Results in Chemistry 4 (2022) 100613

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Results in Chemistry
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Recent reports on hydrogen evolution reactions and catalysis

Sahil Kumar, Rajinder Kaur, Surbhi Sharma *
University Institute of Sciences, Chandigarh University, Department of Chemistry, Gharuan, Mohali, Punjab, India

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

Keywords: Rapidly diminishing fossil fuels as an energy source created a lot of pressure on researchers to find an alternative
Heterogeneous catalyst of clean and renewable energy. As a vast revolution to the energy crisis, Hydrogen has emerged as a promising a
Electrocatalyst fuel prioritized green resource with little environmental impact to replace traditional fossil fuels. A key challenge
Photocatalyst
is the efficient production of hydrogen to meet the commercial-scale demand, for this electrochemical water
HER
Hydrogen production
splitting electrolysis has become an important method for large-scale green production of hydrogen. Hydrogen
evolution reaction (HER) which is the cathodic half-reaction of water splitting to produce pure H2 in large
quantities by active electrocatalysts is a fascinating idea that can provide a feasible pathway to achieve efficient
hydrogen production in terms of energy conversion and storage. Design and development of active, stable, and
low-cost electrocatalysts is an essential prerequisite for achieving the large-scale hydrogen production. Although,
electrocatalysis plays a powerful role in HER like the cost, time of reaction and selectivity, yet its disappointing
performance cannot follow the concerns of industrial-scale applications, including working efficiently and
longtime stability at high current densities (>1000 mA cm− 2). In the present review article, we are collectively
presenting an organized report about different HER electrocatalysts based on their structure and formation. We
also study the crucial issues related to its work efficiency, the future challenges, and opportunities for the
development of HER catalysts.

Introduction selective, stable, and cost-effective materials for efficient hydrogen

production (hydrogen evolution reaction, HER) by electrocatalysis is of
An energy crisis severe disruption in the delivery of energy resources paramount importance for the successful development of hydrogen-
to an economy. In recent years, industrial development and population based alternative energy technologies [5].
growth have resulted in a surge in global demand for energy, With the HER is basically the cathodic half-reaction of water splitting and one
ever-increasing energy demand and environmental effects caused by of the electrochemical reactions. The subsequent equations (1) and (2)
excessive dependency on fossil fuels, the development of clean and given below are showing, it proceeds through the reduction of protons or
sustainable energy technologies has become a crucial task [1,2].With water molecules observed through the following evolution of gaseous
reference to the socioeconomic point, we are planning for clean energy hydrogen simply. In an ancient report of Nicholson and Carlisle in 1800,
sources like Hydrogen which is discovered by Henry Cavendish (1766) platinum wires had been used as running electrodes in a sealed tube
and now has become the most demandable compound in the world of filled with water and powered through a voltaic pile [6,7]. They found a
energy crisis. Hydrogen is a carbon-free alternative energy source for circulated bubble on each electrode, which had been later identified to
use in future energy frameworks with the advantages of environment- be hydrogen and oxygen. This report brought the revolution in hydrogen
friendliness and high energy density [3,4]. evolution-based reactions that could pave the path for alternate clean
As an essential part of the energy conversion technologies, electro­ energy sources. Since then, many reports and findings are continuously
catalysis has made considerable progress during the past few decades being collected which demands further systematic studies of different
owing to the combination of nanoscale catalyst synthesis methods, parameters and activity of electrocatalysts, due to lack of clear insights
advanced characterization techniques, and quantum calculations of re­ on the activity parameters. Mostly electrocatalysis efficiency depends on
action mechanisms. Moreover, the design and synthesis of active, the use and validity of some important parameters namely overpotential

Abbreviations: HER, HYDROGEN EVOLUTION REACTION; TOF, TURNOVER FREQUENCY; OER, OXYGEN EVOLUTION REACTION.
* Corresponding author.
E-mail address: surbhi.e9299@cumail.in (S. Sharma).

https://doi.org/10.1016/j.rechem.2022.100613
Received 29 July 2022; Accepted 28 October 2022
Available online 31 October 2022
2211-7156/© 2022 The Author(s). Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
S. Kumar et al. Results in Chemistry 4 (2022) 100613

Fig. 1. Schematic demonstration of SFCA-Ni-Co electrocatalyst from cocoon synthesis.

