Coordination Chemistry Reviews 474 (2023) 214864

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

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

Review

Water splitting performance of metal and non-metal-doped transition

metal oxide electrocatalysts
Ahmed H. Al-Naggar a, Nanasaheb M. Shinde b, Jeom-Soo Kim b, Rajaram S. Mane a,⇑
a
School of Physical Sciences, Swami Ramanand Teerth Marathwada University, Nanded, India
b
Department of Chemical Engineering (BK21 FOUR), Dong-A University, 37 Nakdong-daero, Saha-gu, Busan 49315, Republic of Korea

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

Article history: Transition metal oxide electrocatalysts have received significant research interest toward the advance-
Received 22 July 2022 ment of environmentally acceptable electrochemical applications and systems, which are considered
Accepted 19 September 2022 to be promising technologies due to their unique physicochemical properties like low cost, robust dura-
Available online 12 October 2022
bility, structural flexibility, and tunable activity. However, transition metal oxide-based electrocatalysts
suffer from poor electrocatalytic activity as well as a limited number of active sites, which result in the
Keywords: obstruction of their applications over the world. To overcome these challenges, heteroatom-doping into
Electrochemical water splitting
transition metal oxide electrocatalysts has been a crucial and rapid way to improve the conductivity of
Transition metal oxides
Metal and non-metal-doping
the catalytic centers and optimize the adsorption of the reactants and intermediates during the catalytic
Electrocatalysts process, and hence, their electrocatalytic activity, which has become widespread in nanomaterials, is
offering the possibility to select the catalytic properties with attractive traits for a specific application
to some extent. We have critically and systematically discussed the recent progress on doping strategy
involves non-noble metallic elements, such as Fe, Co, Mn, Ni, Ru, Mo, W, Cu, etc., and non–metallic ele-
ments, such as S, N, P, B, Se, F, C, etc., in transition metal oxide-based electrocatalysts for water splitting
performance to gain a better understanding of the relationship between effect of heteroatoms doping
engineering techniques and TMOs catalytic properties. Most importantly, doping, elemental incorpora-
tion and alloying perform a significant role with heteroatoms for improving the catalytic activity on;
modifying the electronic configuration of the catalysts, increasing the number of active sites, enhancing
the electrical conductivity, and inducing synergistic effect of the transition metal oxide-based electrocat-
alysts during overall water splitting process. We here also have briefly described the techniques used for
preparing metal and non-metal-doped transition metal oxide-based electrocatalysts for overall water
splitting process. In nutshell, this review is expected to provide a deeper insight on the effect of the metal
and non-metal-doping in transition metal oxide-based electrocatalysts for the rational design of
high-performance catalysts in the future. We also have provided the current challenges and future
perspectives of heteroatom-doped transition metal oxide-based electrocatalysts for the development of
high-performance water splitting processes.
Ó 2022 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Electrochemistry of the water splitting process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.1. Overview of the electrocatalytic water splitting mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.2. Fundamentals of the OER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3. Fundamentals of the HER . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3. Electrochemical water splitting electrocatalysts: A short overview on the evaluation parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.1. Overpotential & Tafel slope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.2. Faradaic efficiency test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

⇑ Corresponding author.
E-mail address: rajarammane70@srtmun.ac.in (R.S. Mane).

https://doi.org/10.1016/j.ccr.2022.214864
0010-8545/Ó 2022 Elsevier B.V. All rights reserved.
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

3.3. Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.4. Turnover frequency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.5. Electrochemical impedance spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
3.6. Electrochemical surface area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4. Techniques used for obtaining heteroatoms-doped TMO-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.1. Hydrothermal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.2. Solvothermal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.3. Ion-exchange . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
4.4. Electrodeposition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.5. Air calcination & plasma treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.6. Precipitation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
4.7. Spray pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5. Doping, elemental incorporation and alloying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
5.1. Elemental incorporation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
5.2. Alloying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
6. Effect of metal and non-metal-doping engineering strategy for transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.1. Modulating the electronic structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.2. Regulating the active sites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.3. Enhancing the electrical conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
6.4. Inducing powerful synergistic effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7. Metal and non-metal-doped transition metal oxide electrocatalysts: Synthesis and catalytic performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.1. Metal (cation)-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
7.1.1. Fe-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
7.1.2. Co-doped transition metal oxide electrocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7.1.3. Ni-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
7.1.4. Mn-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
7.1.5. Mo-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
7.1.6. Cu-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
7.1.7. Ru-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
7.1.8. W, Zn, Ag, and Ce-doped transition metal oxide-based electrocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
7.2. Non-metal (anion)-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
7.2.1. N-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
7.2.2. P-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
7.2.3. B-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7.2.4. S-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7.2.5. Se-doped transition metal oxide-based electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.2.6. Carbon-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
7.2.7. F-doped transition metal oxide electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.3. Anion
cation dual-doped transition metal oxide electrocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
8. Conclusions and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Declaration of Competing Interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

1. Introduction tion reaction (HER), which involves the recombination of protons

Energy generation, storage, and transportation are essential
needs due to the ever-increasing global population followed
warming. Nowadays, the development of clean and durable energy
systems is an extremely important topic due to an increased global
energy consumption and its associated environmental damage.
Nevertheless, their use is often limited by geographic and temporal
intermittences. Consequently, there is an urgent need to find
renewable and sustainable energy resources that can alleviate
these concerns, while sustaining ultra-long-term growth. Fig. 1
shows the potential sustainable pathways for the generation of
key chemicals and fuels, such as hydrogen, hydrocarbons, oxy-
genates, and ammonia, by either substituting or complementing
traditional power generation. Electrochemical water electrolysis
is the most encouraging energy source for addressing future energy
shortages and pollution. In various green technologies, electro-
chemical water splitting (EWS) is considered to be a good method
to produce pure hydrogen quickly and an indirect way to supply
electrical energy from intermittent sources in the form of chemical
fuels, such as H2 and O2 [1–7]. This includes two half-reactions
related to the electrochemical reactions occurring in the elec-
trolyte, namely, oxidation and reduction; a) The hydrogen evolu-
and electrons on the cathode and b) the oxygen evolution reaction
(OER), which involves water being split into oxygen gas and pro-
tons and electrons at the anode, which result in total water split-
ting [8]. Fig. 2 shows both half-reactions in the process include
multi-electron transport on intermediates that vary depending
on the pH conditions; the simplest explanation for the EWS to form
H2 and O2 involves neutral conditions, which are necessary to
obtain the hydrogen needed to power the energy source from a
sustainable source. In principle, EWS demands a voltage of
1.23 V, but in practice > 1.8 V is required to overcome the reaction’s
activation barrier. Both reactions are kinetically slow and demand
overpotential (g) to occur at a practical ratio, even with the best
catalysts available. A greater applied potential is usually needed
in the real water electrolysis process since it includes complicated
electron and ion transfer mechanisms, resulting in slow kinetics
and poor fuel cell efficiency [9–14]. Electrocatalysts are a type of
catalyst used in electrochemical processes that can improve the
rate of these chemical reactions by enabling electron transport
between the electrodes, the reaction conditions, or transfer of the
intermediates without being involved in the reaction mechanism
[15]. In particular, during the electrolysis of water, some unfavor-
able electrode material properties, such as overpotential and ion

