A Comprehensive Review of Hydrogen Production and Storage A Focus On The Role of Nanomaterials

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 0 3 9 8 e2 0 4 3 1
Available online at www.sciencedirect.com
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journal homepage: www.elsevier.com/locate/he
Review Article
A comprehensive review of hydrogen production

and storage: A focus on the role of nanomaterials
Emmanuel I. Epelle a, Kwaghtaver S. Desongu b, Winifred Obande c,

Adekunle A. Adeleke d, Peter P. Ikubanni e, Jude A. Okolie f, Burcu Gunes g,*
a
School of Computing, Engineering and Physical Sciences, University of the West of Scotland, Paisley, United Kingdom
b
Department of Chemical Engineering, Federal University of Technology, Minna Nigeria
c
School of Engineering, Institute for Materials and Processes, The University of Edinburgh, Robert Stevenson Road,
Edinburgh, EH9 3FB, Scotland, United Kingdom
d
Department of Mechanical Engineering, Nile University of Nigeria, Abuja, Nigeria
e
Mechanical Engineering Department, Landmark University, Omu Aran, Nigeria
f
St. Peter's College Muenster, Canada
g
School of Biotechnology and DCU Water Institute, Dublin City University, Glasnevin, Dublin, Ireland
highlights graphical abstract
Different routes for renewable H2

production are discussed.
A comparison of the H2 storage
capabilities of various nano-
materials is presented.
New technological advances on
nanomaterial applications for H2
storage are explained.
Computational methodologies for
H2 storage are evaluated.
Future research recommendations
are presented based on identified
literature gaps.
article info abstract
Article history: Nanomaterials are beginning to play an essential role in addressing the challenges asso-
Received 22 October 2021 ciated with hydrogen production and storage. The outstanding physicochemical properties
Received in revised form of nanomaterials suggest their applications in almost all technological breakthroughs
16 February 2022 ranging from catalysis, metal-organic framework, complex hydrides, etc. This study out-
Accepted 22 April 2022 lines the applications of nanomaterials in hydrogen production (considering both ther-
Available online 20 May 2022 mochemical, biological, and water splitting methods) and storage. Recent advances in
renewable hydrogen production methods are elucidated along with a comparison of
Keywords: different nanomaterials used to enhance renewable hydrogen production. Additionally,
Hydrogen nanomaterials for solid-state hydrogen storage are reviewed. The characteristics of various
* Corresponding author. Bioprocess Engineering, School of Biotechnology, DCU Water Institute, Dublin City University, Ireland.
E-mail address: [email protected] (B. Gunes).
https://doi.org/10.1016/j.ijhydene.2022.04.227
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 0 3 9 8 e2 0 4 3 1 20399
Nanomaterials nanomaterials for hydrogen storage are compared. Some nanomaterials discussed include
Electrolysis carbon nanotubes, activated carbon, metal-doped carbon-based nanomaterials, metal-
Water splitting organic frameworks. Other materials such as complex hydrides and clathrates are out-
Gasification lined. Finally, future research perspectives related to the application of nanomaterials for
Activated carbon hydrogen production and storage are discussed.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20400
Methodology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20400
Hydrogen production routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20401
Reforming reactions (steam, aqueous, alkaline enhanced, and autothermal reforming) . . . . . . . . . . . . . . . . . . . . . . . . 20401
Thermochemical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20401
Biological processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20402
Hydrogen production through water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20402
Nanomaterials for renewable hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20403
Nanoelectrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20403
Nanophotocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20404
Nanomaterials for biological hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20408
Nanomaterials for thermochemical hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20411
Hydrogen storage methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20412
Compressed gas storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20414
Liquefaction/cryogenic storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20414
Solid-state-storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20414
Cyro-compressed H2 gas storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20415
Nanomaterials for solid-state hydrogen storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20415
Carbon nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20415
Carbon nanocomposites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20416
Activated carbon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20416
Complex hydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20417
Metal-organic frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20419
Hydrogen storage in clathrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20420
Perspectives and future directions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20422
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20423
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20423
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20423
List of abbreviation GNP Graphene nanoplatelets

HER H2 evolution reaction
AC Activated carbon
HTF Heat transfer fluid
AER Alkaline enhanced reforming
IRMOF Isorecticular metal-organic frameworks
APR Aqueous phase reforming
LCPs Linear conjugated polymers
CCD Central composite design
LDA Local density approximation
CMH Complex metal hydrides
MHHSS Metal hydride based H2 storage system
CMPs Conjugated microporous polymers
MOF Metal-organic framework
CNT Carbon nanotubes
MWCNT Multi-walled carbon nanotubes
CSHNSs Core/shell heteronano structures
OER Oxygen evolution reaction
DFT Density functional theory
QCNs Quantum Cu (II) nanodots
DOE US Department of Energy
SMR Steam reforming reaction
ENME Electrospun nanomaterials-based electrocatalysts
SWCNT Single-walled carbon nanotube
FT Fischer-Tropsch
TOF Turnover frequency
GDA Generalized gradient approximation
WGSR Water-gas-shift reaction
20400 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 0 3 9 8 e2 0 4 3 1
Introduction Several studies have evaluated different areas where