at a defined current density, are corrected overpotential at a defined in shorts. That why we have also listed some photo catalyst for HER to
current density, Tafel slope, exchange current density (j0), mass activity, have an idea over design and provide a next writing way for such
specific activity, Faradaic efficiency (FE), turnover frequency (TOF), catalyst to other readers in a comparative pattern of both electro-and
electrochemically active surface area (ECSA) and measurement of dou­ photocatalyst for HER [14,15]. Photocatalytic aspects would also be a
ble layer capacitance (Cdl) for different kinds of electrocatalytic mate­ good idea for green hydrogen production because of use water and
rials [8,9]. sunlight which are abundant and practically inexhaustible.
In acidic electrolytes : 2Haq + 2e/H2(g) (1)
Different electro catalysts for HER
In alkaline electrolytes : 2H2 O + 2e/H2(g) + 2OH(aq) (2)
Developing high-efficiency electro catalytic water electrolysis is an
In the discussion of advantages behind electro catalysis different appealing approach for practical hydrogen applications in the sustain­
metals and metal oxide-based materials have received considerable in­ able hydrogen economy. However, due to its slow kinetics, the hydrogen
terest for various applications. Due to the compositional/structural di­ evolution reaction (HER) that occurs during water electrolysis necessi­
versity, flexible tunability, low cost, earth-abundance, easy synthesis tates high electricity consumption, resulting in a high overpotential
and environmental friendliness, Nevertheless, pure metal oxides, espe­ during the electrocatalytic water splitting process. Precious metals, such
cially the bulk materials, were generally believed inactive towards HER as Pt, are typically used as HER electro catalysts to reduce overpotential,
in the past because of poor electrical conductivity, inappropriate but their high cost and scarcity significantly impede their widespread
hydrogen adsorption ability and limited catalytic-active site, although application. As a result, developing highly electro catalytically active
many of them display high activity for the anodic oxygen evolution and cost-effective HER catalysts for hydrogen production are critical.
reaction (OER) [10,11]. Transition metal compounds such as nitrides, sulfides, selenides, and
So far, state-of-the-art HER electro catalysts are mostly noble metal- phosphides have been discovered to be promising HER catalysts with
based materials, which exhibit low reduction over potentials and good great potential as alternatives to precious metal catalysts. Because of
long-term durability [12,13]. However, the expense of scarce metals their metalloid properties and high electrocatalytic performance, tran­
limits the economic values that can be alleviated by designing single- sition metal phosphides are attracting a lot of research attention for HER
atom catalysts, with improve capacity of utilization efficiency while in water splitting.
maintaining high electrocatalytic performance.
Logically, to enhance the catalytic activity for HER morphological
Nano structured based electro catalysts
(self-supportive, porous), chemical (electronic structure of active site)
and combining engineering (by coating or doping) is required and is a
Cobalt-nickel phosphides@carbon spheres as highly efficient and stable
big challenge for the design large-scale hydrogen production technology
electrocatalyst for hydrogen evolution reaction
based on electro catalysis.
Three-dimensional Ni/Co phosphides with amorphous structure
To asset the discussed logistics for better electro catalyst design and
were synthesized on the surface of Ni foam using electroless deposition,
efficiency, in the present review article, we are collectively summarizing
and the resulting phosphides exhibit high catalytic performance of HER
and classifying novel electro catalysts for HER and how it have served
in alkaline electrolyte. Zhang’s group reported a method for preparing
for decades to bridge the gap between fundamental electro catalysis and
Ni2P nanosheets/Ni foam compound as a HER electrocatalyst, and
practical design. Electro catalytic water-splitting for HER is a multidis­
discovered that the obtained Ni2P/Ni can act as a self-supported super
ciplinary research avenue that includes chemistry, chemical engineer­
hydrophobic electrode for catalyzing HER in a wide pH range. The CoNi-
ing, materials science, physics, nanoscience, and nanotechnology.
P@C was synthesized in two steps. The cobalt and nickel phosphides
Therefore, an authentic review report would provide a sound knowledge
were adhered to carbon spheres formed by carbonizing alkoxides during
for the readers including scientist, and engineers to learn about the
high-temperature phosphorylation. When the optimized Co1Ni1-P@C
current status of the field with an understanding of the issues to be
sample was used to catalyze HER, it demonstrated a low overpotential
resolved to create a path forward. Yet, review is basically providing,
and excellent acidic durability. It was discovered that the Co/Ni ratio in
design, classifications of different electrocatalyst and their advantages
the precursors has a significant impact on the HER electrocatalytic
with challenges, we cannot ignore the other methods for HER to discuss
performance. The highest HER activity was obtained when the Co/Ni