2
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 1. The future of sustainable energy. A schematic representation of the landscape of sustainable energy sources based on electrocatalysis. Reproduced with permission
from ref. [4] (Copyright Ó 2017, Science).
Fig. 2. A schematic representation of a water electrolyzer showing the two-half
reactions under acidic and alkaline/neutral conditions. Reproduced with permission
from ref. [9] (Copyright Ó 2019, John Wiley and Sons).
and gas dispersion, and device variables, such as solution concen-
tration, wire and electrode resistance, electrolyte dispersion block-
age, bubble formation, and heat release, should be taken into
consideration [16]. The key criteria for a highly active electrocata-
lyst include; a) high intrinsic catalytic properties, b) numerous
active sites, c) high electrical conductivity, and d) chemical and
electrochemical stability, which are based on the fundamental
water-splitting mechanism [17]. Efficient electrocatalysts must
reduce the input voltage required due to the large thermodynamic
barrier and slow kinetics of the reactions [18]. In most cases, the
overpotential loss caused by the OER is substantially larger than
the loss caused by the HER [19]. It is preferable to integrate the
OER and HER catalysts in an acidic and alkaline solution to achieve
3
Coordination Chemistry Reviews 474 (2023) 214864
total water electrolysis in integrated polymer electrolyte mem-
brane electrolysis [20]. Electrocatalysts, several non-precious cata-
lyst using noble metal-based materials, such as Pt, Ir, Ru, etc., have
been recently discovered to exhibit enhanced activity and perfor-
mance (i.e., efficiency, durability, stability, activity, and product
selectivity), which include little or non-noble metals. Nonetheless,
they are expensive and the finite reserves of noble metals on earth
hamper their widespread utilization in the water splitting process.
Due to their scarcity and high cost, their widespread commercial
applications are extremely limited. Consequently, a tremendous
amount of work has been carried out toward the discovery of
highly efficient non-precious metal-based catalysts suitable for
the water splitting reaction. Alternatively, HER and OER catalysts
based on transition metal atom-doped carbon-based materials
have been designed, synthesized, and described, making total
water splitting more practical. This implies that the effective and
long-lasting catalysts currently used in these reactions should be
improved. In addition, some of these catalysts even outperform
conventional noble metal electrodes in terms of their catalytic
activity. They are low-cost, highly active, highly-scalable, chemi-
cally stable, and mechanically robust under oxidizing circum-
stances. Transition metal-based electrocatalysts, including non-
noble oxides/hydroxides, carbides, phosphides, sulfides, selenides,
and other non-precious transition metal-based electrode materials
as well as their composites with conductive substrates or scaffolds,
have been developed and successfully applied with high catalytic
activity and long-term stability in the water splitting process.
Due to their availability, high catalytic activity, and ease of access,
transition metals have made a substantial contribution to the cre-
ation of improved electrocatalysts [11,12,15–17,21–36]. Nowa-
days, scholars have concentrated their efforts on the
development and use of transition metal-based total water-
splitting catalysts. Their derivatives have also been extensively
reported as alternatives to obtain improved electrocatalytic perfor-
mance due to their strong intrinsic activity, electron transport,
mass transfer mechanism, and mechanical stability [12,22,37–
41]. Therefore, transition metals are good electrocatalysts used
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
for a wide range of chemical processes due to their partially filled
d-orbitals and capacity to accept/donate electron density towards
and away from the substate. Transition metals (either atoms or
ions) can effectively catalyze electron transport processes via
switching between their various oxidation states. They can also
catalyze other sorts of reactions by boosting the dissociation of
reactant molecules upon aiding the bond cleavage reactions [42–
47].
Earth-abundant 3d-transition metal oxides have stimulated
great interest among the emerging alternative systems reported
to date. Ideally, utilizing the benefits of both HER and OER electro-
catalysts to develop and construct effective bifunctional electrocat-
alysts for total water splitting is a promising strategy that not only
improves the catalytic performance, but also simplifies the system,
reducing the overall cost [4,16,48–54]. Recently, transition metal
oxides such as Co3O4, CoO, NiO, MnO2, MoO, CuO, Cr2O3, Fe2O3,
SnO2, ZrO2, and WOx, and other metal oxides have extensively been
used in water splitting applications [50,55–57]. Typically, a high
electrocatalytic activity for total water splitting has been demon-
strated using heteroatom-doped metal oxide materials. Every
day, at least one research paper on transition metal oxide catalysts
publishes in the literature, providing fresh insights on OER and
HER catalysts or describing novel electrocatalysts. The histogram
below depicts the recent and rapid growth in the number of
reports, which has rapidly increased overthe last decade in the
field of electrocatalysis as well as transition metal oxide catalysis
(Fig. 4b). However, there is still a gap for industrial requirements
in terms of the catalytic efficiency despite the fact that some metal
oxides demonstrate good electronic conductivity, robust durabil-
ity, and ultra-high stability; the majority of metal oxides exhibit
poor electronic conductivity, limited metal sites, unmatchable
electronic topologies, inadequate choice, high cost, and shortage
of resources, low specific surface area, and low stability. Conse-
Fig. 3. A schematic representation of the fabrication strategies of doped noble metal-based electrocatalysts as well as the effects of dopants on electrocatalytic activity and
stability. Reproduced with permission from ref. [62] (Copyright Ó 2021, John Wiley and Sons).
4
Coordination Chemistry Reviews 474 (2023) 214864
quently, more emphasis should be placed on improving the elec-
trocatalytic activity of noble metal nanomaterials [24,28,58–60].
Therefore, doping has recently emerged as a fascinating method
to modify the properties of nanomaterials [48,61]. The modifica-
tion of catalysts using foreign elements and their compounds is
well recognized as a dependable method to modify the intrinsic
structures, surface properties, and catalytic performance of nano-
materials with current research focused on this area [62]. There-
fore, Fig. 3 depicts the fabrication strategies of doped noble
metal-based electrocatalysts as well as the effects of dopants on
electrocatalytic activity and stability. First-row non-noble transi-
tion metals as non-noble (Fe, Ni, Co, Mn, Cu, etc.) metal compounds
with heteroatoms have the potential to change the electronic
structure, increase electrical conductivity, improve hydrogen
adsorption energy, and increase the number of active sites in order
to modulate the catalytic characteristics toward overall water
splitting [31,61–74]. Meanwhile, non-metal heteroatom doping
in carbon materials, such as N, Se, F, P, S, B, and C with various elec-
tronegativity, can act as intermediate active sites for the HER and
OER, and may alter not only the surface chemical composition,
but also the electrondensity of carbon nanotubes, resulting in an
improved electrochemical performance [8,31,75,76].
The nitrogen-, carbon- and phosphorous-carbon bonds in these
catalysts can function as electroactive sites for the OER or HER in a
unique way [47]. Recently, doping techniques used for carbon-
based materials, such as non-metal N- and P-doping, have achieved
improved electrocatalytic performance in the OER and HER [16].
Therefore, doped metal oxide nanomaterials have received sub-
stantial interest because of their unique properties followed appli-
cations in a variety of fields including water splitting,
supercapacitors, lithium-ion batteries, solar cells, and gas sensors
[56,64]. Doping-induced localized amorphization, which offers
more accessible active sites and more appropriate local chemical
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 4. a) Effect of heteroatom-doping on the transition metal oxide-based electrocatalysts in overall water splitting process using various configurations (left side). b)
Statistical histogram (right side) showing the research papers published using transition metal oxide and transition metal electrocatalysts on water splitting from 2013 to
2022. Source: Web of Science.
environments than their corresponding completely crystalline
structures, is primarily responsible for the increased catalytic
activity. Therefore, the link between amorphization and catalytic
properties can give fresh insight for an improvement in catalytic
activity [77,78]. Various techniques, such as morphological design,
interface construction, and defect construction, as well as the cre-
ation of single-atom active sites, have been recently addressed to
improve the catalytic performance of earth abundant transition
metal nanomaterials [28,62–84]. Due to the synergistic effects of
doping between cationic and anionic; co-doping have recently
received a lot of interest as a method to increase the catalytic per-
formance. The synergistic effects of the two dopants improve the
electrocatalytic activity along with the electrochemical stability
across a wide range of pH [45]. Thus, creating a variety of vacancies
in tailored nanomaterials is a promising strategy to enhance the
catalytic activity. Therefore, anion and cation doping may be effec-
tive approaches to improve the electrocatalytic performance.
Creating cationic, ionic vacancies from doping would then be a
low-cost option and universal approach to tune the electrocatalytic
performance of important various electrochemical reactions [67].
Doping can have a variety of effects on the electrocatalytic perfor-
mance including; a) the effect on the intrinsic catalytic properties
of the active sites in transition metal oxide electrocatalysts upon
introducing oxygen anion or cation vacancies, b) altering the local
electronic structure of the catalyst, leading to a narrow band gap
and thus, improved electrical conductivity, and c) adjusting the
adsorption energy and oxidation of metal oxide during the reac-
tion, in which an enhanced activity for the HER and OER can be
obtained. This doping engineering methodology has provoked
widespread interest from researchers due to the significant
advances in energy conversion and storage devices, including
water splitting, supercapacitors, and rechargeable metal-air batter-
ies, in order to expand the use of transition metal oxide-based elec-
trocatalyst materials in various sectors by providing more concepts
and methods for the synthesis of rationally constructed TMOs-
based catalysts [31,85,86]. The synergetic interactions of a doped
metal oxide catalyst with a normal or transition metal result in
increased catalytic activity for the HER and OER. In addition, sur-
face doping changes the optical, magnetic, electrical, and catalytic
properties of these materials [52]. Moreover, activation associated
with structural changes has been often observed during stability
tests for numerous electrocatalysts. In reality, in-situ electrochem-
ical activation approaches have been popular in recent years as a
way to improve the catalytic activity [77–82,87]. As a result, future
research may focus on a variety of topics, including reducing the
bandgap and increasing electrical conductivity upon doping with
5
Coordination Chemistry Reviews 474 (2023) 214864
additional metal ions, improving the interactions and increasing
the specific surface areas of 3D hierarchical nanostructures by
investigating the metal oxide interaction mechanism, and altering
the metal oxides between the metal and non-metal-doped metal
oxide-based electrocatalysts, and thus the chemical and electro-
chemical stability for total water splitting process [75]. Further-
more, for enhancing the electrochemical water splitting
performance extensive intrinsic activity, reduced reaction energy
barrier, optimizd hydrogen adsorption/desorption energy, and
fine-tuned surface properties of electrode materials are mandatory
[88].
Making use of these benefits, significant research attention has
been paid toward the construction of extremely low metal and
non-metal-doped transition metal oxide catalysts used for water
splitting. Many highly efficient electrocatalysts have been success-
fully developed to enhance the synergistic effects and increase the
number of active sites that increase the number of oxygen vacan-
cies, which enhance the catalytic performance in full water split-
ting process. Furthermore, the relationship between doping
engineering techniques and catalytic properties may offer a theo-
retical framework for the development of extremely efficient and
resilient multi-functional electrocatalysts for large-scale green
hydrogen production via sustainable water electrolysis. We here
begin by providing a quick overview of the fundamental electro-
chemistry of the water splitting process and certain evaluation
parameters. More importantly, the nature of doping engineering
has been provided by the material used: (cation doping)
metallic-based catalysts, (anion doping) non-metallic-based mate-
rials and (anion-cation dual doping) mixed-based transition metal
oxide electrocatalysts (see Fig. 4a for more details). We also have
described the preparation techniques used for obtaining metal
and non-metal-doped transition metal oxide-based electrocata-
lysts for overall water splitting process. Also, we have systemati-
cally summarized the most significant recent advances in metal
and non-metal-doped transition metal oxide catalysts for water
electrolysis. We have specifically emphasized the effects of
heteroatom-doping on the electrocatalytic performance of transi-
tion metal oxides by modulating the electronic structure, regulat-
ing the energy absorption of the intermediates on the active
sites, and enhancing the electrical conductivity for faster diffusion
kinetics for better performance in the overall water splitting
process.
This review aids scientists to design metal and non-metal-
doped transition metal oxide electrocatalysts for water splitting
activity using doping strategies, identifying the different types of
doped metal oxide electrocatalysts, and determining how to
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
improve their performance not only in electrocatalysis and energy
conversion/storage devices, but also in separation, sensors, and
other fields for future research. This review provides insights into
the process of designing and manufacturing innovative metal and
non-metal-doped transition metal electrocatalysts used in practi-
cal water splitting process with high performance and low cost.
2. Electrochemistry of the water splitting process
2.1. Overview of the electrocatalytic water splitting mechanism
The prototype electrolysis cell for water splitting using electro-
catalysis was initially suggested in 1789, consisting three parts; a)
an anode, b) a cathode, and c) an aqueous electrolyte. The process
involves two half-cell reactions at the cathode and anode, water
reduction and water oxidation, respectively, which are known as
the HER and OER, respectively. Different electrochemical reactions
taking place on the electrodes in different electrolytes are generally
the same [16,89–90].
Overall reaction
1 O þ OH
! HOO þ e

