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Nanomaterials as electrocatalyst for hydrogen and oxygen evolution reaction:

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 Polyhedron 193 (2021) 114871

Contents lists available at ScienceDirect

Polyhedron
journal homepage: www.elsevier.com/locate/poly

Nanomaterials as electrocatalyst for hydrogen and oxygen evolution

reaction: Exploitation of challenges and current progressions
Shujit Chandra Paul a, Shaikat Chandra Dey b, Md. Ashraful Islam Molla b, Md. Shafiul Islam a,c,
Sotan Debnath a, Muhammed Yusuf Miah a, Md. Ashaduzzaman b, Mithun Sarker b,⇑
a
Department of Applied Chemistry and Chemical Engineering, Noakhali Science and Technology University, Sonapur 3814, Noakhali, Bangladesh
b
Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering and Technology, University of Dhaka, Dhaka 1000, Bangladesh
c
Department of Chemistry, Virginia Commonwealth University, Richmond, USA

a r t i c l e i n f o a b s t r a c t

Article history: Electrocatalytic water splitting is considered being an optimistic process and can be a sustainable source
Received 22 June 2020 of renewable energy for the future. Although, the primary overpotential requirement and stability prob-
Accepted 20 October 2020 lem of the electrocatalysts make the process difficult for industrial applications, a cost-effective electro-
Available online 24 October 2020
catalyst with high surface area, stability, and bifunctional activity can eliminate such barriers in the
upcoming eons. To date, metal alloys, metal hydroxides, metal oxides, metal derivatives (phosphides, sul-
Keywords: fides, selenides, and carbides) metal–organic frameworks, hybrid and metal-free materials based electro-
Hydrogen evolution reaction
catalysts have been already developed for the overall water splitting. Herein, the challenges to enhance
Oxygen evolution reaction
Electrocatalyst
the activity, stability and durability in the metal (both noble metal and transitional metal) and metal-free
Metal based and metal free electrocatalyst based electrocatalyst for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER)
Hybrid electrocatalyst are summarized. A general overview of the water splitting mechanism followed by various electrocata-
lyst are discussed mainly. Moreover, it is expected to provide a comprehensive summary and outlook at
the end.
Ó 2020 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Electrochemical water splitting reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. HER mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.2. OER mechanism. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Electrocatalyst for HER/OER activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Metal and alloy based electrocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Metal oxide based electrocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
3.3. Metal hydroxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.4. Other metal derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.5. Metal-organic framework based electrocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.6. Hybrid electrocatalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
3.7. Metal-free electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4. Summery and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
5. Consent for publication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
CRediT authorship contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

⇑ Corresponding author at: Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering and Technology, University of Dhaka, Dhaka 1000,
Bangladesh.
E-mail address: mithun@du.ac.bd (M. Sarker).

https://doi.org/10.1016/j.poly.2020.114871
0277-5387/Ó 2020 Elsevier Ltd. All rights reserved.
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Appendix A. Supplementary data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1. Introduction
Worldwide environment is getting worse day by day due to the
release of various harmful pollutants into the environment from
burning traditional fossil fuels [1,2]. The utilization of fossil fuels
leads to environmental concern including climate change. Hence,
research interest is being shifted from traditional fossil fuels to
other alternative energy sources such solar, wind, wave, etc.
[3,4]. However, these energy resources have some limitations;
wind and solar energy possesses irregular and non-continuous
cycle life [5,6], which could prevent their application to large-scale
operations [7]. Therefore, consideration of sustainable and envi-
ronment friendly energy resources is important for continuous
power supply. In this regard, hydrogen appears as a promising
alternative for fossil fuel replacement due to its environmental
pleasures, and large-scale utilization opportunities [8,9]. In addi-
tion, hydrogen is considered as the cleanest fuel [10]. Traditional
methods for hydrogen production are natural gas reforming and
coal gasification. However, these methods are responsible for CO2
emissions, which is a potential greenhouse gas and largely respon-
sible for global warming [11,12].
Electrochemical water splitting is considered as a promising
technology to produce clean fuel hydrogen which is not only free
from carbon emission but also has conversion efficiency around
80% from the viewpoint of thermodynamics [13]. Electrochemical
water splitting technique consists of hydrogen evolution reaction
(HER) at the cathode and oxygen evolution reaction (OER) at the
anode respectively [14]. During water-splitting reaction, electrocat-
alyst performs three primary functions: (1) stabilizing electron and
holes from recombination, (2) providing adsorption sites for hydro-
gen and oxygen molecules, and (3) reducing activation energy for
water oxidation and reduction [15]. Electrocatalyst having high sur-
face area, higher conductivity, and outstanding stability in elec-
trolyte medium can fulfill the aforementioned steps that enhance
the sustainability of HER and OER activity in any medium [16].
Nanomaterials have attracted great attention in the recent years
as electrode materials because of their unique mechanical, and
electrical properties [17,18]. Considering the large surface area of
nanomaterials, they can lower the energy barrier for electrochem-
ical reactions and can reduce the charge transfer resistance
through promoting the electron charge transfer at the electrode
surfaces [19,20]. To date, Pt group nanomaterials have been con-
sidered as a benchmark electrode material for HER, while IrO2
and RuO2 for OER [21,22]. However, these noble metals are not
abundant in nature and their high cost as well as tendency to
agglomerate in electrolytic medium limits their usage in large-
scale operation [23]. Moreover, Pt exhibits sluggish reaction kinet-
ics in basic media and Ru based catalysts are not suitable for uni-
versal pH condition [24]. Therefore, it is highly essential to
develop low cost, highly active, and stable electrocatalyst for
HER/OER activity. In the last few decades, scientists widely studied
various transitional metal-based derivatives such as alloy, oxides,
hydroxides, sulfides, phosphides, selenides as electrocatalyst for
HER and OER activity in both acidic and basic medium [25-28].
However, transitional metals derivatives are not promising enough
due to their inartistic limitations [29]. For example, CoNi and metal
2
Polyhedron 193 (2021) 114871
sulphides cannot function well in the alkaline medium for OER
[30]. In addition, it was observed that due to difference in catalytic
mechanisms, electrocatalysts that work effectively for HER may
perform poorly in OER. To overcome these challenges, nanomateri-
als can play a vital role in developing next-generation highly active
electrocatalysts for widespread applications.
So far, there have been plenty of reviews based on specific
materials [31-36], but no recent reviews have been found across
all electrocatalysts. Therefore, attempt has been taken in this
review to successfully highlight the potential and limitation of
each and every possible material as electrocatalyst to date. This
review sequentially presents the reported studies on electrocata-
lysts in the form of metals, alloys, metal oxides, metal hydroxides,
metal phosphides, sulfides, selenides, carbides, metal organic
frameworks, hybrid electrocatalysts, and metal-free electrocata-
lysts. In this review, we will mainly focus on the various strategies
such as composition control, doping, variation in synthesis route,
giving supportive materials etc. adopted for improving the electro-
catalyst performance. The review will begin by a brief underlying
of HER/OER mechanism and then focus the various nanomaterials
based electrocatalyst along with their existing challenges and cur-
rent advancement in application. Finally, a probable future
research direction has been predicted based on the available liter-
ature reports, which is expected to be a potential breakthrough of
this current review.
2. Electrochemical water splitting reaction mechanism
2.1. HER mechanism
Electrocatalytic HER is a very significant process since the
hydrogen produced from this reaction can be directly used as
chemical fuel or other useful products. HER consists of two funda-
mental steps in both acidic and basic medium known as Volmer-
Heyrovsky or Volmer-Tafel step [36]. In the first step, known as
Volmer step, H+ (from H3O+ ) form an adsorbed hydrogen interme-
diate (Hads) by coupling with an electron on the active surface of
electrode in an acidic medium whereas in the case of the alkaline
medium the proton is supplied by the water molecules [37]. The
second step in both media depends on the concentration of Hads
on the catalyst surface [38]. If the concentration of Hads is low then
it will combine with another free H+ and an electron simultane-
ously to form H2, which is known as Volmer-Heyrovsky reaction
[39]. In the case of a broad coverage surface of Hads, two such inter-
mediates will recombine with each other to generate H2 molecule,
known as the Volmer-Tafel reaction [40]. However, HER in alkaline
medium is slower than acidic medium because of the possibility of
reversible adsorption of H atom generated from the dissociation of
water molecules [41].
(a) Volmer step:
In acidic medium
H3 Oþ þ M þ e $ MHads þ H2 O ð1Þ
In basic medium
H2 O þ M þ e $ MHads þ OH ð2Þ
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

(b) Heyrovsky step: Followed by either

In acidic medium 
2 O $ 2  þO2 þ 2e ð8Þ
þ 
H3 O þ MHads þ e $ H2 þ M þ H2 O ð3Þ
Or
In basic medium 
O þ H2 O$ OOH þ Hþ þ e ð9Þ
H2 O þ MHads þ e $ H2 þ M þ OH ð4Þ

OOH $  þ O2 þ Hþ þ e ð10Þ
(c) Tafel step:
MHads þ MHads $ H2 þ 2M ð5Þ In basic medium
 þ OH $ OH þ e ð11Þ
The rate determination step for hydrogen evolution depends on
the Tafel slope (obtained from a plot of logi vs. g,) value (n). At 
OH þ OH $ H2 Oþ O þ e ð12Þ
standard conditions n is used for detecting the rate-determining
step of the HER reaction and if it is close to 118, 39, and Followed by either
29.5 mV/dec then Volmer, Heyrovsky, and Tafel reactions respec- 
2 O $ 2  þO2 þ 2e ð13Þ
tively should be the rate determination step for HER reaction. In
general, platinum group metals (Pt, Pd, Ru) follow the Volmer– Or
Tafel mechanism with Tafel slope value of 30 mV/dec [40, 41]. 
O þ OH $ OOH þ e ð14Þ
2.2. OER mechanism 
OOH þ OH $  þ O2 þ H2 O þ e ð15Þ
The OER reaction plays a crucial role in the declining efficiency From the above reaction, it is clear that the OER is complicated
of the overall water splitting reaction, a multistep electron transfer than HER as it involves various intermediates like *HO, *O, and
reaction, due to its high overpotential requirements to overcome *HOO in both acidic and alkaline electrolytes whereas * indicates
the kinetic barriers [13]. The OER depends on the electrolyte pH catalytic active sites. Therefore, the OER reaction efficiency
and in acidic medium, the reaction proceeds via oxidation of two depends on the optimum adsorption energy provided by the cata-
water molecules to produce one oxygen molecule through four lyst surface. Similar to HER electrocatalyst, the lower Tafel slope
proton-coupled electron transfer steps. The hydroxyl group is the indicates the better performance of OER activity.
principal component in the primary medium and is converted into
O2 and water molecules via four electron transfer steps [42,43]. 3. Electrocatalyst for HER/OER activity
In acidic medium:
3.1. Metal and alloy based electrocatalyst
H2 O þ $ OH þ Hþ þ e ð6Þ

Various types of noble (Pt, Ru, Ir) and nonprecious metals (Fe,

OH$ O þ Hþ þ e ð7Þ
Co, Ni, Fe, etc.) are usually well thought out for electrocatalytic

Fig. 1. (a, d) Linear Sweep Voltammetry (LSV) curves for HER and OER performance of IrNiCu HCSA, IrNi NA, IrCu NA, Pt/C and IrO2 in N2-saturated 0.5 mol L1 H2SO4 solution
at the potential scan rate of 5 mV/s, (b) Tafel plots and (c) Electrochemical Impedance Spectroscopy (EIS) of IrNiCu HCSA, IrNi NA, IrCu NA and Pt/C for HER at  0.05 V (vs.
RHE). (e) Tafel plots and (f) chronopotentiometry curve of IrNiCu HCSA, IrNi NA and IrCu NA in 0.5 mol L1 H2SO4 at a constant current density of 10 mA cm2. Reproduced
with permission. [28] Copyright 2020, Springer Nature.

3
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Fig. 2. XPS data (a) Surface valence band photoemission spectra and (b) corresponding d-band centers of the Ru3Ni3 NAs, Ru3Ni2 NAs, Ru3Ni1 NAs, and Ru NAs heated at
250 °C in air for 1 h. Reproduced with permission. [29] Copyright 2019, Elsevier, Inc.
water-splitting reaction. However, sole noble metal-based electro-
catalysts are not currently considered promising because of their
high cost, scarcity in nature, agglomeration tendency, and poor tol-
erability towards electrocatalysis poisoning. On the other hand,
only nonprecious metals are not efficient enough to make them
industrially applicable. By giving support to one of these metals
and making alloys of noble metals with non-precious metals or
vice-versa found effective for water splitting reaction. Because it
not only assists in reducing the utilization of precious noble metals
but also enhances the electrocatalyst performances by enhancing
conductivity, improving stability, refining synergistic effect, tuning
the d-band structure, and oxygen adsorption energy on the catalyst
surface. For instance, Zhang et al. [44] synthesized a 3D hierarchi-
cal Ir-based multimetallic alloy (IrNiCu) by one-pot strategy and
showed excellent HER and OER activity with overpotential of
41 mV and 262 mV in a 0.5 M H2SO4 solution at a current density
of 10 mA/cm2. The Tafel slope value of IrNiCu for HER was
21.4 mV/dec, almost similar to the Pt/C electrode, and for the
OER reaction, it was about 71.4 mV/dec. indicating a notable per-
formance for water splitting reaction (Fig. 1). The impressive
bifunctional activity of the alloy with 100% faradaic efficiency
and admirable stability attributed to the synergistic effect of
three different elements and hierarchical structure that pro-
vided large electrochemical active surfaces for the reaction
[44]. Synthesis of 3D hierarchical Ru-Ni nanosheet assemblies
(NAs) through a wet chemical approach at high temperature
was also found to be promising in both acidic and basic condi-
tions even under extreme conditions as compared to other
noble metals [45]. The lower overpotential and Tafel slope value
than the Pt/C mad Ir/C for both HER and OER respectively in
acidic and basic medium assured that incorporation Ni
improved the catalytic performance Ru. The n value of HER in
1 M KOH (26.9 mV/dec) and 0.5 M H2SO4 solution (53.9 mV/
dec)) indicates that Tafel step is the rate-determining in alkaline
medium while both Volmer and Heyrovsky steps are rate deter-
mining in acidic medium. Higher OER performance was due to
the formation of NiOOH over catalyst surface by the formation
of Ni3+ at a higher temperature. On the other hand, higher HER
performance was for the lowering of hydrogen adsorption
energy as indicated by the downshift of d band as compared
to the Pt (Fig. 2) [45].
4
Polyhedron 193 (2021) 114871
The alloy electrocatalyst of RuCo and CuRu proved that the HER
and OER activity of such catalysts depends on the proportion of
metal contents because incorrect proportion might create large
internal resistance and slower charge transfer rate behavior
[46,47]. Moreover, the hierarchically porous nickel-iridium-ruthe-
nium-aluminum alloys synthesized by two-step dealloying process
(Fig. 3a), showed that an increase in OER and HER activity was
related to Ru and Ir content respectively. The overall water split-
ting capacity was better as compared to the IrO2//Pt/C as ensured
by the decomposition potential (1.464 V vs 1.535 V) and stability
study showed that after 25 h only a positive potential shift of
85 mV at 5 mA/cm2 was observed due to the release of H2 and
O2 bubbles on both electrodes. The mass activity of NiIrRuAl-1/3
catalyst for OER reaction was about 1.5 Amg1 at 1.5 V outshining
its benchmark electrode (IrO2). The smaller nanowire diameter of
NiIrRuAl-1/3 (58.9 ± 23.5 nm) as compared to the NiIrRuAl-3/2
(69.4 ± 26.8 nm) and NiIrRuAl-3/1 (75.2 ± 31.2 nm) ensured the
faster charge transfer kinetics in case of NiIrRuAl-1/3. However,
the strong electronic interaction among Ru to Ni, and Ir further
reduced the charge transfer resistance significantly thus enhance
the OER activity [48]. Furthermore, the stability of the catalyst
was retained because, the nanowire morphology and ultrafine
nanoporous structure maintained even after such a long durability
test due to the presence of Ir (Fig. 3b-c). Wei et al. [49] synthesized
Pt-Co alloy hollow spheres with ultra-thin shells by a sequential
reduction strategy for HER activity. They observed that a Pt:Co of
1:1 not only gives a lower potential (14.8 mV) but also superior
stability in 0.5 M H2SO4. The hollow nanosphere structure
improves the catalytic performance as guaranteed by the higher
DGH* (0.2393 eV) compared to bare Pt (-0.290 eV). The mass
activity of Pt1Co1, Pt4Co1, and Pt5Co1 hollow nanospheres was
5.41, 6.36, 4.50 A/mg, which is about 2.4, 2.8, 2.0 times higher than
commercial Pt/C, respectively. However, 3D PtCu nanospheres
(NSs) consisting of nano-single crystal particles revealed better
results for HER as compared to the PtCo hollow spheres. (Fig. 4
a-b) [49,50].
Although noble metal-based electrocatalysts are costly to apply
for water splitting reaction, a highly reactive and stable electrocat-
alyst might increase its economic feasibility. A recent study
showed that supporting metal or metallic alloys with other con-
ductive non-precious materials not only reduce the metal loading
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 3. (a) Schematic illustration showing the first dealloying step of Al97.8Ni2IrxRu0.2-x precursor alloy ribbons, and (b-c) TEM images of the anode (OER) after long-term
stability measurement of overall water splitting. (Inset in d) Corresponding SAED pattern. Reproduced with permission. [32] Copyright 2020, Royal Society of Chemistry.