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S. Kumar et al. Results in Chemistry 4 (2022) 100613

excellent HER performance in alkaline solutions, with a low over­

potential of 138 mV at 10 mA cm− 2 and a Tafel slope of 100 mV dec-1
[18].

Co2P nanoparticles as HER electrocatalysts

Herein, the author reported a facile one-pot ethylene glycol (EG)
mediated solvothermal synthesis of orthorhombic Co2P with particle
Fig. 2. Schematic illustration of the facile solvothermal synthesis of Co2P. size ~20 ~ 30 nm as an efficient HER catalysts (Fig. 2). The Co2P
catalyst exhibited high catalytic activity for HER. Co2P electrode showed
ratio was 1:1 among all as-prepared phosphide samples. Co1Ni1-P@C excellent stability and durability during HER. Investigation of Co2P as an
has the lowest HER overpotential of any prepared phosphide sample, electrocatalyst for HER in acidic (0.5 M H2SO4) and alkaline medium
measuring 169 mV at 10 mA cm− 2. Although Co1Ni1-P@C has a lower (1.0 M KOH), furnished a low overpotential of 178 mV and 190 mV,
overpotential than Pt/C, its low cost and abundance make it a viable respectively to achieve a current density at 10 mA cm− 2. A simple and
HER catalyst for practical application in water splitting [16]. facile one-pot preparation of Co2P nanoparticles by using water/
ethylene glycol as solvent by the solvothermal method is established
To anchor Nickel-Cobalt (Ni-Co) nanoparticles as for an HER with red phosphorous as the phosphorous source. Co2P nanoparticles
In the design of this CO2-assisted synthesis of N-doped carbon aer­ synthesized by the solvothermal method furnish not only good catalytic
ogel derived from silk fibroin (SFCA) (Fig. 1). The electro catalyst activity but also demonstrate long-term stability and durability during
showed a low over potential and low Tafel slope in the basic medium. HER [19].
The obtained SFCA-Ni-Co electrocatalyst demonstrated outstanding
electrochemical performance having an onset potential of 52 mV and a Pure phase V2O3 for HER catalysis
low overpotential of 179 mV at the current density of 10 mA cm− 2, O. P. Pandey and co-workers synthesized oxygen deficient vanadium
whilst exhibiting long-term stability when tested for 24 h. The oxide (V2O3). Vanadium oxide (V2O3) nanoparticles by the hydrother­
outstanding electrocatalytic performance marks SFCA-Ni-Co as a mal method in a specially designed autoclave at 500 ◦ C for a reaction
favorable electrocatalyst for HER and the synthesis strategy paves way time of 4 h. Effect of reaction temperature, reaction time, and an open
for constructing novel catalysts even for other areas. The intrinsic atmosphere affects the phase formation of V2O3. The calculated crys­
property of carbon aerogel helped to enhance electron and mass trans­ tallite size of the V2O3 nanostructures was found 48.3 nm. The detailed
port. The aggregation/accumulation of Ni-Co nanoparticles was pre­ route followed for the synthesis of V2O3 is discussed below and is shown
vented with improved activity and stability [17]. schematically in Fig. 3.
Characterization technique for the phase confirmation of all pre­
PdSe2 nanosheets as highly active electrocatalyst for HER pared samples were determined by using PANALYTICAL X’PERT PRO X-
PdSe2, a common layered transition metal selenide, has been widely ray diffraction (XRD), field emission scanning electron microscopy
used in the fabrication of photo detectors, field effect transistors, and (FESEM), transmission electron microscopy (TEM), and X-ray photo­
tunable devices in electronics. PdSe2 as a planar electrocatalyst for HER. electron spectroscopy (XPS), respectively. Which were structurally and
Pd atoms in PdSe2 are sandwiched by two layers of Se atoms, like other morphologically characterized to get insights into pure phase V2O3. For
transition metal chalcogenides. However, the Pd atoms and adjacent Se HER differential scanning calorimetry (DSC) and thermal gravimetric
atoms share a plane, resulting in a one-of-a-kind planar coordination analysis (TGA) techniques were employed to confirm the phase transi­
environment. Pd cations are sufficiently exposed to interact with tion of V2O3. The synthesized sample shows higher cyclic stability for
hydrogen intermediates thanks to the planar coordination structure. As 1000 cyclic voltammetry (CV) cycles. It also exhibited a lower Tafel
a result, both Pd and Se sites in PdSe2 are HER-active. To evaluate the slope of 81.2 mVdec− 1. The electrochemical double layer capacitance
HER activity, PdSe2 bulk material was first synthesized using a simple (EDLC) measurement was done via CV measurements performed at
solid-state synthesis method with Pd and Se powder as raw materials. various scan rates which revealed the higher transfer kinetics exhibited
PdSe2 bulk can be easily exfoliated into thin nanosheets due to its by V2O3. All performed studies predict the potential applications of V2O3
layered crystal structure, exposing more reacting sites and breaking nanostructures for electrochemical applications like HER and super­
more bonds at the edges. DFT calculations show that both Pd and Se capacitors [20].
atoms have high activity for hydrogen evolution in a planar coordina­
tion environment, which is comparable to other advanced layered MoS2 nanoplates as an efficient and stable electrocatalyst for HER:
transition metal chalcogenide counterparts. PdSe2 nanosheets exhibit Layered MoS2 is gaining popularity as a viable low-cost alternative to