H 2 O ! H 2 þ O2 ð1Þ
2
In acidic electrolyte
Cathode; 2Hþ þ 2e
! H2 ; gc ¼ 0V ð2Þ
1
Anode; H2 O ! 2Hþ þ O2 þ 2e
; ga ¼ 1:23V ð3Þ
2 and highly time intense process as compared to the cathodic
In an alkaline or neutral electrolyte
Cathode; 2H2 O þ 2e
! H2 þ 2OH
; gc ¼
0:83V ð4Þ
1
Anode; 2OH
! H2 O þ O2 þ 2e
; ga ¼
0:40V ð5Þ
2
Regardless of the reaction media in which the total water split-
ting occurs, the predicted potential for water splitting is 1.23 V at
room-temperature (25 ℃) and under one atmosphere. The overpo-
tential (ga and gc) can be calculated using the standard hydrogen
electrode (SHE) as a reference to complete this task in real water
splitting. The excess potential (gO) is largely utilized in the cell
for water splitting on both the cathode and anode. However, a
greater potential than the thermodynamic potential is always
required to overcome the inherent activation barriers. As a result,
the practical operational potential (VOP) for the overall water split-
ting reaction can be expressed as follows;
Vop ¼ 1:23 V þ ga þ jgc j þ gX ð6Þ
where, g O is the additional overpotential, which is utilized to com-
pensate for the internal system resistance, such as solution and con-
tact resistance, and g a and g c are the overpotentials required to
overcome the inherent activation barriers at the anode and cathode
respectively. By utilizing highly active OER and HER catalysts, the
inherent activation barriers can be reduced. Therefore, the key
research challenge is to produce effective water splitting electrocat-
alysts, in which g a and g c are reduced and the water splitting per-
formance can be enhanced due to the use of inexpensive materials
and components [39].
2.2. Fundamentals of the OER
The OER involved in total water splitting is high on the list of
priorities in electrocatalytic fuel cells. Moreover, the OER is the
anodic reaction of the water splitting process and it is the most
energy-intensive step in the electrolysis reaction because of the
four-electron exchange that occurs in the anode reaction [39,91–
6
Coordination Chemistry Reviews 474 (2023) 214864
94]. Many research groups have hypothesized the mechanisms
for the oxygen release reactions at the anode under acidic and alka-
line conditions. There is more OH* available in the electrolyte,
which may be adsorbed immediately on the electrocatalyst, result-
ing in an OH* intermediate [54]. The mechanism of the OER is pre-
sented below (equations (7–14)) [39]:
OER in an acidic electrolyte:
H2 O þ  ! HO
þ Hþ þ e
ð7Þ
HO ! O þ Hþ þ e
ð8Þ
O þ H2 O ! HOO þ Hþ þ e
ð9Þ
HOO !  þ O2 þHþ þ e
ð10Þ
OER in an alkaline electrolyte:
OH
þ  ! HO þ e
ð11Þ
HO þ OH
! O þ H2 O þ e
ð12Þ
ð13Þ
HOO !  þ O2 þ H2 O þ e
ð14Þ
–
The OH* adsorbents then interact with another OH to make
H2O and a suitable O* intermediate, which subsequently react with
OH– to make HOO* by liberating O2 gas. Because this process
involves the transfer of four electrons, the OER is a more difficult
HER. The most frequently employed precious metal-based com-
pounds used in the actual application of the OER reported to date
involve Ir and Ru. They, like Pt, have a finite supply on Earth, neces-
sitating the creation of appropriate replacements [14]. However,
the scarcity and high cost of these catalysts preclude their large
scale use. Furthermore, the minimal value of the overpotential is
still predicted to be 0.2–0.4 V, indicating that the OER has slow
kinetics [95]. As a result, the improvement of non-noble metal cat-
alysts with high performance can be a priority for current research
in this area [96].
2.3. Fundamentals of the HER
For the widespread deployment of the water splitting reaction,
the best-performing Pt-based catalysts used for the HER are scarce
and expensive. As a result, the development of earth-abundant
homogeneous and heterogeneous alternatives to platinum is of
great importance. The overpotential to achieve a current density
of 10 mA cm
2, Faradaic efficiency for H2 generation and Tafel
slope are all significant parameters used to measure the perfor-
mance of HER catalysts. If a Pt replacement is to be attained, over-
potentials near the thermodynamic potential of the HER and
efficiencies around unity are obtained. The HER can undergo three
different reactions in an acidic electrolyte. There have been several
different catalytic processes proposed to date. The following are
the fundamental steps of the HER that occur on the catalyst surface
(equations (15)–(19)) [39]:
Acidic media; H3 O
þ e
þ  ! H þ H2 O Volmer step ð15Þ
Alkaline medium; H2 O þ e
þ  ! H þ OH
ð16Þ
Acidic medium; H þ H3 Oþ þ e
! H2 þ H2 Heyrovsky step ð17Þ
Alkaline medium; H þ H2 O þ e
! H2 þ OH
ð18Þ