but also enhance the catalytic performance. The hollow spheres
structured catalyst based on transitional metals (NiCu@C and
CoFeP) also found to be possessed a greater catalytic efficiency
for both HER and OER due to the hollow porous structure and syn-
ergistic effect (Supplementary file Table S1) [51,52]. Zhao et al. [53]
observed that the ultrathin structure of RhCo alloy nanosheet
aggregates (ANAs), synthesized by a high-temperature cyanogel-
reduction method, have high activity for both OER and HER in a
wide pH range than spherical RhCo and monometallic Rh-ANAs
because of its structure and ability of Co to regulate the electronic
properties of Rh. Luo et al. [54] proposed a cost-effective Pt-based
catalyst, immobilized on functionalized Vulcan carbon (Pt/Ru/VC)
for HER application. The high mass activity 2.3 Amg1 at 40 mV
was 2.3 times higher than Pt/C and no negative shift in polarization
curve after 3000 cycles ensuring excellent stability. Moreover,
lower charge transfer resistance, and increased electron conductiv-
ity between metal and support was proved by the shift in G band in
Raman data and increase in graphitization tendency in case of
Pt/Ru/VC as compared to the Pt/C electrode (Fig. 5). To overcome
the difficulties for the synthesis of alloy-based electrocatalyst with
the help of MOF analogs, wang et al. [55] recently synthesized
ruthenium-cobalt alloys enriched in hollow carbon sphere shells
(RuCo@HCSs) through a vacuum impregnation method and studied
the stability of the catalyst.

5
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 4. (a) Energy profiles HER pathway on the (1 1 1) facets of the Pt-Co alloy and metallic Pt. Reproduced with permission. [33] Copyright 2020, Elsevier, Inc. (b) Free energy
diagram for hydrogen evolution at Pt (1 1 1) and PtCu (1 1 1). Reproduced with permission. [34] Copyright 2019, Elsevier, Inc.

Fig. 5. (a) Electrochemical impedance spectroscopy (EIS). (b) Raman spectroscopy of the Pt/Ru/VC, Pt/VC, Ru/VC, and 20% Pt/C catalysts. (c) Raman spectroscopy of VC and
commercial VC. (d) XPS spectra of C 1 s region.). Reproduced with permission. [37] Copyright 2019, Front Matter.

A study on anchoring Ru in carbon nanotubes showed that Ru
nanoparticles dispersed uniformly over the multiwalled CNT rather
than agglomeration exposing a huge active site for catalysis. The
electrochemical surface area (ECSA) of Ru@MWCNT was
7996.15 m2/g which was approximately two times higher than
commercial Pt/C (3638.67 m2/g) allowing a higher turnover fre-
quency (TOF) for HER in alkaline medium (0.40 H2 s1) at 25 mV
[56]. However, alloying Ru with Ni and anchoring it within CNTs
showed better results than the Ru@MWCNT, as confirmed by the
TOF value of 3.09 s1 at g = 100 mV for HER which was higher than
Pt/C (0.4 s1). The TOF value of 3.09 s1 at g = 300 mV for OER was
also higher than RuO2 (0.12 s1). The improved results are due to
more synergistic effects between NiRu alloys allowing the effective
regulation of the electronic structure of carbon surface [57]. Usually,

6
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 6. (a) OER polarization curves of N-CoNi/PCS, N-Co/PCS, N-Ni/PCS and CoNi/PCS electrocatalysts in 0.1 M KOH solution. Reproduced with permission. [41] Copyright 2020,
American Chemical Society. (b) OER polarization curves for NiCo/CNF@NC, NiCo/CNF, CNF, RuO2, and Pt/C catalysts in 0.1 M KOH solution and (c) overpotentials derived from
OER polarization curves at 10 mA cm2. Reproduced with permission. [42] Copyright 2020, Royal Society of Chemistry.

CoNi alloy based electrocatalyst is not found to be useful for OER
activity. Therefore, various supporting carbon materials with differ-
ent hetaroatoms (such as N, P and S) are doped on such bimetallic
catalyst to make them more active. Chen et al. [58] synthesized a
bimetallic CoNi alloy nanoparticle via facile solvothermal reaction
followed by annealing, embedded in pomegranate-like nitrogen-
doped carbon spheres for OER activity. The large surface area, lower
agglomeration and corrosion tendency, and fast electron transfer of
the electrocatalyst were observed for the doping of carbon with
nitrogen. However, by giving support of carbon nanofibers to CoNi
alloy before encapsulation of nitrogen-doped carbon (NiCo/CNF@NC
catalyst) did lower both the onset potential (from 1.6 V to 1.5 V vs
RHE) and overpotential (from 540 mV to 400 mV) which were very
close to the RuO2 catalyst certifying better catalytic activity as
shown in Fig. 6 a-c) [58,59].
Cheng et al. [60] prepared 3D freestanding porous Cu foam
in situ armored CoNi alloy nanosheet arrays (CoNi@CF) by a novel
facile chronoamperometry deposition route. The as-prepared
catalyst possesses a higher ECSA (17.8 mF/cm2) than that of the
CoNi@PNC and a lower overpotential value of 240 mV than that
of IrO2 (295 mV) and RuO2 (350 mV) in 1 M KOH medium enabling
the CoNi@CF catalyst to be used for both HER and OER activity.
Such types result was observed because the Cu foam itself has a
porous structure, it allows the growth of nanoparticles without
any agglomeration and the strong interaction between Cu foam
and alloy structure allows faster electron transfer. However,
another bimetallic electrocatalyst like FeNi with different support-
ing materials and doping showed promising OER catalytic activity
in the alkaline medium as also observed by several other recent
studies (Supplementary file Table S1) [61-63].

7
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Fig. 7. XPS of Cr0.6Ru0.4O2 (5 5 0) for Ru 3d and Cr 2p. (a) XPS of Cr0.6Ru0.4O2 (5 5 0) and RuO2 for Ru3d regions. (b) XPS of Cr0.6Ru0.4O2 (5 5 0) and CrO2 for Cr2p regions. The blue
and red smoothing lines are fitting results of the sum of individual components. For Ru3d, color codes are used to distinguish the different spin–orbit components, dark cyan
for primary Ru3d3/2 and 3d5/2 spin states, and light magenta for satellite Ru3d3/2 and 3d5/2 spin states. Reproduced with permission. [48] Copyright 2019, Springer Nature.
3.2. Metal oxide based electrocatalyst
It is well established that noble metal-based oxides (IrO2 and
RuO2) are state of the art catalyst for OER activity due to their
enhanced electrical conductivity and lower overpotential in both
acidic and alkaline medium. However, noble metals have some
limitations such as the lake of abundancy, weak stability of IrO2
and RuO2 in strongly acidic medium, and higher oxidation ten-
dency of RuO2. Therefore, scientists are now looking for a highly
stable and efficient noble metal oxide-based electrocatalyst to
overcome the above challenge for their application on an industrial
scale. Recently, Li et al. [64] developed highly stable a self-sup-
ported ultrafine-grained porous IrO2 through in-situ electrochem-
ical activation of melt-spun ultrathin Ir12Al88 alloy catalyst for OER
activity in acidic medium. They observed that the as-prepared cat-
alyst showed a decrease in overpotential (g10 = 240 mV) and Tafel
slope (40 mV/dec) in 0.5 M H2SO4 which is far lower than the com-
mercial IrO2 catalyst (310 mV and 87 mV/dec respectively). Lin
et al. [65] fabricated two RuO2 based electrocatalysts for OER
reaction in strongly acidic medium namely, CrO2-RuO2 solid solu-
tion and Co-doped nano rod-like RuO2 electrocatalyst through
annealing in the presence of metal–organic frameworks (MOF).
The CrO2-RuO2 solid solution electrocatalyst gave an overpotential
value 178 mV, 186 mV and 200 mV at 10 mA cm2 in 0.5 M H2SO4
solution at 550, 600 and 650 °C respectively with a stability of 10 h
without any change in current density. At 550 °C there is a right
shift in the binding energy of 3d peaks of Ru and left shift in bind-
ing energy for Cr 2p peaks, meaning that Cr imposes an electron-
withdrawing tendency from the Ru surfaces (Fig. 7). The similar
absorption energy value of this catalyst (E0 = 22129.9 eV) with
RuO2 (E0 = 22129.5 eV) implying that the oxidation state of Ru in
8
Polyhedron 193 (2021) 114871
the catalyst is close to + 4. Due to this withdrawing effect electron
from Ru to Cr, the more positively charged Ru alloys causes
improved ability for the oxidation of water to oxygen. The decrease
in Fermi level from 2.01 states/(eV*cell*spin) in naked RuO2 to 1.07
states/(eV*cell*spin) in the solid solution, indicating the reason
behind its stability for catalytic activity. However, in case of Co-
doped RuO2 electrocatalyst, the overpotential value was further
decreased to 169 mV at similar condition due to the larger number
of oxygen vacancies in the electrocatalyst gained by doping with
lower oxidation state Co allowing more active sites available for
catalytic reaction (Fig. 8) [66].
To reduce the cost of noble metal oxide-based electrocatalyst as
well as to use it for longer period of cycle, a covalent organic frame-
work supported small-sized RuO2 catalyst designed for OER with
the lowest overpotential value of 210 mV for the current density
of 10 mA/cm2 in a 1 M KOH solution even after 500 cycles. This
immense catalytic performance was due to the micro-mesoporous
carbon structure supporting (BET surface area 512 m2/g) although
a decline in Faradaic efficiency was observed from 98% to 25% with
a change in disc current from 0.25 mA to 2.65 mA owing to a rapid
release of oxygen at higher current supply [67].
Pt/C electrodes are considered as most proficient for HER activ-
ity, but at the recent time scientist get some light of hope in the Pt
oxide base catalyst with a prominent role of oxygen in the catalyst.
Yang et al. developed a Pt oxide-based catalyst (PtW6O24) having
active Pt-O bond sites which were found to superior to the Pto state
as proved by the lower over potential (22 mV), higher mass activity
(20.17 Amg1) at 77 mV, higher specific activity (35.266 mA/cm2)
at 77 mV, and higher TOF value (33.35 s1) at 100 mV. The Xray
absorption spectroscopy (XAS) data illustrated that the valence
state of Pt decreased from Pt (IV) to Pt (II), and then the state main-
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Fig. 8. Chemical state and structure analysis of Co0.11Ru0.89O2-d (3 5 0) (A) Ru 3d XPS profiles of Co0.11Ru0.89O2-d (3 5 0) and RuO2. (B) O1s XPS profiles of Co0.11Ru0.89O2-d
(3 5 0) and RuO2. Reproduced with permission. [49] Copyright 2019, Elsevier Inc.
tained between Pt (II) and Pt (I), and no metallic Pt0 was found dur-
ing HER reaction [68].
Although transitional metal oxide (TMO) possesses lower active
sites for catalytic reaction as compared to noble metals oxides, 2D
transitional metal oxide-based electrocatalysts are widely consid-
ered as compared to 1D or 3D structured materials because of their
large surface area. Recently, many approaches were undertaken for
the synthesis of TMO based 2D shaped electrocatalyst. The synthe-
sized 2D structured single TMO electrocatalyst showed that the
Co3O4 exhibited the maximum catalytic efficiency in the alkaline
medium due to its amorphous nature. Moreover, the OER activity
depends on the binding energy for intermediate species (MOH,
MO and MOOH), and in the case of Co3O4, the binding energy
was very close to the standard RuO2 indicating that two-dimen-
sional Co3O4 nanosheet possessed an appropriate adsorption
energy for the intermediates [69].
Among various transitional metals Co, Fe, and Ni are mostly
considered because they tend to form oxyhydroxides which exhib-
ited a remarkable catalytic activity for OER, although mixed transi-
tional metal oxide (MTMO) showed better catalytic activity than
single metal oxide catalyst (Supplementary file Table S1). Lind-
strom et al. synthesized Fe-CO-Ni by facile one-step process and
showed the overpotential value (340 mV in 1 M KOH medium) of
the prepared catalyst was very close to the RuO2 catalyst. The
enhanced catalytic activity was observed due to the two different
spinel formation namely, (NiCo2O4 and Fe3O4) and b-Ni(OH)2 on
the catalyst’s surface as well as the formation of ion-permeable
conductive NiOOH due to Co addition [70]. Furthermore, NiCo2O4/
AgO/NF exhibited excellent OER performance with an overpoten-
tial of 232 mV and a current density of 10 mA/cm2 in alkaline elec-
trolyte due to its large surface area and high oxygen vacancies [71].
9
Polyhedron 193 (2021) 114871
Wang et al. developed an amorphous Co-MoAPAO bifunctional
electrocatalyst via facile electrodeposition. The amorphous nature
(rich in surface defects) and CoOOH formation tendency make
the Co-MoAPAO electrocatalyst more effective for overall water
splitting reaction in alkaline medium (Fig. 9) [72]. OER activity of
TMO can further improved by creating more oxygen vacancies in
the catalyst by incorporating with other oxide materials. A recent
study showed that Fe3O4/CoO interfacial nanostructure supported
on carbon nanotubes exhibited better OER activity as compared
to other MTMOs (lower overpotential value of 270 mV at 10 mA/
cm2, lower Tafel slope of 59 mV/dec. The outstanding catalytic
activity in alkaline medium originated from the uniform distribu-
tion of NPs over CNT surface and large oxygen vacancies caused
by the interfacial nanostructure with an improved electronic con-
figuration [73]. Furthermore, by doping on such a hetero-oxide
interface structured catalyst give a better result for both OER and
HER activity as observed by Guo et al., got by synthesizing a 3D
Co-doped CuO-NiO film. The optimized Co-doped CuO-NiO/Ni
foam electrode exhibits comparatively low overpotential of
38 mV and 172 mV at 10 mA/cm2 for HER and OER in 1.0 M KOH
along with high stability due to large surface area and lower charge
transfer resistance [74]. Jin et al. synthesized an ultrathin carbon-
coated CoO nanosheet arrays via in-situ growth on carbon cloth
as efficient electrocatalysts for the HER in alkaline medium. The
carbon-coating over CoO enhances the HER activity as confirmed
by the lower overpotential (120 mV) and Tafel slope (129 mV/
dec) as compared to the CoO/CC. Again, the charge transfer resis-
tance of C@CoO/CC (5.56 X) is superior to CoO/CC (44.33 X) reveal-
ing that the extra carbon coating enhances the electron transfer
through electronic modification of the catalyst [75]. Current work
on doping of TMO (NiFe2O4) with Ru over nickel foam (Ru-doped
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 9. (a) XRD pattern of Co-sample, the as-electrodeposited Co-MoAPAO, Ni substrate, Co (JCPDS No. 05–0727), and Ni (JCPDS No. 04–0805). (b) HRTEM image CoOOH
formation (b) Co2p XPS spectrum of the activated Co-MoAPAO sample. Reproduced with permission. [55] Copyright 2020, American Chemical Society.