Fig. 3. Proposed Synthesis pathways of V2O3.

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S. Kumar et al. Results in Chemistry 4 (2022) 100613

Fig. 4. Schematic Synthesis pathway of MoS2- VN (CTAB).

activity of the Co/NGC-3 by using a standard three-electrode set-up in

0.1 M KOH solution, inspired by the unique structural advantages. Co/
NGC-3 is a possible cathode material for rechargeable Zn-air batteries
as well as a high-performance multipurpose electrocatalyst for HER.
Owing to the smaller ZIF-67 polyhedrons with relatively uniform dis­
tribution, more effective active sites, and strong coupling effect of Co-
pyridinic-N, the proposed Co/NGC-3 catalyst exhibited an impressive
HER activity. The electrocatalytic HER activity of the Co/NGC-3 was
Fig. 5. synthesis of ZIF Nanocrystal-based surface.
assessed using a typical three-electrode set-up in 0.1 M KOH solution.
Co/NGC-3 possessed superior HER activity with a lower overpotential
Pt-based electrocatalysts for the hydrogen evolution process (HER). As (η10) of 293 mV at 10 mA cm− 1and Tafel slop of Co/NGC-3 exhibited the
in this report, a vanadium nitride (VN) with an increased specific surface same value of 130 mV dec− 1 [23]. In Fig. 5, the ZIF nanocrystal is shown
area VN(CTAB), CTAB refers to Cetyltrimethylammonium bromide was below where ZIF-67{Co (C4N2H5)2} is formed. The synthesis provided
synthesized as a substrate. Furthermore, it is the first report where is;
Molybdenum disulfide (MoS2) nanoplates were vertically grown on the
resultant VN(CTAB). As an electrocatalyst for HER, the synthesized Synthesis of ZIF-67Glu/g-C3N4, ZIF-67Glu, and ZIF-67/g-C3N4
MoS2- VN(CTAB) in Fig. 4, exhibited a low initial overpotential (85 mV) Preparation of Co/NGC, Co/NGC-1, Co/NGC-2, Co/NGC-3 and NGC
and a modest Tafel slope (53.31 mVdec-1), as well as excellent stability.
In addition to the advantages of increased conductivity (106 Sm− 1) and Carbon-based electrocatalyst derived from biomass for the HER
improved stability of VN(CTAB) over typical carbon-based substrates, The author reported here a non-pollution method for hydrogen
the expanded interlayer spacing (1.00 nm) and extra defects, along with production as nowadays; carbon-based electrocatalysts derived from
the lower valence states of Mo and S due to the stronger electron biomass have attracted more and more attention thanks to their char­
interaction between VN(CTAB) and MoS2 [21]. acteristics as low-cost, renewable, abundantly distributed, and envi­
ronmentally friendly.
Doped and supportive electrocatalysts Metal-free catalysts performed poorly against HER until Chen’s
group reported a high activity catalyst made of nano porous graphene
Co, Nb-MoS2/TiO2 hollow sphere multifunctional electrocatalyst for HER with N and S co-doped. The coupling effects between heteroatoms and
The author reported a multiple metal transition doping approach lattice defects significantly enhance catalytic ability via high conduc­
that developed through the incorporation of both Co and Nb into hier­ tivity resulting from electron-rich in defective structure and optimized Δ
archical MoS2 ultrathin nanosheets that can directly grow on micro-TiO2 GH. which is infinitely approaching to the Pt catalyst. Following that,
hollow spheres (Co, Nb-MoS2/TiO2 HSs) to boost the HER. The Co and DFT calculations and experiments were used to investigate various
Nb dual-doping effects modify the electronic structure of the host MoS2 heteroatom dual-doped graphene’s (such as S/NG, P/N-G, and so on).
towards maximizing the HER performance. Additionally, the unique Graphene’s electron acceptor–donor properties are altered by the syn­
hollow spherical structure and heterostructure synergistic effects be­ ergistic coupling effect of two heteroatoms. The heteroatom doping
tween the TiO2 core and MoS2 shell provide effective channels for strategy can also be applied to biomass-derived carbon materials,
electron transfer and a large surface area with abundant exposed void potentially improving their HER properties. The abundant heteroatom
spaces for ion diffusion/penetration. Therefore, the Co, Nb-MoS2/TiO2 in biological components can form self-doped atoms, which can signif­
catalyst demonstrates extraordinary activities and stabilities with small icantly improve HER performance while reducing the use of chemical
overpotentials of 58.8 and 260.0 mV at 10 mA cm− 2 for the HER reagents.
respectively. The effective improvement of the intrinsic catalytic activ­ Furthermore, high conductivity graphitized carbon materials will be
ities of MoS2-based nanomaterial towards HER, via the doping effect, obtained through high temperature treatment or catalytic graphitiza­
upgrades its advantaged properties, thus leading to it being suitable for tion. As a result, building the heteroatom self-doped graphitization
multifunctional applications in the forthcoming critically needed green carbon material is a promising catalytic option. Furthermore, doping
energy conversion and storage technologies [22]. with exogenous atoms derived from chemical reagents is a method of
producing heteroatom-doped biomass-based carbon material. The
Ultrafine Co nanoparticles supported by nitrogen-doped graphitic carbon as original carbon material was derived from biomass and then doped with
an efficient multifunctional electrocatalyst for HER N or S for HER electrocatalysis for better electrochemical performance
Here authors evaluated the electro catalytic activity towards HER