nanomaterials could improve hydrogen production and stor-
Recently there has been a tremendous increase in the number age. Reddy et al. [9] reported recent research progress in the
of researchers, scholars, countries, and stakeholders consid- use of plasmonic photocatalyst nanoparticles for hydrogen
ering hydrogen energy as a panacea for the increasing energy production. Mao et al. [10] reviewed the application of
demand, environmental pollution, and overdependency on different nanostructured materials for renewable hydrogen
fossil fuels. More specifically, the world is facing greenhouse production, storage, and utilization. However, the review is
gas emissions, climate change, energy security, and water solely focused on solar hydrogen production and does not
pollution challenges [1]. Therefore, developing alternative consider renewable hydrogen from biomass conversion pro-
energy sources that are environmentally friendly and sus- cesses [10]. Recently, Abdalla et al. [11]outlined hydrogen
tainable over a long duration is imperative. production and storage challenges and prospects. However,
Hydrogen is preferred as an energy carrier and a prom- recent advances on nano-based materials for hydrogen stor-
ising alternative to carbon-based fuels due to its renew- age and production were lacking. This has partly motivated
ability and pollution-free characteristics. It should be the work herein. To the best of the authors’ knowledge, there
mentioned that hydrogen is pollution-free when combusted is no comprehensive review that summarizes the advance-
because it does not have CO2. However, its renewability and ment in the use of nanomaterials for hydrogen production
“pollution-free” characteristics are based on the production and storage. Therefore, this study outlines the applications of
routes. The combustion of H2 of hydrogen releases water nanomaterials in hydrogen production (considering both
vapour, and its calorific value (141.9 kJ/g) is three times more biological and water splitting methods) and storage. Other
than that of gasoline (47 kJ/g) and 2.6 times greater than materials such as complex hydrides and clathrates used for
natural gas (54 kJ/g) [2]. Compared with other fuels such as hydrogen storage are also outlined in this study.
ethanol and natural gas, hydrogen is lighter with a density This review is organized as follows. The first section starts
of 0.08988 g/L at standard temperature and pressure (STP) with the introduction, after which the methodology is briefly
and a molar mass of 1.008 g/mol [3]. Moreover, the energy outlined. Different hydrogen production methods are
density per volume of hydrogen (0.09 kg/m3) is relatively low comprehensively discussed in Section 3. The next section
at STP compared to other fuels [3]. Due to the low volu- outlines various studies related to the application of nano-
metric energy density, storing hydrogen in vehicles requires materials for renewable hydrogen production with a focus on
a large tank at a higher pressure than other gaseous fuels biological and thermochemical conversion processes. In Sec-
[4]. Therefore, it is imperative to develop advanced storage tion 5, different hydrogen storage methods are discussed and
technologies to increase energy density per volume. The compared. Section 6 reviews previous research on the appli-
lightweight properties of hydrogen makes it a unique and cation of various nanomaterials to facilitate hydrogen storage.
versatile energy carrier with a broad spectrum of applica- The study ends with a conclusion and future perspectives.
tions. Okolie et al. [5] recently summarized different in-
dustrial applications of hydrogen. Although hydrogen is a
promising fuel, its production and storage are associated Methodology
with several technical and scientific challenges that impede
its worldwide implementation [6]. Google Scholar, Scopus, Web of Science, and PubMed were
Steam reforming of natural gas (SMR) is a widespread used as search engines for the initial search. The following
hydrogen production method. However, Acar and Dincer's [6] keywords and/or phrases were used: complex metal hydrides,
studies reveal that fossil-based hydrogen production is one of hydrogen storage nanomaterials, limitations of hydrogen
the most environmentally harmful processes. As such, there storage, nanomaterials for renewable hydrogen storage,
is an urgent need to develop large-scale, cost-effective, hydrogen storage nanoconfinement nanoelectrocatalysts,
renewable, and ecologically benign hydrogen production nanophotocatalysts, carbon nanotubes, catalytic nano-
processes. materials, carbon-based nanocomposites, carbon cryogel
Another challenge, as noted earlier, is associated with the nanocomposites, fullerene-based nanocomposites, and metal
lack of practical, easy, safe and cheap storage methodologies organic framework. The search was narrowed down to two
[7]. Additionally, the onboard storage of hydrogen in vehicles categories. Category 1 is for articles published within the last
is another bottleneck because of the stringent requirements in eight years to ensure that the information presented is recent
its storage. Currently, hydrogen is often stored in the gaseous and relevant. The second category is for articles published in
or liquid form in pressurized or cryogenic tanks [8]. However, the 30 years to provide the readers with the research progress
these technologies do not meet the requirements of large- and pioneering findings in nanomaterials for hydrogen pro-
scale storage. Therefore, there is a need to develop cost- duction and storage.
effective, reliable, and safe storage systems to foster the The articles were screened into two subcategories. In
development of a hydrogen economy. screening Category 1, studies related to the application of
Engineered nanomaterials have a size ranging from 1 to nanomaterials to renewable hydrogen production were
100 nm and are produced and designed specifically to simu- considered. Category 2 focuses specifically on the applications
late their properties for specific applications. Nanomaterials of nanomaterials for hydrogen storage. Literature screening
are beginning to play a significant role in the development of was performed by an initial reading of the articles' title, ab-
new fields in addition to their tremendous impact on stract, and conclusions to obtain the overall scope and
improving hydrogen production and storage [9].
objectives. Based on this, articles that fit the objectives of this moderate temperature (225e265 C) and pressures (27e54 bar)
study were selected. About 120 papers were chosen to fit the [18]. Under these conditions, steam formation is inhibited, and
criteria. the reaction would proceed in the aqueous phase. The APR
produces high hydrogen yield and low CO yield due to its
ability to thermodynamically promote WGSR [19]. APR process
Hydrogen production routes with biomass-based feedstock has been reported by several
researchers [16,19,20]. A recent experimental study proposed
Pure hydrogen hardly exists alone due to its high reactivity; a novel pathway that utilized the aqueous liquid from Fischer-
instead, it is attached to carbon and oxygen in various com- Tropsch (FT) synthesis to produce biohydrogen through APR
pounds such as hydrocarbons, water, etc. A significant [21].
quantity of energy is needed to separate hydrogen from such Alkaline enhanced reforming (AER) is another approach
compounds. Based on the separation methods, conversion used to convert water-containing organics into hydrogen at
processes, and the feedstock used for hydrogen production, low temperatures (<220 C) and pressures in an alkaline me-
colour codes such as green, grey, black, and blue are used, as dium (usually NaOH). The addition of an alkaline ensures that
shown in Fig. 1. The hydrogen produced from natural gas via the reaction medium maintains a basic pH to create an envi-
stream reforming without carbon capture and storage (CCS) is ronment that promotes conventional SMR [18]. The carbon
called grey hydrogen. Moreover, if bituminous or lignite coal is produced from APR precipitates as solid Na2CO3 rather than
used as feedstock, the hydrogen is called black or brown gaseous pollutants (CO and CO2) in SMR. Therefore, APR pro-
hydrogen [12]. Steam reforming of natural gas coupled with duces fewer greenhouse gases and is more environmentally
CCS produces blue hydrogen. This type of hydrogen is carbon friendly.
neutral if all the CO2 is captured and stored underground. Partial oxidation, autothermal reforming, combined steam
However, the process is termed “low carbon” if CO2 is not methane reforming with partial oxidation are also promising
captured completely. Hydrogen produced from electrolytic hydrogen production methods from hydrocarbons. During
splitting using clean energy sources such as wind is green autothermal reforming, the hydrocarbon feed is partially
hydrogen [13]. Thermochemical and biological conversion oxidized in the presence of oxygen and steam to produce
processes also produce green hydrogen. Integrating biomass hydrogen-rich syngas [22].
conversion processes with CCS produces even more greener
hydrogen with negative CO2 emissions. Thermochemical processes
Reforming reactions (steam, aqueous, alkaline enhanced, Thermochemical processes for hydrogen production such as
and autothermal reforming) pyrolysis and gasification use heat and chemical reactions to
decompose organic materials into hydrogen [23]. During py-
Steam reforming reaction (SMR) is the dominant process for rolysis, biomass is converted to bio-oil, char, tar, a mixture of
large-scale hydrogen production, accounting for more than H2, CO, CO2, and hydrocarbons in an oxygen-depleted envi-
59% of the global production from fossil fuels (natural gas, ronment at around 400 C and 0.1e0.5 MPa [24]. Increased
heavy oils/naphtha, and coal). The other common methods hydrogen production can be achieved by reforming the pyrol-
for hydrogen production from fossil fuels are alkaline ysis by-products such as aqueous liquid (bio-oil) or further
enhanced reforming, aqueous reforming, and autothermal conversion of the CO in the gaseous product to produce more
reforming [14]. hydrogen via WGSR. The pyrolysis gas mixture is purified,
SMR refers to the conversion of the hydrocarbons, usually typically by a pressure swing adsorption or a CO2 removal
methane and steam, into hydrogen and carbon dioxide at high process [14]. Reaction temperature, residence time, and most
temperatures (~800 C) in the presence of a catalyst and under importantly, the type of biomass and catalyst used in the pro-
pressure (~3.5 MPa) (Equation (1)). The CO present in the cess are the key factors affecting hydrogen yield during pyrol-
syngas also reacts with water to produce hydrogen and carbon ysis [25,26]. Based on these factors, pyrolysis can be classified as
dioxide through the water-gas-shift reaction (WGSR) (Equa- slow, fast, or flash, as detailed and compared in Table 1.
tion (2)) [15]. The produced gas mixture is then sent to Gasification is a thermochemical process that converts
sequential purification steps to achieve 100% hydrogen purity. organic matter into hydrogen-rich syngas at high tempera-
To prevent catalyst poisoning, an additional desulphurization tures and can be either conventional or hydrothermal (also
stage is required for high sulphur feedstocks before syngas known as supercritical water gasification). Although both
generation [14]. Several metal catalysts such as Co, Ni, Rh, and conventional and thermochemical gasification processes are
Pt have been used to elevate hydrogen yield from steam comparable in terms of the desired product, they differ based
reforming reactions [16,17]. on the composition of the gaseous products and the operating
conditions. In conventional gasification, biomass is converted
CH4 þ H2 O4CO þ 3H2 DH ¼ 206kJ=mol (1)
to syngas (mixture of H2, CO, CO, CH4, and other hydrocar-
bons), tar, and char in the presence of a gasifying agent like
CO þ H2 O4CO2 þ H2 DH ¼ 41kJ=mol (2)
oxygen and/or steam. The process occurs at an operating
Aqueous phase reforming (APR) of different types of temperature and pressure range of 500e1400 C and 0e4 MPa,
oxygenated hydrocarbons such as glycerol, methanol, respectively [27]. The process yield is mainly dependent on the
ethanol, or propanol is another route for hydrogen production. type of biomass, type of catalyst, particle size, steam-to-
The process occurs in the presence of a metal catalyst at biomass ratio, and reaction temperature [28,29].
Fig. 1 e Hydrogen production routes and the associated colour codes. Note: the colour codes presented here are solely based
on the present authors' perspectives and experiences; moreover naming convention and colour codes often differ across
countries and over time. (For interpretation of the references to color in this figure legend, the reader is referred to the Web
version of this article.)
Hydrothermal gasification is the thermochemical conver- oxygen [14]. In the metabolic process of dark fermentation,
sion of organic materials into hydrogen-rich syngas under sequential carbon chain reactions are carried out by the obli-
supercritical conditions (temperature >374 C, pressure gate and facultative anaerobic bacteria to convert organic
>22.1 MPa) [30]. Water displays unique physicochemical substrates into hydrogen, ethanol, and volatile fatty acids in
properties such as gas-like viscosity and liquid-like density at the absence of light [36]. An initial pre-treatment step might
supercritical conditions, leading to improved dissolution and be required to increase glucose digestibility when recalcitrant
mass transfer [31,32]. Despite being more advantageous in lignocellulosic biomass is used as a substrate [14]. For suc-
terms of improved hydrogen yield and the ability to handle cessful operations, pH should be maintained in a range of 5e6,
wet feedstock without drying, hydrothermal gasification has and the produced hydrogen should constantly be removed
several challenges limiting large-scale production. The high from the system to stimulate the hydrogenase enzyme [37,38].
temperatures and pressures needed to attain supercritical Photo-fermentation relies on the nitrogenase enzyme in
conditions lead to an elevation in the operating cost compared photosynthetic bacteria to convert organic acids into H2 and
with other biomass conversion technologies [23] and potential CO2 [39]. In the case of using industrial wastewater as the
noise, explosion, injury, and odour risks [33,34]. substrate, an additional pre-treatment step is required for
heavy metal and colour removal to attain sufficient light
Biological processes penetration [36]. Although photo-fermentation achieves
higher theoretical H2 production yields, the limited availabil-
Biological processes use microorganisms to decompose ity of organic acids, low efficiency in solar energy conversion,
organic matter into hydrogen. Examples of such processes and complicated bioreactor demand with large surface areas
include biophotolysis and dark/photo fermentation. Biological are major limitations of this technology compared with dark
hydrogen production processes have attracted global research fermentation [37,38]. Nonetheless, higher H2 production
interest owing to their applicability at ambient operating yields with minimum solar energy dependency can be ach-
temperatures and pressures and waste recycling ability [35]. ieved by an integrated sequential dark/photo fermentation
In direct biophotolysis, water undergoes prior splitting into system with anaerobic and photogenetic bacteria.
hydrogen and oxygen ions by the photosynthetic activity of
green algae. The hydrogen ions are then converted into H2 Hydrogen production through water splitting
(hydrogen gas) by the hydrogenase enzyme [36] under strictly
anaerobic conditions (O2 content <0.1%) due to the extreme Water splitting involves water decomposition into H2 and O2
enzyme sensitivity [37]. The major drawbacks of the bio- through a reaction involving charge carriers. This promising
photolysis process are complex bioreactor design with large H2 generation process has improved over time, and there are
surface areas for light capturing and low hydrogen conversion currently four distinct methods explored for this purpose;
yields [36,38]. these include thermochemical (thermolysis), electrochemical
On the other hand, fermentative processes achieve (electrolysis), photochemical (photolysis), and photo-
simultaneous organic waste treatment and hydrogen pro- electrochemical methods [40]. These methods are still sub-
duction via microbial biomass transformation with or without jected to ongoing research and are at different levels of
Table 1 e Comparisons between different types of pyrolysis and hydrothermal liquefaction Nanda et al. [2], Okolie et al. [5].
Biomass conversion Main products Residence Reaction Biomass particle Heating
processes time (s) temperature (oC) size (mm) rate (oC/s)
Fast pyrolysis Biochar < Gases < Bio-oil 0.5e10 400e800 <1 10e200
Slow pyrolysis Gases < Bio-oil < Biochar 600e6000 300e700 5e50 0.1e1
Flash pyrolysis Biochar < Gases < Bio-oil <0.5 800e1000 <0.2 1000
development. The thermolysis process is very similar to cathode through the electrolyte, while the electrons travel
electrolysis except for the use of thermal energy for water through an external circuit to react with the Hþ at the cathode
splitting instead of electricity. to produce H2 [45].
Thermochemical water splitting involves the decompo- Water splitting can also be caused by sunlight and elec-
sition of water into O2 and H2 through repetitive series of tricity, in the presence of photocatalysts [46] absorbing sunlight
chemical reactions, usually at temperatures between 500 to generate electrons and holes. The charges are separated and
and 2000 C [41]. In theory, heat is the only form of energy migrate to the catalyst's surface. After that, a surface reaction
required for this reaction to occur, as every other resource is with the H2O molecules occurs, facilitating water splitting into
recycled and reused. As a result of the high heat energy H2 and O2 (redox). In most cases, photocatalysis requires a
requirement, the process is costly. Therefore, it has limited sacrificial (electron) donor that removes the photogenerated
its application in the large-scale production of H2, despite holes from the catalyst [40]. The sacrificial donors, which are
offering more than 77% efficiency [40,41]. During thermo- primarily carbon-based molecules, get oxidized in the process
chemical water splitting, the water should be heated above to form CO2. This has environmental implications and must be
2500 C to achieve hydrogen separation [14]. Besides, several addressed to make the process more attractive. There is,
thermolysis cycles (CueCl and MgeCl) are preferred to help therefore, a recommendation that the term “water splitting”
lower the reaction temperature. In these cycles, sequential should not be used when a sacrificial donor is involved [40]. In
chemical reactions are carried out at different temperatures addition, there are also concerns about the low conversion ef-
where the heat is converted into a chemical energy carrier in ficiency, high cost of conversion, and unstable catalysts asso-
the form of H2 [42,43]. ciated with photocatalytic water splitting [46]. These concerns
Electrochemical water splitting involves splitting water indicate that there is substantial progress required before
into H2 and O2 by the passage of electrical energy in electro- photocatalytic water splitting becomes a credible and sustain-
chemical cells. A typical electrolysis unit consists of an anode able alternative for hydrogen production.
(negatively charged) and cathode (positively charged) probes Photoelectrochemical hydrogen production involves split-
submerged in an electrolyte. Following the passage of electric ting water with sunlight and specialized semiconductors
current, H2 is produced in the cathode while O2 accumulates called photoelectrochemical materials [40]. The semi-
around the anode [44]. The redox reaction, where two half- conductor materials are similar to those used in photovoltaic
reactions occur simultaneously, is one of the most prom- solar electricity generation. However, they are immersed in a
ising methods of renewable H2 production. An oxidation half- water-based electrolyte in which sunlight facilitates the
reaction, commonly called oxygen evolution reaction (OER), water-splitting process. The process is promising because it
occurs at the anode of the electrochemical cell. In contrast, a can produce cost-effective hydrogen with improved conver-
reduction half-reaction, commonly called H2 evolution reac- sion efficiency. However, the current limitations are the
tion (HER), occurs at the cathode of the electrochemical cell. semiconductor materials' durability, cost, and lifetime and
The OER and HER are represented by Equations (3) and (4), low sunlight absorption [47]. Table 2 outlines the advantages
respectively. and limitations of different hydrogen production methods
discussed in this section.
2H2 O / O2 þ 4Hþ þ 4e (3)
2Hþ þ 2e / H2 (4) Nanomaterials for renewable hydrogen

Alkaline, proton exchange membrane, and solid oxide production
electrolysis cells are currently the most developed technolo-
gies for pure hydrogen production from water splitting. Nanoelectrocatalysts
However, the electrochemical reactions are extremely endo-
thermic, leading to high electricity consumption, rendering The application of nanomaterials has gained popularity in
these technologies economically unfeasible [14]. electrochemical, photochemical, and photoelectrochemical
The photolysis process is very similar to electrolysis; water splitting. Electrocatalysts have a crucial role in facili-
however, the energy requirement of the water splitting is tating water splitting to unlock its full potential of producing
provided by the absorbed sunlight by the semiconducting pure hydrogen that can meet the world's fast-growing energy
materials. An electron-hole pair is produced and separated demand. This is because the two half-reactions of water
due to the electric field between the electrolyte and semi- splitting e HER, and especially OER, are kinetically limited,
conductor. The holes stay at the anode and decompose water requiring electrocatalysts to speed them up as well as to make
into hydrogen ions (Hþ) and oxygen. The Hþ travels to the them less energy-consuming [40].
Table 2 e Major advantages and disadvantages of different hydrogen production technologies.

