within controlled en­
vironments as gaseous or liquid forms. The predominant mechanism of
solid-state hydrogen storage involves the adsorption or absorption of
hydrogen into solid substrates, achieved through various physical or
chemical interactions. Based on the underlying principles of adsorption Fig. 2. Principles and materials of solid-state hydrogen storage [25,26,28,
and absorption [25–32], solid-state hydrogen storage is classified into 29,38].

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quasi-molecular bond storage is optimal for solid-state hydrogen storage the effectiveness and stability of these biochar materials in this appli­
under ambient temperature and pressure conditions [42]. However, cation (as shown in Fig. 3(b) and (c)).
research on hydrogen storage utilizing quasi-molecular bonds is still Inorganic porous materials, such as zeolites and borides, exhibit
relatively limited, and further extensive exploration is necessary to properties similar to carbon-based materials, including high specific
assess its feasibility for large-scale applications. surface area, chemical stability, and adjustable pore structures, which
enhance hydrogen adsorption. As a result, these materials have attracted
considerable attention in the realm of solid-state hydrogen storage [50,
2.1. Materials of physisorption hydrogen storage 51]. Zeolites, which are characterized as adsorbents with tunable pore
sizes made from aluminosilicate material, have been the focus of
The physical adsorption method employed for hydrogen storage is extensive research. For instance, Langmi et al. [51] reported that NaY
defined by the weak interactions between hydrogen molecules and the zeolite can achieve a maximum
adsorbent material’s surface, primarily driven by van der Waals forces. Hydrogen storage capacity of 1.81 wt% at − 196 ◦ C and 15 bar.
This approach offers several advantages, including rapid adsorption However, zeolites’ relatively heavy elemental composition and reduced
kinetics and significant reversibility [43]. The efficiency of hydrogen pore fraction may limit their efficiency as hydrogen storage materials
storage in physical adsorption materials depends on various factors, [52]. Borides, with a pore structure similar to carbon-based materials,
such as the specific surface area and the pore structure of the materials exhibit a higher specific surface area, offering enhanced advantages for
used. Common materials suitable for this method include carbon-based hydrogen storage applications. Nonetheless, previous studies indicate
substances, inorganic porous materials, and metal-organic frameworks that the original adsorption capacity of boron benzene for hydrogen is
(MOFs). Research on these materials provides substantial theoretical insufficient. Consequently, studies have been devoted to improving the
and empirical data that supports the advancement of effective solid-state interaction between borides and hydrogen to overcome these limitations
hydrogen storage technologies [34–36,43]. [43,53–55].
Carbon-based materials, including graphene and carbon nanotubes MOFs are materials known for their exceptionally high surface areas
(CNTs), are widely acknowledged in the field of physical adsorption and tunable pore sizes (as illustrated in Fig. 4), which provide significant
hydrogen storage research. These carbon materials are noted for their potential for physical adsorption in solid hydrogen storage applications
lightweight properties, excellent electrical conductivity, and significant [56]. The mechanism of hydrogen adsorption in MOFs is primarily
specific surface area, making them ideal candidates for hydrogen storage attributed to their remarkable specific surface area — reaching up to
applications [44,45]. Graphene, a two-dimensional material with a 4500 m2/g, which enables reversible hydrogen gas adsorption through
planar structure formed from a single layer of atoms, exhibits a van der Waals interactions within their porous structures. These mate­
hydrogen adsorption capacity of up to 3.1 wt%, indicating promising rials have been shown to achieve hydrogen storage capacity of up to 7.5
possibilities for solid-state hydrogen storage [44,46]. However, the wt% at 77 K and 60 bar [25,57]. However, the limitations imposed by
interaction between hydrogen and pristine graphene is relatively weak, low temperature and high pressure present considerable challenges for
necessitating various methods to enhance this interaction and improve applying MOFs at ambient temperature and pressure. Consequently,
its hydrogen storage capacity [47]. Alongside traditional carbon-based research efforts should focus on improving hydrogen storage conditions
materials, biomass-derived porous carbon materials have gained atten­ for these materials. Covalent organic frameworks (COFs) are another
tion as viable hydrogen storage options due to their diverse sources (as type of porous crystalline materials characterized by significant surface
illustrated in Fig. 3 (a)) [32]. Researchers have investigated the poten­ area and porosity (as shown in Fig. 4), making them promising candi­
tial of porous biochar, produced from poplar sawdust and pig skin, as a dates for solid-state hydrogen storage [58]. COFs exhibit a markedly
hydrogen storage medium [48,49]. Their findings have demonstrated

Fig. 3. Carbon materials from biomass and their hydrogen storage properties [32,48,49].