NiFe2O4/NF) showed an excellent HER activity in alkaline medium
with an overpotential value of 18 mV versus a reversible hydrogen
electrode (RHE) at a current density of 10 mA/cm2 and a Tafel slope
of 27 mV/dec. Despite its lower ECSA (28.6 mF/cm2) value as com-
pared to the other catalyst, it possesses a negligible charge transfer
resistance (0.43 X). The lower charge transfer resistance is origi-
nated from the strong electronic interaction among Ru, Ni, and
Fe as assured by the lowering of the binding energy of Ni and Fe
after incorporation of Ru. Due to its outstanding catalytic activity,
the catalyst owns higher stability even after 10, 000 continuous CV
cycles and for 38 h with a negligible change in overpotential value
which might due to the strong adhesion of the catalyst with
10
supported nickel foam [76]. Perovskite oxides, compared with
other types of oxides, have flexible structure and composition
but it is not as competent as other metal oxides even after doping
(Table S1) [77].
3.3. Metal hydroxides
The OER of water splitting reaction consisting of four proton-cou-
pled electron transfer (PECT) limiting the water splitting efficiency
due to its large overpotential requirement. In search of alternatives
of noble metal-based electrocatalyst, various metal hydroxides (Lay-
ered Metal Hydroxides-LDH), particularly transitional metal-based
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Fig. 10. XPS analysis: (a) O1s spectra of NiFe-LDH/NEGF, (b) O1s spectra of NEGF; (c) XPS spectra of Ni2p in NiFe-LDH and NiFe-LDH/NEGF. (d), XPS spectra of Fe2p in NiFe-
LDH and NiFe-LDH/NEGF. Reproduced with permission. [65] Copyright 2020, Royal Society of Chemistry.
(Co, Ni, Fe), are now considering significantly for the reason that it
consists of a 2D structure with metal cation tunable host layers
and exchangeable interlayer anions with a large surface area. How-
ever, like metal and metal oxide catalysts, multi-metallic hydroxides
possess higher efficiency than the single metal hydroxides because
bi-metal or tri-metal center can lower the thermodynamic barrier
during PECT pre-equilibrium and boost the formation of OAO bonds
[28,78]. A group of researchers synthesizes, via a one-step
hydrothermal method, and showed that trimetallic NiCoFe-LDH
nanosheets efficient for oxygen evolution as compared to NiCo-
LDH and NiFe-LDH in 1 M KOH (alkaline) medium [79]. They
observed the lower overpotential (280 vs 304/365 mV at 10 mA/
cm2), lower Tafel slope (92 vs 115/108 mV/dec), lower charge trans-
fer resistance (1 vs 2.1/1.4 X), and higher Cdl (2.62 vs 1.94/2.22 mF
cm2) in NiCoFe-LDH nanosheets. Thus, the introduction of the third
element (Fe3+) can change the electronic environment of Ni2+ and
Co2+ and the electronically synergetic effect can contribute to better
catalytic activities [79]. A similar study on trimetallic (FeCoNi) oxy-
hydroxide synthesized by utilizing a facile microwave-assisted
hydrothermal synthetic strategy presented that trimetallic combina-
tion gives better performance of OER in the alkaline medium as
11
Polyhedron 193 (2021) 114871
compared to the bimetallic one (Supplementary file Table S1) [80].
In the cases mentioned earlier, iron played a vital role in enhancing
OER activity, and a recent study showed that it is not the bulk iron
but the surface iron, which played the most crucial role in such cases
[81]. Amorphous based catalyst usually possesses high surface
defects suitable for OER reaction also give the catalyst more
extended stability as compared to the crystal-based catalyst coun-
terpart. The highly amorphous structure of the CoFe(OH)x micro-
spheres is superior OER electrocatalyst in alkaline medium
(overpotential value of 293 mV at a current density of 10 mA cm2)
compared to commercial RuO2 as well as other reported metal
hydroxide catalyst. Moreover, the high ECSA area of 245.5 cm2 (15
times higher than Co(OH)2), massive mass activity (183.4 A g1),
and TOF value (55.7  103 s1) at 350 mV indicated that the hollow
and amorphous structure along with bimetallic synergistic effect
makes the catalyst more suitable for OER activity [82].
Alike metal based-electrocatalyst, supporting with a carbon-
based conducting material also improves the OER activity and sta-
bility of LDH based catalyst. Very recently, Manna et al. [83]
demonstrated that decorating a NiFe Layered double hydroxide
over nitrogen-doped graphene (NiFe-LDH/NEGF) improved the
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
OER activity as compared to the NiFe-LDH. OER’s over potential
reduced from 350 to 290 mV to reach the current benchmark den-
sity of 10 mA cm2 in 1 m KOH solution. From Fig. 10 it is con-
firmed that in NEGF oxygen binds with carbon in the form of
CAO, C@O, and epoxy group but in NiFe-LDH/NEGF it is coordi-
nated in the form of Ni(OOH), Fe-OH, Ni-OH which accelerates
the OER reaction. Again, shift in the binding energy (XPS data) of
the metals evidencing the electron transfer from the doped nitro-
gen to the metal, which originated from the electronegativity dif-
ference between N doped and NiFe. This excess electron transfer
reduces the charge transfer resistance to 46-ohm cm2 as compared
to the commercial RuO2 catalyst (86- ohm/cm2) and increases the
OER activity. The N doped graphene also improvised the stability of
the catalyst and retain in its stability for 20 h. [83]. Parida et al.
proposed that LDH based materials have metal-to-metal charge
transfer ability which enables it to absorb visible light to be used
for photocatalysis [84]. Based on this hypothesis, Ding et al. devel-
oped photo-induced ultrathin-layered double hydroxide
nanosheets having the ability to boost the oxygen evolution reac-
tion. The results specified that the induction of sunlight reduces
the overpotential from 281 mV to 247 mV at a current density of
10 mA/cm2, and light irradiation causes the mass activity of
CoFe-LDH NSs to increase to 98.6 A g1 at 1.53 V, which is nearly
3-fold higher than that in the absence of light [85].
Modulations in the electronic configuration of LDH by various
heteroatoms like electron-withdrawing F or electron-donating S
Fig. 11. Density functional theory (DFT) calculations. a The atomic model of NiVRu-LDH and the proposed HER pathway. b The free energy diagram of HER on the NiV-LDH,
NiVRu- LDH, and NiVIr-LDH catalysts. c The atomic model of NiVIr-LDH and the proposed OER pathway. d The free energy diagram of OER on the NiV-LDH, NiVRu-LDH, and
NiVIr-LDH catalysts Reproduced with permission. [71] Copyright 2019, Springer Nature.
12
Polyhedron 193 (2021) 114871
through creating numerous structural defects is found to be useful
as observed by a recent study. The heteroatoms reduce the charge
transfer resistance to 8.98-ohm cm2 and overpotential as low as to
268 mV to reach the current density of 10 mA/cm2 of the Co3Fe
LDHs-SF6 electrocatalyst through a one-step synthesis route using
SF6 plasma treatment [86]. However, considering the industrial
applications, researchers are now looking for a practical electrocat-
alyst for OER having the workability at high current densities.
Recently, two such catalysts namely, CoFe–LDH electrodeposited
on Ni-Foam and Ni3+ doped ultrathin NiZn-LDH nanomeshes,
exposed promising OER activity at a current density 400 and
500 mA/cm2 in alkaline medium (Table S1) [87,88].
Transitional metal-based LDH is usually considered for OER
activity in the alkaline medium because LDH possesses high-
energy barriers in the Volmer step of HER reaction [89,90].
Researchers are trying to develop LDH based electrocatalyst for
HER activity by incorporating noble metals. For instance, modula-
tion of self-supported NiV-LDH with Ru and Ir exposed that incor-
poration of both Ir and Ru disrupted the electronic configuration
and created more vacancies (especially in V) as compared to the
bare NiV-LDH. This electronic configuration disturbance and
vacancy creation reduce the Volmer step water dissociation energy
(DG(H2O)) barrier to 0.27 eV and 0.05 eV for NiVIr-LDH and
NiVRu-LDH respectively as compared to the NiV-LDH (-0.5 eV).
Besides, the hydrogen adsorption energy (DG(H2)) of NiVRu-LDH
(0.25 eV) is lower than that of the NiVIr-LDH (-0.46 eV) and
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
NiV-LDH (-0.55 eV) indicating that Ru is more conductive to HER in
alkaline medium. However, Ru doping is beneficial to the MOOH
step and Ir doping is more conducive to the MOH and MO pro-
cess making the NiVIr-LDH electrocatalyst better for OER perfor-
mance (Fig. 11). The overall phenomena reduce the overpotential
value of HER (12 and 47 mV) and OER (190 and 180 mV) for
NiVRu-LDH and NiVIr-LDH respectively in 1 M KOH medium to
reach a current density of 10 mA/cm2 [91]. An analogous study
was carried out by Wang et al. [91], by doping of Ru on Ni(OH)2
with polyaniline coating (RuNi-NSs@PANI) showed better HER
activity in both alkaline and acidic medium. Ru based electrocata-
lysts are now found to be effective to be used for a wide pH range
because the Ru-hydrogen interaction is almost similar to Pt. How-
ever, polyaniline has the capability of capturing H+ due to the lone
pair electron in it, which makes the electrocatalyst operative.
Moreover, both PANI and Ru have a similar hexagonal-closed-
packed (hcp) phase, which eases the hcp Ru phase formation and
PANI also promotes the conductivity due to the synergistic effect
[91]. Nonetheless, doping with transitional metals like Co, Ce, Mn
did not show much comparable HER activity in alkaline medium
with noble metal-based doping [92,93]. Recently Parvin et al.
[94] developed a noble NiCo layered double hydroxide (LDH)
wrapped around Cu nanowires (Cu-Ws) grown on top of commer-
cially available Cu mesh (Cu-m) with highly HER active electrocat-
alyst. The overpotential was 15 ± 6 mV in 1 M KOH and 27 ± 2 mV
in 0.5 M H2SO4 at 10 mA/cm2 which someway outshine the activity
of 40 wt% Pt/C that needs overpotentials of 22 and 18 mV in 1 M
KOH and 0.5 M H2SO4 respectively. The introduction of the Cu-m
and Cu-Ws decrease the charge transfer although the density of
states (DOS) calculation showed that Cu-Ws had a better probabil-
ity of electron transferring to NiCo-LDH than that of Cu-m [94].
Alike metal and metal oxide-based electrocatalyst, supporting
electrocatalyst with Ni foam gives a better result for both HER
and OER activity in alkaline medium. A current study on nanopor-
ous NiAl-LDH nanosheet arrays over Ni foam showed an overpo-
tential of 90 and 180 mV to deliver the 10- mA/cm2 current
density for the HER and OER in alkaline media. This is because
the active site created by Ni foam reduces the charge transfer resis-
tance of np- NiAl-LDH/NF (8.88- ohm/cm2) which is smaller than
that of NiAl-LDH/ NF (27.01- ohm/cm2) [95].
3.4. Other metal derivatives
Current research trend signposts that beside metal, metal oxide,
and LDH based electrocatalyst various metal derivatives like phos-
phides, sulfides, selenides, carbides based electrocatalysts are con-
sidering promising for both HER and OER activity [96-99]. Both
noble metal and transitional metals are well-thought-out for this
purpose. However, both are still suffering from some form of lim-
itations; for example, noble metals are not abundant in nature,
while transitional metals-based derivatives lack active sites due
to reduced intrinsic activity and severe corrosion problems in both
acidic and basic environments.
Despite its limited abundancy, researchers are always keeping
their trust in noble metal-based derivatives due to their unique
properties [99]. However, making them superior to the commercial
electrodes can only make it possible to consider them for the
electrocatalytic reaction. Some new studies based on noble met-
als-based phosphides showed better activity as compared to the
commercial Pt/C electrode for HER activity although their synthesis
process is complicated enough. Recently Pu et al. [100] developed a
novel iridium diphosphide (IrP2) electrocatalyst embedded within
an ultrathin nitrogen-doped carbon (NC) layer (IrP2@NC) at ambi-
ent pressure and moderate temperature. The as-prepared catalyst
possesses the overpotential values of 8 and 28 mV to achieve the
current density of 10 mA/cm2 in 0.5 M H2SO4 and 1.0 M KOH,
13
Polyhedron 193 (2021) 114871
respectively, which are lower than commercial Pt/C (18 and
42 mV correspondingly). XPS study revealed that P had a partially
negative charge while Ir is partially positive indicating the electron
transfer from Ir to P favorable for HER activity [100]. Among vari-
ous transitional metal phosphides (TMP), CoP is considered
promising although they have major limitations in practical appli-
cation [101]. Doping CoP with various heteroatoms is a convenient
method to improve the electronic configuration of TMPs [102].
Among a number of studies, depending on single or multi-doping,
Ar plasma-assisted NiCoP nanosheets through V doping showed
better HER and OER activity in the alkaline medium as specified
by lower overpotential of 58 and 246 mV respectively to reach
the current density of 10 mA/cm2 [103]. Both the Ar plasma and
V doping created the excess P vacancies and enhancing HER and
OER activity through modulating electron density around the
active sites of the catalyst. Again, further study showed that, due
to oxidation, the content of V decreased indicating the additional
cation vacancies created which is suitable for adsorption of OH
thus boosting the OER activity. However, iron-doped CoP
electrocatalyst is promising for OER, because it exhibits a lower
overpotential of 251 mV at a current density of 10 mA/cm2 and
able to maintain its current density for upto 40 h without a
remarked change in overpotential [104]. Furthermore, nitrogen-
doped CoP nanoarray over 3D porous Co foam showed excellent
OER catalytic activity at a high current density of 50 mA/cm2 due
to the extra vacancies in the catalyst surface [105].
The 3D structured Mo-CoP3-2@CC possessed highly dispersed
nanoparticles of 4–10 nm size allowing more actives sites for cat-
alytic reaction and the Mo doping enhance the conductivity
through a synergistic effect [106]. Li et al. [107] synthesized ultra-
fine CoP nanocrystal/graphene sandwiched structure by in situ
precipitation and phosphorization, which exhibited excellent
water splitting capacity in both acidic and basic medium. The 2D
graphene supported not only provides high surface area for graft-
ing CoP but also act as an electron connecter to promote the charge
transfer during the catalytic process [107]. Hollow structure-based
catalysts are shown to be possessed excellent HER activity whereas
3D NiCoP hollow spheres showed an overpotential value of 160 mV
at a current density of 10 mA/cm2 although it was only 14.8 mV for
Pt-Co alloy hollow spheres [108]. Furthermore, some modification
processes (like doping, supporting with nonmetal conductive
materials, structural variation, etc.) are being applied for enhanc-
ing the activity of NiP or MnP electrocatalyst, but no promising
results are found yet as compared to the CoP electrocatalyst
[109,110].
Among numerous metal derivatives, metal sulphides are con-
sidered as one of the promising electrocatalysts at the current time
due to its unique properties although they are still suffering from
enhanced catalytic activity and stability in alkaline and acidic med-
ium due to its corrosive nature. Still, most of the state-of-the-art
metal sulphides catalysts are developed for HER activity in alkaline
medium. Monometallic sulphides are not effective for HER activity
due to its lower conductivity. However, Liang et al. [105] showed
that Ni2S nanocrystals with (1 1 1) planes improved the HER activ-
ity (ƞ10 = 138 mV in 1 M KOH). Fig. 12a-b display that the NiS2 octa-
hedra nanocrystals consist of (1 1 1) planes and cubic NiS2
nanocrystals consist of (1 0 0) planes. During HER activity the sur-
face energy of (1 1 1) planes have much higher surface energy than
the (1 0 0) planes indicating that the (1 1 1) planes are more active
and may have better catalytic activity than the (1 0 0) planes which
is further assured by the lower adsorption energy of (1 1 1) planes
for H2 [111].
Metal sulphides electrocatalyst based on another important ele-
ment of group 5, Niobium disulphide (NbS2), also exhibited
promising HER activity at both acidic and alkaline environments,
although single metal-based sulphides are still suffering from
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
Fig. 12. (a) TEM images of NiS2-octa; (b) TEM images of NiS2-cube. Reproduced with permission. [87] Copyright 2020, Elsevier Inc. (c) Schematic illustration for the self-
template synthesis of 3D flower-like CoMoO4 NSAs and in situ topotactic sulfurization to CoS2/MoS2 HNSAs. Reproduced with permission. [89] Copyright 2020, Royal Society
of Chemistry.
stability problems massively [112]. Therefore, bimetallic and
mixed metal- based sulphides are getting more concern to improve
HER activity and stability of the electrocatalyst in the alkaline
medium. Shi et al. [113] obtained the most promising results for
HER activity in alkaline environment using flower-like CoS2/MoS2
hetero-nanosheet array prepared by a self-template hydrothermal
method (Fig. 12-c). The heterostructure of CoS2/MoS2 reduced the
HER overpotential to almost 50 mV at 10 mA/cm2, and a small Tafel
slope of 76 mV/dec in 1.0 M KOH as compared to other reported
NiS or MoS nanosheet, nanoarrays and nanowires [113]. The anal-
ogous study carried out by other researchers also showed that such
types bimetallic or mixed sulphides reduced the overpotential
value and increased the stability up to 100 h (Supplementary file
Table S1) [114,115]. While transitional metal sulphides (TMS) are
mostly considered for HER activity but at the recent time doping
of TMS with heteroatoms makes it suitable for HER and OER activ-
ity with improved efficiency. Zhu et al. [116] synthesized a Se-
MnS/NiS electrocatalyst through facile hydrothermal and chemical
deposition treatments and observed that the essential overpoten-
tials of Se-NiS/MnS were 56 mV and 211 mV to deliver a
14
Polyhedron 193 (2021) 114871
10 mA/cm2 current density for HER and OER in alkaline media,
respectively. Thus, the introduction of the Se dopant modifies the
electronic structure and assist in increasing the electrochemically
active surface area and thus favoring the electrocatalysis of HER
and OER. Also, the synergistic effect caused by two different metals
of the Se-MnS/NiS heterojunctions encouraged the adsorption of
hydrogen atoms on the surface of the catalyst as compared to
the NiSe, NiS, and Se-NiS catalysts [116].
Again, multimetal doping on single metal sulphides with sup-
porting Ni foam (Mo,Co-NiS/NF) showed promising HER and OER
activity as indicated by the lower overpotential of 92 mV and
117 mV for HER and OER activity respectively, to deliver a
10 mA/cm2 current density. The higher ECSA (438.74 cm2 and
150 cm2) and TOF value (1.09 s1 for HER) for HER and OER respec-
tively, designates that both multi-doping and Ni foam-based sup-
porting materials are the main contributors of higher catalytic
activity. The catalytic efficiency of this catalyst was dependent
on the sulfurization temperature, and the optimum temperature
for sulfurization was found to be 400 oC. Furthermore, the doping
with Mo and Co enhance the HER activity, and the utilization of
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 13. (a) HER free energy for the Co24Ni8Se32 and Ni32Se32 Products. (b) Calculated density of states for Co24Ni8Se32 and Ni32Se32. Reproduced with permission. [94]
Copyright 2019, Royal Society of Chemistry.