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S. Kumar et al. Results in Chemistry 4 (2022) 100613

and hydrogen yield at 10 mA cm− 2, the over potential is typically greater Ni foam. The second step involved the introduction of S during calci­
than 100 mV, far inferior to Pt-based catalysts. As a result, biomass- nation to react with portions of the Ni2P substrate to form Ni0.96S, and
based carbon materials with transition metal and/or trace amounts of the final step involved the formation of the target catalyst in the form of
precious metal were introduced to improve HER performance. As a Ni2P/Ni0.96S/NF. To obtain Ni2P/NF, NaH2PO2 and pre-cleaned NF were
result, biomass-based carbon materials with transition metal trace placed in a tube furnace and heated to 400 ◦ C for two hours in an N2
amounts of precious metal to improve HER performance. It has already atmosphere. The prepared Ni2P/NF and S powder was then placed in a
been studied by various reports [24,25,26] that the synergistic effect tube furnace and heated for one hour in nitrogen at 400 ◦ C to produce
between metals and heteroatoms can significantly enhance electro­ the final Ni2P/Ni0.96S heterostructure. To serve as a comparison, S
catalytic activity. The limitations and challenges in this area are; powder was calcined on Ni foam as the substrate under the same con­
ditions to produce a Ni0.96S/NF catalyst with HER activities of 1.0 mol/
i. In-depth investigation of conversion and electrocatalytic L. The overpotentials of 72 and 239 mV to reach 10 and 100 mA cm− 2,
mechanism, respectively, KOH clearly demonstrated the MS-Ni2P/Ni0.96S/NF’s
ii. Metal modification via in-situ growth, optimal performance. These overpotentials were higher and were
iii. Reproducibility for biomass transformation, and comparable to those of noble metal Pt/C (overpotential of 168 mV to
iv. Catalyst assembly with renewable energy equipment. reach 100 mA cm− 2). Catalytic HER activity and stability were at 8
mol L− 1. The results that tell us about the large specific surface areas and
In summary, the synergistic effect between heteroatoms and metals conductive networks of 3D materials can provide faster electron con­
can significantly optimize △GH*, improving the HER performance. duction and more active sites after catalyst loading for enhanced cata­
Remarkably, the hybrid catalyst decorated with the Ru NPs exhibits a lytic HER performance [28].
prominent performance regardless of commercial Pt/C [27].
Nickel-cobalt phosphide, like a nest, for powerful standard water splitting
Ru@CQDs electrocatalyst The highly performance non-precious electrocatalysts for hydrogen
Despite not being a noble metal, Ru was chosen in this study to evolution reaction (HER) is of great significance for renewable energy
investigate the role of CQDs in HER catalysis. Regardless, the synthesis technologies. Ni-CoP/CC is prepared by before being placed separately
procedure revealed that the Ru nanoparticles were evenly distributed in a porcelain boat; 2 g of NaH2PO2 and NiCo2O4/CC were heated for 2 h
throughout the CQD matrix, with a mean size of less than 3.28 nm. in a tube furnace at 300 ◦ C in an N2 atmosphere. The rate of heating was
Because of their highly tunable photoluminescence ability, quick elec­ maintained at 2 ◦ C min− 1. The prepared NiCo2O4/CC was washed with
tron transfer, huge electron storage ability, and catalytic activity, carbon deionized water, then washed with ethanol and deionized water before
quantum dots (CQDs), which are unique carbon nanomaterials smaller being dried in a vacuum at 80 ◦ C.
than 10 nm, have garnered considerable attention. Electrochemical ex­ In this paper, we describe the direct growth of a 3D nest-like Ni-CoP
periments show that the Ru@CQDs display excellent catalytic perfor­ architecture on carbon cloth (CC) that can be controlled. With excep­
mance even under strongly alkaline conditions (1 M KOH), with an tional overpotentials of 44 mV and 62 mV at a current density of 10 mA
initial overpotential of 0 mV, a Tafel slope of 47 mV dec-1, and good cm− 2 and small Tafel slopes of 39 and 66.5 mV dec-1 in acidic and
durability. Most impressively, the current density of 10 mA cm− 2 may be alkaline solutions, respectively, the as-synthesized Ni-CoP/CC demon­
attained with just a 10 mV overpotential. From recent papers we find, on strated excellent electrocatalytic performance toward HER. Here, it
pyrolysis of RuCl3 that on annealing at 480 ◦ C (designated as provides successive hydrothermal, oxidation and phosphorating method
Ru@CQDs480) produces an inexpensive and easily fabricated to make 3D nest-like ternary Ni-CoP/ (carbon cloth) CC electrocatalyst
Ru@CQDs hybrid with remarkable catalytic ability for HER and an onset with superior catalytic activity and stability toward HER [29].
overpotential of 0 mV and a Tafel slope of 47 mV dec-1. Ru@CQDs480
also has remarkable stability after 10,000 CV cycles and outperforms Pt/ 3D nickel foams in highly alkaline medium for HER:
C in 1 m KOH solution in terms of catalytic durability. In this work, 3D Ni foams were put on stainless steel via galvanostatic
deposition from different electrolytes. The foams activity toward HER
3D electro catalyst and overall stability in strongly alkaline media were investigated in
relation to the electrolyte composition’s effect on surface micro size
3D materials are solid figures, objects, or shapes with three di­ pores and deposit morphology by using cyclic voltammetry, linear scan
mensions of length, width, and height. 3D materials, as opposed to 2D voltammetry, and chronoamperometry. The 3D Ni foams electro­
materials, have thickness or depth. Many supported catalyst materials, chemical performance in alkaline media was evaluated with optical and
for example, can be thought of as 3D materials. Because many catalysts scanning electron microscopy to examine the surface of the foams.
have insufficient electrical conductivity and specific surface area, Ni foams were synthesized catholically electrodeposited from three
selecting suitable substrates to support catalysts is critical for improved different chloride-based solutions. NiCl2⋅6H2O (Sigma-Aldrich, 98 wt
electrical conductivity and specific surface area with maximized active %), NH4Cl (Sigma-Aldrich, 99.5 wt%) and NaCl (Panreac, 99 wt%) were
sites from a catalytic standpoint. 3D electrocatalyst has the advantages used as received without purification. The deposition process was car­
of a large specific surface area and a low cost, making it a suitable ried out in a 2- electrode cell (75 mL) connected to a power source
catalyst substrate to maximize active reaction sites. These are discussed (Sorensen LH110). A graphite plate was used as counter electrode and a
below. stainless-steel plate (AISI 304, Goodfellow) with an active area of 1.65
cm2 was employed as the working electrode. All foams were deposited
Low-cost Ni2P/Ni0.96S hetero-structured acts as a bifunctional by applying a current density of − 1A cm− 2 for 150 s. Then, they were
electrocatalyst thoroughly rinsed with distilled water to remove the remaining elec­
Here, a new low-cost bifunctional Ni2P/Ni0.96S heterostructure trolyte. The electrolytic bath composition, as well as the morphology
electrocatalyst is created for high-efficiency overall breaking. It is active and porosity of the foam, influence the material’s catalytic efficiency
for the HER at the cathode. Superior catalytic efficiency and stability are and are easily manipulated by altering the electrodeposition process
displayed by a Ni-foam (NF) supporting Ni2P/Ni0.96S catalyst electrode conditions [30].
in a systematic configuration. This improves the development of a
cheap, extremely effective, bifunctional electrocatalyst. RhSe2: An outstanding 3D electrocatalyst with multiple active facets for
In this the two-step process of synthesizing Ni2P/Ni0.96S/NF involved hydrogen evolution reactions in acid and alkaline solutions
the first step of calcination with NaH2PO2 and the formation of Ni2P on W. Zhong et al. recently reported RhSe2 as a “3D” electrocatalyst for