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Fig. 4. SEM images of MOFs [56] and COFs [58].

elevated hydrogen storage density compared to MOFs due to their conversion technologies. Their cost-effectiveness and efficiency further
comparatively lower material density [26,52,59]. This distinctive underscore their potential in solid hydrogen storage applications.
property positions COFs as potential materials of interest in hydrogen Various metal oxides have demonstrated electrochemical hydrogen
storage research. storage capacities, synthesized from a range of materials and employing
different fabrication methods [29,61,65,66], achieving a maximum of
2.2. Materials of chemisorption hydrogen storage 16.8 wt% (as illustrated in Fig. 6). However, hydrogen storage using
metal oxides faces several challenges, particularly regarding production
Storing hydrogen in materials via chemical adsorption requires costs and surface area [57]. Consequently, additional research is
dissociating diatomic hydrogen molecules, forming strong chemical essential to overcome these limitations.
bonds with the hydrogen storage medium. This process leads to a sig­ Research on carbon-based hydrogen storage materials indicates
nificant enhancement in hydrogen storage efficiency [60]. Typically, notable discrepancies in various carbon nanomaterials’ reported
materials exhibiting chemisorption properties include metal hydrides hydrogen storage capacities. For example, Geng et al. [67] stated that
and metal oxides. Certain carbon-based materials have also been iden­ multi-walled carbon nanotubes (MWCNTs) achieve a maximum
tified as having sufficient chemisorption capacities for practical hydrogen storage capacity of 0.4 wt% at room temperature. In contrast,
hydrogen storage [21,30,61]. Dillon et al. [68] found that single-walled carbon nanotubes (SWCNTs)
Metal hydrides are among the most extensively explored materials exhibit a significantly higher hydrogen storage capacity, ranging from 5
for hydrogen storage. Metal hydrides (MgH2) exhibit a high hydrogen to 10 wt% under similar conditions. These considerable differences
storage density and excellent cycling performance. Research has indi­ underscore the impact of structural characteristics, surface modifica­
cated that magnesium-based hydrides possess a substantial hydrogen tions, and experimental conditions on hydrogen adsorption
storage capacity, with a reversible capacity of up to 7.6 wt% based on performance.
Mg (as illustrated in Fig. 5). This is attributed to the formation of stable To address these discrepancies, Barghi et al. [27] conducted a thor­
chemical bonds between hydrogen and metals [63]. Additionally, given ough investigation that revealed notable differences in the adsorption
the abundant availability of aluminum, it also shows great promise as a dynamics of hydrogen based on pressure variations. Their study indi­
hydrogen storage material. Studies indicate that aluminum can achieve cated that at room temperature, physical and chemical adsorption
a hydrogen storage capacity of 10.1 wt% [64]. However, the high contributions are nearly balanced when the pressure is below 20 bar.
temperature necessary for hydrogen release from metal hydrides and the However, as pressure increases beyond 20 bar, physical adsorption
slow kinetics of the reaction highlight the need for further research to emerges as the predominant mechanism, resulting in a significant
lower the reaction temperature and enhance the reaction rate. enhancement in hydrogen uptake (as illustrated in Fig. 7). This finding
Metal oxides can enhance hydrogen storage in solution through suggests the pressure-dependent nature of adsorption behavior in
electrochemical reactions, making them effective mediums for hydrogen CNT-based hydrogen storage materials, offering valuable insights for
storage and contributing to advancements in energy storage and optimizing their storage performance through targeted structural and

Fig. 5. Storage mechanism and performances of metal hydrides [62,64].

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Fig. 6. Structure and performances of metal oxides [29].

Fig. 7. Performances of hydrogen storage in CNT [27,34].

environmental modifications. hydrogen storage capacity while maintaining commendable stability

and reversibility. Empirical data indicate that calcium-doped graphene
materials surpass traditional carbon-based materials in terms of
2.3. Materials of quasi-molecular bond hydrogen storage hydrogen storage capacity. This finding lays a vital material foundation
for the future large-scale implementation of quasi-molecular bond
Excimer bond hydrogen storage technology introduces a novel hydrogen storage technology. However, the hydrogen storage capacity
method for hydrogen storage by utilizing hydrogen molecules to achieve of many quasi-molecular bond materials in practical applications re­
non-dissociative adsorption on the surfaces of specific materials. In this mains below their theoretical limits, highlighting the urgency of
process, the internal connections between hydrogen molecules are achieving higher hydrogen storage capacities. Nonetheless, it is
weakened, but dissociation does not occur, as demonstrated in Fig. 8. reasonable to infer that future research into hydrogen storage based on
This approach offers several notable advantages, such as low energy quasi-molecular bonds could pave the way toward a hydrogen-based
consumption and high reversibility [42], making it an ideal solution for society.
storing hydrogen at ambient temperature and pressure.
Recent advancements in hydrogen storage research involving quasi- 3. Optimization of hydrogen storage materials
molecular bonds have showcased remarkable progress [31,41], partic­
ularly in the realm of carbon-based materials, graphene quantum dots Solid-state hydrogen storage exhibits theoretically high hydrogen
(GQDs), and heteroatom-doped single-atom materials, all of which storage density, robust safety performance, and enhanced environ­
exhibit significant potential for practical application. The dual-doping mental compatibility. Nevertheless, it faces significant challenges
strategy applied to graphene has been shown to substantially enhance