Fig. 14. Density functional theory (DFT) calculations. a Calculated spin density distribution in the Co0.85Se supercell before and after Pt atoms doping. The blue and yellow
balls refer to Co and Se atoms. Yellow and cyan isosurfaces represent positive and negative spin densities (0.005 e/Å3), respectively. b Calculated DOS of Co0.85Se and Pt/
Co0.85Se. c Calculated adsorption free energy diagrams for the Volmer step on the as-built np- Co0.85Se, Pt (1 1 1) and Pt/ Co0.85Se models. d Free energy diagrams for hydrogen
adsorption at different active sites of Co0.85Se (0 0 4), Pt (1 1 1), and Pt Co0.85Se (0 0 4). Reproduced with permission. [97] Copyright 2019, Springer Nature.

nickel foam rendered the catalyst to disperse uniformly preventing
agglomeration during the electrocatalytic process [117].
Metal selenides are mostly dedicated to OER activity because
they are more conducive as compared to the metal oxide counter-
part [118]. The higher electrical conductivity originated from the
covalent bond between metal and selenide, and the accessible d
orbitals of selenide results in a broader valence band and lower
the band gap. To further improve the OER activity of metal sele-
nides, Ghaemmaghami et al. [119] developed a Fe-doped Ni3Se2
supported nickel foam via a facile electrodeposition method. The
as-synthesized electrocatalyst showed excellent performance,
exhibiting a current density of 10 mA/cm2 at an overpotential of

15
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

225 mV and a low Tafel slope (35.3 mV/dec). To make transitional
metal selenides (TMS) effective for both HER and OER activity, vari-
ous bimetallic selenides along with doping and suitable supporting
materials are being anticipated by scholars [120-122]. Among them,
metallic Cobalt-Nickel selenide nanorods supported on Ni foam are
found to be most promising for HER (106 mV at 10 mA/cm2) and
OER (269 mV at 50 mA/cm2) in alkaline medium [120]. The lower
free energy of adsorption for water indicated that water adsorption
occurs more easily on Co24Ni8Se32 surface (Fig. 13). Again, density of
states (DOS) of Co24Ni8Se32 near the Fermi level is much greater than
that of Ni32Se32, indicating the high electrical conductivity and fast
electron transport of this compound as compared to the Ni32Se32.
Although platinum-based catalysts are not economically feasible,
they can enhance the catalytic activity of transitional metal sele-
nides even in a small amount. Jiang et al. [123] recently showed that
a small number of single platinum atoms embedded in nanoporous
cobalt selenide (Pt/np-Co0.85Se) enhance HER activity. The Pt/np-
Co0.85Se catalyst possesses a near-zero onset overpotential, low Tafel
slope of 35 mV/dec, and high TOF of 3.93 s1 at  100 mV in neutral
media, which is even better than commercial Pt/C catalyst and other
reported transition-metal-based compounds [123]. Density-functional
theory (DFT) calculation presented that the charge density difference
at Pt-bonding region (red arrows) of Pt/Co0.85Se promotes the increase
in the internal electron attentiveness and enhances the HER perfor-
mance. Additionally, the higher electron density at Fermi level and
lower adsorption energy for water and hydrogen for Pt/np-Co0.85Se
assured the higher performance for HER activity at neutral medium
(Fig. 14) [123].
Among the metal carbides, MoC is being studied more impor-
tantly because the d band electronic structure one of the variants
of MoC (b- MoC) is analogous to the Pt benchmark. Although a
recent study on self-supported composite of (Ni,Co)3C mesoporous
nanosheets/N-doped carbon showed excellent HER activity in
acidic medium. Both the supporting materials and synergistic
effect lowers the free energy value of adsorption to 0.09 eV,
resulting in a lower overpotential of 58 mV at 10 mA/cm2 [124].
3.5. Metal-organic framework based electrocatalyst
Metal-organic frameworks (MOFs) are receiving increased
attention as electrocatalysts due to their ability to support and dis-
tribute nanoparticles (NPs). The high surface area and porosity of
MOF skeleton enhance mass transfer diffusion and reduce charge
transfer resistance with consequent increase in HER and OER activity

Fig. 15. Morphology and structure characterizations of Ru-HPC. a) and (b) SEM images of the hierarchically porous structures of Ru-HPC. Inset: the enlarged region of the
dashed rectangular area, which showed abundant mesopores. c) TEM image of the Ru-HPC. Inset showed the ultrafine Ru nanoparticles; (d) Specific overpotential map of each
electrocatalytic material. For HER and (e) Specific overpotential map of each electrocatalytic material for OER. Reproduced with permission. [100] Copyright 2019, Elsevier
Inc.

16
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
[125]. Noble metal-based electrocatalysts suffer from agglomeration
problem, which could be resolved through the incorporation of MOF
derivatives. Tremendous efforts have been made to date for develop-
ing highly efficient MOF-based electrocatalysts. Qiu et al. developed
a bimetallic (Ru, Cu) MOF-based electrocatalyst, where the Ru parti-
cles were insulated by the Cu and organic ligands (1,3,5-benzenetri-
carboxylic acid -H3BTC). The as-synthesized and highly exposed Ru
nanoparticles were immobilized on the hierarchically porous carbon
(Ru-HPC) and possessed macropores and mesopores with a fine dis-
tribution of Ru NPs over the surface (Fig. 15). These unique proper-
ties enabled the electrocatalyst to achieve a high current density of
25 mA/cm2 at an overpotential of 22.7 mV with a high TOF (1.79 H2
s1 at 25 mV) that is almost double compared to the commercial Pt/
C for HER activity. Additionally, the lower overpotential values
(ƞ25 = 22.7 mV and ƞ50 = 44.6 mV) and Tafel slope (33.9 mV/dec)
ensured the superiority of this electrocatalyst system over commer-
cial 20% Pt/C electrode [126].
The face controlling feature revealed that (1 1 1) plane of Pt is
more active than any other faces of Pt crystal particularly in case
bimetallic based electrocatalyst [127]. Ye et al. reported Fe-MOF
nanosheet arrays, which was engineered by Pt (1 1 1). The research-
ers found that only an overpotential of 33 mV and 191 mV was
required to achieve 10 and 100 mA/cm2 current density in 1 M
KOH for HER. Similar to the Pt/C electrode, Tafel step was under-
stood to be the rate-determining step for HER activity based on
the Tafel slope value (28.6 mV/dec). The inertness of Pt gave the
catalyst appreciable stability for at least 100 h without any change
in overpotential value [128].
Considering the high cost of noble metals, research is moving
towards developing transitional metal-MOF based electrocata-
lyst. It is very important to state that the synthesis process of
such catalyst greatly influence their catalytic properties. A
recent study based on the direct synthesis of 2D MOF-based
electrocatalyst by convenient spray method using CoNi bimetal
over carbon cloth showed enhanced performance for both HER
and OER in the alkaline medium as compared to other conven-
tionally produced MOF-based electrocatalysts. The spray
method allowed well dispersion of metal ions droplets on the
surface of carbon cloth and provided accessible active sites for
the catalytic reactions (Supplementary file Table S1). From the
XPS data, a shifting of binding energy of CoNiBDC was observed
as compared to the pure NiBDC, originated from the electron
transfer tendency of Ni to Co, thus promoting the OER catalysis
activity [129,130].
Since metals could be uniformly distributed on the MOF surface,
appropriate doping of such nanomaterials might increase the per-
formance of MOF derived electrocatalysts [131]. A study on MOF-
derived and metal doped (Fe, Ni, Zn, and Mo) Co9S8 nanoarrays
reported the significant effect of doping on the overall catalytic
activity. The catalytic activity of the electrocatalysts followed the
order: Ni-Co9S8 > Zn-Co9S8 > Fe-Co9S8 > Mo-Co9S8 > Co9S8 for both
HER and OER activity in alkaline medium. Due to the lower adsorp-
tion energy for intermediates and higher ECSA, Ni-Co9S8 showed
better performance as compared to other metal doping. The syner-
gistic effect between Ni+2 and Co+3 ions as compared to any other
ions might play a vital role behind such variations. Besides, mor-
phological investigation of Ni-Co9S8 showed numerous rough sur-
faces, which allowed unique active sites and ion diffusion channels
[132]. Another similar study on CoP-doped MOF-based electrocat-
alyst also reported better HER activity at universal pH conditions
with an overpotential value of 49, 27, and 34 mV in neutral, acidic,
and basic medium respectively. The decreased electron density of
Co d-orbital in CoP species, induced by Co-MOF, led the DGH* value
close to zero and made it a promising candidate for HER activity.
Additionally, the lower free energy for water adsorption than CoP
indicated that water could be easily adsorbed on the CoP/Co-MOF
17
Polyhedron 193 (2021) 114871
surface ensuring more availability of Hads for hydrogen production
[133].
In general, MOF provides extra sites for catalytic activity in case
of both HER and OER. In case of OER, the lower overpotential (less
than 300 mV) is observed because it helps to ensure an easier
transportation of the oxygen bubbles produced during reaction.
However, with an overall assessment it can be concluded that,
MOF derived electrocatalyst are more useful for HER reaction in
acidic media. In case of alkaline medium, H2O and OH– are the
reacting species to produce H2. Conversion of these species to H2
is kinetically slower than the transformation of H+ to H2 as in case
of acidic solution. Therefore, future studies should concern about
the performance improvement of MOF based electrocatalyst for
HER in case of alkaline medium.
3.6. Hybrid electrocatalyst
Hybrid electrocatalysts are composed of different metals and
metal derivatives at different proportions to obtain sacrificial prop-
erties [134]. When one single element cannot meet all of the
requirements effectively, then the combination with other hetero
elements might develop such properties successfully. For example,
metal oxide electrocatalyst shows excellent stability in the alkaline
medium for HER activity, however, the sluggish reaction kinetics
makes it inappropriate in some cases. This issue could be resolved
through forming hybrid structures. Developing a metal–metal
oxide heterostructure could form a Mott–Schottky hybrid and
valence electrons would transfer across the heterostructure inter-
face to balance the Fermi levels of both sides thus improving the
HER activity [135]. Based on this hypothesis, a Co/CoO hybrid
was developed by Cao et al. on C cloth, which displayed efficient
electrocatalytic performance for HER in alkaline solution. The
observed overpotential was only 158 mV with a Tafel slope of
68.1 mV/dec. The electrocatalyst showed good stability for at least
24 h, which was satisfactory enough compared to the C@CoO/CC
electrocatalyst. Although a lower active site was observed for Co/
CoO-10 as compared to the Co/CoO-30, the higher HER activity
was observed for Co/CoO-30 due to the higher inartistic activity
per active site [136].
On the other hand, binary spinel metal oxides have been enor-
mously studied by researchers although they are still suffering
from lower conductivity and inferior catalytic performance. Ni-Fe
nanoparticles on flower-like MnCo2O4 nanowires, synthesized by
in-situ electrodeposition method, showed excellent performance
for HER and OER in alkaline medium as guaranteed by lower over-
potential of 98 mV and 271 mV at 10 mA/cm2 for HER and 100 mA/
cm2 for OER. The flower-like morphology, heterojunction, and syn-
ergistic effect worked combined to give HER and OER activity with
high stability (48 h). NiFe nanoparticles were found very effective
for OER activity because compared to the MnCo2O4/NFF, 158 mV
lower overpotential was required for NiFe-MnCo2O4/NFF to reach
a TOF value of 0.6 s1 [137].
Bimetallic sulphides are more promising than the monometallic
sulphides although the stability problem of such electrocatalysts
makes them challenging for such application. Lin et al. reported
hierarchical self-assembly of NiFe-LDH nanosheets on CoFe2O4@-
Co3S4 over a 3D carbon fiber paper (CFP). The heterostructure
(NiFe-CoFe2O4@Co3S4/CFP) was prepared via hydrothermal elec-
trodeposition method and showed a promising HER and OER activ-
ity than commercial benchmark electrocatalyst in alkaline medium
with outstanding stability for 48 h. The study showed that CFP was
mainly responsible for excellent conductivity and stability of the
heterostructures. The flowerlike structure provided special sites
for adsorption reaction intermediates and the synergistic effect
between NiFe-LDH and CoFe2O4@Co3S4 improved the electronic
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al. Polyhedron 193 (2021) 114871