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S. Kumar et al. Results in Chemistry 4 (2022) 100613

Table 1 HER with top-class activity, synthesized by a facile solid-state method.

Electrochemical parameters of GO-incorporated Cu-MOF composite. Superior to 2D materials, multiple crystal facets of RhSe2 exhibit near-
Parameters Cu- (GO 6 wt%) Cu- (GO 8 wt%) Cu- Pt zero free energy change of hydrogen adsorption (ΔGH), which guaran­
MOF MOF MOF tees high performance in most common morphologies. DFT Calculations
Tafel slop(mV dec-1) 135 96 84 30 show that the low-coordinated Rh atoms act as active sites in acid,
Current density 39.12 104.71 122.48 313.11 enabling the modified Kubas-mediated route, whereas the Se atoms act
(mA cm− 2) at as active sites in an alkaline medium. The over potentials of RhSe2 HER
− 0.4 V activity is 49.9 and 81.6 mV at 10 mA cm− 2 in acid and alkaline solu­
tions, respectively. It lay the path for the development of novel transi­
tion metal chalcogenide catalysts [31].
Table 2
photocatalytic H2 evolution on TiO2 by structural and morphological control. Molecular electro catalyst
Photocatalyst Type of TiO2 H2 evolution
rate Highly stable molecular catalyst [Ni(DHMPE) 2]2+
(µmol/h g− 1)
For the hydrogen evolution reaction (HER) at pH 1, the electro­
TiO2 4–95 mol % anatase and the remaining is rutile; 4250 catalytic activity of a water-soluble nickel complex, [Ni (DHMPE)2]2+
Nanoparticles {DHMPE = 2-bis[di(hydroxymethyl)phosphino]ethane}, is reported. The
Anatase; Nanotubes 12
catalyst operates with high Faradaic efficiency at a rate of ~103 s− 1
Anatase; Tapered tetragonal nanorods 703.4
Anatase; Nanoparticles and nanotubes 172 (knobs). Under catalytic conditions, quantification of the complex prior
Anatase/rutile; Uniform ordered mesoporous 12,600 to and after 18 + hours of electrolysis reveal negligible decomposition.
microspheres This is a rare instance of a homogeneous catalyst for HER those functions
Rutile; Three-dimensional; Facet heterojunction 1441
with high stability at low pH, despite the fact that electrolytic cells
structure
Nanotube arrays 2
typically experience conditions that are extremely acidic. The com­
Anatase; Ordered mesoporous 1362 pound’s stability and the proposed catalytic intermediates made it
Brookite; nanosheets 8010 possible to conduct in-depth mechanistic studies. Which utilized the
Anatase; Twinned nanocrystal 1272.66 thermodynamic parameters that govern electron and proton transfer,
Anatase; Hollow microspheres 6600
the appropriate reductants and acids were selected to step-by-step access
Anatase; Mesoporous nanoparticles 175
Rutile 900 the catalytic cycle, allowing for the direct spectroscopic identification of
Anatase; Nanorods films 1874 intermediates. These studies support a mechanism for proton reduction
Anatase/rutile; Nanocrystalline 4.87 that proceeds through two electron reduction of the nickel (II) complex,
protonation to generate [HNi (DHMPE)2]+, and further protonation to
initiate hydrogen bond formation. The catalyst functions at high rates at
Table 3 a modest overpotential under acidic conditions, which are most appli­
TiO2-based photo catalysts in pure water or seawater splitting systems without cable to current electrolytic cells for solar fuels [32].
sacrificial agents.
Photocatalysts Light source Reactant H2 Productivity Metal-organic framework based on tetra-carboxylic acid as a high-
(μmol h− 1 g− 1) performance bi-functional electrocatalyst for HER
TiO2 300-W, Xe lamp Pure water 41.8 Authors reported the hydrothermal synthesis of tetra-carboxylic
TiO2 (P25) 300-W, Xe lamp Pure water 106 acid-based 3D porous MOFs having formal {[Co2.5(L)].5H2O} n and
Colloidal TiO2 450-W, Xe lamp Water@ pH 1.5 125 0.5{[Cu(L)].2H2O} n. The pristine MOFs were immediately used for
TiO2 (anatase) 450-W, Xe lamp Water vapors 449
electrocatalysis, and low HER activities were achieved in an alkaline
Brookite TiO2 UV light, natural light Seawater 7200
TiO2 nanobelts 300-W, Xe lamp Pure Water 614
solution, which encouraged the design and production of a mixed-metal
TiO2: Ga UV lamp, 300-W Pure Water 20.8 Co/Cu-MOF in the future. As outperforms in terms of HER performance,
SrTiO2: TiO2 300-W, Xe lamp Pure Water 10.6 with an overpotential of 391 mV (10 mA cm− 2 current density), a low
CuO/ TiO2 300-W, Xe lamp Stimulated 3.1 Tafel slope of 94 mV dec-1, and long-term operating stability (14 h). The
seawater
improved electrocatalytic performance of pure can be attributed to a
TiO2-C3N4 300-W, Xe arc lamp Pure Water 374.2
hybridizing technique for manufacturing MOFs using a hydrothermal
process, which may provide a synergistic effect and more open metal
sites. These studies revealed a thorough knowledge of hybrid pristine
Table 4
MOFs for electrocatalysis. indicates a great potential as a high-
HER catalytic property of various CeO2-based photocatalysts.
performance bi-functional electrocatalyst for HER, which may pro­
Photocatalysts H2 production rate [μ mol/h g− 1) mote the extensive exploits of pristine MOFs as electrocatalysts [33].
CdS QDs/CeO2 101
Pt/CeO2 19,700 Graphene oxide and copper-centered metal–organic framework composite as
CeO2 QDs/C 582 a tri-functional catalyst for HER
Cu2ZnSnS4/CeO2 2930
N-CeO2-x/g-C3N4 43
Here authors reported a composite composed of Graphene oxide
CeO2-xSx@CdS 1147 (GO) and a copper-centered metal–organic framework (MOF) performed
Mn0.2Cd0.8S/CeO2 8730 tri-functional catalyst in the hydrogen evolution process, which is
CeO2-CuO QDs/graphene 2481 essential for electrocatalysis reaction (HER). At moderate temperatures,
CeO2-Au-CdS QDs 12,475
electrocatalysis is an efficient catalyst that can perform both activities
CeO2 5
CeO2/g-C3N4 830 viz., decrease and produce oxygen. The unique porous scaffold structure,
CeO2@Ni4S3/g-C3N4 3740 better charge transport, and synergistic interactions between the GO and
CeO2-Fe2O3 584 [µmol h− 1] MOF all contribute to the GO-MOF composite’s superior electrocatalytic
p-MoS2/n-CeO2 721 [µA cm− 2] capabilities and acid stability. In polymer electrolyte membrane fuel cell
testing, the GO-incorporated Cu-MOF composite delivers a power den­
sity that is 76 % that of the commercial Pt catalyst. Table 1 shows the

6
S. Kumar et al. Results in Chemistry 4 (2022) 100613

Fig. 6. Synthetic illustration of the NiS- CdS composite.

Fig. 7. Schematic preparation of g-C3N4.

electrochemical parameters of GO-incorporated Cu-MOF composite for Photocatalysts for photocatalytic H2 evolution made of non-precious
HER [34]. metals

Different photo catalysts for HER Several non-noble-metal photocatalysts have been covered in this
review, including metal oxides (TiO2, etc.), metal sulphides (CdS), metal
The production of hydrogen from water using a catalyst and solar phosphides (NiP), and metal-free catalysts (g-C3N4, etc.).
energy is a clean ideal future energy source, independent of fossil re­
serves. For an economical use of water and solar energy, catalysts that Metal oxide-based photo catalyst
are sufficiently efficient, stable, inexpensive, and capable of harvesting
light are required. Here, we are throwing light on some photocatalysts TiO2 – based photocatalyst. Because of its high efficiency and stability,
for HER, which show that can produce hydrogen from water under TiO2 is the most used photocatalyst. However, it had broad bandgap
visible-light irradiation in the presence of a sacrificial donor. (3.2 eV), which limits visible light absorption and solar energy utiliza­
tion. TiO2 photocatalysts light absorption and charge separation/
transmission are increased through structural and morphological con­
trol. It can also increase the surface area and yield new active sites, thus
improving their performance and stability. The Table 2 is shown below