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Fig. 8. Mechanism, structure, and performance of hydrogen storage by the mode of quasi-molecular bond [31,41].

concerning hydrogen storage materials, storage capacity, operational costs associated with hydrogen storage [27,60,61,63,64]. In light of
parameters (such as temperature and pressure), cycle stability, and recent advancements in the research of hydrogen storage materials, this
economic feasibility. Key strategies for optimizing hydrogen storage section will review various methodologies aimed at optimizing the
materials include enhancing the kinetics of chemical reactions, performance and efficiency of these materials.
improving storage reversibility and cycling efficiency, and reducing

Fig. 9. Optimized paths of physisorption materials [20,54,71,74,80–83].

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3.1. Optimization of physisorption materials an effective optimization strategy, allowing for flexible cation replace­
ment within the pores without permanently altering the zeolite frame­
Physical adsorption hydrogen storage materials utilize weak van der work through doping. For example, zeolite X that underwent Ca ion
Waals forces to facilitate the adsorption of hydrogen onto their surfaces, exchange exhibits a hydrogen storage capacity of 2.19 wt% under
enabling reversible hydrogen storage. However, the inherent limitations low-temperature conditions [80].
of these interactions require that physical adsorption materials typically Borides, including compounds like boron benzene, have received
function under low temperature and/or high pressure to achieve optimal considerable attention in the field of materials science due to their high
performance in hydrogen storage [27,43,69]. These requirements pose hydrogen storage density and impressive reversible hydrogen storage
several challenges that hinder their large-scale application. Conse­ capacity. However, the performance of these materials is limited by
quently, research efforts have been focused on optimizing the opera­ variations in temperature and pressure conditions. Consequently,
tional conditions of physical adsorption materials, aiming to enable their numerous studies have aimed to enhance the hydrogen storage capacity
effectiveness at room temperature and pressure while maintaining su­ of borides through the doping of additional elements. For instance,
perior hydrogen storage performance, thus improving their practicality lithium (Li) doping has been found to increase the hydrogen storage
[35,43,47], as illustrated in Fig. 9. capacity of boron benzene to approximately 10.85 wt% [28,53].
Carbon-based materials have emerged as promising candidates for Moreover, investigations by Wang et al. [54] and Tang et al. [55] into
solid-state hydrogen storage due to their abundant availability, tunable Ca-doped borides revealed that the maximum hydrogen storage capac­
structures, and high specific surface areas. Researchers have proposed ities of Ca-doped alpha boron flakes and B30⋅4Ca complexes were
various optimization strategies to further enhance hydrogen storage increased to 12.68 wt% and 8.92 wt%, respectively. Additionally, boron
performance, with doping using additional elements being recognized as benzene has the potential to form composite materials with graphene.
a practical approach. This technique modifies the internal structure or Notably, the Li-doped boron benzene/graphene bilayer structure, as
properties of the materials, optimizing their binding energy and reported by Kumar et al. [43], exhibited an extraordinary hydrogen
adsorption characteristics [20,47,70]. For instance, a study conducted storage capacity of up to 13.64 wt% under ambient conditions.
by Rice et al. [71] explored the stability of solid-state hydrogen storage MOFs have emerged as a pivotal focus in the field of physical
in nitrogen-doped carbon-based materials, revealing that the hydrogen adsorption hydrogen storage due to their high specific surface area,
adsorption capacity significantly increases with higher nitrogen doping tunable pore structures, and diverse chemical compositions. MOF-5
concentration or pyramid angle. Notably, the impact of doping con­ synthesized by Zhu et al. [81] through mechanochemical methods
centration is particularly pronounced, highlighting its essential role in demonstrated a remarkable 207% increase in specific surface area,