Advantages Disadvantages
Fossil Fuel Treatment Most established industrial process. Causes massive GHG emissions and increased
Steam reforming Higher production yields. carbon footprint.
Partial oxidation Economically more feasible. Limited feedstock availability due to the
Autothermal steam High purity hydrogen is produced. depletion of fossil fuels.
reforming High operation temperature requirement
Lack of adequate carbon capture storage tech-
nologies (CCS).
Catalyst poisoning due to sulphur-containing
feedstock.
Thermochemical Higher production yields than biological High operation temperature requirement.
Processes processes. Increased tar formation.
Gasification CO2 neutral Varying H2 content based on biomass season-
Pyrolysis Sustainable feedstock supply. ality and impurities.
Short hydraulic retention times.
Negative CO2 emission when CCS is used.
Biological Processes Sustainable feedstock availability Low production yields and rates
Biophotolysis Negative CO2 emission when CCS is used. Long hydraulic retention times requirement
Dark/photo More environmentally friendly than fossil fuel Difficulty in maintaining process stability
fermentation production routes and thermochemical High O2 sensitivity
processes Large surface area requirement for collecting
Less energy-intensive due to mild operating adequate light (biophotolysis)
conditions No waste recycling (biophotolysis)
Provides H2 production and waste treatment
simultaneously (fermentation).
Water splitting Sustainable feedstock supply High investment and operational costs
Electrolysis O2 is the sole by-product Low conversion efficiency
Thermolysis CO2 neutral Corrosion problems
Photolysis Sunlight demand (photolysis)
Photoelectrochemical
Nanomaterials are taking centre stage in recent electro- reaction intermediates, adsorption free energy (eV), Faradaic
catalytic and photocatalytic research because they exhibit efficiencies (%), electrochemical surface area (cm2), stability
desirable and tenable mechanical and electrical properties, of- time with unchanging overpotential, mass activity (mAmg1),
fering large surface areas that significantly lower energy barriers specific activity (mAcm1), charge transfer resistance (ohm),
and promote electron transfer at the electrodes. For instance, disruption of electronic, electron density at the Fermi level. It
electrospun nanomaterials-based electrocatalysts (ENME) can is also important that suitable nanoelectrocatalysts are
undergo electronic modulation and interface engineering to bifunctional, environmentally friendly, and inexpensive to
enhance their catalytic performance [48]. Electronic modulation minimize hydrogen production costs by water splitting while
refers to catalyst doping with heteroatoms, while interface en- maintaining a safe environment. Currently, no single catalyst
gineering is the construction of hybrids with unique interfaces possesses all the characteristics mentioned above [48,50,62].
that can contribute to more active sites on the catalysts. While electrocatalysts and photocatalysts are both applied
Pt-group-metal-based electrocatalysts (Pt, Pd, Ru, Ir, and Rh) to catalyze water-splitting reactions for hydrogen production,
have proven to be excellent nanoelectrocatalysts for water they have notable differences in properties [63]. Electro-
splitting hydrogen production [49]. However, they are scarce, catalysts utilize externally induced electrical energy, and
expensive, vulnerable to electrocatalysis poisoning, and tend to photocatalysts use solar energy. Qian et al. [63] highlighted the
agglomerate [50], preventing their commercial application. superior performance of electrocatalysts compared to photo-
Therefore, researchers are focusing on improving the catalytic catalysts and other differences between them. Nonetheless,
efficiencies of non-noble metal-based electrocatalysts for water this review expounds on the performance of a wide range of
splitting-based hydrogen production since they are cheaper electrocatalysts for H2 production based on recent research
and more earthly abundant [50,51]. Some popular non-noble contributions, as shown in Table 3. Subsequently, it presents a
metal elements under study are Ni, Co, P, Fe, Cu, C, N, Se, W, detailed review of photocatalysts for H2 production in
Mo, and S. Table 3 shows some notable, recent findings of Nanophotocatalysts.
nanoelectrocatalysts for water splitting hydrogen production.
Some key parameters that can be used to measure and Nanophotocatalysts
compare nanoelectrocatalysts performances include, but are
not limited to: overpotential values (mV), Tafel slopes Generally, photocatalytic H2 generation can be attained via
(mVdec1), turnover frequency (TOF), binding energy for photo splitting of water or photo reforming of organic species
[64,65]. These processes usually require catalysts capable of synthesis, and nanoprecipitation of polymer dots. Further
absorbing radiation in the visible range and exciting electrons details of these methods are provided by Mahzoon et al. [68].
to the energy level needed for H2 production [64]. Some Moreover, the anisotropic 1D nanostructures have been
nanomaterials, which are currently used for the photo- adopted in several studies due to the different behaviours of
catalytic production of H2 include SiC, TiO2, CdS, and CuInSe2, charge carriers obtained in different directions. One dimen-
which can be generally categorized into metal-oxide (such as sional hierarchical structure comprising of Ni3S2 nanosheets
TiO2 and WO2) and non-metal oxide (such as g-C3N4, B4C, grown on a carbon nanotube backbone was constructed by
CuInSe2, and CdS) photocatalysts [66]. The current attainable Zhu et al. [77]. Remarkably, this hybrid 1D hierarchical struc-
H2 productions efficiencies (solar-to-fuel) using these photo- ture showed significantly enhanced photocatalytic activity in
catalysts are low and far from meeting the required opera- H2 production from water splitting. Similarly, the work of
tional requirements for industrial applications [64]. Chava et al. [78] featured the development of 1D CdSeAu/
Research advancements in the field of photocatalytic MoS2 hierarchical core/shell heteronano structures (CSHNSs)
water splitting have led to the development of more than 100 by a facile two-step hydrothermal method; high stability and
new catalysts, including carbides, sulphides, and oxides [67]. efficiency toward hydrogens production were observed with
Despite these advancements, several challenges affecting this nanophotocatalyst.
their industrial applicability still exist. Some of these include 2D nanostructures, on the other hand, are desirable
the selective activeness of photocatalysts to ultraviolet light because they provide numerous reaction sites due to their
(low visible-light quantum efficiency), rapid recombination of increased specific area. Their short diffusion length reduces
photogenerated charges, poor durability and physicochem- the probability of recombination of photoexcited charge car-
ical stability, high toxicity, and difficulty in preparing the riers compared to the bulk forms of the photocatalysts [68].
catalyst on a large scale [68e70]. The factors affecting the Ganguly et al. [70] provide a detailed review with emphasis on
performance of nanophotocatalysts for water splitting are 2D nanomaterials for photocatalytic H2 production. Zhang
outlined in Table 4. et al. [79] formulated a 2D nanophotocalyst by doping ultra-
Poor light absorption and insufficient charge separation are thin nanosheets of TiO2 with quantum Cu(II) nanodots (QCNs).
the main reported factors; these are, in turn, a consequence of Their analysis further demonstrated that suppressing the
large bandgaps of the photocatalysts [71,72]. These large band recombination rate of the photogenerated electron-hole pair
gaps (mainly associated with metal oxides) often lie outside enhances the materials' photocatalytic performance. Xu et al.
the visible light region in the electromagnetic spectrum [66]. [80] showed that the photocatalytic activity of g-C3N4 nano-
Hence, they are incapable of utilizing the solar spectrum, sheets was improved by 13-fold after electrostatically
regardless of their highly active catalytic properties (photo- assembling it with hematite a-Fe2O3 nanoplates. Pt was
catalysts, which are active under visible light, are more effi- applied as a co-catalyst, whereas triethanolamine was utilized
cient and effective because visible light constitutes a as a hole scavenger. A cost-effective and straightforward
significant portion of electromagnetic radiations) [71]. For method for fabricating a hybrid 1D-2Dg-C3N4 heterojunction
instance, TiO2 (with a bandgap of 3.2 eV) is limited to a solar- nanophotocatalyst has been proposed by Mahsoon et al. [68].
to-H2 conversion efficiency of 1%, whereas Fe2O3 (with a 2.2 eV At present, modifications via co-catalysts for performance
bandgap) has a theoretical efficiency of 15% [66,73]. improvement, as shown in Fig. 2, have been exploited to
Some of the popular photocatalysts include a group of enhance the catalytic performance [81].
materials known as graphitic carbon nitrides, conjugated Morphology adjustments, band edge repositioning, and
microporous polymers (CMPs), linear conjugated polymers surface structure alterations have also been a subject of
(LCPs), and covalent organic frameworks [69,71,74]. Among immense interest using these co-catalysts [66,85]. Their
these photocatalysts, graphitic nitrides (g-C3N4), which belong application may be carried out in several forms, such as ion
to the class of organic semiconductors) have been widely doping, noble metal doping, metal-ion implantation, and
studied. They have emerged as viable candidates for solar- sensitization [67,70]. Pt is the best noble metal for this
driven H2 production via water splitting [75]. This may be purpose; however, its very high cost has led to the appli-
attributed to their optoelectronic properties and reduced cation of alternative cheaper noble metals such as Ag, Ni,
environmental footprints compared to inorganic and metal- Ru, Cu, Pd, and Ir [67]. Sensitization, a promising strategy,
complex materials. However, their inherent large molecular involves using a sensitizer (nanosized-metal particles). The
structures often yield bulky particles in water, which are sensitizer harvests sunlight (thus promoting visible light
higher than the penetration length scale of light [69]. The absorption), and thereafter, injects electrons into the con-
inevitable effect of this bulkiness is significantly optical losses, duction band of the main photocatalyst ea process referred
which ultimately reduce the catalytic performance. Thus, the to as plasmon-induced resonance energy transfer [64].
particle size of the photocatalyst is a predominant factor Furthermore, the tunable optical properties of semi-
affecting the catalyst's performance. conductor polymer photocatalysts (usually achieved by
The size reduction of the particles to a few tens of nano- altering the polymer building blocks) has also gained
metres can enhance their photocatalytic performance [76]. research attention; poly (p-phenylene), poly (azomethine)s,
Enhancing photocatalytic performance can be done using polybenzothiadiazoles, covalent organic frameworks, and
specialized methods like nano-structure engineering to ach- microporous organic nanorods have been applied for pho-
ieve thin layer nanosheets from bulk g-C3N4 [68,71]. Some of tocatalytic H2 production [86]. Better light-harvesting effi-
the methods include physical exfoliation (liquid and chemi- ciency may be attained with these polymers when used
cal), emulsion polymerization, sonification, template with g-C3N4 compared to g-C3N4 alone [62].
20406
Table 3 e Summary of some recent research contributions on nanoelectrocatalytic generation of H2.
Reference Approach Overpotential Current density Tafel slope Comments
Kumar et al. [51] Experimental 1.4e2.0 V 1e10 mA cm2 134 and 152 mVdec1 A multi-step solvothermal process was used to
assessment using (HER) synthesize multi-shelled NiO/Ni/Graphene and
Teflon-lined autoclave Co3O4/Co/Graphene nano-spheres from MOFs,
and centrifuge producing a highly efficient and stable catalyst
for both HER and OER in acid media. The Co-
based catalyst proved more efficient.
Narwade et al. [49] Experimental 582 mV for HER in an 10 mA cm2 63 mVdec1 for HER in A bifunctional, noble metal-free electrocatalyst
assessment via acidic medium an acid medium; 41 was synthesized by a chemical process using Ni/
morphological mVdec1 for OER in NiO on reduced graphene oxide (Ni/NiO @ rGO).
characterization (TGA, basic media
TEM, FESEM, EDAX,
XRD)
Wang et al. [52] An experimental study 325e540 mV for OER and 10 mA cm2 97-157 mVdec1 (HER); A promising, high-active and stable bifunctional
using HRTEM 337e404 mV for HER in 65e162 mVdec1 (OER) electrocatalyst (CeNiFeOx) was proposed using a
an alkaline media. facile one-pot combustion approach. A new
height of 20% solubility of Ni/Fe in the ceria
lattices was achieved for the first time.
Ce0.8Ni0.15Fe0.05Ox showed more excellent
bifunctional catalytic performance.
Wan et al. [53] Experimental 133 mV for HER in an 10 mA cm2 e CoSe2 nanostructured particles were synthesized
assessment via acidic medium on 3D nano-netlike carbon fibres (CoSe2-CFN) by
electrostatic spinning a spinning technique. The CoSe2-CFN is
and characterization characterized by high CoSe2 particle dispersion,
high electrical conductivity, and catalytic
activity.
Han et al. [54] An experimental study 290 for OER and 77 mV 10 mA cm2 56 mVdec1 Cobalt phosphide incorporated with Vanadium
via FE-SEM, EDS, TEM for HER, in alkaline (CoVP) self-supported catalyst on carbon cloth
and XRD) media. (CoVP@CC) was proposed in the study as a highly