7
S. Kumar et al. Results in Chemistry 4 (2022) 100613

Table 5 photocatalytic activity, according to research by Dong et al. who syn­

Summarizes the merits and demerits of different methods for the construction of thesized CeO2 nanorods. Under solar light irradiation, a rate of 5.02 mol
g-C3N4. g-1h-1hydrogen production was attained, and the photocatalytic activity
Synthesis Methods Advantages Disadvantages was connected to the conversion of Ce3+/Ce4+ and oxygen vacancies.
Supramolecular pre- Produced g-C3N4 with an Low efficiency, time & cost
CeO2 was widely used to composite with other catalytically active
assembly strategy. ordered texture and consuming, and components to construct the special structure with enhanced electro
controllable morphology sophisticated. (photo)catalytic performance. CeO2 mainly disperse and anchor active
Produced g-C3N4 with a component nanoparticles to increase the number of active sites, which
relatively low crystallinity
proves a strong electronic interaction with active components to attain
Molten salt strategy Produced g-C3N4 with high Time cost consuming &
crystallinity complicated preparation the regulation of their electronic structures, aiming to improve the
step intrinsic activity. The two important features of CeO2, abundant oxygen
Microwave-assisted Facile, time-saving, and Produced g-C3N4 without vacancies and flexible transitions between Ce3+ and Ce4+, play a key
heating strategy highly efficient. an ordered texture, role to advance the electro(photo)catalytic activity of catalysts. In order
Produced g-C3N4 with controllable morphology,
relatively high crystallinity, and porous structure.
to give CeO2 enhanced charge separation, a lower rate of electron-hole
thinner layer, and decreased pair recombination, and visible region absorption, Krishnan et al.
structural imperfections. decreased the bandgap of CeO2 to 2.5 by adding Fe2O3. The Table 4
Template-assisted Produced g-C3N4 with Time- and cost-consuming summarizes the HER catalytic property of various CeO2-based photo­
strategy porous structure and high and complicated
catalysts [40].
crystallinity. preparation process.
Chemical exfoliation Facile, time-saving, and The danger of strong acid
strategy highly efficient. and not eco-friendly. Metal sulphide based photocatalyst
Produced g-C3N4 with Produced g-C3N4 without Metal sulfides are well-known photocatalysts for water splitting to
relatively high crystallinity, an ordered texture, produce H2. Due to their comparatively high CB locations, metal sulfides
and thinner layer. controllable morphology,
are ideal for water reduction and display superior light sensitivity than
and porous structure.
Fast flash frozen The fast, high-effect, and The complicated oxides [41]. The most studied metal sulfide-based photocatalysts are
strategy eco-friendly preparation process and CdS (E.g., = 2.4 eV) and ZnS (E.g.,= 3.6 eV). However, photo corrosion
expansive affects metal sulfide photocatalysts, which could lead to reduced sta­
Hydrothermal Facile, eco-friendly, and Complicated preparation
bility. Their photocatalytic H2 production efficiency has been enhanced
pretreatment highly efficient. process.
strategy Produced g-C3N4 with by techniques including elemental doping and heterojunction fabrica­
relatively high crystallinity, tion. Multi-metal sulfides exhibit a tunable band energy structure, like
and a thinner layer single-metal sulfides. This can improve the productivity of photo­
Ionic liquid strategy Produced g-C3N4 with Time- and cost-consuming, catalytic H2 production by enhancing the materials’ light responsiveness
porous structure, thinner complicated preparation
and charge separation/transfer. Hollow bimetallic sulfides were created
layer, and high crystallinity. process, and low efficiency.
by Huang et al [42].
A heterojunction made up of a zero-dimension (0D) nickel sulfide
which had summarized the photocatalytic H2 evolution on TiO2 by (NiS) nanoparticle and cadmium sulfide (CdS) flower was created
structural and morphological control [35]. cleverly. They produced nanocomposite, with a nickel sulfide molar
Elemental doping is another plan to tune the H2 generation rate of ratio of 25 % has a remarkable photocatalytic activity. H2-production
TiO2. Taheri Nia et al. [36] successfully combined N and S atoms into rate is roughly 69.6 times greater than that of pure CdS, at 18020 µmol
TiO2 adopting a sol–gel method. The ultraviolet–visible spectra of the h− 1 g− 1. Different metal sulphide-based catalysts have been discussed in
catalysts revealed that the S-doped TiO2 sample had a narrower bandgap Table 6 with its H2 productivity rate. The Fig. 6 shown below represents
than the N-doped one, resulting in improved visible light absorption, the synthesis of the NiS- CdS composite.
even though the presence of sulfur ions influences catalytic activity.
Moreover, the photocatalytic productivity of N-doped TiO2 grew with an Metal phosphide based photocatalyst
enlarge in the number of N atoms. The highest H2 yield was obtained at Metal phosphides have strong chemical stability, mechanical sta­
the N-doping amount of 6 wt% [36].By low-temperature stripping of the bility, and electron conductivity. The photocatalytic H2 production ef­
Maxine supernatant, Jia et al. created a hierarchical structure of highly ficiency of phosphide-based photocatalysts has been increased using
carbon-doped TiO2 (HC-TiO2) [37]. The resultant HC-TiO2 showed a metal doping. Man et al. reported the doping of NiP with transition
flower-like morphology with tightly packed petals. The improved metal elements including Mo, Mn, Fe, and Co through a facile wet-
photocurrent on HC-TiO2 can be attributed to the increased lifetime of chemical method. H2 evolution rates of 15.3, 16.7, 17, 20.4, and 17.7
its carriers, which in turn better-quality its H2 production efficiency. The mmol h− 1g− 1 were observed for NiMoP, NiMnP, NiFeP, NiCoP, and
H2 generation rate on HC-TiO2 was 8.9 times larger than that upon P25. Ni2P, respectively, [43]. Song et al. prepared MoP–Cu3P hybrids and the
Separately from binary non-metal elemental doping, binary metal- Schottky junctions were formed between intimate interfaces. The
element Fe, Ni [38] co-catalysts have also been applied to boost the improved photocatalytic H2 generation of 855 µmol h− 1 g− 1 was ach­
efficiency of H2 production on TiO2. By adjusting TiO2′ s energy band ieved by the hybrids because they displayed boosted properties for
structure, metal/non-metal doping can enhance light absorption and visible-light harvesting, carrier separation, and transfer[44]. Different
electron transport. The activity on TiO2 was enhanced by the synergistic metal phosphide-based catalysts have been described in Table 6 with its
effect of metal and metalloid (non-metal) caused by the combined H2 productivity rate.
doping strategy. By regulating light absorption and allowing charge
separation/transfer at the interface, heterojunction construction is Metal-free catalysts
another successful method for taming the photocatalytic behavior of This review focuses on the most recent advances and challenges in
TiO2. TiO2 has also been combined with co-catalysts such oxides, sul­ selected metal-free photocatalysts for hydrogen production. The scope
fides, and others. Table 3 is showing the TiO2-based photocatalysts in of this review is limited to metal-free elemental photocatalysts (i.e., B, C,
pure water or seawater splitting systems without sacrificial agents [39]. P, S, Si, Se, and so on), binary photocatalysts (i.e., BC3, B4C, CxNy, h-BN,
and so on) and their heterojunction, ternary photocatalysts (i.e., BCN),
CeO2-based photocatalyst. The bare CeO2 material exhibits and their heterojunction, and various types of organic photocatalysts (i.
e., linear, covalent organic frameworks, microporous polymer, covalent