optimizing hydrogen storage performance. Chen et al. [72] synthesized significantly enhancing hydrogen adsorption performance at low tem­
nitrogen-doped carbon nanotubes through the catalytic pyrolysis of peratures. Furthermore, Yang et al. [82] doubled the hydrogen storage
melamine utilizing FeCl3, achieving an impressive hydrogen storage capacity of MOF-5 by modifying its pore structure and markedly
capacity of 0.17 wt% at a pressure of 19 bar at room temperature [73]. improving the material’s thermal stability. Despite the notable perfor­
Furthermore, Achqraoui et al. [20] developed a two-dimensional ma­ mance of MOFs for low-temperature hydrogen storage, challenges
terial, BC6Be, doped with boron and beryllium, which exhibits a remain in achieving effective hydrogen storage at ambient tempera­
hydrogen storage capacity of 11.63 wt%, and an average desorption tures. Future research should concentrate on optimizing storage condi­
temperature of 247.15 K, making it more compatible with practical tions to enhance efficiency at standard ambient conditions. COFs,
working conditions. similar to MOFs, demonstrate considerable promise for applications in
In addition to doping technologies, surface modification plays a vital hydrogen storage. For instance, Ke et al. [83] presented a dual-step
role in improving the hydrogen storage performance of carbon-based modification protocol for COF-108, which significantly enhances the
materials [73]. Guo et al. [74] made significant strides in this area by operational temperature of hydrogen storage to 233 K through struc­
enhancing the specific surface area of porous carbon materials through tural modifications and the incorporation of Li-doping.
treatment with potassium hydroxide. As a result, the hydrogen storage Table 1 lists a systematic overview of the performance parameters of
capacity of the APC-3 samples produced via this method reached an physisorption hydrogen storage materials, highlighting notable
impressive 6.24 wt%. Meanwhile, Zhu et al. [75] discovered that
palladium (Pd) nanoparticles, when uniformly distributed on the sur­
faces of porous carbon substrates, considerably improved the diffusion Table 1
characteristics of hydrogen gas within the material matrix. Furthermore, Properties of physisorption materials.
the palladium-porous carbon composite, after undergoing potassium Material Capacity Temperature Pressure Reference
hydroxide treatment, exhibited an astonishing 154% increase in
BC6Be 11.63 wt% 247.15 K ​ [20]
hydrogen storage capacity under ambient temperature conditions. MWCNTs 0.13 wt% 298 K 100 bar [27]
Inorganic porous materials, including zeolites and borides, are 2Li-β12-borophene 10.85 wt% ​ ​ [28]
widely recognized as exceptional mediums for physical adsorption and f4 0.149 wt% 298 K 50 bar [34]
hydrogen storage due to their unique structural characteristics. How­ β12-borophene/ 13.64 wt% 300 K 30 bar [43]
graphene
ever, untreated inorganic porous materials typically exhibit suboptimal Graphene 3.1 wt% 298 K 100 bar [44]
hydrogen storage performance, highlighting the need for structural CNT(13,0) 5.60 wt% ​ 1 bar [45]
optimization and functional enhancement to improve their effectiveness S-2–800 3.03 wt% 77 K 1 bar [48]
[53,76]. For zeolites, critical factors influencing hydrogen storage ca­ CPC-800 2.49 wt% 77 K 1.13 bar [49]
NaY zeolite 1.81 wt% 77 K 15 bar [51]
pacity include specific surface area, pore size, and synthesis methods.
B8Li2 10.7 wt% ​ ​ [53]
Notably, the synthesis technique employed for layered zeolites can Ca2B8(H2)12 12.68 wt% 210 K ​ [54]
significantly affect their specific surface area and pore dimensions, B30⋅4Ca 8.92 wt% ​ ​ [55]
leading to a marked increase in their hydrogen storage potential [76, AC-MIL-100 6.93 wt% 77 K 40 bar [56]
77]. Furthermore, the incorporation of dopant atoms has been shown to MOF-177 7.5 wt% 77 K 70~80 bar [57]
N-doped CNTs 1.21 wt% 77 K 7 bar [72]
effectively enhance the hydrogen storage performance of zeolites [78]. Porous carbon material 6.24 wt% 77 K 20 bar [74]
For instance, research by Wang et al. [79] demonstrated that doping Ca Pd/PC-850 4.6 wt% 77 K 20 bar [75]
LSX zeolite with nickel increased its hydrogen storage capacity from Ni-doped Ca-LSX zeolite 1.15 wt% 298 K 100 bar [79]
0.50 wt% to 1.15 wt% at ambient temperature and 100 atm, signifying CaX 2.19 wt% 77 K 15 bar [80]
MOF-5 2.0 wt% 77 K 1 bar [82]
an increase of more than twofold. Moreover, ion exchange technology is