On the Tafel : H þ H ! H2 ð19Þ
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
For the HER, the most common mechanisms are the Volmer–
Tafel and Volmer–Heyrovsky, which are specified by the relative
ratio of each reaction. As a result, the catalytic performance of
the HER can be increased by adjusting the binding strength of
the adsorbents, such as H* or OH–, which is directly related to
the adsorption strength and catalytic reaction using the rational
design of the electrocatalyst [90]. A higher electrode reaction rate
is indicated by a lower Tafel slope. Catalysts with quick electrode
reaction dynamics must have the following structural and morpho-
logical features; a) high specific surface area and well-developed
pore structure with a high number of active sites for better mass
transfer, b) high electrical conductivity for rapid electron transfer,
c) high hydrophilicity, which helps the reactants come in contact
with the catalyst surface, d) enhanced morphology with more
active sites, such as oxygen vacancies, and e) multi-component
synergism to maximize the adsorption free energy to speed up
the process [97]. As a result, the development of highly-efficient
alkaline HER electrocatalysts to couple with OER catalysts in alka-
line solutions for effective total water splitting process is critical
[89].
3. Electrochemical water splitting electrocatalysts: A short
overview on the evaluation parameters
A perfect HER–OER performance for total water electrolysis is
one that is inexpensive, effective, and stable in a similar elec-
trolyte. The performance of an electrocatalyst can be evaluated
using a variety of kinetic parameters including the overpotential,
Tafel slope, and current density, as well as the turnover frequency,
stability, and Faradaic efficiency.
3.1. Overpotential & Tafel slope
In any electrolyte used for the water splitting reaction, the ther-
modynamic equilibrium potentials are 0 V vs. reversible hydrogen
electrode (RHE) for the HER and 1.23 V vs. RHE for the OER. To
overpower the high thermodynamic energy barrier for total water
splitting requires an ultra-high overpotential (g). The overpotential
is the term used for these excess potentials. The activation, concen-
tration, and resistance overpotentials are the three types of over-
potential that contribute to the overall value. Different
techniques are employed to reduce these overpotentials. The acti-
vation overpotential of the catalyst can be significantly reduced by
selecting an appropriate catalytic material. Stirring the solution
during an electrochemical test can help to lower the concentration
overpotential. The resistance overpotential can be manually with-
drawn from the original data by multiplying the current density
and resistance acquired from the Nyquist curve or using IR com-
pensation direct from the electrochemical workstation [90,96].
Another key measure that shows the kinetics of water splitting
(HER, OER) is the Tafel slope (b). The Tafel slope is the growing rate
of overpotential (g) in corresponding current density calculated
from the Tafel equation (Equation (20)).
g ¼ b log jjj þ a ð20Þ
where, g is the overpotential, b is the Tafel slope value, j is the cur-
rent density, and a is a constant [6,26]. A smaller Tafel slope sug-
gests a rapid increase in current density with increasing
overpotential, indicating quick HER, OER kinetics of the
electrocatalyst.
3.2. Faradaic efficiency test
The Faradaic efficiency refers to the efficiency of electron trans-
fer provided by the external circuit to promote the electrochemical
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Coordination Chemistry Reviews 474 (2023) 214864
reaction in which the electrons participating in the reaction (i.e.
HER or OER) are utilized. It is the ratio between the amount of
gas collected in the experiment and the amount calculated using
theoretical calculations [71]. Gas chromatography (GC) or the
water displacing method can be used to directly measure the gen-
eration of the target gas (i.e. H2 or O2). The Faradaic efficiency in
the HER refers to the efficiency in which the electrons supplied
by an outside circuit are transferred to power the HER. Faradaic
losses can occur when heat or by-products of the electrode reac-
tion are created. Theoretical and practical levels of H2 production
are required to assess the Faradaic efficiency. Integration can be
used to compute the theoretical hydrogen generation from gal-
vanostatic or potentiation electrolysis. At the same time, GC or
the water–gas replacement approach can be used to determine
the practical hydrogen production capacity [90–91,97].
3.3. Stability
Another key parameter for catalysts is the stability. Either cyclic
voltammetry (CV) or electrolysis are used to determine the cat-
alytic stability (galvanostatic or potentiation electrolysis). CV can
also be used to accelerate catalytic deterioration for analysis and
is often performed for the HER over thousands of cycles and the
OER over hundreds of cycles [84]. The stability of the catalyst is
shown by a shift in the onset overpotential. For a stable system this
shift will be low. When galvanostatic or potentiostatic electrolysis
is used for stability testing, it is usually performed for at least 12 h.
The duration can range from a few hours to dozens of hours with a
longer period indicating greater stability [96,97].
3.4. Turnover frequency
The turnover frequency (TOF) is commonly used to assess the
intrinsic catalytic activity at each catalytic site. Due to the multiple
atoms in the catalyst with different catalytic activity, this TOF cal-
culation method cannot provide an exact TOF value. The TOF (s
1)
value may be computed using the following formula:
TOF ¼ ðjAÞ= ðaFnÞ ð21Þ