efficient, bifunctional electrocatalyst for OER and
HER in alkaline medium.
Jadhav et al. [55] Experimental study 240 and 401 mV for OER 100 mA cm2 189 mVdec1 (OER); 103 This study fabricated an organic-inorganic
using electrosynthesis. and HER. mVdec1 (HER) nanohybrid, namely BSeF/Ni(OH)2, using one-
step reductive electrosynthesis. The synthesized
BSeF/Ni(OH)2 was demonstrated to be a
bifunctional electrocatalyst with an excellent
performance:
Yan et al. [56] Experimental and 67 mV (HER) in acidic 10 and 100 mA cm2 57 mVdec1 and 82 A self-supported, hierarchical, and edge-rich
theoretical study using media and 89 mV (HER) mVdec1 in acidic and electrocatalyst from nickel phosphide
VASP (Viena ab initio in basic media. basic media. nanosheets arrays on nickel foam (Ni2P NSs)
Simulation Package) showed highly efficient catalytic ability for HER in
both acidic and basic media.
Dai et al. [57] Experimental/Density 171 and 243 mV for HER 10 mA cm2 28.1 mVdec1 A new bifunctional electrocatalyst for water
Functional Theory (DFT) and OER, respectively splitting was found in CoNi2S4/Ni3S2 on nickel
foam (CoNi2S4/Ni3S2@NF) in alkaline media. The
obtained electropotentials supersede those of
metallic NF and Ni3S2 separately. DFT
calculations showed that the strong coupling
between CoNi2S4 and Ni3S2 improves the
electrochemical performance.
Kumar and Experimental 271 and 197 mV for OER 10 mA cm2 48 mVdec1 (OER); 130 A bifunctional electrocatalyst for efficient water
Bhattacharyya [58]. assessment applying and HER in alkaline mVdec1 (HER) splitting was manufactured from porous NiFe-
thermal treatment in medium oxide nanocubes (NiFe-NC). It also shows
air. corrosion-resistant properties for water splitting,
in addition to its long-term stability.
Zeng et al. [59] Experimental in 80 and 210 mV for HER 10 mA cm2 65 mVdec1 (HER); 62 A nanoelectrocatalyst was produced through a
combination with DFT and OER, respectively mVdec1 (OER); formation of a 3D-heterogeneous-nickel
phosphide and its sulphide (Ni2P and Ni3S2) on
nickel foam (Ni2P/Ni3S2@NF), which enhances its
catalytic performance for water splitting in
alkaline media.
Mugheri et al. [60] Experimental study on a 0.31 V 10 mA cm2 42 mVdec1 Pristine SnCo and Cu-doped SnCo
solarton potentiostat nanoelectrocatalysts were synthesized and
studied. Cu-doped with 46% Cu showed an
excellent HER catalytic performance comparable
to the precious Pt/C.
Wang et al. [61] Experimental in a 117 mV for HER 10 mA cm2 66 mV dec1 MoSe2@Ni8$85Se electrocatalyst was shown to
Teflon-lined stainless- have excellent conductivity and abundant
steel autoclave) exposed sites that greatly improved HER in an
alkaline medium.
20407
Table 4 e Factors affecting nanophotocatalyst performance and selection Bhatt and Lee. [66], Ganguly et al. [70].
Factors based on photocatalyst conversion Factors based on practical application &
efficiency operating conditions of the photocatalytic
process
Extent of light absorption (specific photoactivity Resistance and stability under visible light
> 104 mmoles H2/h.g e (photohydrostability without undergoing
photocorrosion in aqueous solution).
Bandgap and exciton generation/charge mobility. Nature of co-catalyst and preparation method.
Ability to promote HeO bond cleavage via a pH and operating temperature.
reduction of the reaction energy barrier (500 kJ/
mol).
The extent of separation and recombination of Size and shape tunability of photocatalyst
photogenerated holes and electrons (charge particles, including morphology/structure and
carriers). crystallinity.
Charge collection rate at electrodes. The concentration of sacrificial agent
(photoreforming).
Specific area (1D or 2D nanostructure) Cost-effectiveness
The removal of nanoarchitectures by photons so Toxicity level
that they reach the reactive site
Suitability of sacrificial electron donor Suitability for large scale preparation
Inorganic co-catalysts such as NieP have also been applied consequent enhancement of photocatalytic ability (up to 5275
with pristine g-C3-N4 to enhance their photocatalytic activity mmole of H2 (mmole protein1h1) [72].
[87]. The importance of this doping strategy has been effec- The discussion presented thus far demonstrates that a
tively demonstrated in the work of Kalisman et al. [83], where majority of the research efforts on the use of nano-
a record 100% photon to H2 conversion efficiency was attained photocatalysts for H2 production have been mainly studied via
using Pt-tipped CDSe@CdS nanophotocatalysts. However, the experiments. Very few studies focusing on the application of
photochemical instability of CdS and the high cost of Pt are the theoretical/computational methods exist. These
main limitations of this strategy [83]. computational-based studies on nanophotocatalytic mate-
The application of metal oxide co-catalysts, which can act rials have mainly applied density functional theory (DFT) to
as photocatalysts themselves, has also been demonstrated by predict ground-state properties as a function of the electronic
Zada et al. [71]. SnO2 as a metal oxide has an outstanding UV density, primarily using TiO2 photocatalysts. However, sig-
response, although with a bandgap of 3.5eV. Its modifiable nificant underestimations of the bandgap have been reported
optical properties and exceptional stability make it suitable in many DFT-based studies [66]. The parameter is computed
for photocatalysis. The authors showed that the heterojunc- using the Kohn-Sham methods (via the generalized gradient
tional combination with g-C3N4 with SnO2 enhances charge approximation (GDA) or the local density approximation
separation for increased photocatalysis in comparison to g- (LDA). Nonetheless, using hybrid approaches, which utilized
C3N4 alone. For photocatalytic water splitting, Clarizia et al. approximate DFT functionals (such as LDA) with the exact
[64] recommended that an efficient photocatalyst should have Hartree-Fock method, can potentially improve computational
a bandgap greater than 1.6e1.8 eV and should be narrower accuracy. A summary of some modelling-based studies in this
than 2.2eV to allow efficient activation under natural solar regard is presented in Table 5.
irradiation. Fig. 3 shows the required energy for both solar
driving and reforming photocatalytic reactions. Nanomaterials for biological hydrogen production
Since photocatalytic reforming relies on the oxidation of
organic sacrificial agents by photogenerated holes (which are Nanomaterials can be applied at different stages of bio-
in turn reduced by photogenerated electrons to form H2 gas), it hydrogen production, including biomass pre-treatment,
is required that the valence band be more positive than the improved sugar and enzymes production, and enzymatic hy-
redox potential of the sacrificial species, for efficient H2 pro- drolysis (Fig. 4) [95].
duction [64]. Photoreforming of organics yields H2 generation Nanomaterials such as Ni, Fe, and Cu play a significant
rates, which are more than 2 orders of magnitude higher than role in improving biomass-to-biohydrogen processes. Fe
that of photocatalytic water splitting [88]. Hence, there is a and Ni behave like a cofactor on the active site of nitroge-
need for an optimal selection of a sacrificial agent for these nase and hydrogenase enzymes, thereby elevating bio-
reactions. Further details of this photoreforming process can hydrogen production yield [96]. They could also act as
be found in the study of Clarizia et al. [64]. oxygen scavengers during fermentation by removing all the
Biological systems, which are naturally nanoscaled, have undesired oxygen present and minimizing the oxidation-
also been employed as reliable platforms for engineering reduction potential [95]. The removal of oxygen during
nanophotocatalysts. Photoelectrochemical analysis on TiO2 fermentation creates a favourable anaerobic environment
catalyst shows effective charge transfer between a biological for the action of the hydrogenase enzyme and improves
protein (bacteriorhodopsin) and TiO2 nanoparticles and a biohydrogen yield [97].
Fig. 2 e (a) Pt co-catalyst appended to CdSe/CdS nanorods; (b,c) TEM images of CdSE/CdS nanorods showing Pt co-catalyst on
one side; (d) Photocatalytic/photoelectrochemical H2 evolution for aqueous Na2S solution; (e) H2 evolution on CZTS-Pt
nanoparticles. Adapted from Xu et al. [80], Khon et al. [82], Kalisman et al. [83], Moroz et al. [84], respectively.
Fig. 3 e (a) Required energy gap for solar-driven photocatalytic water splitting and (b) photocatalytic reforming of organic
species. Reprinted from Clarizia et al. [64].
Previous studies also indicate that the addition of magnetic improved hydrogen yield, a low production rate is often
nanoparticles could influence the thermal stability and pH of observed [98]. Nanomaterials can create anoxic conditions,
cellulase enzymes and reduce the lag phase of microorgan- permitting fast e transfer from e donors to the corre-
isms leading to improved hydrolysis [98]. In addition, the sponding e acceptors, improving reaction kinetics and bio-
incorporation of magnetic nanoparticles (specifically Fe and hydrogen yield [100].
Ni) to the bioreactor can enhance hydrogen yield because of Engliman et al. [101] showed that the addition of Fe and Ni
their ability to bond to the active sites of the enzymes [99]. as metallic co-factors at the enzyme active sites during
During dark fermentation, the hydrogenase enzymes are fermentative hydrogen production could act as a biocatalyst
employed in breaking down sugar-rich organic substrates in towards improving biohydrogen yield. The addition of Iron (II)
the absence of oxygen. Although dark fermentation produces oxide and nickel oxide under thermophilic conditions of 60 C
20410
Table 5 e Summary of some recent research contributions on nanophotocatalytic generation of H2.
Reference Approach Band gap Comments
information
Yu et al. [69] Combination of e By applying a facile approach for the synthesis of nanoparticulate organic photocatalysts, a 70-fold
hydrophilic polymers However, a HOMO-LUMO improvement in the H2 evolution rate was obtained (37.2 mmol h1 g1) under sunlight irradiation.
with a gap is provided
nanoprecipitation
technique
Anthony Raja and Experimental evaluation Reduction from 2.5 eV to Using synthesized CNT doped CdZnS/Fe2O3 nano-photocatalyst, a H2 production rate of 2679 mmol/h
Preethi [89]. using a novel 2.32 eV after CNT doping was obtained compared to CdZnS/Fe2O3 only (2009 mmol/h).
trapezoidal
photoreactor
Zada et al. [71] Robust experimental 2.7 eV (g-C3N4) and g-C3N4 nanosheets were constructed and functionalized with SnO2 nanoparticles for H2 production
catalyst 3.5 eV (SnO2) from water splitting. The hybrid catalyst fabrication (g-C3N4 e SnO2) enhanced H2 production
characterization compared to the individual application of g-C3N4 and SnO2.
Mahzoon et al. [68] Novel synthesis method 2.70 (C3N4(1D)) A method for the fabrication of 1D-2D g-C3N4 heterojunction nanophotocatalyst was developed, which
for (C3N4(1D-2D)) 2.84 (C3N4(2D) exhibited enhanced activity under visible light irradiation for H2 production (2.6 and 4.1 times that of
catalyst 2,78 (C3N4(1D-2D)) C3N4(1D) and C3N4(2D), respectively).
Maghrabi et al. [90] Simplex centroid design 2.33 eV Statistical optimal design of experiments was applied to fabricate a photocatalyst via optimal
(SCD) and BoxeBehnken combinatorial ratios of a-MoO3, WO3 and CdS catalysts. The produced catalyst showed high potential
design (BBD) for H2 production from wastewater under a broad range of wavelengths.
Pati et al. [86] Nanoprecipitation of 2.38 eV, 1.98 eV, and Converting an organic polymer into polymer nanoparticles via nanoprecipitation is an efficient way of
polymer Pdots coupled 2.46 eV for Pdots 1, 2 and significantly improving photocatalytic performance. An H2 evolution rate of up to 50 mmol g1h1 is
with DFT validation 3, respectively achieved. N in the benzothiadiazole unit is the main reactive site.
Pavliuk et al. [81] Experimental e A nano-hybrid assembly is produced by combining natural product stabilized Ag nanoparticles, TiO2,
assessment using a and Ru nanoparticles as a co-catalyst. A solar-to-fuel efficiency of up to 20% was achieved compared to
photocatalytic reactor 10e12% efficiencies obtainable in conventional photovoltaic electrolysis.
Balasubramanian et al. H2 evolution e A light-harvesting biological proton pump (bacteriorhodopsin) was applied to enhance the visible light
[72] measurements in a reactivity of TiO2 photocatalysts for photon reduction (to H2) using a Pt nanocrystalline catalyst.
sealed reaction vessel
Kaur and Singh [91]. DFT calculations: 72-, 2.85 eV, 2,85 eV & 2.7 eV The electronic properties of amorphous and crystalline TiO2 for photocatalytic H2 production were
96- and 216-atom for the 72-, 96- and 216- compared. Amorphous TiO2 may be utilized as a cheaper, more abundant, but slightly less efficient
models utilized for atom models photocatalyst than TiO2 in crystalline form.
amorphous TiO2
representation
Hanaor et al. [92] Theoretical assessment 3 meV difference Cationic doping of TiO2 stabilizes the anatase phase relative to the rutile phase at standard conditions;
using DFT between the rutile and anionic doping similarly inhibits anatase to rutile transformations. The effects of the tested dopants on
anatase phase the stability of the anatase phase are shown to be in the order: F > Si > Fe > Al
led to an increase in hydrogen yield by 34.38% and 5.47%,
nanocrystals and MoO3 molecules with TiO2. In HCOOH aqueous solutions, high photocatalytic activity
respectively, compared to the control test [101]. Moreover, the
nanoparticles (TiO2, ZnO, Fe3O4, Ni) was established. The possibility of tailoring the optoelectronic
microbes did not consume the metal nanoparticles at the end