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disparities in hydrogen storage capacity and operational conditions explored, including mechanical ball milling and catalytic processes, as
among materials. shown in Fig. 10.
For carbon-based materials, including BC6Be and graphene, Reactive Mechanical Alloying (RMA) technology is proposed to
hydrogen storage capacity was significantly improved through enhance hydrogen storage capability. Li et al. [88] synthesized
elemental doping (e.g., nitrogen, boron, beryllium) and surface modi­ magnesium-based composite materials containing 20 wt% nickel and
fication (such as KOH activation or palladium nanoparticle loading). yttrium (MgH2 and Mg2NiH4), achieving hydrogen absorption capacity
Notably, BC6Be and Li-β12-boronobenzene/graphene bilayer structures of 3.92 wt% and 5.59 wt% within 10 min at 393 K and 473 K, respec­
achieved impressive capacities of 11.63 wt% and 13.64 wt%, with some tively. Notably, this composite also achieved a reduction in the dehy­
materials demonstrating potential for near-room temperature (247.15 drogenation temperature by 100 K. The remarkable performance is
K) [20,43]. In the case of inorganic porous materials, optimizing pore attributed to the catalytic effects of Mg2Ni and YH3, which are uniformly
structure and adsorption sites via ion exchange (Ca2+ doping) and dispersed throughout the Mg matrix during the mechanical alloying
elemental doping (Li, Ca) has shown promising results. For instance, process, alongside the significant presence of crystal defects that facili­
Ni-doped Ca-LSX zeolites increased their capacity up to 1.15 wt% at 298 tate enhanced hydrogen diffusion.
K and 100 atm [79]. MOFs and COFs exhibit high capacities at Moreover, advancements in the microstructure refinement of
near-room temperature (247.15 K), attributed to their ultra-high specific magnesium-based materials, such as extended mechanical ball milling
surface areas (such as MOF-177 at 77 K with 7.5 wt%). However, their durations, have led to significant improvements in both hydrogen ab­
performance at room temperature remains limited by weak van der sorption and release rates, as well as reductions in the dehydrogenation
Waals forces, and this underscores the need for further pore engineering temperature. The work by Liu et al. [89] involved a 40-hour mechanical
(e.g., pore structure optimization of MOF-5) and functionalization (such ball milling process on a Mg-40 wt% composite material, revealing
as Li-doped COF-108) to reduce operational temperature [57,82,83]. hydrogen storage capacity of 3.2 wt%, 3.5 wt%, and 4.0 wt% within 10
In summary, the optimization of physisorption materials primarily min at temperatures of 298 K, 368 K, and 548 K, respectively. Addi­
concentrates on enhancing the interaction between the materials and tionally, the composite material lacks activation requirements during
hydrogen through chemical modification and structural design. None­ the hydrogen absorption process while exhibiting exceptional dynamic
theless, most materials are still rely on low temperature or high pressure response capabilities.
conditions. Therefore, exploring multifunctional composites and inno­ Incorporating catalysts is an effective strategy to enhance the
vative doping strategies will be crucial for developing high-efficiency hydrogen storage capabilities of metal hydrides, as these catalysts
hydrogen storage solutions at room temperature. significantly improve hydrogen storage characteristics by facilitating
the dissociation, adsorption, diffusion, and subsequent formation of
3.2. Optimization of chemisorption materials hydrogen molecules. The remarkable catalytic efficiency of transition
metals and their corresponding oxides highlights their considerable
Magnesium-based materials have become a significant focus of research potential in evaluating hydrogen storage mechanisms within
research in the field of solid-state hydrogen storage using metal hy­ metal hydrides. Aguey-Zinsou et al. [84] conducted a synthesis of
drides, due to their advantageous properties such as low cost and a high transition metal oxides, specifically Nb2O5, in conjunction with MgH2
hydrogen storage capacity of approximately 7.6 wt% [63]. However, through mechanical ball milling (as illustrated in Fig. 10), which
MgH2 presents certain challenges, including elevated dehydrogenation markedly enhances the kinetics of hydrogen absorption and desorption
temperatures and slow kinetics for hydrogen absorption and desorption, in magnesium. Including Nb2O5 acts as a dispersant during the me­
which hinder its practical applications. In response to these issues, chanical grinding process, reducing the particle size of MgH2 and opti­
various optimization strategies for chemisorption materials have been mizing its crystalline structure. Consequently, this approach achieves

Fig. 10. Optimized paths of chemisorption materials (Elements from the literature [84–87], drawn by the authors)