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S. Kumar et al. Results in Chemistry 4 (2022) 100613

Table 6
Summarize the Photocatalytic H2 evolution based on non-noble-metal catalyst.
Categories Catalysts Co-catalysts Merits Demerits H2 production
rate
(µmol.h-1g− 1)

Metal oxide TiO2 Doped N Reduced microcrystalline rate and band gap Small light absorption 1800

Doped S Reduced particle size, increased special surface area, better light Hydrogen production activity 800
capture reduced by sulfur ions
Doped high Improved lifetime of photogenerated carriers, widened the light Expensive raw materials 33.04
content C absorption range
Doped Fe and Ni Widened light absorption range, improved electron-hole separation An alcohol solvent is necessary for H2 361.64
efficiency production
3+
Doped Fe and Enhanced charge separation Narrow visible–light-response range 724
P5+

Loaded NiO Reduced band gap energy, more exposed area of TiO2 Glycerin is the main source of H2 1230
production
Loaded NiS Promoted fast carrier transport, more active sites limited reported examples 7486

Loaded Cu Inhibited electron-hole recombination No H2 production on TiO2 without Cu 283

ZnO Doped S Increased surface area, enhanced light capture Complex preparation process 3640
Doped Y and Al Improved light absorption and stability, boosted electrons transfer Crystal size increases with the 5710
increase of Y
Loaded g-C3N4 Improved visible-light absorption and charge carrier separation, Narrow visible-light-response range 322
NSs extended carrier life
Coated MoS2 Favored charge transfer, inhibited electron-hole recombination Only responds to ultraviolet light 768
Loaded CdS QDS Promoted photogenerated electron-hole separation and migration, High demand for morphology 22,120
inhibited electron-hole recombination, improved stability
Metal Sulfide CdS Loaded Ni3C NPs Increased visible light absorption, promoted carrier separation and Poor cycling stability 18,020
transfer, improved surface H2 production kinetics
Loaded Co3O4 Formation of p-n heterojunction, enhanced light capture, charge No H2 production compounded with 3014
transfer and separation capabilities P25, no stability test
Loaded TiO2 Formation of Z-scheme structure, promoted electron-hole separation Limited cycles stability tests 1028
Loaded MoS2/ Synergetic effects, inhibited charge recombination Complicated preparation process 1913
graphene
ZnS Doped Cu Improved visible light absorption Low oxidation potential 973.1
Doped In and Cu Improved visible light absorption, enhanced photogenerated charge Photocatalytic H2 production is not 752.7
transfer and carrier separation as effective
Loaded ZnO/g- Plentiful active sites, effective electron-hole separation Narrow visible-light-response range 301.25
C3N4
Metal NiP Doped Mo Electron filling can regulate the activity Sacrificial agents are needed 15,300
Phosphides Doped Mn 16,700
Doped Fe 17,000
Doped Co 20,400
Cu3P Hybridized MoP Construction of heterojunction, promoted carrier separation and / 855
transfer, expanded visible–light-response range
Metal Free g-C3N4 Doped O Reduced band gap, improved light capture No stability test 348
Doped P Effective charge transfer Reduced oxidation potential 427
Doped N Improved light harvesting, promoted photo-excited charge carrier Aromatic heterocycles contained 1280
separation and transfer, extended and delocalize π-conjugated system
Doped B & F Enhanced visible-light absorption by B doping, promoted Complicated preparation process, 7020
photoelectron generation, transfer, and separation by B–F co-doping narrow visible-light response range
and post-activation

triazine frameworks etc.) and their heterostructures. have been described in the last section of Table 6 with its H2 productivity
rate. Table 6 also summarize the different Photocatalytic HER based on
Photocatalysts made of semiconductor polymeric graphitic carbon nitride (g- non-noble-metal catalyst [35].
C3N4). In this recent report the development in the rational design of g-
C3N4 and g-C3N4-based composite photocatalysts for HER is demon­ Conclusion and outlook
strated. g-C3N4 is a polymeric material, metal free composed of triazine-
based pattern with the C/N ratio= ¾ and small amount of H. Its common In recent times, where we all are dependent on continuous energy
synthesis involved thermal polymerization of dicyandiamide, cyana­ sources, we would ultimately need a clean and renewable way of energy
mide, urea, melamine or thiourea under different temperatures generation. Hydrogen production in a clean way via catalytic dehy­
(450–650 ℃). g-C3N4 is highly promising catalyst for removing CO2 drogenation or water splitting involving electrochemical and photo­
from atmosphere and it is used for conversion of energy, waste water chemical catalysis is in top demand. At present, most of the research has
remediation or organic synthesis. The structure of g-C3N4 is shown in investigated precious metals are the most prominent electrocatalysts
Fig. 7, from where it can be synthesized at different temperatures [45]. due to their specificity and efficacy. However, the main challenge in the
Table 5 mentioned below represents the synthesis method with its ad­ field of electrocatalyst/photocatalyst design is that the precious cata­
vantages and limitations [46]. lysts are rare on earth and, at a high cost, hindered the technology’s
The effectiveness of photocatalytic H2 production can be increased extensive application. That’s why researchers are in continuous efforts
through a variety of techniques, including elemental doping, creating to replace the noble metals-based catalysts with the transition metal-
heterojunctions, and increasing reactivity. Different metal free catalysts based environmentally benign catalysts. Additionally, it has been com­
ing in reports that there is a decrease in the use of precious metals by

9
S. Kumar et al. Results in Chemistry 4 (2022) 100613

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Declaration of Competing Interest electrocatalyst for HER, ACS Appl. Energy Mater. 2 (2019) 2854–2861, https://doi.
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The authors declare that they have no known competing financial [22] D.C. Nguyen, T.L. Luyen Doan, S. Prabhakaran, D.T. Tran, D.H. Kim, J.H. Lee, N.
H. Kim, Hierarchical Co and Nb dual-doped MoS2 nanosheets shelled micro-TiO2
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