2
where, j (mA cm ) denotes the samples current density at a partic-
ular potential during linear sweep voltammetry measurements, A is
the working electrodes surface area, a represents the electron num-
ber of the catalyst and the target products electron number (elec-
trons/mol), F is Faraday’s constant (96485.3 C mol
1), and n is the
number of moles (mol) of metal elements on the electrode com-
puted from m (g) divided by the catalysts molecular weight (M;
gmol
1) [26]. The TOF demonstrates the intrinsic activity of each
electrocatalytic site in the catalyst, although getting an exact TOF
value is challenging due to the difficulties in determining the elec-
trocatalytic sites present in the catalyst [93]. Nonetheless, evaluat-
ing the catalytic activity of similar electrocatalytic water splitting
materials is still regarded an efficient and significant technique.
3.5. Electrochemical impedance spectroscopy
Electrochemical impedance spectroscopy (EIS) is a powerful
instrument for determining the electrochemical properties of cata-
lysts, surfaces, interfaces, coatings, and other materials. The EIS
measurement in several fields of energy research considers cur-
rent, potential, and charge determine performance. One such sec-
tor focusing on generating high purity hydrogen is
electrocatalytic water splitting, where EIS is utilized to correlate
performance behavior by monitoring charge transfer resistance
(Rct) [98]. Moreover, EIS is a technique used for characterizing
energy storage and conversion materials at different frequencies
in order to explore the electrochemical kinetics and conductivity
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
of various catalysts [99,100]. The charge transfer resistance, calcu-
lated from the high frequency region, is determined by the radius.
The smaller the radius the faster the reaction rate [101]. As a result,
EIS is a very adaptable approach that may be used to investigate
metal oxide electrodes in a wide range of energy applications.
The frequency dependency of essential circuit elements utilized
to characterize current flow over the metal oxide interface is a
major aspect of this measurement. The ability to model EIS data
to well-supported equivalent circuits is crucial for obtaining phys-
ically relevant information [102].
3.6. Electrochemical surface area
Electrochemical surface area (ECSA) is another key parameter
that strongly influences the electrocatalytic behavior [103]. Elec-
trochemical double-layer capacitance, which is linearly propor-
tional to ECSA, is well-accepted to be an effective criterion to
evaluate the ECSA of electrocatalysts. In connection to this, estima-
tion of the electrode ECSA is particularly important for evaluating
the performance of the catalyst [104]. One of the most commonly
employed ECSA estimation methods is measuring CV in the non-
faradaic regions at various scan rates [105].
Typically, the non-faradaic region is a potential window of 0.1 V
centered at the open-circuit potential of the system. A plot of the
charging current as a function of the scan rate yields a straight line
with a slope equal to the electrochemical double layer capacitor.
Generally, a specific double-layer capacitance (Cs) of 40 lF cm
2
is employed for a smooth flat metal surface, and the ECSA-
normalized LSV curves.
ECSA ¼ C dl =Cs ð22Þ
where, Cs is the specific capacitance (SC) with the normalized value
of 40 lF cm
2 for transition metal-based materials in 1 M KOH. The
double-layer capacitance was also measured using EIS in the same
non-Faradaic region [106–110].
4. Techniques used for obtaining heteroatoms-doped TMO-
based electrocatalysts
Doping techniques in TM are primarily classified into metal
doping like Fe, Co, Ni, Mn, W, Mo, and so on and non-metallic ele-
ment doping like N, P, B, S, Se, C, Te, etc. However, synthetic tech-
nique plays a critical role in controlling shape, phase composition,
and particle size of the prepared nanostructure. Furthermore, due
to sustainable development in nanotechnology, several eco-
friendly, low-cost and large-scale production methodologies have
been utilized for obtaining metal and non-metal-doped transition
metal oxides. Several doping approaches including the hydrother-
mal, solvothermal, co-precipitation, electrodeposition, thermal
treatment, and ion exchange, spray pyrolysis, air/vacuum calcina-
tion at high temperatures & plasma treatment etc., are being used
to accomplish non-metal-doped TMOs as electrocatalysts for water
splitting application. In this section, the most common approaches
used for producing metal and non-metal doped TMO-based elec-
trocatalysts toward water splitting performance are briefed mostly
with a purpose for helping new researchers to choose the best
appropriate and easy doping synthesis method for their interest.
4.1. Hydrothermal
A hydrothermal method is a basically chemical reaction taking
place in water or organic solvents as reaction medium at suitable
temperature and moderate pressure in a sealed pressurized vessel
[19,52]. Moreover, being one of the effective strategies for metal
and non-metal-doping it has been extensively utilized for con-
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Coordination Chemistry Reviews 474 (2023) 214864
structing ultralow metal and non-metal-doped transition metal-
based electrocatalysts. This method has several advantages such
as simplicity, universality, and flexibility in controlling the compo-
sition and morphology of the product material. The key of this
method to obtain high-performance catalysts is to choose appro-
priate precursor i.e. metal salt and non-metal source, and the reac-
tion conditions such as temperature, concentration, reaction time,
pH and so on [82,108,111–113]. For instance, as is known to all, the
hydrothermal method is favorable for the construction of low-
dimensional nanocatalysts, such as 1D nanowires and 2D
nanosheets. On choosing appropriate amount of heteroatom-
containing precursor, the chemical composition of TMOs can be
altered with a homogeneous distribution of dopants. Through
adjusting the types of precursors or changing the reaction temper-
ature, a variety of dopants including cations and anions can be
incorporated for obtaining different nanostructure of desired prop-
erties. Hydrothermal method provides many significant advan-
tages over other conventional and non-conventional synthetic
methods for the production of metal and non-metal-doped transi-
tion metal oxide-based electrocatalysts. Over the past decade,
many advanced metal and non–metal-doped transition metal
oxide electrocatalysts are being developed via the hydrothermal
method.
4.2. Solvothermal
The solvothermal method is very similar to the hydrothermal
method except that an organic solution (non-aqueous) is a reaction
media in sealed autoclave instead of water [112,114]. In this
method, the operation temperature is above the critical point of
the solvent so that the pressure is too high. Ethanol, ethylene gly-
col, isopropanol, polyethelene glycol, tertiary butanol, and
dimethylformamide etc., are commonely preferred solvents for this
method [82,111,115]. In this method, easily decomposed metal
and non-metal precursors are used to produce active gases with
transition metal oxides. It is well-known that the morphology,
phase, and structure of the product nanostructures can be regu-
lated by varying the pH, temperature, and solvent. Therefore, the
reaction between TMO-based catalysts and active gases in the
solvothermal method is milder. Benefitting from the multiple mer-
its, solvothermal method, one of the versatile effective strategies
for heteroatoms doping, has also been applied for the fabrication
of metal and non-metal-doped TMO-based electrocatalysts.
4.3. Ion-exchange
Ion exchange refers to the exchange of ions (cations or anions)
between the solution and solid particles, which can be used to con-
trol the composition of the product material by allowing the rapid
replacement of ions in parent materials without changing their
original size and morphology [82,113,115]. Benefitting from the
multiple merits, the ion-exchange method has extensively been
researched and utilized for the construction of ultralow metal
and non-metal-doped transition metal oxides. On the one hand,
the introduced metals and non-metal metals could greatly enhance
the electrocatalytic performance by tailoring the electronic proper-
ties and adsorption energy of intermediates, and increasing the
surface active sites of the electrocatalysts. On the other hand, the
ion-exchange method is favorable for the preparation of hollow
transition metal oxide nanostructures which can provide plenty
of structural merits toward electrochemical reactions, including
high specific surface area and rich electron transfer channels. Bear-
ing these considerations in mind, a large number of researchers
have focused on the fabrication of metal-doped hollow transition
metal oxide nanocatalysts via a facile ion-exchange method. This
method is also appropriate for cation exchange reactions, which
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
involve the direct replacement of cations without the use of a sec-
ondary phase, stoichiometric control, or impurities. Specifically, in
the case of dual or multiple atomic incorporation, particularly co-
doping with both cations and anions, the post doping strategy
has widely been used to modulate the structures of heteroatoms-
doped TMO catalysts.
4.4. Electrodeposition
Electrochemical deposition is one of the most efficient and cost-
effective methods for creating metal-based nanomaterials for
energy storage and conversion applications [19,112,113]. The main
advantages of the electrodeposition method include requirement
of a short synthesis time at room-temperature and under normal
pressure, vacuum-free, inexpensive and use of limited instruments.
Selecting appropriate parameters desired product with exepected
moprhology can be obatined. Most importantly, this method is a
binder-free method for producing electrodes with high electrocat-
alytic activity [52,116]. For example, the as-obtained monotonous
nanostructures limit the number of exposed active sites. To pro-
mote electrocatalytic reaction kinetics, it is critical to use novel
and simple method to synthesize metal and non-metal-doped
transition metal oxides.
4.5. Air calcination & plasma treatment
Chemical compounds e.g., NaH2PO2, (NH4)2CO3, CH4N2S that
breakdown quickly to active gases e.g., PH3, NH3, and H2S are fre-
quently used as non-metal precursors which often put upstream
of TM-based nanomaterials to allow the aforementioned active
gases to completely react with them. This process relies heavily
on the calcination temperature and time. This is due to the fact that
too high a temperature and too long a period may cause the crystal
phase of TM-based nanomaterial’s to shift. For example, on doping