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superior hydrogen storage performance under milder operational con­ can enhance the electrochemical hydrogen storage performance of
ditions. Furthermore, the integration of rare earth metal-based com­ metal oxides to varying degrees, primarily by optimizing their
pounds, such as LaNi5, has demonstrated remarkable catalytic activity, morphology, structure, and size. A systematic investigation into the
enhancing the material’s hydration and dehydration kinetics while underlying mechanisms and thorough testing of various preparation
maintaining commendable phase stability during hydrogen cycling, techniques is expected to become a crucial research direction in the
thereby providing innovative perspectives for enhancing hydrogen future.
storage efficiency [90]. MOFs utilized for chemical adsorption serve predominantly as cat­
Moreover, carbon-based materials play a critical role as catalysts in alysts or scaffolds, facilitating support for chemical adsorption mate­
improving the hydrogen storage performance of metal hydrides. rials, which exhibit considerable catalytic efficacy in enhancing the
Graphite carbon has been shown to significantly facilitate the hydrogen hydrogen storage performance of magnesium hydride (MgH2). For
adsorption process when combined with mechanical ball milling and instance, the stable Ni-BTC300 MOF (5–15 wt%) retains its structural
MgH2 composites. While graphite has a relatively limited effect on the integrity post-calcination and is uniformly dispersed throughout MgH2
dehydrogenation characteristics of MgH2, it significantly accelerates the during the ball milling process, significantly improving its kinetic per­
re-hydrogenation rate at 250 ◦ C. Following an 8-h ball milling process, formance. This material can release 5.14 wt% of hydrogen gas within 3
the composite material containing graphite was able to reabsorb 5 wt% min at a temperature of 300 ◦ C, exhibiting capacity stability of 98.2%
of hydrogen gas within just 30 min. This improvement is attributed to after 10 cycles [87]. Furthermore, a novel flower-shaped nickel MOF
the interaction between the graphite surface and H2 molecules, which acts as a catalyst that substantially reduces the dehydrogenation tem­
promotes the dissociation and adsorption of hydrogen molecules while perature of MgH2 (by 78 ◦ C), facilitating the release of 6.4 wt% of
preventing the formation of an oxide layer on the surface of Mg particles hydrogen gas within 600 s at 300 ◦ C, attributed to the synergistic cat­
[91]. Furthermore, optimizing synthesis methodologies for metal hy­ alytic effect of in-situ generated Mg2Ni/Mg2NiH4 alongside amorphous
drides and catalysts can further enhance their hydrogen storage capa­ carbon [95]. The study demonstrated that the optimal Ni MOF catalyst
bilities [92]. content ranges from 2 to 5 wt%. The MgH2 adsorption/desorption
The synthesis of complex metal hydrides through the combination of temperature of MgH2 doped with 10 wt% Ni1Mn1-MOF catalyst was
metals with various elements significantly enhances stability, regulates reduced to a minimum and its fast adsorption/desorption rate could be
thermodynamic properties, and improves the kinetics of hydrogen ab­ increased up to 39 times [96]. Carbon materials derived from MOFs also
sorption and desorption by optimizing the relevant reaction pathways. demonstrate exceptional hydrogen storage performance; for example,
For instance, in the Mg–Na–Al system, substantial improvements in nitrogen-doped porous carbon synthesized via ZIF-8 markedly enhances
hydrogen absorption and desorption rates were achieved through ball the dehydrogenation efficiency of LiBH4, releasing over 6.13 wt% of
milling and the incorporation of catalytic agents. Particularly during the hydrogen gas within 100 min at 320 ◦ C. This enhancement is linked to
dehydrogenation phase, the formation of new phases such as Al12Mg17 the synergistic effects of nitrogen impurity loading and a high specific
and NaMgH3 plays a crucial role in facilitating the decomposition of surface area [97]. Concurrently, ZIF-67 Co@CNTs nano catalysts exhibit