Fig. 16. Schematic Representation of the Synthesis of Ly-rGO: (I) Graphite to Graphene Oxide (GO), (II) GO to GO-Cl, and (III) GO-Cl to Ly-rGO; Scanning electron microscopic
(SEM) images of (b) GO and (c) Ly-rGO, and (d) Schematic Representations for the Mechanistic Path of Oxygen Evolution Reaction (OER) on (i) Ly-rGO, (ii), rGO-Ly- OH and
rGO-Ly-O  or (iii) rGO-Ly-OOH and O2. Reproduced with permission. [118] Copyright 2020. American Chemical Society.

configuration of the electrocatalyst with ultimate reduction of the
charge transfer resistance [138].
Ni3S2, another emerging electrocatalyst for OER activity in the
alkaline medium, suffers from lower catalytic efficiency and
needs to be improved as it is lower in cost and plentiful in
availability. A new study on a hybrid electrocatalyst of Ni 3 S 2
with binary spinel cobaltites (CoFe 2 O 4 ) on a 3D Ni foam via
facile hydrothermal method showed excellent OER perfor-
mance. The electrocatalyst demonstrated a low overpotential
of 231 mV at 10 mA/cm 2 in KOH solution and stability for
20 h. The presence of Co 3+ and formation of NiOOH were asso-
ciated with the higher activity of OER. Although binary spinel
cobaltites possess attractive OER activity due to more available
active sites, they have a stability problem. However, making a