different non-metal elements into TM-based nanomaterials, differ-
ent calcination conditions, including calcination temperature and
duration, should be used. Plasma treatment is a more efficient
and environmentally friendly way for doping non-metals as
plasma treatment not only significantly decreases the doping per-
iod, even to several minutes, but also renders the doping conduct
at ambient temperature. Furthermore, post-synthesis thermal
treatments such as plasma treatment, thermal treatment with a
nitrogen (precursor) source, and hydrazine hydrate (N2H4) treat-
ment may result in surface doping [111,117]. However, non-
metal containing gases such as N2, NH3, H2S, and PH3 are always
considered as non-metal resources. The aforesaid gases are dis-
solved into active non-metal species after plasma treatment, and
these active species may easily react with metal species, resulting
in non-metal element doping. Notably, the plasma treatment can
cause flaws in metal-based nanomaterials during non-metal dop-
ing process. Also, the template-assisted technique is a popular
way for fabricating three-dimensional (3D) nanostructured cata-
lysts, and it is a dependable method for synthesizing well-
ordered nanomaterials through preparing the original templates,
inserting the target precursors into the templates, and removing
the templates steps [19,118].
4.6. Precipitation
The precipitation process involves precipitating the active ele-
ments of raw materials by a chemical reaction, followed by filter-
ing, washing, drying, and roasting to develop nanostructures. The
precipitation technique is appealing due to its inexpensiveness,
flexibility, gentle reaction conditions, and a large area deposition.
Because of its simplicity and convenience of mass scale production,
the homogeneous co-precipitation approach has been widely used
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Coordination Chemistry Reviews 474 (2023) 214864
for the manufacture of metal and non-metal-doped TMOs [82,85].
Similarly, when selections of the precursors are substituted with
foreign dopants, this approach is ideal for the production of
heteroatom-doped TMOs. TMOs with uniform doping distributions
may be produced under proper reaction conditions by simply vary-
ing the kinds and concentrations of used precursors.
4.7. Spray pyrolysis
Spray pyrolysis, being simple, effective, highly scalable, and sui-
ted for on-line continuous production, holds a great promise for
the logical design and synthesis of a wide range of useful nanos-
tructured materials with tailored shapes [119–122]. Spray pyroly-
sis is a rapid and relatively low-cost technique that has been
widely used to produce large area metal and non-metal-doped
metal oxide catalysts. It has potential of mass scale production
for various industries in the future (see section 7, there are more
notable examples about this methods for preparation of metal
and non-metal- doped transition metal oxide-based electrocata-
lysts for water splitting application).
5. Doping, elemental incorporation and alloying
These terms are very broad. Logically, doping proportion must
be less than 10% and one has to take in account the ionic radius dif-
ference between the doped cations or anions and cation/anion of
host material. Doping, elemental incorporation, addition (alloying),
and substitution are general practices used to change the electrical,
optical, magnetic etc., properties of a host matrix material by add-
ing guest material in suitable proportion so called synergistic effect
in application of interest. Doping allows atoms of doped elements
to be incorporated in the lattice sites of host material without dis-
turbing its lattice planes by considering internal and external
strain factors. Interstitial doping and substitutional doping are
two major categories for classifying doping of carbonaceous mate-
rials, metal hydroxides/oxides/halides, polymers, metal chalco-
genides, and MXenes etc. In the interstitial doping, the dopants
are located in the spaces between the atomic levels of the lattice
and ionic radius of dopent. In principle, size of dopen should be
smaller/equal to that of the host material. When a element is intro-
duced into a material at a certain atomic position then this process
is known as substitutional doping (namely the dopant). This is
because doping can change the lattice structure of the host mate-
rial. Dopants are impurities that have the same/lower atomic sizes
as that of the host atoms but either a higher or lower valency.
Dopants with atomic sizes smaller than those of the host lattice
can occupy the interstitial positions in the lattice, leading to gener-
ate impurity levels in the energy gap which potentially act as
recombination centers. However, these dopants are not stable.
They may be distortions, defects, or disorders in the host lattice.
If the dopant atom size is bigger than the host atom size the dopant
atoms replaces one or more host atoms and may create deforma-
tions or stacking faults within the crystal structure
[117,123,124]. In nutshell, doping means the introduction of differ-
ent metallic or non-metallic impurities into a host crystal structure
to gain definite modifications in the conductivity, morphology, and
bang gap energy followed performance (for device case). Control-
ling conductivity, band gap and electron band structure i.e. posi-
tions of valance and conduction bands or highest occupied and
lowest occupied molecular orbitals (HOMO and LUMO) can be
obtained by hetero-atom doping for enhanced performance
[125]. For example an ionic radius of oxygen in ZnO is 0.140 nm
and Zn has 0.074 nm. As ionic radius of sulfur is 180 pm, sulphur
with CdS (size of Cd is 158 pm) can easily be doped into ZnO by
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
decreasing its band gap energy from 3.20 eV to 2.4 eV without
changing its crystal structure [126].
5.1. Elemental incorporation
The incorporation of heteroatoms like cations, anions, or both
has a vital impact on the material’s properties, which is reflected
in the enhancement of the catalytic activity in many applications
like magnetic, water splitting, and solar cells. Regulation of elec-
tronic structure through heteroatom incorporation represents
one of the most powerful strategies to enhance the HER and OER
performances [105,124,125,127–145]. The incorporation of other
transition metals can modify the lattice parameters and electron
density states of the metal catalyst to change the adsorption ener-
gies on the metal surface toward the optimal electrocatalytic activ-
ity [105]. Such as cation/anion incorporation has been extensively
adopted to modulate the adsorption states of reaction intermedi-
ates and the charge transfer properties, thus resulting in higher
electrocatalytic activity. In addition, elemental synergy could effec-
tively regulate the electronic structure of the active sites, thereby
improving the intrinsic activity towards HER and OER
[17,39,146–162]. The positive incorporation of active sites is bene-
ficial for tuning the electronic structure and increasing the concen-
tration of catalytically active sites. Incorporation of Ru into CoOx,
electrical structure can be drastically altered for improved binding
strength with oxygen-containing intermediates [163]. Incorpora-
tion of metal/non-metal ions may be within the lattice structure,
if ionic size is smaller or over crystal structure as like parasite, if
is comparable or higher. The RuMoCeOx with different Ru/Mo/Ce
ratios fabricated through pyrolysis strategy exhibited lower over-
potentials than RuMoOx compounds, suggesting the importance
of Ce incorporation. On the other hand, presence of Mo greatly
improved the electrocatalytic performance by electron redistribu-
tion [148]. The electrochemical incorporation of heteroatom Fe
into/over NixO nanosheets derived from in-situ electrochemical
oxidation on NiSe nanorod endowed enhanced OER activity
[164]. Theoretically, the incorporation of heteroatom like Fe into
Ni vacancy in NixO nanosheets leads to a preferable electronic
state, which significantly reduces the overpotential of the whole
reaction. The water-splitting cell displayed an exceptional durabil-
ity of 100 h, surpassing state of the art Pt/C & RuO2 electrolyzer
where the synergistic effect of W and Co metal cations in the
heterogeneous phase of Se and O anions could increase the charge
transfer and electronic modulation of the material followed cat-
alytic performance [142]. Most importantly, elemental incorpora-
tion not only optimizes the electronic structure of the catalyst,
leading to the improved electrical conductivity and facilitated elec-
tron transport, but also down shifts the d-band center from the
Fermi level, degrading the adsorption energy of oxygen intermedi-
ates that produces favorable kinetics and high OER performance
[147,158]. The crystalline transition metal oxides, and non-noble
catalysts are suffering from the large excess overpotential and
unsatisfactory performance where an incorporation of electroneg-
ative sulfur into crystalline cobalt oxide (S-CoOx) to create struc-
tural disorder via a facile room-temperature ion exchange
strategy can boost the catalytic performance [150]. The fluoride
incorporation into CoO/Co by a simple electro-deposition method
enhanced the HER activity of CoO/Co as compared to the reported
noble-metal catalysts in alkaline medium i.e. 1.0 M KOH as fluoride
incorporation improves the electrodeposition particle size, elec-
tronic density, conductivity and hydrophilicity of CoO–F/Co
[165]. On incorporating aliovalent F-anion into CoO nanowires
(F-CoO) superior catalytic activities for both HER and OER were
obtained as aliovalent F-anion substitution improves the intrinsic
activity of CoO for overall water splitting process [166].
10
Coordination Chemistry Reviews 474 (2023) 214864
5.2. Alloying
Alloying by definition is a solid solution where one of the two
components is a metal. In alloying, the addition is much larger
and different materials with two or more phases may coexist.
Alloying takes place when two or more metals are mixed together
to form a new material of desired properties, different than indi-
viduals. This is also possible even in case of the liquids for example,
aqua regia is the combination of nitric acid and hydrochloric acid.
Moreover, both alloying and doping can change the lattice param-
eters of alloy. Metal alloys usually exhibit enhanced catalytic activ-
ities for chemical and physical reactions wherever used by
harnessing the synergistic effect between two metals. The syner-
gistic effect of using multi-metals, heteroatom-doping, and
support/substrate-modified catalysts could achieve the optimized
adsorption for better catalytic performance. The main principle of
alloying is to modulate the electronic structures of surface and
near surface atoms of an electrocatalyst (for example, the d-band
center position), thus optimizing the adsorption/desorption