The existence of charge transfer between graphene and deposited semiconductor and magnetic
A green and straightforward photodeposition technique was utilized for the coupling of MoS2
of the experiments. Wang et al. [102] studied the effect of
nickel nanomaterial addition on biohydrogen production
from dark fermentation. Optimal hydrogen production and
biohydrogen yield of 288.6 ml and 296.1 ml per g glucose
consumed, respectively, were reported at 5 C and pH of 7.0
[102]. Taherdanak et al., [97]. Used the central composite
design (CCD) to study the effect of Fe and Ni nanoparticles on
biohydrogen production from dark fermentation. The addi-
tion of both nanomaterials elevated the biohydrogen yield up
to 200% higher than those in the corresponding control test
properties of graphene for H2 production was demonstrated.
[97]. Studies have shown that nanomaterials have the po-

tential to modify the morphology of the microorganisms
of the MoS2/TiO2 system is observed for H2 generation.
during dark fermentation in such a way that it could lead to

improved biohydrogen yield [103].
Nanomaterials could also be impactful in elevating the
hydrogen yield of photo-fermentation [104]. The nitrogenase
enzymes used during photo-fermentation are dominated by
Fe acting as a major co-factor at the enzyme's active site [99].
Besides, the inclusion of Fe and Ni during photo-fermentation
helps maintain the enzymes' structural integrity. Moreover,
photocatalytic nanomaterials such as ZnO and TiO2 can
improve the photo-conversion efficiency of the bacteria while
supplying the required energy for hydrogen production [104].
The use of nanomaterials during photo-fermentation also
results in the fast transfer of a photo-induced electron to the
enzyme system, thereby improving the yield and productivity
of hydrogen [104].
Nanomaterials for thermochemical hydrogen production
Nanomaterials are often used as active metals of heteroge-

neous catalysts or promoters during thermochemical pro-
Bulk value of 1.75 eV
cesses [105]. Specifically, Ni-based catalysts are promising for

hydrothermal gasification due to their small active metallic
particle size, high dispersion rate, and effective catalytic ac-
tivity [106]. Other nanocatalysts used for thermochemical
hydrogen production via gasification include Fe, Cu, Pt, Ru,
e
and Mg. The Ni nanocatalysts are preferred due to their low

cost and effective hydrogen selectivity in hydrothermal con-
ditions. Magnetic nanoparticles for thermochemical H2 pro-
with first-principles DFT
duction can be classified as metal oxides, alloys, active

characterization of a
assessment coupled
metal chalcogenide.
metals, and ferrites, as shown in Fig. 5 [107].

FeeNi supported on g-Al2O3 showed improved catalysts
Experimental
Experimental
ability during the gasification of algae under hydrothermal

calculations
conditions [106]. Zn nanoparticles were used as a promoter

for Ru/g-Al2O3, to improve H2 yield during the hydrothermal
gasification of bagasse. The addition of Zn nanoparticles led
to an elevation in the H2 and total gas yield by 16.67% and
6.6%, respectively [108]. Similarly, the addition of Cu promoter
to Ni/CNT increased H2 yield by a factor of 5.84 during the
hydrothermal gasification of bagasse [109].
Metal oxide catalysts for thermochemical hydrogen pro-
Kanda et al. [94]
duction have been subjects of interest among several re-

Das et al. [93]
searchers because of their stability, low price, and

regeneration ability when compared to transition metals
catalysts [110]. Furthermore, the transition metal catalysts are
prone to sintering, agglomeration, and deactivation due to the
Fig. 4 e Application of nanomaterials at different stages of biological hydrogen production.
harsh SCW conditions and not being cost-efficient at large- hydrogen production include WO3, TiO2, MgO, ZrO2, ZnO, and
scale applications. Metal oxides are easy to store, and trans- NiO [111]. WO3, TiO2, and ZrO2 are effective in elevating the
port and are more stable than metal catalysts [111]. Different gasification efficiency of glucose under hydrothermal condi-
metal oxide catalysts that have been used for thermochemical tions [111]. ZrO2 and TiO2 are widely known as thermally
stable solid catalysts because of their ability to prevent
methanation reactions while promoting hydrogen production
[110].
Nanoparticles, specifically Ni and Fe, can also be directly
impregnated into biomass pores before thermochemical
conversion processes to eliminate the need for external het-
erogeneous catalysts [112]. This technique showed promising
hydrogen yield and gasification efficiency [112,113].
Hydrogen storage methods
As the efforts to maximize the potential of H2 as a clean and

efficient energy source intensify, its efficient, safe and
economical storage is critical for a thriving H2 economy [114].
As a result of this realization, H2 storage technologies have
gained the attention of researchers over time [11,115,116].
Principally, H2 is usually stored in four forms: compressed gas,
Fig. 5 e Classification of different nanoparticles used as liquefaction (cryogenic), cryo-compressed, and solid-state
catalysts for thermochemical conversion processes. storage. These various methods of storage are at different
Table 6 e Pros and cons of different H2 storage methods.
Hydrogen storage methods Advantages Limitations References
Compressed gas Technology is matured and presently Gravimetrically and volumetrically Durbin and Malardier-Jugroot [118].
the best-understood method. inefficient (low storage density) Peschel [119].
For underground storage, it is safer, High energy cost required to compress
saves space and can be stored for a long the gas
time Large Storage vessels are required,
Lighter storage vessels are being leading to high space consumption,
developed. except in geological storage of com-
H2 is stored in its natural form and can pressed gas where gases are stored
be directly used when needed underground
Not suitable for long term storage (due
to high pressure) except for geological
storage
It is considered unsafe, as leakage may
result in massive explosions
Liquefaction Gravimetrically and volumetrically effi- High energy is required for liquefaction. Durbin and Malardier-Jugroot [118].
cient (high storage density). Relatively high cost, mainly if carried Peschel [119]. Berstad et al. [120]
Technology is matured, hence out on a small scale.
developed. Storage vessels are expensive and
Relatively smaller storage vessels are consume land space (relatively less than
required. compression vessels).
Safer compared to compressed gas
storage.
Solid-state-storage It is safer. Regeneration is required before solid Abdalla et al. [11] Rusman and Dahari
Large amounts of H2 can be stored in storage can be reused. [115]. Zhevago et al. [116] Tarhan and Cil
small volumes at moderate tempera- It can be expensive, especially for metal [121],
tures and pressures. hydrides.
It can store H2 for a long time and rela- Regeneration is often slow.
tively more conveniently.
It is highly efficient.
Cyro-compressed It has more storage density than cryo- High cost. Bhatt and Lee [66]. Moradi and Growth
genic storage. Lack of available infrastructure. [114].
It is a safe method of H2 storage
20413
Table 7 e Properties of pressure vessel types. Adapted from Elberry et al. [122], Moradi and Groth [114], Ozaki et al. [123].
Pressure Composition () Density of storage vessel Relative cost () Pressure Limit (MPa)
Vessel Type (kg_steel/m3_steel)
Type I Metallic (carbon steel 1360 Least expensive 50
and low alloy steel)
Type II Thick metallic hooped 816 to 952 50% more than Type I No documented limit
ewrapped composite
(aluminum or steel and
fibre resin)
Type III Carbon fibre composite 340 to 454 Double of Type II 45

and aluminum (liner)
Type IV Polymer like HDPE Very light Very costly 100

(liner) and carbon fibre
or carbon-glass
composite
Type V Full composite (fibre 20% lighter than Type IV Very costly Very limited
reinforced shell) (unfit for large-scale storage)
stages of development. They have their strengths and weak- compressed gas, leading to higher storage density and less
nesses, making them apt for various applications, as dis- storage volume. Few experimental studies have been pub-
cussed in the following sections and summarized in Table 6. lished in this area over two decades [120].
As a result of this low boiling point (20 K), refrigeration,
Compressed gas storage insulation, and vacuum superinsulation may be used to
liquefy H2 and maintain this liquid state [117,118,119,125]. For
Compressed gas storage involves reducing the gas volume instance, refrigeration was successfully applied in the Ingol-
(while the pressure rises) to make it containable in a storage stadt and Leuna H2 liquefaction plants to bring H2 to 20 K
medium. Since H2 has a relatively large volume for any given temperature [126]. H2 liquefaction in the Ingolstadt plant was
mass (due to its density), it is challenging to store it by carried out in four stages; two catalytic converters operating
compression. Moreover, its compression is energy-intensive at isothermal conditions with liquid N2 and liquid H2 bath
and costly. For instance, the energy required to compress followed by two adiabatic steps. Bracha et al. [126] estimated
hydrogen gas to 600 bar is 20.48 MJ/kg, while the energy the exergy efficiencies of the Ingolstadt and Leuna plants to be
needed for methane gas to 600 bar is 1.25 MJ/kg. This differ- 21.0 and 23.6%, respectively. Modelling studies of large-scale
ence is significant (more than 16 times higher) [124]. plants have yielded up to 56.8% higher exergy efficiencies,
In compressed H2 storage systems, the storage means and with ortho-para conversion steps ranging from 2 stages to
the compressor involved are integral parts of the system, as continuous technologies [120]. A detailed comparison of
they significantly affect the system's safety, cost, and reli- modelling and existing liquefiers is presented elsewhere in
ability. This section discusses two common storage means the literature [120].
storage vessels and geological storage. H2 can be stored in Although liquid H2 storage is a matured technology with
aquifers, depleted natural gas and oil reservoirs, salt caverns, improved gravimetric and volumetric efficiency, it still faces
abandoned mines, and rock caverns in geological storage. several challenges, including, but not limited to, high energy
Among these, only the salt caverns have been explored so far. demand for liquefaction, storage tank cost, heat transfer, and
A detailed description of underground H2 storage methodol- H2 boil-off [114,125]. Between 35 and 40% of the energy content
ogies is presented elsewhere [122]. in the stored H2 is spent on liquefaction. This amount triples
In contrast, storage vessels could either be at low pressure the energy required to store the gas by compression [118]. As a
(0.95 MPa) or high pressure ( 35 MPa) vessels [123]. Detailed result, H2 liquefaction is capital intensive with its cost,
information about H2 storage in vessels can be found else- essentially dependent on the scale of production and plant
where [123]. Moreover, pressure vessels are made from location. About 60% of the capital investment is attributable to
various materials, and they are usually classified as Type IeV equipment costs, 30% for infrastructure, and 10% for planning
vessels [114,122,123]. Their properties are summarized in [125]. These highlighted challenges, among others, have hin-
Table 7. dered and limited the application of cryogenic technology.
Liquefaction/cryogenic storage Solid-state-storage
Hydrogen can also be stored in liquid form at temperatures H2 can also be stored in solid-state, a more efficient method
below 20 K, a method commonly referred to as cryogenic than the first two discussed because the solid material can
storage. In this form, the concentration of H2 doubles that of store relatively more significant quantities of H2 in smaller
volumes [121]. This can be done using nanostructured mate- directly with the H2 supply pressure. The cooling tempera-
rials and hydrides, with the former having relatively lower ture also has a marked impact on absorption, especially at
storage efficiencies, although with great potential. The latter low supply pressure.
can be classified into complex hydrides, chemical hydrides,
metal hydrides, and Magnesium-based alloys. Cyro-compressed H2 gas storage
The potential of solid-state storage to meet the rising H2
storage demand has attracted attention, bringing it to the This is a method of H2 storage in which the gas is compressed
centre of recent H2 storage discussions. Though most of the in its supercritical state (~233 C). At this stage, the gas cannot
hydrides, like borate hydrides of Na and Li, have high H2 liquefy no matter how much it is compressed. This method
storage capacities, they face the problem of regeneration ef- produces higher storage density than liquefied storage (about
ficiency and cost because most metals are expensive. Nitrides 10 g/L more than the liquefied storage) and is safer [114].
are promising due to the ease with which they release H2 Although promising, the Cyroecompressed hydrogen storage
when applied to solid-state H2 storage. Chemical hydrides, method currently lacks the infrastructure for large-scale ap-
which are compounds of lighter elements than metals, have plications. A detailed discussion on this technology is outside
high storage capacity and easily decompose to H2. the scope of this review but outlined by Abdalla et al. [11] and
Magnesium-based alloys are light, cheap, readily available, Zhevago et al. [116].
and have increased storage capacity but suffer from slow re-
action rates even at high temperatures. This is currently a
subject of further research investigation and increasing the Nanomaterials for solid-state hydrogen storage
reaction rate [121].
Kumar et al. [127] designed a large-scale metal hydride- Carbon nanotubes
based H2 storage system (MHHSS) and studied the effect of
supply pressure, temperature, and heat transfer fluid (HTF) Carbon nanotubes (CNT) are promising hydrogen storage
flow rate on the absorption and desorption rates of H2. They materials due to their high adsorption capacity at room tem-
found that as supply pressure increased, the mass of H2 peratures, synthesizing simplicity from renewable feedstocks
absorbed and the absorption rate also increased. Chauhan [130], along with their highly microporous structure, chemical
et al. [128] conducted a study on the uptake of H2 by graphene stability, and low mass density [131,132]. Carbon nanotubes,
nanoplatelets (GNP) at temperatures of 298 K, 243 K, and 99 K made of a graphene sheet rolled into a cylindrical tube shape,
and the maximum adsorption was seen at 99 K and 2 bar. are categorized as single-walled carbon nanotube (SWCNT)
This result agrees with that of Kumar et al. [127] as both and multi-walled carbon nanotubes (MWCNT). The SWCNT
demonstrate the significant impact of temperature and and MWCNT are characterized with an outer diameter range
pressure on adsorption and desorption rates of H2 gas. of 0.4e2 nm and 2e100 nm, respectively and 0.2e5 mm in
Another experiment conducted by Souahlia et al. [129] on length [133]. A conceptual diagram outlining the dimensions
metal hydrides concluded that H2 storage rates varied of SWCNTs and MWCNTs is given in Fig. 6.
The electrical, thermal, mechanical characteristics of the
SWCNT and MWCNT and production technologies are
recently reported in detail by Patel et al. [134]. The structure,
geometry, accessible surface area purity of the CNT, and the
operating temperature and pressure, are the key factors
affecting the hydrogen storage capacity [135]. Experimentally
measured hydrogen storage capacities of different types of
CNTs are given in Table 8.
The theoretical maximum hydrogen storage capacity of
SWCNT was initially reported to be 5e10 wt% of CNT by Dillon
et al. [143]. However, the possibility of reaching 11.2 wt%
(Table 8) was predicted and achieved in a study conducted by
Dillon and Heben [140]. The increase in the carbon storage
capacity was attributed to arranging the carbon structure in a
square lattice instead of a hexagonal lattice and the operation
conditions 77 K and 10 MPa [140]. However, hydrogen storage
at 77 K would not be feasible for onboard transportation on a
commercial scale [132]. Therefore, most research focuses on
hydrogen storage at around ambient temperature (~278).
On the other hand, MWCNTs can achieve higher hydrogen
storage due to their greater surface-to-volume ratio. Their
multi-layered nature allows the potential hydrogen uptake in
between the multiple graphene sheets [144]. However, the
Fig. 6 e Typical structure and dimensions of SWCNTs and overall hydrogen storage capacity of the MWCNT depends on
MWCNTs. Reprinted from Patel et al. [134] with permission operational conditions and the purity level, as the increased
from Elsevier. purity is directly linked to the increased number of available
Table 8 e Hydrogen storage capacity of various CNTs.