18
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
hybrid with Ni3S2 improved each other properties effectively
[139].
Molybdenum disulfide (MoS2), another important transitional
metal dichalcogenides (TMDs), is widely considered for HER activ-
ity due to the ease of synthesis and high stability. Double layer
hexagonal phase MoS2 has available active sites along S edges
(DGH*= 0.08 eV) which provides the binding energy for hydrogen
close enough to the state-of-the-art Pt, but the basal plans of
hexagonal MoS2 are almost inactive (DGH*= 2 eV) making it
unsuitable for HER activity. Nanohybridization of MoS2 with both
bismuth selenide (Bi2Se3) and molybdenum carbide (Mo2CTx)
brought improved HER activity. The overpotential value of MoS2@-
Bi2Se3 (134 mV) was found lower than the MoS2@Mo2CTx
(176 mV) hybrid. This is because the DGH* values for the Mo and
S edges (MoS2@Bi2Se3) were 0.08 eV and 0.55 eV respectively,
suggesting favorable HER activity on the Mo edges, which was
far lower than the MoS2@Mo2CTx (-0.44 eV) at the Mo edges
[140,141].
Furthermore, fabrication of MoS1.5Se0.5 with conductive
NiCoSe2 nanosheet arrays via hydrothermal and thermal sel-
enization processes gave the most excellent HER activity in
alkaline medium as reflected by the lower overpotential of 57,
88, and 102 mV for current densities of 10, 50, and 100 mA/
cm2 respectively. The partial substitution of S by Se in MoS1.5-
Se0.5 enhanced the active sites and the synergetic effect and
heterojunction reduced the charge transfer resistance to 2.5 O
and made it a unique HER electrocatalyst for alkaline medium
[142].
Transitional metal phosphides (TMPs) have also received atten-
tion as electrocatalyst for HER and OER. HER activity of TMPs in
both acidic and basic environment could further be improved by
hybridization with other conducting materials. Immobilization of
hierarchical nanoporous Ni(Cu) alloy on amoprphous NiFeF,
through facile electrodeposition strategy, exhibited remarkable
HER activity in 1 M KOH. The amorphous structure of NiFeP layer,
oxidized species at the catalyst surface, and strong synergistic
effects between metallic Ni(Cu) films reduced the overpotential
value to 33 and 110 mV to achieve 10 and 100 mA/cm2 in 1 M
KOH, which is similar to the commercial Pt/C/NM electrode
(ƞ10 = 33 mV and ƞ100 = 110 mV). The significant effect of hybridiza-
tion on catalytic activity was realized from the lower Tafel slope
Fig. 17. (a) Top (upper) and side (lower) views of hydrogen adsorption sites on the optimized CNT@C–pNP models. The grey, orange, green and white balls represent C, N, P
and H atoms, respectively, and the unit cells of models are indicated by a pink dashed line. (b) The calculated free energy (DGH*) diagrams for the HER at the equilibrium
potential (URHE = 0 V) of CNT@C, CNT@C–pN, CNT@CAP and CNT@C–pNP. (c) The DOS plots of CNT@C, CNT@C–pN, CNT@CAP and CNT@C–pNP. Reproduced with permission.
[119] Copyright 2019, Royal Society of Chemistry.
19
Polyhedron 193 (2021) 114871
and charge transfer resistance of Ni(Cu)@NiFeP/NM than that of
both Ni(Cu)/NM and NiFeP/NM [122].
The coupling of ultrasmall PtCu nanoalloys with highly porous
CoP nanosheets was found to possess mentionable HER activity
in both acidic and alkaline medium. The overpotential was
20 mV with a smaller Tafel slope of 28 mV/dec in 0.5 M H2SO4
and 1.0 M KOH respectively. This catalytic performance was com-
paratively better than Pt/C electrode (overpotential of 40 mV and a
Tafel slope of 49 mV/dec to reach the current density of 10 mA/
cm2). Due to the difference in electronegativity between Pt and
Cu, there was a possibility for electron transfer, which could have
been further enhanced with the addition of CoP with an ultimate
improvement in HER activity. An additional advantage of the cata-
lyst was continuous functionality for at least 100 h in both media,
without noteworthy degradations. The excellent stability might be
attributed to the inherent coupling of PtCu clusters with CoP. The
strong interaction probably hindered the aggregation of PtCu dur-
ing the electrocatalytic reactions [143].
3.7. Metal-free electrocatalysts
To date, metal-based materials (both noble and transitional) are
mostly considered for the electrocatalytic applications, however,
the limitation of these materials demand finding highly active
and stable metal-free electrocatalyst in the upcoming years. Car-
bon-based materials such as graphene, CNT, etc. are promising
alternatives in such cases due to their tunable molecular struc-
tures. A recent study demonstrated good OER activity of L-Lysine
functionalized graphene in alkaline media (Fig. 16a). The success-
ful functionalization was understood from the layer of L-Lysine
over the graphene layer and edges, as understood from the SEM
images (Fig. 16b). Ly-rGO showed an overpotential of g = 1.56 V
to reach the current density of 10 mA cm2, which was smaller
than that of GO (g = 1.88 V) confirming that Ly-rGO could be a
potential electrocatalyst for OER purpose. The active sites of the
Ly-rGO electrocatalyst surface were originated by the adsorption
of OH species from water. Elimination of an electron produced
rGO-Ly-OH, which additionally reacted with OH to give rGOLy-
O species. The mechanistic pathway for OER is schematically
described in Fig. 16c [144]. Another study on metal-free catalyst
disclosed that doping carbon-coated CNT with N and P reduced
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
the free energy of adsorption compared to the bare carbon-coated
CNT. Besides, the electron density of doped carbon-coated CNT at
Fermi level was higher than the undoped one (Fig. 17). As a result,
to reach a current density of 10 mA cm2, the overpotential value
for HER was reduced to 167, 440, and 304 mV in acidic, neutral,
and alkaline electrolytes respectively [145]. Very recently, Chan
et al. developed a metal-free electrocatalyst based on porous red
phosphorus nanoparticles (P-RPNPs), which showed promising
HER activity in acidic medium, reflected by lower overpotential
value of 218 mV to reach 10 mA/cm2, and superior long-term dura-
bility for 50 h. The higher HER activity and stability originated from
the porous structure of P-RPNPs. The iodine used during NPs for-
mation was vaporized at about 140 °C, which was responsible for
the formation of porosity [146].
However, these electrocatalyst are still not able to compete
with other noble or earth abundant metal based electrocatalysts
based on their electrocatalytic performance. Various doping
approach were undertaken over the last few years to improve
the their electrocatalytic performance. The shortage of information
about their concrete electrocatalytic mechanism and actives sites
hinders their activity enhancement. Therefore, more attention
should be given on exploring the unknown information and on
new synthetic strategies as well.
4. Summery and outlook
The main function of an electrocatalyst is to provide the surface
area for the reaction to proceed for a longer period with a reduced
barrier. Therefore, the major criteria of an efficient electrocatalyst
are (1) large surface area with high-density active sites for adsorp-
tion reaction intermediates (2) lager open spaces along heterojunc-
tion for efficient charge transfer (3) good catalytic and stability
over a wide pH range, and (4) low in cost and usable for both
HER and OER simultaneously. The common performance indicators
of an efficient electrocatalyst are; lower overpotential (mV), lower
Tafel slope (mV/dec), higher turnover frequency (TOF), optimum
binding energy for reaction intermediates, optimum free energy
of adsorption DGH* (eV), high Faradaic efficiency (%), high electro-
chemical surface area (ECSA) (cm2), higher stability time without
changing in overpotential, higher mass activity (mAmg1), higher
specific activity (mA/cm2), lower charge transfer resistance
(ohm), higher oxygen vacancies, higher electronic configuration
disruption, higher electron density at the Fermi level, etc. However,
no single catalyst usually possesses all the mentioned characteris-
tics therefore; they need to be modified to incorporate the desired
properties in it. The properties of electrocatalyst can be modified
by forming multimetal alloy, variation in doping with heteroatoms,
providing highly conductive and porous supporting materials,
making a structural variation, developing amorphous structure,
controlling the growth of crystal face, and hybridization of differ-
ent metal derivatives.
We discussed the different mechanisms of HER and OER reac-
tion in the both acidic and alkaline medium along with a common
strategy for enhancing the catalytic activity of the electrocatalyst.
This review also introduced the recent progress in designing and
developing metal-based and metal-free electrocatalyst for active
HER or OER activity, with a short-term summary of their prepara-
tion methods and electrocatalytic performances for water splitting.
Additionally, we also discussed how metal alloying, giving
conductive supporting materials, doping heteroatoms, tuning
materials nature, face controlling features, and introducing oxygen
vacancies/defects are contributed in developing an optimum cata-
lyst for HER and OER process.
To our observations the following strategies and materials give
the best performance:
20
Polyhedron 193 (2021) 114871
1) Multi-metallic alloy, oxides, and hydroxides are found to be
more promising than the single metal-based electrocatalyst
because the synergistic effect enhances the conductivity and
reduces the charge transfer resistance.
2) The amorphous structure of materials is effective than the
crystal structure because such structure creates defects on
catalyst surface which are acting as the additional active sur-
face for electrocatalytic activity.
3) Giving a super porous and highly conductive supporting
material also plays a vital role in improving the overall per-
formance of electrocatalyst.
4) Hybrid structure, mixing of various metal derivatives and, or
with conductive supporting materials are more proficient
than the single structure electrocatalyst for both HER and
OER.
5) Finally, transitional metal-doped MOFs are now considered
as promising for HER activity due to their lower adsorption
energy for intermediates and higher ECSA.
5. Consent for publication
Not applicable.
Funding
There was no funding for the work.
CRediT authorship contribution statement
Shujit Chandra Paul: Conceptualization, Data collection, Writ-
ing - original draft. Shaikat Chandra Dey: Conceptualization, For-
mal analysis, Writing - original draft. Md. Ashraful Islam Molla:
Investigation, Methodology, Writing - review editing. Sotan Deb-
nath: Visualization, Writing - review editing. Md. Shafiul Islam:
Visualization, Formal analysis. Muhammed Yusuf Miah: Formal
analysis, Writing - review editing. Md. Ashaduzzaman: Formal
analysis, Writing - review editing. Mithun Sarker: Conceptualiza-
tion, Investigation, Supervision, Writing - review editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
Declared none.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.poly.2020.114871.
References
[1] M.S. Dresselhaus, I.L. Thomas, Alternative energy technologies, Nature 414
(6861) (2001) 332–337, https://doi.org/10.1038/35104599.
[2] International Energy Agency (IEA) (2016) Energy and Air Pollution: World
Energy Outlook Special Report. https://doi.org/10.1016/B978-0-12-809597-
3.00127-9
[3] B. Becker, D. Fischer, Promoting renewable electricity generation in emerging
economies, Energy Policy 56 (2013) 446–455, https://doi.org/10.1016/j.
enpol.2013.01.004.
[4] Y. Kumar, J. Ringenberg, S. Depuru, V.K. Devabhaktuni, J. Lee, E. Nikolaidis, B.
Andersen, A. Afjeh, Wind energy: Trends and enabling technologies, Renew.
Sustain. Energy Rev. 53 (2016) 209–224, https://doi.org/10.1016/j.
rser.2015.07.200.
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
[5] J. Wang, X. Yue, Y. Yang, S. Sirisomboonchai, P. Wang, X. Ma, A. Abudula, G.
Guan, Earth-abundant transition-metal-based bifunctional catalysts for
overall electrochemical water splitting: A review, J. Alloy. Compd. 819
(2020) 153346, https://doi.org/10.1016/j.jallcom.2019.153346.
[6] V. Devabhaktuni, M. Alam, S. Shekara Sreenadh Reddy Depuru, R.C. Green II,
D. Nims, C. Near, Solar energy: Trends and enabling technologies, Renew.
Sustain. Energy Rev. 19 (2013) 555–564, https://doi.org/10.1016/j.
rser.2012.11.024.
[7] P.A. Owusu, S. Asumadu-Sarkodie, A review of renewable energy sources,
sustainability issues and climate change mitigation, Cogent Eng (2016),
https://doi.org/10.1080/23311916.2016.1167990.
[8] S. Dutta, A review on production, storage of hydrogen and its utilization as an
energy resource, J. Ind. Eng. Chem. 20 (4) (2014) 1148–1156, https://doi.org/
10.1016/j.jiec.2013.07.037.
[9] B. Johnston, M.C. Mayo, A. Khare, Hydrogen: the energy source for the 21st
century, Technovation 25 (6) (2005) 569–585, https://doi.org/10.1016/j.
technovation.2003.11.005.
[10] N.P. Brandon, Z. Kurban, Clean energy and the hydrogen economy, Phil. Trans.
R. Soc. A. 375 (2098) (2017) 20160400, https://doi.org/10.1098/
rsta.2016.0400.
[11] C.G. Morales-Guio, L.-A. Stern, X. Hu, Nanostructured hydrotreating catalysts
for electrochemical hydrogen evolution, Chem. Soc. Rev. 43 (18) (2014) 6555,
https://doi.org/10.1039/C3CS60468C.
[12] M. Pujara, M. Sheth, N. Rachchh, R. Bhoraniya, A.B. Harichandan ( 2020 ).
https://doi.org/10.1007/978-981-32-9578-0_24.
[13] I. Roger, M.A. Shipman, M.D. Symes, Earth-abundant catalysts for
electrochemical and photoelectrochemical water splitting, Nat. Rev. Chem.
1 (1) (2017), https://doi.org/10.1038/s41570-016-0003.
[14] B.o. You, Y. Sun, Innovative Strategies for Electrocatalytic Water Splitting, Acc.
Chem. Res. 51 (7) (2018) 1571–1580, https://doi.org/10.1021/acs.
accounts.8b00002.
[15] S. Sultan, J.N. Tiwari, A.N. Singh, S. Zhumagali, M. Ha, C.W. Myung, P.
Thangavel, K.S. Kim, Single Atoms and Clusters Based Nanomaterials for
Hydrogen Evolution, Oxygen Evolution Reactions, and Full Water Splitting,
Adv. Energy Mater. 9 (22) (2019) 1900624, https://doi.org/10.1002/
aenm.201900624.
[16] H. Jin, J. Wang, D. Su, Z. Wei, Z. Pang, Y. Wang, In situ Cobalt–Cobalt Oxide/N-
Doped Carbon Hybrids As Superior Bifunctional Electrocatalysts for Hydrogen
and Oxygen Evolution, J. Am. Chem. Soc. 137 (7) (2015) 2688–2694, https://
doi.org/10.1021/ja5127165.
[17] X. Chen, C. Li, M. Grätzel, R. Kostecki, S.S. Mao, Nanomaterials for renewable
energy production and storage, Chem. Soc. Rev. 41 (23) (2012) 7909, https://
doi.org/10.1039/c2cs35230c.
[18] S.S. Mao, S. Shen, L. Guo, Nanomaterials for renewable hydrogen production,
storage and utilization, Prog. Nat. Sci. Mater. Int. 22 (6) (2012) 522–534,
https://doi.org/10.1016/j.pnsc.2012.12.003.
[19] Z. Cai, Q. Yao, X.i. Chen, X. Wang, in: Novel Nanomaterials for Biomedical,
Environmental and Energy Applications, Elsevier, 2019, pp. 435–464,
https://doi.org/10.1016/B978-0-12-814497-8.00014-X.
[20] M.U. Niemann, S.S. Srinivasan, A.R. Phani, A. Kumar, D.Y. Goswami, E.K.
Stefanakos, Nanomaterials for Hydrogen Storage Applications: A
Review, J. Nanomater. 2008 (2008) 1–9, https://doi.org/10.1155/2008/
950967.
[21] K. Ojha, S. Saha, P. Dagar, A.K. Ganguli, Nanocatalysts for hydrogen evolution
reactions, PCCP 20 (10) (2018) 6777–6799, https://doi.org/10.1039/
C7CP06316D.
[22] S. Cherevko, T. Reier, A.R. Zeradjanin, Z. Pawolek, P. Strasser, K.J.J. Mayrhofer,
Stability of nanostructured iridium oxide electrocatalysts during oxygen
evolution reaction in acidic environment, Electrochem. Commun. 48 (2014)
81–85, https://doi.org/10.1016/j.elecom.2014.08.027.
[23] F.-D. Kong, S. Zhang, G.-P. Yin, Z.-B. Wang, C.-Y. Du, G.-Y. Chen, N.a. Zhang,
Electrochemical studies of Pt/Ir–IrO2 electrocatalyst as a bifunctional oxygen
electrode, Int. J. Hydrogen Energy 37 (1) (2012) 59–67, https://doi.org/
10.1016/j.ijhydene.2011.09.087.
[24] Y. Zheng, Y. Jiao, Y. Zhu, L.H. Li, Y.u. Han, Y. Chen, M. Jaroniec, S.-Z. Qiao, High
electrocatalytic hydrogen evolution activity of an anomalous ruthenium
catalyst, J. Am. Chem. Soc. 138 (49) (2016) 16174–16181, https://doi.org/
10.1021/jacs.6b11291.s001.
[25] S. Anantharaj, S.R. Ede, K. Sakthikumar, K. Karthick, S. Mishra, S. Kundu,
Recent trends and perspectives in electrochemical water splitting with an
emphasis on sulfide, selenide, and phosphide catalysts of Fe, Co, and Ni: A
Review, ACS Catal. 6 (12) (2016) 8069–8097, https://doi.org/10.1021/