strength of adsorbents on the catalyst surface through improving
the electrochemical properties [69].
In the 20th century, transition metal alloys with d-orbital metals
have widely been studied as cathode materials to replace pure
metal electrodes for HER in alkaline solutions because of their
low cost. Compared with the elemental doping in the lattice of host
material, developing alloyed by means of atomic substitution in a
wider concentration range could lead to a broader range for the
modulation of electronic structures. For precious metallic materi-
als, alloying with non-precious metals like Fe, Co and Ni can reduce
the use of high-cost precious metals besides improving the cataly-
sis performance. However, alloying between two or more than two
non-precious transition metals can sometimes bring a strong syn-
ergistic effect, on modifying the electronic structure of each com-
ponent. The binding strength of the adsorbents of the alloy
surface could therefore be optimized for availing desired proper-
ties [167]. It has been shown that alloying hetero-metal elements
is an effective route to modify the surface chemical properties of
the host metal derived from the formation of heteroatom bonds
and the alteration of the lattice parameters and charge distribu-
tions [101]. The synergistic effect may arise from the optimized
electronic structure that favors the electrocatalytic process. In
addition to the alloyed catalysts, modulating the crystallinity is
another effective method for the optimization of the electrocat-
alytic activity [168]. More importantly, the alloying or doping of
electrocatalysts with transition metals has been shown to be an
effective means to tune electrochemical properties at the atomic
level [169,170]. Generally, it is effective approach to tune the elec-
tronic structure and optimize the intermediate absorption energy
in electrochemical process for obtaining the better intrinsic prop-
erties [62]. Multimetal alloyed oxides often exhibit superior OER
activity to single-component metal oxides, among which NiFe-
based oxides have been extensively studied [171]. Meanwhile,
alloyed electrodes with nanowire, nanocone, and nanosheet-type
morphologies demonstrated an engaged active surface area
[116]. The V and Fe doping can change the electronic structure of
Co to yield nearly optimal adsorption energies for OER intermedi-
ates, giving rise to the superior activity. A critical obstacle is a dif-
ficulty in incorporating V into Co-Fe oxides to obtain Co-Fe-V
oxides as CoaFebVcOx with well-defined structure, morphology
and properties [172]. The CoRu-O/A@hollow nitrogen-doped car-
bon fabricated successfully by tannic etching and ion exchange
method that adduced superb ultralow overpotintials of 234 mV
for OER in 0.1 M KOH and 85 mV for HER at 10 mA cm
2 in 1 M
KOH as the Ru modification impacts on generation of other similar
TMOs and noble metals which paved the way for a new generation
of ZIF-derived trifunctional electrocatalytic [173].
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
General approach for fabricating Ru–MoO2 nanocomposites via
in-situ carburization of a noble metal-modified Mo–MOF under an
inert atmosphere exhibited higher electrical conductivity, optimal
water adsorption energy, and faster charge transfer kinetics, fol-
lowed enhanced electrocatalytic activity for the HER under both
acidic and alkaline conditions [174]. The MoNi alloy nanograins
embedded in Mo-doped NiO nanosheets on nitrogen-doped
graphene-foam substrate synthesized recently through the facile
hydrothermal reaction method with a thermal reduction treatment
produced superb HER and OER catalytic activity and excellent
long-term stability in alkaline medium. The MoNi nanograins were
in full contact with the electrolyte and reducing the transfer resis-
tance during the reaction. The outstanding performance was
obtained due to the Mo doping and the interface engineering
between Mo-NiO and MoNi [175]. Moreover, the relationship
between doping, elemental incorporation, and alloying points to
the ability of selective metal and non-metal, carbon and polymer
dopants to successfully modify the electronic structure of resultant
electrocatalysts to improve water splitting performance. Therefore,
the doping, elemental incorporation, alloying of foreign elements
into the host transition metal oxide-based catalysts are broadly
adopted approaches to optimize lattice structure to regulate phys-
ical and chemical properties to producing enhanced electrocata-
lysts water splitting activity.
6. Effect of metal and non-metal-doping engineering strategy
for transition metal oxide-based electrocatalysts
Doping is one of the most successful methods used to fine-tune
the electrical configurations of catalysts. Once the metal ions are
integrated into the catalyst, electron exchange between the doped
metal and active sites will change the electronic structure of the
active sites, hence increasing the intrinsic HER and OER activity.
Elemental doping is mostly employed to adjust the electronic
structure, enhance electronic conductivity, and increase the num-
ber of exposed active sites, thanks to the huge effort done by
researchers. However, it is critical to expose the real active centers
of the dopants in the host materials during the catalytic process.
Doping with heterogeneous metal ions, inserting dopants into
the lattice, building hybrid structures with other materials, several
processes have been used to modulate the electronic microstruc-
ture of transition metal-based electrocatalysts. Furthermore, metal
dopants are advantageous for the overall water splitting perfor-
mance; metal dopants help to boost the electrical conductivity of
the catalysts, which increases the HER and OER reaction kinetics
[58,82]. In general, the number of catalytically active sites can be
increased by changing the shape and microstructure of the porous
microstructure. Furthermore, the Schottky barrier for such rapid
electron transport can be facilitated by the high electrical conduc-
tivity generated via combining the catalyst with a substrate that
can transfer heat and electricity. Despite these benefits, techniques
focused on tuning the morphology of conducting carbon substrate
usually produce minor improvements in the electrochemical water
splitting performance [45]. Doping techniques in transition metal
oxides generally include inserting the dopants into the structure
of the host materials to produce an electrocatalyst with compara-
ble, stable, and effective active sites for electrocatalysis. The doping
approach in transition metal oxides is primarily split into cation-
doping and anion-doping based on the kind of heteroatoms used.
Furthermore, efficient doping techniques to prevent dopant loss
in the electrocatalytic process can greatly improve their durability
[2,63,65,74,100,176–188]. The effect of metal and non-metal-
doped TMOs on catalysis activity through the change in the elec-
tronic structure, the effect on the electrochemical reaction process,
11
Coordination Chemistry Reviews 474 (2023) 214864
effect on the electrical conductivity, and inducing powerful syner-
gistic effects is discussed as follows;
6.1. Modulating the electronic structure
The electronic structure is one of the most significant factors
controlling the intrinsic performance of electrocatalysts which
has consequently been given a considerable amount of research
attention. Tuning the electronic structure of transition metal
oxide-based nanomaterials using heteroatom-doping is a useful
method to promoting their overall water splitting performance,
which involves manipulating the electronic states, band morphol-
ogy, and adsorption capability. Elemental doping has been shown
to be useful in adjusting the electronic structure, improving the
wettability characteristics, lowering the kinetic energy barrier,
and adding more active sites. It is a brilliant way to change the sur-
face electronic structure of the host material [55,97,176]. More-
over, the electronic structure of electrocatalyst is important for
modifying its electrocatalytic performance in order to optimize
the binding energy with oxygen-based intermediates. Therefore,
it can be changed upon doping engineering, or other methods.
Redistribution of the spin and charge occurs as a result of changing
the electronic structure, resulting in an increase in the electrocat-
alytic performance. Doping can affect the initial stoichiometric
ratio, causing a distorted electric field and, as a result, a shift in
the electronic distribution. Overall, modification of the electronic
structure using doping engineering can increase electrocatalytic
performance due to the enhanced surface adsorption/desorption
capabilities of the proposed catalysts and is therefore an active
way to steadily move the Fermi-energy of electrocatalysts, which
plays a significant role in the overall water splitting process.
6.2. Regulating the active sites
Determining the active sites in an electrocatalyst is important
for understanding the catalytic process and designing novel cat-
alytic materials [31]. The intrinsic activity of the active sites is con-
nected with the interactions formed between the electrocatalyst
and critical oxygen-containing species and hydrogen-containing
intermediates on the catalyst surface. The position where an elec-
trochemical reaction occurs is referred to as the active site in the
electrocatalyst. The inclusion of doping on the electrocatalyst influ-
ences the active sites in two ways; a) improving the number of
active sites, resulting in a higher overall density of active sites,
which improves the electrocatalytic activity, and b) improving
the catalytic reaction potential or tendency by tuning the species
in the active sites of the catalyst. As previously stated, cation and
ionic doping can enhance or regulate the catalytic active sites to
modify the reaction kinetics, which has the potential to increase
the reaction rate.
6.3. Enhancing the electrical conductivity
For carefully designed electrocatalysts, the electrical conductiv-
ity can speed up electron transport throughout the electrocatalytic
process, which is the cornerstone of their total water splitting per-
formance. The presence of doing in catalysts increases the electri-
cal conductivity, followed catalytic activity. Metal oxides with
doping develop new defect states closer to the band gap and the
conduction band is simplify triggered via two electrons adjacent
to the oxygen vacancies, lowering the electrochemical resistance.
Indeed, these doping may have a variety of beneficial effects, but
one of them plays a critical role in regulating the electrocatalytic
performance. Specifically, an altered electronic structure has an
impact on the reaction mechanism and electron transfer rate,
which become interdependent. On the other hand, the primary
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