Hydrogen Storage (wt%) Loading Temperature (K) Loading Pressure (MPa) References
CNT 9.6 77 10 Cheng et al. [130]
SWCNT 4.5 77 6 Panella et al. [136]
SWCNT 4.5 298 0.4 Mohan et al. [135]
MWCNT 6.3 298 14.8 Mohan et al. [135]
SWCNT (low purity) 5e10 406 0.04 Park and Keane [137].
SWCNT (high purity 8.25 80 7 Li et al. [138]
Aligned SWCNT 4 298 11 Chem et al. [139]
SWCNT 11.2 77 10 Dillon and Heben [140].
Li-doped MWCNT 20 200e400 0.1 Dillon et al. [141]
K-doped MWCNT 14 300 0.1 Dillon et al. [141]
K-doped MWCNT 1.8 <313 0.1 Huang et al. [142]
sites for hydrogen adsorption [145]. Ioannatos et al. [145] re- volume can yield better high-pressure and low-pressure
ported higher hydrogen storage capacities with higher purity hydrogen adsorption capacity for Nickel-activated carbon
CNTs when the operating temperature was 298 K. The CNT nanocomposites [157].
synthesis methods and structural modifications play an It has been suggested that the viability of carbon-based
essential role. Mechanically bent CNTs are theoretically nanoconfinement of light metal hydrides for hydrogen stor-
proven to have better thermodynamic properties owing to age applications depends significantly on the purity, func-
their DH value of the adsorption process is being in the range tionality, and surface properties of the carbon employed.
of 20e50 kJ/mol H2, in comparison to the regular CNTs, which These factors are believed to influence the reaction pathways
are likely to have thermodynamic dead end with a DH smaller and thus, ultimately control desorption efficiency and
than zero or greater than 80 kJ/mol H2 [146]. Similarly, cup- reversibility. Comparing the reversibility of carbon nano-
stacked carbon nanotubes (CSCNT) have shown a 25% in- composites with high and low oxygen-based functionality on
crease in hydrogen storage (has risen 1.13 w%) in comparison the carbon constituent, Gao et al. [154] reported a reduction
to regular MWCNT [131]. from 95% to 66% with successive rehydrogenation cycles.
Interestingly, despite reporting the presence of hydroxyl and
Carbon nanocomposites carboxyl groups on the surface of hexagonal mesoporous
carbon frameworks used in their analysis, Li et al. [152] did not
Carbon-based nanocomposites are multi-constituent mate- remark on the possible effects of these oxygen-rich functional
rials with high specific areas and low-cost processibility. Be- groups on the irreversibility of the carbon-based ammonia
sides, they are highly attractive for solid-state hydrogen borane nanocomposites investigated in their study. However,
storage [147,148]. They exhibit excellent sorption kinetics due the authors did highlight the beneficial effects of nano-
to their physicochemical attributes and facilitate low- confinement in suppressing the evolution of volatiles, which
temperature desorption due to the presence of carbon as a (owing to the risks of catalytic poisoning) precludes ammonia
metal-free dehydrogenation catalyst [148e150]. borane in hydrogen storage applications.
Advanced concepts such as nanoconfinement, using suit- The importance of the appropriate selection of the carbon
ably selected carbonaceous nano-scaffold/nano-porous constituent cannot be undermined. For example, when com-
frameworks constitute promising routes for realizing revers- bined with ammonia borane, carbon cryogels can suppress
ible solid-state hydrogen storage solutions [151,152]. More- ammonia and reduce dehydrogenation onset temperatures,
over, the presence of carbon can also enhance desorption whereas activated carbon can initiate room-temperature
rates in nanocomposites by inhibiting the formation of un- dehydrogenation [158]. Another important consideration for
desirable ternary intermediates, which can form during using carbon nanocomposites is that some carbon species can
sorption and limit rehydrogenation (and invariably revers- enhance sorption kinetics by reducing the desorption tem-
ibility) [149,153,154]. perature and participating in reversible hydrogen storage.
The inherent tailorability of the constituents of these This can be observed in LiBH4eC60 nanocomposites where
nanocomposites renders them exceptionally tuneable. Fac- hydrogenation potential can be exploited with the lithium
tors like pore size can play a significant role in tailoring the borohydride and fullerene [150]. Table 9 summarizes some
sorption/desorption kinetics [154,155]. It has been shown by desorption characteristics of binary and ternary carbon
Sepehri et al. [156] that a reduction in pore size from 16 nm nanocomposites in recently published works.
to 7 nm for carbon cryogel-ammonia borane nano-
composites results in a corresponding 20% reduction in Activated carbon
activation energy for desorption from 150 kJ/mol and up to
9% in peak dehydrogenation temperatures. These trends are Activated carbon (AC) is a physically or chemically modified
in agreement with those reported by Gross et al. [151], who form of carbon consisting of small graphite crystallites and
observed a 7% reduction in activation energy for desorption amorphous carbon with a specific surface area of 3000 m2/g. In
by decreasing pore size by 48% in carbon-based LiBH4 physical activation, the starting material is carbonized at high
nanocomposites. Unsurprisingly, an increase in micro-pore temperatures (700e1000 C) by steam or CO2. In contrast,
Table 9 e Comparative summary of sorption and desorption parameters reported in published literature.
a b c
Non-carbon Carbon-based Preparation Wc Pore Desorption TD Ea,D References
constituents constituent methodology (%) size capacity (K) (kJ/mol)
(nm) (wt%)
MgeNb@d Amorphous carbon Reactive gas e 2e 4.8 573 59.7 Zhu et al. [159]
layer evaporation
Mg(BH4)2ed Carbon aerogel Melt infiltration 90 10 e 433 102 Yan et al. [149]
Mged Carbon aerogel Infiltration 77.5 19 2.15f 623 29.4 Liu et al. [160]
Carbon aerogel 111 Gross et al. [151]
LiBH4ed Mesoporous carbon Solution impregnation 67 4 3.4 573 e Cahen et al. [161]
LiBH4eMg(BH4)2d Activated carbon IRH33 Melt impregnations 72 <4 4 573 e Zhao-Karger et al. [153]
ABed Carbon cryogel Solution impregnation 76 2e50 9 358e383 120e150 Feaver et al. [155],
Sepehri et al. [156]
Lithium-doped Solution impregnation & 50 4.54 7 333 98 Li et al. [152]
mesoporous calcination
carbon Li-CMK-3
Graphene High-energy ball milling 67 e 4.5 386 e Bravo Diaz et al. [158]
Activated carbon High-energy ball milling 60 e 5.4 277 34 Bravo Diaz et al. [158]
Activated carbon Solution impregnation 60 e 5.4 285 e Bravo Diaz et al. [158]
The use of.

a
Wc: Weight fraction of carbon constituent (%).
b
TD: Desorption temperature (K).
c
Ea,D: Activation energy for desorption.
d
Denotes the carbon-based constituent.
e
denotes a layer thickness.
f
denotes a sorption capacity.
chemical activation treats the starting materials (i.e., ligno- precursor weight ratio. Furthermore, combined chemical and
cellulosic biomass, anthracite, coal precursor etc.) with physical activation, using CO2, was reported to be effective in
chemicals such as H3PO4, KOH, NaOH, H2SO4, and ZnCl2at creating more micropores which resulted in an increased
500e800 C [162,163]. It should be mentioned that ZnCl2 is not specific surface area [165].
a desirable activating agent due to zinc emissions in the
environment. Complex hydrides
AC is suitable for both physisorption and hydrogen
chemisorption due to its large surface area and microporosity. Complex metal hydrides (CMH) are a class of compounds with
However, choosing the right activating agent and precursor the general formula M(XHn)m, where M usually represents a
for the individual applications is vital as these are the signif- metal cation, whereas X is a metal or nonmetal element,
icant factors affecting the pore size and structure [164]. The which is covalently bonded to hydrogen [174]. These com-
KOH activation has been reported to be a particularly suitable pounds are hydrogen-rich and can be selectively decomposed
method of hydrogen sorption as it provides large surface to produce H2; thus, making complex hydrides of lightweight
areas, large pore volumes with a 1e2 nm uniform micropore elements efficient H2 storage media. Complex hydride
size distribution in the structure [144]. The result of the recent hydrogen storage mechanism occurs as a two-stage process
studies is given in Table 10. involving dihydrogen dissociation into surface H atoms and
The hydrogen storage capacity is mainly dependent on the the subsequent diffusion of the H atoms into the bulk phase
specific surface area, the bulk density, and the loading tem- [175]. The many possible combinations of H2 with elements
perature. Improved hydrogen storage capacities are achieved like nitrogen boron, oxygen, carbon, aluminum, and transition
with the experiments conducted under cryogenic conditions metals for CMH formation is an attribute that allows func-
with moderate pressure (1e10 MPa). In contrast, an average of tional property modification for H2 storage purposes [176].
3 wt% hydrogen sorption was seen in the experiments carried In comparison to other H2 storage methods such as lique-
out at around room temperature due to the weak interaction faction, compression, and metal-organic framework (MOF),
between the adsorbate (H2) and the adsorbent (AC) at room CMHs have high H2 density with the capability of de/rehy-
temperature. However, the reversible hydrogen storage ca- drogenation without the requirements of very high pressures
pacity can be enhanced by heteroatom doping as it dissociates and low temperatures [177]. Ley et al. [178] reported that only
the chemically bonded H2 and subsequently allows the 0.034 m3 H2 stored in d-Mg(BH4)2 is required to power a family
diffusion of hydrogen atoms into the pores [144]. car for 500 km. This volume is significantly smaller than the
Chemical activation is another essential technique that equivalent 60 m3 of H2 required when standard fuel-cell-based
impacts the hydrogen storage capacity as it is directly linked storage is applied at ambient temperature and pressure. This
to stimulation of micropores and correspondingly an volumetric storage efficiency is one of the factors that has led
increased adsorbent porosity. The pore structure is also to extensive research contributions relating to the use of CMH
dependent on the activation temperature and the KOH/ for H2 storage. However, their strong interaction with H2 (40 ≤
Table 10 e Hydrogen storage capacities of various AC.