acscatal.6b02479.
[26] Q.i. Hu, G. Li, Z. Han, Z. Wang, X. Huang, H. Yang, Q. Zhang, J. Liu, C. He, Recent
progress in the hybrids of transition metals/carbon for electrochemical water
splitting, J. Mater. Chem. A 7 (24) (2019) 14380–14390, https://doi.org/
10.1039/C9TA04163J.
[27] M.I. Jamesh, Recent progress on earth abundant hydrogen evolution reaction
and oxygen evolution reaction bifunctional electrocatalyst for overall water
splitting in alkaline media, J. Power Sources 333 (2016) 213–236, https://doi.
org/10.1016/j.jpowsour.2016.09.161.
[28] F. Song, L. Bai, A. Moysiadou, S. Lee, C. Hu, L. Liardet, X. Hu, Transition metal
oxides as electrocatalysts for the oxygen evolution reaction in alkaline
solutions: an application-inspired renaissance, J. Am. Chem. Soc. 140 (25)
(2018) 7748–7759, https://doi.org/10.1021/jacs.8b04546.
21
Polyhedron 193 (2021) 114871
[29] L. Osmieri, A.H.A. Monteverde Videla, P. Ocón, S. Specchia, Kinetics of oxygen
electroreduction on Me–N–C (Me = Fe, Co, Cu) catalysts in acidic medium:
insights on the effect of the transition metal, J. Phys. Chem. C 121 (33) (2017)
17796–17817, https://doi.org/10.1021/acs.jpcc.7b02455.
[30] N. Yuan, Q. Jiang, J. Li, J. Tang, A review on non-noble metal based
electrocatalysis for the oxygen evolution reaction, Arabian J. Chem. 13 (2)
(2020) 4294–4309, https://doi.org/10.1016/j.arabjc.2019.08.006.
[31] S. Li, X. Hao, A. Abudula, G. Guan, Nanostructured Co-based bifunctional
electrocatalysts for energy conversion and storage: current status and
perspectives, J. Mater. Chem. A 7 (32) (2019) 18674–18707, https://doi.org/
10.1039/C9TA04949E.
[32] J. Yu, Q. He, G. Yang, W. Zhou, Z. Shao, M. Ni, Recent Advances and Prospective
in Ruthenium-Based Materials for Electrochemical Water Splitting, ACS Catal.
9 (11) (2019) 9973–10011, https://doi.org/10.1021/acscatal.9b02457.
[33] H. Sun, Z. Yan, F. Liu, W. Xu, F. Cheng, J. Chen, Self-supported transition-
metal-based electrocatalysts for hydrogen and oxygen evolution, Adv. Mater.
32 (3) (2020) 1806326, https://doi.org/10.1002/adma.201806326.
[34] J. Liu, H. Zhang, M. Qiu, Z. Peng, M.K.H. Leung, W.-F. Lin, J. Xuan, A review of
non-precious metal single atom confined nanomaterials in different
structural dimensions (1D–3D) as highly active oxygen redox reaction
electrocatalysts, J. Mater. Chem. A 8 (5) (2020) 2222–2245, https://doi.org/
10.1039/C9TA11852G.
[35] J. Liu, H. Zhang, M. Qiu, Z. Peng, M.K.H. Leung, W.-F. Lin, J. Xuan, The
dimension matters: A review of non-precious-metal single atom nanocatalyst
in different structural dimensions for oxygen redox reaction, J. Mater. Chem.
A (2020), https://doi.org/10.1039/c9ta11852g.
[36] J. Mohammed-Ibrahim, X. Sun, Recent progress on earth abundant
electrocatalysts for hydrogen evolution reaction (HER) in alkaline medium
to achieve efficient water splitting – A review, J. Energy Chem. 34 (2019) 111–
160, https://doi.org/10.1016/j.jechem.2018.09.016.
[37] V. Vij, S. Sultan, A.M. Harzandi, A. Meena, J.N. Tiwari, W.-G. Lee, T. Yoon, K.S.
Kim, Nickel-based electrocatalysts for energy-related applications: oxygen
reduction, oxygen evolution, and hydrogen evolution reactions, ACS Catal. 7
(10) (2017) 7196–7225, https://doi.org/10.1021/acscatal.7b01800.
[38] X. Zou, Y.u. Zhang, Noble metal-free hydrogen evolution catalysts for water
splitting, Chem. Soc. Rev. 44 (15) (2015) 5148–5180, https://doi.org/10.1039/
C4CS00448E.
[39] M. Fang, G. Dong, R. Wei, J.C. Ho, Hierarchical nanostructures: design for
sustainable water splitting, Adv. Energy Mater. 7 (23) (2017) 1700559,
https://doi.org/10.1002/aenm.201700559.
[40] X. Yu, J. Zhao, L.-R. Zheng, Y. Tong, M. Zhang, G. Xu, C. Li, J. Ma, G. Shi,
Hydrogen evolution reaction in alkaline media: alpha- or beta-nickel
hydroxide on the surface of platinum?, ACS Energy Lett. 3 (1) (2018) 237–
244, https://doi.org/10.1021/acsenergylett.7b01103.s001.
[41] V.R. Stamenkovic, D. Strmcnik, P.P. Lopes, N.M. Markovic, Energy and fuels
from electrochemical interfaces, Nature Mater 16 (1) (2017) 57–69, https://
doi.org/10.1038/nmat4738.
[42] T. Reier, H.N. Nong, D. Teschner, R. Schlögl, P. Strasser, Electrocatalytic oxygen
evolution reaction in acidic environments - reaction mechanisms and
catalysts, Adv. Energy Mater. 7 (1) (2017) 1601275, https://doi.org/10.1002/
aenm.201601275.
[43] Y. Jiao, Y. Zheng, M. Jaroniec, S.Z. Qiao, Design of electrocatalysts for oxygen-
and hydrogen-involving energy conversion reactions, Chem. Soc. Rev. 44 (8)
(2015) 2060–2086, https://doi.org/10.1039/C4CS00470A.
[44] J. Zhang, Z. Chen, C. Liu, J. Zhao, S. Liu, D. Rao, A. Nie, Y. Chen, Y. Deng, W. Hu,
Hierarchical iridium-based multimetallic alloy with double-core-shell
architecture for efficient overall water splitting, Sci. China Mater. 63 (2)
(2020) 249–257, https://doi.org/10.1007/s40843-019-1176-6.
[45] J. Yang, Q.i. Shao, B. Huang, M. Sun, X. Huang, pH-Universal water splitting
catalyst: Ru-ni nanosheet assemblies, iScience 11 (2019) 492–504, https://
doi.org/10.1016/j.isci.2019.01.004.
[46] Q. Wu, M. Luo, J. Han, W. Peng, Y. Zhao, D. Chen, M. Peng, J.i. Liu, F.M.F. de
Groot, Y. Tan, Identifying electrocatalytic sites of the nanoporous copper–
ruthenium alloy for hydrogen evolution reaction in alkaline electrolyte, ACS
Energy Lett. 5 (1) (2020) 192–199, https://doi.org/10.1021/
acsenergylett.9b02374.s001.
[47] Y. Bao, J. Dai, J. Zhao, Y. Wu, C. Li, L. Ji, X. Zhang, F. Yang, Modulation in
ruthenium–cobalt electronic structure for highly efficient overall water
splitting, ACS Appl. Energy Mater. 3 (2) (2020) 1869–1874, https://doi.org/
10.1021/acsaem.9b02315.s001.
[48] N.a. Liu, K. Yin, C. Si, T. Kou, Y. Zhang, W. Ma, Z. Zhang, Hierarchically porous
nickel–iridium–ruthenium–aluminum alloys with tunable compositions and
electrocatalytic activities towards the oxygen/hydrogen evolution reaction in
acid electrolyte, J. Mater. Chem. A 8 (13) (2020) 6245–6255, https://doi.org/
10.1039/D0TA00445F.
[49] M. Wei, L. Huang, S. Huang, Z. Chen, D. Lyu, X. Zhang, S. Wang, Z.Q. Tian, P.K.
Shen, Highly efficient Pt-Co alloy hollow spheres with ultra-thin shells
synthesized via Co-B-O complex as intermediates for hydrogen evolution
reaction, J. Catal. 381 (2020) 385–394, https://doi.org/10.1016/j.
jcat.2019.11.014.
[50] W. Li, Z.-Y. Hu, Z. Zhang, P. Wei, J. Zhang, Z. Pu, J. Zhu, D. He, S. Mu, G. Van
Tendeloo, Nano-single crystal coalesced PtCu nanospheres as robust
bifunctional catalyst for hydrogen evolution and oxygen reduction
reactions, J. Catal. 375 (2019) 164–170, https://doi.org/10.1016/j.
jcat.2019.05.031.
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
[51] L. Lin, M. Chen, L. Wu, Facile synthesis of nickel–copper hollow spheres as
efficient bifunctional electrocatalysts for overall water splitting, Mater. Chem.
Front. 4 (3) (2020) 996–1005, https://doi.org/10.1039/C9QM00697D.
[52] Y. Du, H. Qu, Y. Liu, Y.i. Han, L. Wang, B. Dong, Bimetallic CoFeP hollow
microspheres as highly efficient bifunctional electrocatalysts for overall
water splitting in alkaline media, Appl. Surf. Sci. 465 (2019) 816–823, https://
doi.org/10.1016/j.apsusc.2018.09.231.
[53] Y. Zhao, J. Bai, X.-R. Wu, P. Chen, P.-J. Jin, H.-C. Yao, Y.u. Chen, Atomically
ultrathin RhCo alloy nanosheet aggregates for efficient water electrolysis in
broad pH range, J. Mater. Chem. A 7 (27) (2019) 16437–16446, https://doi.
org/10.1039/C9TA05334D.
[54] W. Luo, J. Gan, Z. Huang, W. Chen, G. Qian, X. Zhou, X. Duan, Boosting HER
performance of pt-based catalysts immobilized on functionalized vulcan
carbon by atomic layer deposition, Front Mater. (2019), https://doi.org/
10.3389/fmats.2019.00251.
[55] H. Wang, C. Gao, R. Li, Z. Peng, J. Yang, J. Gao, Y. Yang, S. Li, B. Li, Z. Liu,
Ruthenium–cobalt nanoalloy embedded within hollow carbon spheres as
a bifunctionally robust catalyst for hydrogen generation from water
splitting and ammonia borane hydrolysis, ACS Sustainable Chem. Eng. 7
(23) (2019) 18744–18752, https://doi.org/10.1021/
acssuschemeng.9b02126.s001.
[56] D.H. Kweon, M.S. Okyay, S.-J. Kim, J.-P. Jeon, H.-J. Noh, N. Park, J. Mahmood, J.-
B. Baek, Ruthenium anchored on carbon nanotube electrocatalyst for
hydrogen production with enhanced Faradaic efficiency, Nat. Commun. 11
(1) (2020), https://doi.org/10.1038/s41467-020-15069-3.
[57] Z. Peng, J. Liu, B. Hu, Y. Yang, Y. Guo, B. Li, L.i. Li, Z. Zhang, B. Cui, L. He, M. Du,
Surface Engineering on Nickel–Ruthenium Nanoalloys Attached Defective
Carbon Sites as Superior Bifunctional Electrocatalysts for Overall Water
Splitting, ACS Appl. Mater. Interfaces 12 (12) (2020) 13842–13851, https://
doi.org/10.1021/acsami.9b21827.s001.
[58] L.u. Chen, Z. Xu, W. Han, Q. Zhang, Z. Bai, Z. Chen, G.e. Li, X. Wang, Bimetallic
CoNi alloy nanoparticles embedded in pomegranate-like nitrogen-doped
carbon spheres for electrocatalytic oxygen reduction and evolution, ACS Appl.
Nano Mater. 3 (2) (2020) 1354–1362, https://doi.org/10.1021/
acsanm.9b02201.s001.
[59] T.T. Gebremariam, F. Chen, Y. Jin, Q. Wang, J. Wang, J. Wang, Bimetallic NiCo/
CNF Encapsulated in N-doped Carbon Shell as Electrocatalyst for Zn-Air
Battery and Water Splitting, Catal. Sci. Technol. (2019), https://doi.org/
10.1039/c9cy00266a.
[60] C. Cheng, F. Zheng, C. Zhang, C. Du, Z. Fang, Z. Zhang, W. Chen, High-efficiency
bifunctional electrocatalyst based on 3D freestanding Cu foam in situ
armored CoNi alloy nanosheet arrays for overall water splitting, J. Power
Sources 427 (2019) 184–193, https://doi.org/10.1016/j.
jpowsour.2019.04.071.
[61] J.-T. Ren, L. Chen, Y.-S. Wang, W.-W. Tian, L.-J. Gao, Z.-Y. Yuan, FeNi
Nanoalloys encapsulated in N-Doped CNTs tangled with N-doped carbon
nanosheets as efficient multifunctional catalysts for overall water splitting
and rechargeable Zn–air batteries, ACS Sustainable Chem. Eng. 8 (1) (2020)
223–237, https://doi.org/10.1021/acssuschemeng.9b05238.s001.
[62] D. Chen, J. Zhu, X. Mu, R. Cheng, W. Li, S. Liu, Z. Pu, C. Lin, S. Mu, Nitrogen-
Doped carbon coupled FeNi3 intermetallic compound as advanced
bifunctional electrocatalyst for OER, ORR and zn-air batteries, Appl. Catal. B
268 (2020) 118729, https://doi.org/10.1016/j.apcatb.2020.118729.
[63] S.A. Shah, Z. Ji, X. Shen, X. Yue, G. Zhu, K. Xu, A. Yuan, N. Ullah, J. Zhu, P. Song,
X. Li, Thermal synthesis of FeNi@Nitrogen-doped graphene dispersed on
nitrogen-doped carbon matrix as an excellent electrocatalyst for oxygen
evolution reaction, ACS Appl. Energy Mater. 2 (6) (2019) 4075–4083, https://
doi.org/10.1021/acsaem.9b00199.s001.
[64] Q. Li, J. Li, J. Xu, N. Zhang, Y. Li, L. Liu, D. Pan, Z. Wang, F.L. Deepak, Ultrafine-
grained porous ir-based catalysts for high-performance overall water
splitting in acidic media, ACS Appl. Energy Mater. 3 (4) (2020) 3736–3744,
https://doi.org/10.1021/acsaem.0c00201.s001.
[65] Y. Lin, Z. Tian, L. Zhang, J. Ma, Z. Jiang, B.J. Deibert, R. Ge, L. Chen, Chromium-
ruthenium oxide solid solution electrocatalyst for highly efficient oxygen
evolution reaction in acidic media, Nat. Commun. 10 (1) (2019), https://doi.
org/10.1038/s41467-018-08144-3.
[66] Y. Tian, S. Wang, E. Velasco, Y. Yang, L. Cao, L. Zhang, X. Li, Y. Lin, Q. Zhang, L.
Chen, A Co-doped nanorod-like Ruo2 electrocatalyst with abundant oxygen
vacancies for acidic water oxidation, iScience 23 (1) (2020) 100756, https://
doi.org/10.1016/j.isci.2019.100756.
[67] D. Chakraborty, S. Nandi, R. Illathvalappil, D. Mullangi, R. Maity, S.K. Singh, S.
Haldar, C.P. Vinod, S. Kurungot, R. Vaidhyanathan, Carbon derived from soft
pyrolysis of a covalent organic framework as a support for small-sized RuO2
showing exceptionally low overpotential for oxygen evolution reaction, ACS
Omega 4 (8) (2019) 13465–13473, https://doi.org/10.1021/
acsomega.9b01777.s001.
[68] F.-Y. Yu, Z.-L. Lang, L.-Y. Yin, K. Feng, Y.-J. Xia, H.-Q. Tan, H.-T. Zhu, J. Zhong, Z.-
H. Kang, Y.-G. Li, Pt-O bond as an active site superior to Pt0 in hydrogen
evolution reaction, Nat. Commun. 11 (1) (2020), https://doi.org/10.1038/
s41467-019-14274-z.
[69] R. Elakkiya, G. Maduraiveeran, Two-Dimensional Earth-Abundant Transition
Metal Oxides Nanomaterials: Synthesis and Application in Electrochemical
Oxygen Evolution Reaction, Langmuir 36 (17) (2020) 4728–4736, https://doi.
org/10.1021/acs.langmuir.0c00714.s001.
[70] Mary Lou Lindstrom, Ruchi Gakhar, Krishna Raja, Dev Chidambaram, Facile
synthesis of an efficient Ni–Fe–Co based oxygen evolution reaction
22
Polyhedron 193 (2021) 114871
electrocatalyst, J. Electrochem. Soc. (2020) 167, https://doi.org/10.1149/
1945-7111/ab6b08, 046507.
[71] L. Wang, J. Wang, M. Wang, P. Li, J. Tong, F. Yu, AgO-decorated multi-
dimensional chrysanthemum-like NiCo2O4 mounted on nickel foam as a
highly efficient and stable electrocatalyst for the oxygen evolution reaction,
Nanoscale 12 (13) (2020) 7180–7187, https://doi.org/10.1039/C9NR10141A.
[72] X. Wang, G. She, L. Mu, W. Shi, Amorphous Co–Mo–P–O Bifunctional
Electrocatalyst via Facile Electrodeposition for Overall Water Splitting, ACS
Sustainable Chem. Eng. 8 (7) (2020) 2835–2842, https://doi.org/10.1021/
acssuschemeng.9b06929.s001.
[73] Y. Luo, H. Yang, P. Ma, S. Luo, Z. Zhao, J. Ma, Fe3O4/CoO interfacial
nanostructure supported on carbon nanotubes as a highly efficient
electrocatalyst for oxygen evolution reaction, ACS Sustainable Chem. Eng. 8
(8) (2020) 3336–3346, https://doi.org/10.1021/acssuschemeng.9b07292.
s001.
[74] Z. Guo, X. Wang, Y. Gao, Z. Liu, Co/Cu-modified NiO film grown on nickel foam
as a highly active and stable electrocatalyst for overall water splitting, Dalton
Trans. 49 (6) (2020) 1776–1784, https://doi.org/10.1039/C9DT04771A.
[75] W. Jin, X. Guo, J. Zhang, L. Zheng, F. Liu, Y. Hu, J. Mao, H. Liu, Y. Xue, C. Tang,
Ultrathin carbon coated CoO nanosheet arrays as efficient electrocatalysts for
the hydrogen evolution reaction, Catal. Sci. Technol. 9 (24) (2019) 6957–
6964, https://doi.org/10.1039/C9CY01645G.
[76] S. Niu, S. Li, J. Hu, Y. Li, Y. Du, X. Han, P. Xu, Fabrication of uniform Ru-doped
NiFe 2 O 4 nanosheets as an efficient hydrogen evolution electrocatalyst,
Chem. Commun. 55 (97) (2019) 14649–14652, https://doi.org/10.1039/
C9CC07651D.
[77] C. Wang, L. Zeng, W. Guo, C. Gong, J. Yang, Enhancing oxygen and hydrogen
evolution activities of perovskite oxide LaCoO 3via effective doping of
platinum, RSC Adv. 9 (61) (2019) 35646–35654, https://doi.org/10.1039/
C9RA05491J.
[78] J.S. Kim, B. Kim, H. Kim, K. Kang, Recent progress on multimetal oxide
catalysts for the oxygen evolution reaction, Adv. Energy Mater. 8 (11) (2018)
1702774, https://doi.org/10.1002/aenm.201702774.
[79] M. Zhang, Y. Liu, B. Liu, Z. Chen, H. Xu, K. Yan, Trimetallic NiCoFe-Layered
double hydroxides nanosheets efficient for oxygen evolution and highly
selective oxidation of biomass-derived 5-hydroxymethylfurfural, ACS Catal.
10 (9) (2020) 5179–5189, https://doi.org/10.1021/acscatal.0c00007.s001.
[80] J. He, T. Wu, S.-Y. Chen, R. Miao, Y. Dang, W. Zhong, M. Wang, T. Jiang, S.L.
Suib, Structure-property relationship of graphene coupled metal (Ni, Co, Fe)
(oxy)hydroxides for efficient electrochemical evolution of oxygen, J. Catal.
377 (2019) 619–628, https://doi.org/10.1016/j.jcat.2019.08.006.
[81] R. Farhat, J. Dhainy, L. Halaoui, OER catalysis at activated and co-deposited
nife-oxo/hydroxide thin films is due to post-deposition surface-fe and is not
sustainable without Fe in solution, ACS Catal. (2019), https://doi.org/10.1021/
acscatal.9b0258.
[82] X. Yue, W. Ke, M. Xie, X. Shen, Z. Yan, Z. Ji, G. Zhu, K. Xu, H.u. Zhou, Amorphous
CoFe(OH) x hollow hierarchical structure: an efficient and durable
electrocatalyst for oxygen evolution reaction, Catal. Sci. Technol. 10 (1)
(2020) 215–221, https://doi.org/10.1039/C9CY02092F.
[83] N. Manna, N. Ayasha, S.K. Singh, S. Kurungot, A NiFe layered double
hydroxide-decorated N-doped entangled-graphene framework: a robust
water oxidation electrocatalyst, Nanoscale Adv. 2 (4) (2020) 1709–1717,
https://doi.org/10.1039/C9NA00808J.
[84] L. Mohapatra, K. Parida, M. Satpathy, Molybdate/Tungstate Intercalated Oxo-
Bridged Zn/Y LDH for Solar Light Induced Photodegradation of Organic
Pollutants, J. Phys. Chem. C 116 (24) (2012) 13063–13070, https://doi.org/
10.1021/jp300066g.
[85] P. Ding, F. Luo, P. Wang, W. Xia, X. Xu, J. Hu, H. Zeng, Photo-induced charge
kinetic acceleration in ultrathin layered double hydroxide nanosheets boosts
the oxygen evolution reaction, J. Mater. Chem. A 8 (3) (2020) 1105–1112,
https://doi.org/10.1039/C9TA12377F.
[86] Z. Liu, Y.-C. Huang, Y. Wang, J. Cen, H. Yang, X. Chen, X. Tong, D. Su, C.-L. Dong,