hydrides, resulting in enhanced kinetic performance and greater cycling remarkable capabilities in improving the hydrogen storage of MgH2,
stability within the system [93]. Additionally, studies have shown that with the ability to release 6.89 wt% of hydrogen gas within 15 min at
the mixture of 2LiNH2 and MgH2 generates new intermediate phases 300 ◦ C and effectuate 6.15 wt% of hydrogen gas absorption within 2 min
through complex phase transitions during the hydrogenation process. In at 250 ◦ C. These findings signify their efficiency in catalysis and notable
initial stages of dehydrogenation, the system displays characteristics cycling stability, facilitated by the phase transition of Mg2Co/Mg2CoH5
consistent with exothermic phase transitions and endothermic decom­ and the physical transformation mechanisms within the carbon matrix
position, highlighting the synergistic interactions among the involved [86]. Collectively, these studies elucidate that MOFs and their derivative
components. Significantly, the addition of 2 mol% TiCl3 enables the materials, when serving as catalysts and scaffolds, not only significantly
composite material to retain commendable kinetic properties enhance the hydrogen storage performance of chemisorbed materials
throughout hydrogenation and dehydrogenation processes while but also pave new avenues for advancing efficient hydrogen storage
simultaneously optimizing thermodynamic properties, further reducing materials.
hydrogen release temperature [94]. Table 2 demonstrates the hydrogen storage properties of chem­
Metal oxides possess a complex chemical composition and a tunable isorbed materials, highlighting the synergistic optimization of kinetics
microstructure, facilitating substantial enhancements in hydrogen and thermodynamics by catalytic modification and composite design.
storage efficacy through various synthesis techniques. Conventional Magnesium-based materials (such as MgH2) significantly reduce the
precipitation methods for synthesizing mesoporous Zn2SnO4 materials dehydrogenation temperature (MgH2-Co@CNTs releases 6.89 wt% at
via thermal treatment show remarkable performance that depends on 573 K) by mechanical alloying (Mg-20 wt% Ni–Y composites) and
careful control of morphology; specifically, the nanoparticle introduction of catalysts (Nb2O5) and enhance the hydrogen adsorption
morphology maintains a discharge capacity of 4650 mAh/g or greater and release rate (Mg-40 wt% Ti0.28Cr0.50V0.22 composite absorbed 4.0 wt
after 13 cycles [29]. The synthesized Ce0.75Zr0.25O2 nanopowder, pro­ % at 548 K for 10 min) [84,86,88,89]. Metal oxides (e.g., Ce0.75Zr0.25O2)
duced via the sol-gel method, exhibits a hydrogen storage capacity of
2000 mAh/g (approximately 7.8 wt%), featuring a uniform cubic
structure with nanoscale dimensions ranging from 35 to 60 nm, effec­ Table 2
tively enhancing both reaction kinetics and thermodynamic properties Properties of chemisorption materials.
[65]. The synthesized CoCe2(MoO4)4 truncated octahedral nanocrystals, Material Capacity Temperature Pressure Reference
prepared using the solution combustion method, exhibit remarkable
AZ31-3G ~6.83 wt 648 K [30]
hydrogen storage capabilities in alkaline media. This enhanced perfor­ %
mance is attributed to the nanocrystals’ optimized morphology and Ce0.75Zr0.25O2 7.8 wt% [65]
increased surface activity, achieving a discharge capacity of up to 4750 HT-MWCNTs 1.31 wt% [67]
mAh/g [66]. Even when combined with renewable materials like green MgH2-Co@CNTs 6.89 wt% 573 K [86]
MgH2-10/Ni-BTC300 5.14 wt% 573 K [87]
tea extract as a precipitant, NiAl2O4/NiO composite substances made Mg–20 wt% Ni–Y 5.59 wt% 473 K 30 bar [88]
through thermal decomposition, whose hydrogen storage performance Mg–40 wt% 4.0 wt% 548 K [89]
can be controlled by the calcination temperature, like the sample Ti0.28Cr0.50V0.22
calcined at 700 ◦ C still retains a discharge capacity of 450 mAh/g after MgH2 5 wt% 523 K [91]
MgH2-5 wt.% Ni MOF 6.4 wt% 573 K [95]
15 cycles [85]. It can be summarized that various preparation methods