a
AC Precursor Hydrogen SBET Activating Loading Loading References
Storage (m2/g) Agent Temperature (K) Pressure (MPa)
(wt%)
Pine lignin 1.61 1055 CO2 11 0.1 Czarna-Juszkiewicz et al. [165]
1.93 1409
Coal from palm 0.29 640 KOH 268 0.4 Kapasiti et al. [166]
oil shell
Coal from palm 6.7 3503 KOH 77 0.4 Zhao et al. [167]
oil shell
Spent coffee 0.6 2070 KOH 298 12 Akasaka et al. [168]
beans 0.4 2070 77 4
Anthracite 3.2 1149 KOH/NaOH 77 4 Fierro et al. [169]
6.0 2849
5.7 3220
2.7 1308
Carbon monolith 1.28 973 CO2 293 60 Series et al. [170]
Commercial AC 0.67 1060 N/A 303 10 Xu et al. [171]
5.7 3306 77 3
Anthracite 6.6 3441 KOH 77 4 Izquierdo and Celzard [172].
Anthracite 5.5 2451 KOH/Pd doped 298 8 Zhao et al. [173]
a
BET (Brunauer-Emmett-Teller) analysis to measure the specific surface area available for adsorption.
DHads ≤ 100 kJ/mol), very high desorption temperatures NaAlH4 CMHs with timeframes as low as 20 min observed
(>350 C), irreversibility issues, slow kinetics, and challenging [185]. The use of NaAlH4 confined in carbon fibres has been
synthesis procedures are formidable hindrances to their suc- reported to rapidly decrease the H2 desorption temperature to
cessful implementation [179]. For example, the thermal 70 C [186]. Similarly, NaAlH4 confined in ordered mesoporous
decomposition of LiAlH4 yields Li3AlH6 and Al, which is silica achieved dehydrogenation within a temperature range
accompanied by an exothermic release of H2 gas. This initial of 125e150 C [187]. Ti and TiO2 nanoparticles embedded in
exothermic decomposition has been shown to hinder the amorphous carbon have also shown promising potential for
complete reversibility of the system [176]. enhancing the H2 storage capability of NaAlH4, with remark-
Research efforts targeted at mitigating these challenges able stability obtained after 100 adsorption/desorption cycles
have led to the development of several thermodynamic and [188]. TiN nanoparticles (nano-TiN@NeC) have also been
kinetic improvement strategies [175]. These include nano- demonstrated as reliable candidates for enhancing the ther-
confinement via the application of nanoporous hosts for modynamics and kinetics of NaAlH4 de/rehydrogenation
interface contact improvement [180], catalytic modification [189,190]. Arora et al. [191] employed DFT to explain the sig-
for enhancing H2 sorption and desorption [181], and compo- nificant impact of experimental conditions (environmental
sitional alteration via anionic or cationic substitution for effects) on the thermodynamic stability (the free energy of
composites formation in the CMH [182]. We present a dis- formation) of metal-doped-NaAlH4. Similarly, DFT calcula-
cussion of past contributions in light of these advancements tions implemented by Kang et al. [192], further verified the
while capturing the different classes of CMHs (including ala- dependence between the reaction energy and the chemical
nates, borohydrides, amide-hydride composites, as well as environmental conditions as well as the morphological
metalorganic hydrides). features.
Alanates, a class of widely explored CMHs are generally Interest in metal borohydrides has been spurred by their
composed of a metal cation and the [AlH4]-/[AlH6]-3 anion, with very high H2 contents and the existence of a correlation be-
storage capabilities of up to 10.4 wt% (LiAlH4), 9.3 wt% tween their experimentally determined decomposition tem-
(Mg(AlH4)2) and 9.7 wt% (LiMg(AlH4)3), respectively [175]. perature and the metal's electronegativity (which strongly
NaAlH4 is the most extensively studied alanate, given its coordinates to the BH 4 anionic groups) [178]. One of the first
relatively high gravimetric and volumetric H2 densities, studies to propose the use of metal borohydrides as an H2
moderate heat of de/rehydrogenation, and low cost of raw storage medium was that of Zuttel et al. [193], achieving a H2
materials [183]. The successful application of NaAlH4 as H2 capacity of up to 18.5 wt%. Recently, the nanoconfinement of
storage material, when combined with catalysts such as Ca(BH4)2 and Mg(BH4)2 into porous hosts (Cu2S) has been
nano-TiN to reduce the dissociation temperature, instigated actively investigated; dehydrogenation at 50 C and full
the search for other compatible metals [184]. Transition and rehydrogenation at 300 C were achieved [194]. The kinetic
rare earth metals, such as Ti, Nb, Ce, Sm, Sc, have been applied improvement of H2 storage over M(BH4)m and M(NH2BH3)m has
via ball milling and wet doping methods to reduce further the been demonstrated using catalytic dopants (including Fe2O3
temperature required for the commencement of dehydroge- and SiO2) [195]. Bimetallic and trimetallic borohydrides and
nation [178,180]. Nanoparticles such as CeO2, CeB6, and CeFe3 neutral molecule-modified metal borohydrides (e.g. LiK(BH4)2,
have been applied to improve the hydrogenation duration of Li3MgZn5(BH4)15, Li2Al(BH4)5·6NH3), have also demonstrated H2
Table 11 e Comparison of the different classes of CMHs.

Class of CMH Advantages Limitations References
Alanates Favourable dehydrogenation enthalpies Insufficient reversible capacities for Orimo et al. [174], He
Rapid kinetics rehydrogenation et al. [175]
Moderate H2 capacities Contact with water is a safety concern
Relatively easy preparation with readily
available components
Borohydrides High gravimetric H2 capacities Very slow kinetics Let et al. [178], Møller
Side product formation (diborane) et al. [176] He et al. [175],
Irreversibility Luo et al. [180]
Poorly understood de/rehydrogenation
mechanism
Amide-Hydride Good thermodynamic stability Very slow kinetics Orimo et al. [174], He
Moderate H2 capacities Side product formation (mainly et al. [175]
ammonia)
storage capabilities as documented by Møller et al. [176]. primary safety concern worth mentioning here relates to
Nanoporous g-Mg(BH4)2 has been shown to efficiently store H2 alanates, which have very high reactivity with water e
via adsorption onto the hydride's inner surface and via yielding large amounts of heat [174]. This exothermic hydro-
chemical bonding to Boron [178]. Similarly, a study by Chen lysis reaction can initiate the hydride's thermal decomposi-
et al. [196] demonstrated kinetic barrier reduction for tion in the case of accidental exposure to large amounts of
enhancing the reversibility of Mg(BH4)2 using MgH2 nano- water. Besides storage capacity improvements, the opera-
particles. A recent study by Wood et al. [197] showed that tional safety of this H2 storage technology is also worth
mechanical stresses posed by an external confining medium investigating further. Moreover, a comparison of different
could affect the thermodynamics and kinetics of phase classes of CMHs is presented in Table 11.
transformations that occur during the de/rehydrogenation of
some CMHs; they focused on incorporating more realistic ef- Metal-organic frameworks
fects in their models which are usually neglected in compu-
tations based on ideal conditions. Metal-organic frameworks (MOFs), otherwise called porous
Some unresolved challenges still plague the application of coordination polymers, are a category of porous materials
metal borohydrides for H2 storage. The exact mechanism of formed from metal ions or metal-containing nodes (secondary
dehydrogenation and rehydrogenation of metal borohydrides building units e mostly d-block transition metals) and organic
is not well understood (a possible consequence of the complex linkers or multidentate ligands joined by coordinate bonds
boron-hydrogen chemistry); furthermore, the avoidance of [200]. The available number of binding sites for these ligands
effects such as diborane release, and the segregation of at the metal centre often ranges from 2 to 12, yielding linear,
amorphous boron, are still unresolved [178,193]. Moreover, cubic, octahedral, tetrahedral geometries [201]. An essential
alkali metal borohydrides possess higher stability (higher requirement in the selection of ligands for the development of
decomposition temperatures >350 C) than alkali metal ala- porous MOFs is that the overall network be neutral. Other-
nates (with decomposition temperatures between 60 and wise, charged networks will cause the positioning of counter
300 C); on this basis, Møller et al. [176] reported that alkali ions within the framework, which eventually reduces the
metal alanates might be better suited for H2 storage porosity and H2 storability of the framework material
applications. [202,203]. Unlike mesoporous oxide-based materials like zeo-
As with the alanates, catalytic modification can be simi- lites, the structure and topology of the interior surface (of
larly pursued with amide hydrides using transition metals, MOFs) on which H2 is adsorbed can be easily modified for H2
alkali metal hydrides, borohydrides, and other carbon-based storage enhancement (via metal selection and ligand func-
materials [198]. However, these hydrides often portray very tionalization) [204]. MOFs' modular construction and large
slow kinetics, which may be attributable to interface re- surface areas and pore volumes allow for this modification
actions, diffusion processes, and nucleation [198]. Mechanical [205].
milling is an effective method, which can be applied to miti- According to the ultimate target set by the US Department
gate this problem via grain size reduction and homogeniza- of Energy (DoE), onboard H2 storage systems should be able to
tion of the amide and hydride particles [199]. This process has achieve a gravimetric capacity of 6.5 wt% (U.S Department of
been applied to K2 [Zn(NH2)4] as documented in Cao et al. [198]. Energy, 2017) [206]. Although MOFs such as (MOF-5) have
A further effect of this milling process is lowering the already surpassed the ultimate DoE targets (in terms of
decomposition temperature [176]. gravimetric capacity) [207], sufficiently high surface area &
The presented discussion demonstrates a need to develop pore volume and the formation of viable (high-energy) H2-
further methods for stabilizing H2 storage capacity at ambient binding sites (within the framework) are essential factors for
conditions and particularly for long-term multiple usages. A the continual development of other high-capacity MOFs, as
Table 12 e Some applied methods for improving MOF performance.