S. Wang, Quinary Defect-Rich Ultrathin Bimetal Hydroxide Nanosheets for
Water Oxidation, ACS Appl. Mater. Interfaces 11 (47) (2019) 44018–44025,
https://doi.org/10.1021/acsami.9b10315.s001.
[87] K. Sliozberg, Y. Aniskevich, U. Kayran, J. Masa, W. Schuhmann, CoFe-OH
double hydroxide films electrodeposited on Ni-foam as electrocatalyst for the
oxygen evolution reaction, Zeitschrift fur Phys. Chem. (2020), https://doi.org/
10.1515/zpch-2019-1466.
[88] Y. Gong, J. Huang, L. Cao, K. Kajiyoshi, D. Yang, Y. Feng, L. Kou, L. Feng,
Methanol-assisted synthesis of Ni 3+ -doped ultrathin NiZn-LDH nanomeshes
for boosted alkaline water splitting, Dalton Trans. 49 (4) (2020) 1325–1333,
https://doi.org/10.1039/C9DT04282B.
[89] M. Zeng, Y. Li, Recent advances in heterogeneous electrocatalysts for the
hydrogen evolution reaction, J. Mater. Chem. A 3 (2015) 14942–14962,
https://doi.org/10.1039/C9TA03220G.
[90] Z. Cai, X. Bu, P. Wang, J.C. Ho, J. Yang, X. Wang, Recent advances in layered
double hydroxide electrocatalysts for the oxygen evolution reaction, J. Mater.
Chem. A (2019), https://doi.org/10.1039/D0NJ00021C.
[91] D. Wang, Q. Li, C.e. Han, Q. Lu, Z. Xing, X. Yang, Atomic and electronic
modulation of self-supported nickel-vanadium layered double hydroxide to
accelerate water splitting kinetics, Nat. Commun. 10 (1) (2019), https://doi.
org/10.1038/s41467-019-11765-x.
[92] H.S. Jadhav, A. Roy, B.Z. Desalegan, J.G. Seo, An advanced and highly efficient
Ce assisted NiFe-LDH electrocatalyst for overall water splitting, Sustainable
Energy Fuels 4 (1) (2020) 312–323, https://doi.org/10.1039/C9SE00700H.
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
[93] M. Xie, K. Jia, J. Lu, R. Zhao, Bi-functional Mo and P co-doped ZnCo-LDH
nanosheets as high performance electrocatalysts for boosting overall water
splitting, CrystEngComm 22 (3) (2020) 546–553, https://doi.org/10.1039/
C9CE01575B.
[94] S. Parvin, A. Kumar, A. Ghosh, S. Bhattacharyya, An earth-abundant bimetallic
catalyst coated metallic nanowire grown electrode with platinum-like pH-
universal hydrogen evolution activity at high current density, Chem. Sci. 11
(15) (2020) 3893–3902, https://doi.org/10.1039/D0SC00754D.
[95] L. Feng, Y. Du, J. Huang, L. Cao, L.i. Feng, Y. Feng, Q. Liu, D. Yang, K. Kajiyoshi,
Nanoporous NiAl-LDH nanosheet arrays with optimized Ni active sites for
efficient electrocatalytic alkaline water splitting, Sustainable Energy Fuels 4
(6) (2020) 2850–2858, https://doi.org/10.1039/D0SE00050G.
[96] S. Chandrasekaran, L. Yao, L. Deng, C. Bowen, Y. Zhang, S. Chen, Z. Lin, F. Peng,
P. Zhang, Recent advances in metal sulfides: from controlled fabrication to
electrocatalytic, photocatalytic and photoelectrochemical water splitting and
beyond, Chem. Soc. Rev. 48 (15) (2019) 4178–4280, https://doi.org/10.1039/
C8CS00664D.
[97] H. Du, R.-M. Kong, X. Guo, F. Qu, J. Li, Recent progress in transition metal
phosphides with enhanced electrocatalysis for hydrogen evolution,
Nanoscale 10 (46) (2018) 21617–21624, https://doi.org/10.1039/
C8NR07891B.
[98] M. Miao, J. Pan, T. He, Y.a. Yan, B.Y. Xia, X. Wang, Molybdenum Carbide-Based
Electrocatalysts for Hydrogen Evolution Reaction, Chem. Eur. J. 23 (46) (2017)
10947–10961, https://doi.org/10.1002/chem.201701064.
[99] Z. Chen, X. Duan, W. Wei, S. Wang, B.-J. Ni, Recent advances in transition
metal-based electrocatalysts for alkaline hydrogen evolution, J. Mater. Chem.
A 7 (25) (2019) 14971–15005, https://doi.org/10.1039/C9TA03220G.
[100] Z. Pu, J. Zhao, I.S. Amiinu, W. Li, M. Wang, D. He, S. Mu, A universal synthesis
strategy for P-rich noble metal diphosphide-based electrocatalysts for the
hydrogen evolution reaction, Energy Environ. Sci. 12 (3) (2019) 952–957,
https://doi.org/10.1039/C9EE00197B.
[101] X. Li, S. Li, A. Yoshida, S. Sirisomboonchai, K. Tang, Z. Zuo, X. Hao, A. Abudula,
G. Guan, Mn doped CoP nanoparticle clusters: an efficient electrocatalyst for
hydrogen evolution reaction, Catal. Sci. Technol. 8 (17) (2018) 4407–4412,
https://doi.org/10.1039/C8CY01105B.
[102] Y. Sun, T. Zhang, C. Li, K. Xu, Y. Li, Compositional engineering of sulfides,
phosphides, carbides, nitrides, oxides, and hydroxides for water splitting, J.
Mater. Chem. A 8 (27) (2020) 13415–13436, https://doi.org/10.1039/
D0TA05038E.
[103] Y. Yan, J. Lin, J. Cao, S. Guo, X. Zheng, J. Feng, J. Qi, Activating and optimizing
the activity of NiCoP nanosheets for electrocatalytic alkaline water splitting
through the V doping effect enhanced by P vacancies, J. Mater. Chem. A 7 (42)
(2019) 24486–24492, https://doi.org/10.1039/C9TA09283H.
[104] C. Lin, P. Wang, H. Jin, J. Zhao, D. Chen, S. Liu, S. Mu, Iron-doped Cobalt
Phosphide Nano-Electrocatalyst Derived from Metal-Organic Framework for
Efficient Water Splitting, Dalton Trans. (2019), https://doi.org/10.1039/
c9dt03619a.
[105] Z. Liu, X.u. Yu, H. Xue, L. Feng, A nitrogen-doped CoP nanoarray over 3D
porous Co foam as an efficient bifunctional electrocatalyst for overall water
splitting, J. Mater. Chem. A 7 (21) (2019) 13242–13248, https://doi.org/
10.1039/C9TA03201K.
[106] S. Zhang, M. Guo, S. Song, K. Zhan, Y. Yan, J. Yang, B. Zhao, Hierarchical Mo-
doped CoP3 Interconnected Nanosheet Arrays on Carbon Cloth as an Efficient
Bifunctional Electrocatalyst for Water Splitting in Alkaline Electrolyte, Dalt
Trans (2020), https://doi.org/10.1039/d0dt00671h.
[107] L. Li, X. Wang, Y. Guo, J. Li, Synthesis of an Ultrafine CoP Nanocrystal/
Graphene Sandwiched Structure for Efficient Overall Water Splitting,
Langmuir 36 (8) (2020) 1916–1922, https://doi.org/10.1021/acs.
langmuir.9b03810.s001.
[108] J.K. Das, A.K. Samantara, S. Satyarthy, C.S. Rout, J.N. Behera, Three-
dimensional NiCoP hollow spheres: an efficient electrode material for
hydrogen evolution reaction and supercapacitor applications, RSC Adv. 10
(8) (2020) 4650–4656, https://doi.org/10.1039/C9RA09714G.
[109] Y. Li, L. Cai, Q. Huang, J. Liu, R. Tang, W. Zhou, Highly Efficient Synthesis of
Carbon-Based Molybdenum Phosphide Nanoparticles for Electrocatalytic
Hydrogen Evolution, Nanoscale Res. Lett. 15 (1) (2020), https://doi.org/
10.1186/s11671-020-3246-x.
[110] D. Yang, L.i. Gao, J.-H. Yang, New Insights into Layered Graphene Materials as
Substrates to Regulate Synthesis of Ni–P Nanomaterials for Electrocatalytic
Oxidation of Methanol and Water, ACS Appl. Mater. Interfaces 11 (48) (2019)
45189–45198, https://doi.org/10.1021/acsami.9b14020.s001.
[111] Y. Liang, Y. Yang, K. Xu, T. Yu, S. Yao, Q.i. Peng, C. Yuan, Crystal plane
dependent electrocatalytic performance of NiS2 nanocrystals for hydrogen
evolution reaction, J. Catal. 381 (2020) 63–69, https://doi.org/10.1016/j.
jcat.2019.10.038.
[112] L. Najafi, S. Bellani, R. Oropesa-Nuñez, B. Martín-García, M. Prato, V. Mazánek,
D. Debellis, S. Lauciello, R. Brescia, Z. Sofer, F. Bonaccorso, Niobium disulphide
(NbS2)-based (heterogeneous) electrocatalysts for an efficient hydrogen
evolution reaction, J. Mater. Chem. A 7 (44) (2019) 25593–25608, https://
doi.org/10.1039/C9TA07210A.
[113] M. Shi, Y. Zhang, Y. Zhu, W. Wang, C. Wang, A. Yu, X. Pu, J. Zhai, A flower-like
CoS2/MoS2 heteronanosheet array as an active and stable electrocatalyst
toward the hydrogen evolution reaction in alkaline media, RSC Adv. 10 (15)
(2020) 8973–8981, https://doi.org/10.1039/C9RA10963C.
[114] L. Diao, B. Zhang, Q. Sun, N. Wang, N. Zhao, C. Shi, E. Liu, C. He, An in-plane
Co9S8@MoS2 heterostructure for the hydrogen evolution reaction in alkaline
23
Polyhedron 193 (2021) 114871
media, Nanoscale 11 (44) (2019) 21479–21486, https://doi.org/10.1039/
C9NR06609H.
[115] F. Si, C. Tang, Q. Gao, F. Peng, S. Zhang, Y. Fang, S. Yang, Bifunctional
CdS@Co9S8/Ni3S2 catalyst for efficient electrocatalytic and photo-assisted
electrocatalytic overall water splitting, J. Mater. Chem. A 8 (2020) 3083–
3096, https://doi.org/10.1039/C9TA11921C.
[116] J. Zhu, M. Sun, S. Liu, X. Liu, K. Hu, L. Wang, Study of active sites on Se-MnS/
NiS heterojunctions as highly efficient bifunctional electrocatalysts for
overall water splitting, J. Mater. Chem. A 7 (47) (2019) 26975–26983,
https://doi.org/10.1039/C9TA10860B.
[117] C. Wu, Y. Du, Y. Fu, D.i. Feng, H. Li, Z. Xiao, Y. Liu, Y.u. Yang, L. Wang, Mo, Co
co-doped NiS bulks supported on Ni foam as an efficient electrocatalyst for
overall water splitting in alkaline media, Sustainable Energy Fuels 4 (4)
(2020) 1654–1664, https://doi.org/10.1039/C9SE00822E.
[118] X. Xia, L. Wang, N. Sui, V.L. Colvin, W.W. Yu, Recent progress in transition
metal selenide electrocatalysts for water splitting, Nanoscale 12 (23) (2020)
12249–12262, https://doi.org/10.1039/D0NR02939D.
[119] M. Ghaemmaghami, Y. Yamini, E. Saievar-Iranizad, A. Bayat, Straightforward
fabrication of robust Fe-doped Ni3Se2 supported nickel foam as a highly
efficient electrocatalyst for the oxygen evolution reaction, Sustainable Energy
Fuels 4 (3) (2020) 1150–1156, https://doi.org/10.1039/C9SE00896A.
[120] S. Liu, Y. Jiang, M. Yang, M. Zhang, Q. Guo, W. Shen, R. He, M. Li, Highly
conductive and metallic cobalt–nickel selenide nanorods supported on Ni
foam as an efficient electrocatalyst for alkaline water splitting, Nanoscale 11
(16) (2019) 7959–7966, https://doi.org/10.1039/C8NR10545F.
[121] X.i. Cao, J.E. Medvedeva, M. Nath, Copper Cobalt Selenide as a High-Efficiency
Bifunctional Electrocatalyst for Overall Water Splitting: Combined
Experimental and Theoretical Study, ACS Appl. Energy Mater. 3 (3) (2020)
3092–3103, https://doi.org/10.1021/acsaem.0c00262.s001.
[122] Y.-Y. Sun, M.-Y. Jiang, L.-K. Wu, G.-Y. Hou, Y.-P. Tang, M. Liu, Ultra-thin NiFeSe
nanosheets as a highly efficient bifunctional electrocatalyst for overall water
splitting, Sustainable Energy Fuels 4 (2) (2020) 582–588, https://doi.org/
10.1039/C9SE00905A.
[123] K. Jiang, B. Liu, M. Luo, S. Ning, M. Peng, Y. Zhao, Y.-R. Lu, T.-S. Chan, F.M.F. de
Groot, Y. Tan, Single platinum atoms embedded in nanoporous cobalt
selenide as electrocatalyst for accelerating hydrogen evolution reaction,
Nat. Commun. 10 (1) (2019), https://doi.org/10.1038/s41467-019-09765-y.
[124] M. Yao, B. Wang, N.i. Wang, S. Komarneni, Y. Chen, J. Wang, X. Niu, W. Hu,
Self-Supported Composite of (Ni,Co)3C Mesoporous Nanosheets/N-Doped
Carbon as a Flexible Electrocatalyst for pH-Universal Hydrogen Evolution,
ACS Sustainable Chem. Eng. 8 (13) (2020) 5287–5295, https://doi.org/
10.1021/acssuschemeng.0c00268.s001.
[125] A. Mahmood, W. Guo, H. Tabassum, R. Zou, Metal-Organic Framework-Based
Nanomaterials for Electrocatalysis, Adv. Energy Mater. 6 (17) (2016)
1600423, https://doi.org/10.1002/aenm.201600423.
[126] T. Qiu, Z. Liang, W. Guo, S. Gao, C. Qu, H. Tabassum, H. Zhang, B. Zhu, R. Zou, Y.
Shao-Horn, Highly exposed ruthenium-based electrocatalysts from
bimetallic metal-organic frameworks for overall water splitting, Nano
Energy 58 (2019) 1–10, https://doi.org/10.1016/j.nanoen.2018.12.085.
[127] B.o. Ye, L. Huang, Y. Hou, R. Jiang, L. Sun, Z. Yu, B. Zhang, Y. Huang, Y. Zhang, Pt
(111) quantum dot decorated flower-like aFe2O3 (104) thin film nanosheets
as a highly efficient bifunctional electrocatalyst for overall water splitting, J.
Mater. Chem. A 7 (18) (2019) 11379–11386, https://doi.org/10.1039/
C9TA01975H.
[128] B.o. Ye, R. Jiang, Z. Yu, Y. Hou, J. Huang, B. Zhang, Y. Huang, Y. Zhang, R. Zhang,
Pt (1 1 1) quantum dot engineered Fe-MOF nanosheet arrays with porous
core-shell as an electrocatalyst for efficient overall water splitting, J. Catal.
380 (2019) 307–317, https://doi.org/10.1016/j.jcat.2019.09.038.
[129] J.-T. Yuan, J.-J. Hou, X.-L. Liu, Y.-R. Feng, X.-M. Zhang, Optimized trimetallic
benzotriazole-5-carboxylate MOFs with coordinately unsaturated active
sites as an efficient electrocatalyst for the oxygen evolution reaction,
Dalton Trans. 49 (3) (2020) 750–756, https://doi.org/10.1039/
C9DT04295D.
[130] X.-J. Bai, H. Chen, Y.-N. Li, L. Shao, J.-C. Ma, L.-L. Li, J.-Y. Chen, T.-Q. Wang, X.-
M. Zhang, L.-Y. Zhang, Y.u. Fu, W. Qi, CoNi-based metal–organic framework
nanoarrays supported on carbon cloth as bifunctional electrocatalysts for
efficient water-splitting, New J. Chem. 44 (5) (2020) 1694–1698, https://doi.
org/10.1039/C9NJ06204A.
[131] D. Banerjee, C.M. Simon, A.M. Plonka, R.K. Motkuri, J. Liu, X. Chen, B. Smit, J.B.
Parise, M. Haranczyk, P.K. Thallapally, Metal–organic framework with
optimally selective xenon adsorption and separation, Nat. Commun. 7 (1)
(2016), https://doi.org/10.1038/ncomms11831.
[132] X. Du, H. Su, X. Zhang, Metal-organic framework-derived M (M = Fe, Ni, Zn
and Mo) doped Co9S8 nanoarrays as efficient electrocatalyst for water
splitting: The combination of theoretical calculation and experiment, J. Catal.
(2020), https://doi.org/10.1016/j.jcat.2020.01.015.
[133] T. Liu, P. Li, N.a. Yao, G. Cheng, S. Chen, W. Luo, Y. Yin, CoP-Doped MOF-Based
Electrocatalyst for pH-Universal Hydrogen Evolution Reaction, Angew. Chem.
Int. Ed. 58 (14) (2019) 4679–4684, https://doi.org/10.1002/anie.201901409.
[134] J. Li, Z. Zhao, Y. Ma, Y. Qu, Graphene and Their Hybrid Electrocatalysts for
Water Splitting, ChemCatChem 9 (9) (2017) 1554–1568, https://doi.org/
10.1002/cctc.201700175.
[135] J. Chen, C. Fan, X. Hu, C. Wang, Z. Huang, G. Fu, J.-M. Lee, Y. Tang,
Hierarchically Porous Co/Co x M y (M = P, N) as an Efficient Mott–Schottky
Electrocatalyst for Oxygen Evolution in Rechargeable Zn–Air Batteries, Small
15 (28) (2019) 1901518, https://doi.org/10.1002/smll.201901518.
Shujit Chandra Paul, Shaikat Chandra Dey, Md. Ashraful Islam Molla et al.
[136] J. Cao, X. Chen, H. Li, J. Pu, L. Liu, L.i. Ma, K. Zhou, Z. Zhang, Q. Wei, F. Luo, A Co/
CoO hybrid rooted on carbon cloth as an efficient electrocatalyst for the
hydrogen evolution reaction in alkaline solution, Sustainable Energy Fuels 4 [142]
(4) (2020) 1924–1932, https://doi.org/10.1039/C9SE01128E.
[137] Y.u. Lin, Z. Yang, D. Cao, Y. Gong, Electro-deposition of nickel–iron
nanoparticles on flower-like MnCo2O4 nanowires as an efficient
bifunctional electrocatalyst for overall water splitting, CrystEngComm 22 [143]
(8) (2020) 1425–1435, https://doi.org/10.1039/C9CE01921A.
[138] Y.u. Lin, J. Wang, D. Cao, Y. Gong, Hierarchical self-assembly of NiFe-LDH
nanosheets on CoFe2O4@Co3S4 nanowires for enhanced overall water
splitting, Sustainable Energy Fuels 4 (4) (2020) 1933–1944, https://doi.org/
10.1039/C9SE01300H. [144]
[139] J. Wang, Z. Yang, M. Zhang, Y. Gong, Vertically stacked bilayer heterostructure
CoFe2O4@Ni3S2 on a 3D nickel foam as a high-performance electrocatalyst for
the oxygen evolution reaction, New J. Chem. 44 (4) (2020) 1455–1462,
https://doi.org/10.1039/C9NJ05077A. [145]
[140] D. Li, J. Lao, C. Jiang, Y. Shen, C. Luo, R. Qi, H. Lin, R. Huang, G.I.N. Waterhouse,
H. Peng, Heterostructured MoS2@Bi2Se3 nanoflowers: A highly efficient
electrocatalyst for hydrogen evolution, J. Catal. 381 (2020) 590–598,
https://doi.org/10.1016/j.jcat.2019.11.039. [146]
[141] J. Ren, H. Zong, Y. Sun, S. Gong, Y.u. Feng, Z. Wang, L.e. Hu, K.e. Yu, Z. Zhu, 2D
organ-like molybdenum carbide (MXene) coupled with MoS2 nanoflowers
enhances the catalytic activity in the hydrogen evolution reaction,
24
View publication stats
Polyhedron 193 (2021) 114871
CrystEngComm 22 (8) (2020) 1395–1403, https://doi.org/10.1039/
C9CE01777A.
J. Sun, F. Tian, F. Yu, Z.e. Yang, B.o. Yu, S. Chen, Z. Ren, H. Zhou, Robust
Hydrogen-Evolving Electrocatalyst from Heterogeneous Molybdenum
Disulfide-Based Catalyst, ACS Catal. 10 (2) (2020) 1511–1519, https://doi.
org/10.1021/acscatal.9b03030.s001.
J. Gao, X. Tang, P. Du, H. Li, Q. Yuan, G. Xie, H.-J. Qiu, Synergistically coupling
ultrasmall PtCu nanoalloys with highly porous CoP nanosheets as an
enhanced electrocatalyst for electrochemical hydrogen evolution,
Sustainable Energy Fuels 4 (5) (2020) 2551–2558, https://doi.org/10.1039/
C9SE01182J.
V.S. Sapner, P.P. Chavan, B.R. Sathe, L-lysine Functionalized Graphene Oxide
as Highly Efficient Electrocatalyst for Enhanced Oxygen Evolution Reaction,
ACS Sustainable Chem. Eng. (2020), https://doi.org/10.1021/
acssuschemeng.9b06918.
F. Xiao, Z. Chen, H. Wu, Y. Wang, E. Cao, X. Lu, Y. Wu, Z. Ren, Phytic acid-
guided ultra-thin N,P co-doped carbon coated carbon nanotubes for efficient
all-pH electrocatalytic hydrogen evolution, Nanoscale 11 (47) (2019) 23027–
23034, https://doi.org/10.1039/C9NR07362K.
C.-Y. Chan, C.-H. Chang, H.-Y. Tuan, Colloidal synthesis of porous red
phosphorus nanoparticles as a metal-free electrocatalyst for the hydrogen
evolution reaction, Chem. Commun. 56 (19) (2020) 2937–2940, https://doi.
org/10.1039/D0CC00543F.