9
Y.-L. Du et al. International Journal of Hydrogen Energy xxx (xxxx) xxx

and composite hydrides (Mg–Na–Al system) achieved high capacity (7.8

wt%) with cycling stability through nanosizing (35–60 nm particles) and
phase modulation (Al12Mg17 nanophase generation) [65,93].MOFs as
catalyst supports (such as Ni-BTC300) not only improved the kinetic
performance of magnesium-based materials (5.14 wt% release at 300 ◦ C
for 3 min), but also enhanced the cycling stability (98.2% capacity
retention after 10 cycles) by in situ generation of active phases
(Mg2Ni/Mg2NiH4) [87,95]. However, some materials (e.g., AZ31-3G
magnesium alloy) still face high dehydrogenation temperature (648 K)
and cost issues, and in the future, it is necessary to develop efficient and
low-cost transition metal catalysts and explore the synergistic effects of
multiscale composites to balance capacity, kinetics, and practicality.
The optimization path of chemisorption materials suggests that catalytic
interface engineering and microstructure modulation are the keys to
breaking through the bottleneck of existing technologies.

3.3. Optimization of quasi-molecular bond hydrogen storage materials

Fig. 11. Conformations of Li14&B40 and their H2 adsorption complexes [98].
Quasi-molecular hydrogen storage functions as a bridge between
physisorption and chemisorption, allowing hydrogen molecules to stay reversible adsorption characteristics.
intact while forming moderate binding interactions with storage mate­ Despite significant advancements, several key challenges remain in
rials. Recent research on graphene quantum dots (GQDs), heteroatom- the field, particularly the need for improved hydrogen uptake under
doped graphene, and lithium-decorated borospherene (B40) has ambient conditions, enhanced long-term material stability, and cost-
revealed effective strategies for improving hydrogen storage effective synthesis methods. Future research should focus on the
capabilities. following areas.
GQDs, particularly those functionalized with transition metals such
as titanium (Ti), show enhanced hydrogen storage capacities due to (a) Multifunctional material design, integrating both physisorption
Kubas interactions. Computational studies indicated that Ti-doped and chemisorption mechanisms to achieve high-capacity,
GQDs can attain a maximum hydrogen storage capacity of 6.1 wt% by reversible hydrogen storage;
optimizing the number of anchored Ti atoms, which effectively weakens (b) Catalyst development, investigating advanced catalysts,
the H–H bond without leading to full dissociation [41]. Additionally, including transition metal oxides and MOF-derived catalysts, to
research on heteroatom-doped, graphene-supported Ca single-atom improve reaction kinetics;
materials has highlighted their potential for achieving high hydrogen (c) Hydrogen storage at room temperature, optimizing material
storage densities through non-dissociative chemisorption. Both experi­ properties to facilitate efficient storage at near-ambient temper­
mental and theoretical studies indicate that dual-doped graphe­ atures and pressures;
ne-supported Ca materials surpass their single-doped counterparts by (d) Cycling stability and economic feasibility, assessing the long-
offering stronger hydrogen binding and cycling stability [31]. term performance of materials and developing scalable, cost-
Another promising area of research is Li-decorated borospherene effective production techniques.
(B40), which utilizes charge transfer from Li atoms to enhance hydrogen
adsorption. Studies have indicated that the structurally optimized By addressing these essential factors, hydrogen storage technology
Li14B40 can accommodate up to 42H2 molecules in a quasi-molecular can advance towards industrial applications, thereby facilitating the
bonding state (as shown in Fig. 11). This is a significant increase from development of a sustainable hydrogen energy infrastructure.
the pre-optimized state, which held 18H2 molecules, ultimately boosting
the hydrogen storage density to a maximum of 13.8 wt% [98]. Opti­ CRediT authorship contribution statement
mization strategies for quasi-molecular hydrogen storage materials
emphasize dopant engineering, metal decoration, and surface func­ Ya-Long Du: Writing – original draft, Visualization, Validation,
tionalization to achieve a balance between adsorption strength and Methodology, Investigation, Formal analysis, Data curation. Z.Y. Sun:
reversibility. Albeit research on quasi-molecular hydrogen storage re­ Writing – review & editing, Supervision, Project administration, Meth­
mains relatively limited, further exploration and optimization are odology, Investigation, Funding acquisition, Formal analysis, Concep­
needed to enhance its practical applicability. tualization. Bi’an Fu: Formal analysis, Conceptualization. Qin Huang:
Writing – original draft, Formal analysis.
4. Conclusions
Declaration of competing interest
This study thoroughly investigates the optimization of solid-state
hydrogen storage materials, emphasizing the significance of structural The authors declare that they have no known competing financial
modifications, catalyst integration, and hybrid material designs in interests or personal relationships that could have appeared to influence
enhancing storage efficiency. Physical adsorption materials, including the work reported in this paper.
carbon-based structures and metal-organic frameworks (MOFs), have
shown improved hydrogen storage capacities due to increased surface Acknowledgments
areas and advancements in dopant engineering, though their reliance on
low temperatures poses a challenge. In contrast, chemical absorption This research was financially supported by the Hydrogen Energy and
materials, particularly magnesium-based hydrides, exhibit high storage Space Propulsion Laboratory (HESPL) (Beijing Jiaotong University,
capacities but necessitate further enhancements in dehydrogenation China) [grant number HEL24sus02]. Thanks to all the editors and the
kinetics and cycling stability. Additionally, emerging quasi-molecular reviewers for their work on this article.
hydrogen storage materials, such as lithium-decorated borospherene,
present promising opportunities for high-density hydrogen storage with

10
Y.-L. Du et al. International Journal of Hydrogen Energy xxx (xxxx) xxx

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