Method Comments References
Sample preparation and Compared to traditional MOF pre-treatment methods (soaking Ma et al. [213], Cooper
activation via drying samples in low boiling point solvents for porosity and Rosseinsky. [214],
enhancement), freeze-drying and supercritical drying have Xiang et al. [215]
been shown to improve pore performance significantly.
Unsaturated metal sites These sites show significant H2 binding potential and are Zhou et al. [216], Bagheri
modification usually the first loading sites for H2 molecules. This depends on et al. [217]
the cationic radius of the exposed metal site. Thermal-based
activation has been applied to access the increased gas-
adsorption potential of a MOF material.
Catenation/ While this method increases the interaction between the k

Sule et al. [204], Zelena
Interpenetration framework and H atoms, it may also result in reduced pore and Saldan [202]
volume, consequently reducing H2 storage. The effect of this
method is also somewhat pressure-dependent.
Functionalization of Covalent, coordinate, and covalent-coordinate modification are Rowsell et al. [218]
ligand structure the primary enhancement routes. Aromatic substituents have
shown promising potential for functionalizing ligand structures
(due to additionally provided binding sites); thus, yielding
improved H2 uptake compared to the pristine MOFs.
Chemical doping This is a post-synthetic modification method using metals like Mavrandonakis et al.
cationic or atomic Lithium. As high as 7.5 times the storage [219], Cheng et al. [220]
capacity of the undoped IRMOF-14 has been reported using
lithium. Doping with metal nanoparticles such as palladium
nanoparticles is also a promising approach to achieving H2
storage at ambient conditions.
Crystal size and A strategy that enhances MOFs' poor volumetric packing/ Suresh et al. [221]
morphology control storage density has been presented in the literature. Packing
density enhancement is achieved using the benchmark
sorbent, MOF-5.
Rapid evaluation of the An empirical expression correlating the pore volume (V) or Kolotilov and
surface area and pore surface area (S) to the H2 uptake of selected MOFs allows the Pavlishchuk [222].
volume prediction of the sorption capacity of a new MOF using it V and S
alone.
well as their sustained cyclic performance. While the first enhancement via increasing the ligand length, implement-
factor influences the H2 uptake rate, the second influences the ing mixed ligands, and supercritical CO2 drying [210,211].
H2-framework interaction. Thus, the kinetics and thermody- More so, the use of multifunctional groups within the same
namics of H2 uptake and release must be accurately consid- framework has also been demonstrated, with up to 84%
ered, for effective H2 storage capacity. MOFs can also improvement attained [212]. A summary of some key
potentially address the limitations of other physisorbents methods of improving the H2 uptake capacities of MOFs is
(such as activated carbon and zeolites, which yield a similar presented in Table 12.
H2 uptake at low temperatures but have reduced H2 affinity at High storage capacities and rapid release kinetics have
ambient temperatures) and chemical sorbents (e.g., hydrides, maintained MOFs at the forefront of established H2 storage
which possess reasonably high H2 uptakes but poor release methodologies in light of the US Department of Energy (DoE)
kinetics and thermodynamics). Storage methods, which uti- ultimate H2 storage targets. Increasing MOF-H2 interactions at
lize chemical sorbents (like CMHs) particularly suffer from the ambient temperatures and their volumetric packing efficiency
very tight binding of H2 (DHads in the range of 50e200 kJ/mol); are areas that will benefit from further investigations; thus,
in contrast, the DHads of physisorption techniques is minimal aiding the technological translation of this H2 storage method.
[208]. Fig. 7 compares the performance of different H2 storage ma-
Isorecticular metal-organic frameworks (IRMOF) based on terials with the DoE ultimate targets.
Zn4O are some of the widely studied MOFs. The earliest
demonstration of the H2 storage capability of MOFs was re- Hydrogen storage in clathrates
ported by Yaghi et al. [209]. Since this contribution, many
MOFs have been studied with different H2 storage potentials Clathrate hydrates or hydrogen hydrates are compounds that
[200]. These studies have applied several routes for incorporate guest molecules inside a host framework (poly-
increasing the H2 uptake, e.g. surface area and pore volume hedral cages) comprising of H2-bonded water molecules e on
Fig. 7 e Comparison of different H2 storage materials. Reprinted from Gupta et al. [179] with permission from Elsevier.
Table 13 e Structures of commonly formed hydrogen hydrates Chattaraj et al. [225].

Type Number of water molecules Unit cell structure
sI 46 Two pentagonal dodecahedron (512) and six hexagonal truncated
trapezohedron (51262) cages.
sII 136 Sixteen 512 and eight 51264 cages.
sH 36 Three 512, two 435,663, and one 51268 cages.
mixing water and H2 gas at low temperatures, and high pres- to 5 MPa at 279.6 K; however, this caused a substantial drop in
sures, the guest molecules (H2) are entrapped into the poly- the H2 storage capacity (1 wt%).
hedral cages of the host framework to form the hydrate [223]. Through the use of promoters such as THF, TBAB, and
Hydrogen bonding, van der Waals (dispersion) forces, and TBPB, Du et al. [228,229] formulated H2 hydrate at ambient
intermolecular interactions govern this process and are linked pressure conditions. The effect of a simultaneous change in
to the structure's stability [224]. Without the encasement and temperature and pressure has been shown to be favourable on
corresponding support of these gas molecules, the structure of the formation rate of H2 hydrates (21% increase) while using a
the hydrogen hydrates collapses into the water. Table 13 shows THF promoter [230]. Liu et al. [231] performed ab initio molec-
the structural properties of typical hydrate structures. ular dynamics simulations to investigate the impact of THF on
A pioneering study by Mao et al. [226] demonstrated that H2 storage capacity in clathrates and obtained capacities be-
pristine H2 hydrates could store as high as 5 wt% of H2 at a tween 1.6 and 3.8 wt% depending on THF concentration. Their
pressure of 200 MPa and 243 K. This elevated pressure is a computations also illustrated that a single H2 molecule oc-
severe concern that limits its usage in mobile applications. cupies the small cages of the hydrate, whereas the large cages
One notable approach to mitigate this high-pressure require- are likely to contain one THF molecule together with one H2
ment for H2 hydrate formation is to develop binary hydrates molecule. Ghaani et al. [232] utilized non-equilibrium molec-
which contain a helper molecule (gas or liquid) and H2 as the ular dynamics (NEMD) simulations to analyze H2 release and
second molecule. Further developments by Florusse et al. [227] uptake from propane planar clathrate surfaces at 180e273 K.
involved the application of a water-soluble compound (THF) The obtained experimental H2 storage capacity (using a fixed
as an additive to significantly reduce the formation pressure bed reactor) was 1.04 wt% in comparison to the theoretically
obtained 1.13 wt% of the propane hydrate. A novel dual- provide new insights into the development of optimal and
function (thermodynamic and kinetic) promoter, 1,3- cost-effective hydrogen production processes.
dioxolane (DIOX), was proposed by Zhang et al. [233] for H2- As far as nanoelectrocatalytic and nanophotocatalytic H2
bearing sII hydrate formation. Within 2 h, a H2 uptake of up to production is concerned, the development of 2D nanomaterials
26.51 v/v (gas/hydrate) was attained, corresponding to a 30.2% with hybrid structures and multifunctional properties may
increase over the maximum H2 uptake obtained using the provide new opportunities to enhance their H2 production po-
conventional THF promoter. Besides the above-mentioned tential via water splitting. Their large-scale production in
promoters, other suggested promoters explored in the litera- controlled environments is also worth investigating; however,
ture include tertiary alcohols [234], argon [235], nitrogen [236], this is dependent on the novel research endeavours which
alkyl amines [237], methane [238], and SF6 [239]. A summary of provide insights into the complex catalytic mechanisms rather
important promoter molecules used in the past 20 years and than their catalytic performance for H2 production alone.
their H2 storage properties is presented in Gupta et al. [179]. Further research on the application of physisorbents ma-
Despite the recent developments in enhancing the ther- terials (particularly activated carbon and MOFs) for H2 storage
modynamics of H2 hydrate storage performance, formation may focus on designing new functional materials with higher
and stabilization at moderate conditions, improving hydrate surface areas and pore volumes, increased hydrostability, and
formation kinetics is still a formidable challenge. The kinetics sufficient interaction energy the retainment of H2 at ambient
of hydrate formation in supercooled water-hydrogen solution temperatures. Furthermore, the application of carbon nano-
(without promoters) has been studied by del Rosso et al. [240] tubes for H2 storage is significantly affected by the purity and
at 2000 bar and 263 K. It was postulated that the diffusion rate uncertainties governing their preparation. Further research
of H2 limits the rate of hydrate formation through the liquid developments in this area may target robust synthesizing
phase. Immediately the transformation to solid is complete procedures that yield increased purity and thus better H2
(after 18 h), the reaction rate rapidly increases. The applica- storage capability. There is a need to study the effect of
tion of surfactants, nanoconfinements, and guest molecule oxygen-rich carbon groups on the reversibility of carbon-
replacement (mainly via computational methodologies) are based nanocomposites; this is particularly important for
emerging research trends targeted at resolving this problem of ammonia-borane variants. In addition, the identification of
slow kinetics [241e243]. Recent developments by Di Profio carbon-based nanomaterials that afford the enhancement in
et al. [244], which apply a reverse micelles formation method, adsorption kinetics and the ability to participate in the
have shown significantly reduced time of H2 hydrate forma- reversibility of hydrogen storage is vital.
tion (20e30 min) using promoters like THF, THT, CP, and THT. The hybrid application of earlier-discussed improvement
An important advantage of H2 hydrate systems is the rapid strategies for CMHs (e.g. nanoconfinement and catalytic
and straightforward release of H2. Thus, no chemical re- doping) has strong potential to enhance their performance
actions are needed for H2 release since the binding energy is further and requires further analysis. As earlier pointed out,
minimal [224](Struzhkin et al., 2007). This eliminates the the mechanisms of dehydrogenation and rehydrogenation of
possibility of high dissociation heat requirements as with some CMHs are not well understood (e.g., the mechanism of
metal hydrides. Stirring and the use of memory water (previ- H2 dissociation and diffusion into and out of the bulk phase);
ously used water for hydrate formation) have been investi- this also increases the difficulty of distinguishing the main
gated for further improving the release rate [230,241,242]. This mechanism of performance improvement when enhance-
memory effect of water (during freezing and refreezing cycles) ment strategies are applied. These strategies are also often
can be attributed to the occurrence of microscopic hydrate associated with a high synthesis cost; more research en-
residues in the water phase after low-temperature melting. deavours are required for simplification and cost reduction.
These residues subsequently act as nuclei for recrystallization The sensitivity of CMHs to air makes their characterization
during the hydrate formation phase, thus accelerating the difficult for H2 storage analyses; thus, novel technologies are
formation process [245]. One of the most recent studies [246], required for efficient characterization. Accidental exposure of
which experimentally illustrated this memory effect, further CMHs (particularly alanates) to large amounts of water may
confirmed this earlier proposed mechanism. instigate their thermal decomposition. Safety analyses of their
large-scale application is also worth investigating.
The presented discussion has summarized some of the
Perspectives and future directions challenges associated with H2 hydrate systems, including
(extreme operating conditions in the absence of a promoter,
Nanomaterials have shown great promise in biological slow formation kinetics, low storage capacity, prolonged cy-
hydrogen production; however, the mechanism of clic storage performance uncertainties, mass transfer con-
nanomaterial-influenced hydrogen production via biological straints). However, the most significant of these challenges,
routes is not well understood. Moreover, the nanomaterial limiting the application of this technology for onboard stor-
integrated approach for biological hydrogen production is a age, appears to be slow formation kinetics. Further de-
study area that has not been explored. For instance, the velopments are particularly needed in this direction. In
combination of photo fermentation and dark fermentation addition, H2 hydrate formation appears to be mainly studied
assisted with nanomaterials is an area that has not been using computational techniques; to enhance their accuracy
explored. Integration of different biological routes could via robust parameterization, more experiments on the
mechanism of H2 hydrate crystallization are needed. The references

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A Comprehensive Review of Hydrogen Production and Storage A Focus On The Role of Nanomaterials

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 2 0 3 9 8 e2 0 4 3 1

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

A comprehensive review of hydrogen production

Emmanuel I. Epelle a, Kwaghtaver S. Desongu b, Winifred Obande c,

highlights graphical abstract

Different routes for renewable H2

article info abstract

List of abbreviation GNP Graphene nanoplatelets

Introduction Several studies have evaluated different areas where

2Hþ þ 2e / H2 (4) Nanomaterials for renewable hydrogen

Table 2 e Major advantages and disadvantages of different hydrogen production technologies.

led to an increase in hydrogen yield by 34.38% and 5.47%,

microbes did not consume the metal nanoparticles at the end

[97]. Studies have shown that nanomaterials have the po-

during dark fermentation in such a way that it could lead to

Nanomaterials for thermochemical hydrogen production

Nanomaterials are often used as active metals of heteroge-

cesses [105]. Specifically, Ni-based catalysts are promising for

and Mg. The Ni nanocatalysts are preferred due to their low

duction can be classified as metal oxides, alloys, active

metals, and ferrites, as shown in Fig. 5 [107].

ability during the gasification of algae under hydrothermal

conditions [106]. Zn nanoparticles were used as a promoter

duction have been subjects of interest among several re-

searchers because of their stability, low price, and

Fig. 4 e Application of nanomaterials at different stages of biological hydrogen production.

Hydrogen storage methods

As the efforts to maximize the potential of H2 as a clean and

Type III Carbon fibre composite 340 to 454 Double of Type II 45

Type IV Polymer like HDPE Very light Very costly 100

Liquefaction/cryogenic storage Solid-state-storage

Table 8 e Hydrogen storage capacity of various CNTs.

The use of.

Table 10 e Hydrogen storage capacities of various AC.

Table 11 e Comparison of the different classes of CMHs.

Table 12 e Some applied methods for improving MOF performance.

Catenation/ While this method increases the interaction between the k

Table 13 e Structures of commonly formed hydrogen hydrates Chattaraj et al. [225].

mechanism of H2 hydrate crystallization are needed. The references

Res 2021;60:5770e82. https://doi.org/10.1021/ Hydrogen Energy 2010;35:4512e23. https://doi.org/10.1016/

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