effects on the structure, optical, electronic, and electrocatalytic ductor material may be changed via varying the dopant type and
performance are dependent on the experimental results and theo- doping amount, resulting in changes to their electrical characteris-
retical calculations [67]. tics [177]. Doping is a common method of improving the catalytic
activity by adding active sites, adjusting the electronic microstruc-
ture, causing phase changes, and managing the reaction energy
6.4. Inducing powerful synergistic effects
barrier among other things. Heteroatom doping engineering with
various electron configurations introduced into the lattice of tran-
Heteroatom doping is one of the most promising ways for
sition metal oxide-based electrocatalysts can result in a subtle dis-
improving electrocatalysis by modulating the intrinsically slow
tortion of the atomic structure, further control over the oxidation
electronic conductivity and kinetic response of transition metal
state of the active centers, increasing the number of active sites,
oxides [189]. The doping method allows for a synergistic impact,
modifying the electronic structures and geometric engineering,
which is naturally related to the optimal electronic structures
and also a noticeable tuning of the adsorption/desorption abilities
resulting from the electronegativity disparity between different
of the electrocatalyst surface. Therefore, heteroatom-doping
elements. To put it in another way, adjusting the valence states
results in moderate adsorption of energy which introduces a bi-
on the reactive species is critical for increasing the intrinsic HER
functional synergistic effect to aid in quicker water dissociation,
and OER activity [6,190]. The powerful synergistic effect of modi-
yielding sufficient protons and electrons to enhance the generation
fied TMOs and heteroatom doping can significantly increase the
of hydrogen and oxygen [31,115,193–196]. As a result, modifying
overall electron conduction, interfacial charge transfer, and struc-
the electrocatalyst via heteroatom-doping has been proposed as a
tural stability of TMOs, endowing the catalyst with sufficient elec-
useful technique to improve the catalytic performance during the
trocatalytic activity, durability, and stability [182]. In conclusion,
electrolysis of water [93]. Transition metal oxides demonstrate
synergistic effects can govern morphology, modify the electronic
various advantages as electrocatalysts including high inherent cat-
structure of the heterostructure to enhance the number of accessi-
alytic activity, a wide range of compositions and structures, easy
ble active sites, and speed up mass/charge transfer on the heteroin-
control of the exposed facets in their crystals, and extreme durabil-
terface. Because of the synergistic effects of heterostructures, the
ity under alkaline conditions [68]. However, there are certain dis-
adsorption ability of intermediates can also be adjusted, resulting
advantages; a) most of the transition metal oxides are
in lower energy barriers of the rate-determining step, accelerating
semiconductors and their conductivity must be increased to match
reaction kinetics for both the HER and the OER half reactions and
the requirements for electrocatalysis, and b) transition metal oxi-
enhancing total water splitting performance [145]. Thus, develop-
des have poor activity due to their low intrinsic catalytic properties
ing a systematic strategy for synergistic structural and electronic
for reduction processes, such as the OER and HER. Recently, various
modulations is critical for achieving excellent performance in
techniques for resolving these issues have been reported [31].
hydrogen-evolving electrocatalysis, which piques the interest of
Currently, a number of metal/non-metal elements are being
chemists and materials scientists [191].
doped into the structures of transition metal oxides in order to
To a certain extent, increasing the doping content leads to an
achieve adjustable catalytic activity. Non-metals can be utilized
increase in the number of unoccupied sites in transition metal oxi-
as dopants in metal oxide materials to tune the bandgap and Fermi
des, which is advantageous for electrocatalysis. Overly high dopant
level. Elements like nitrogen, carbon, phosphorus, fluorine, chlo-
content, on the other hand, causes negative consequences in the
rine, iodine, sulfur, and various selenides and tellurides are the
physicochemical structural characteristics. An increased amount
most often utilized non-metal dopants. Non-metal dopants act as
of doping reduces the distances between them, resulting in dopant
interstitial dopants or a replacement for oxygen or the parent
aggregation and the development of secondary phases. This sup-
metal sites [68]. Cationic metal dopants such as Fe, Co, Ni, Ru,
ports the conclusion that the doping level should be kept within
Mo, W, and Cu can reduce the bandgap in metal oxides. Transition
the solid solution limit in order to ensure homogenous doping
metals are the most widely utilized metal dopants. The most com-
[192]. Meanwhile, electrocatalysts containing both anion and
monly used transition metals include first-row transition metals,
cation doping exert a synergistic effect on their catalytic perfor-
as well as d8 and d9 transition metals, in which the 3d-orbital of
mance [65]. It should also be mentioned that the oxygen surface
the dopant metals injects electronic states between the initial band
doping, which is caused via partial oxidation with oxygen in the
gaps and Fermi level. Metal ion dopants can also cause defects and
air, is extremely difficult to prevent in some transition metal
alterations in the atomic distribution, enhancing charge transport
oxide-based electrocatalysts. In particular, this doping changes
and electron mobility with improving the electrical performance
the electronic structure and adsorption energies of both water
[67,68]. Basically, doping cations and anions with lower oxidation
molecules and intermediates to acceptable values dramatically
states formation energy results in an increased number of oxygen
by reducing the overpotentials of the HER and OER. Overall, the
vacancies in metal oxides [76]. Electrocatalysts are divided into
doping is a viable technique for improving the electrocatalytic per-
two parts for further consideration depending on the relative metal
formance, although several obstacles remain a considerable chal-
and non-metal alignment of the metal oxide. In the following sec-
lenge. As a result, researchers must delve deeper into the
tions, several recent instances to demonstrate the effects of
important roles of metal and non-metal-doped TMOs in adjusting
heteroatom-doping strategies on overall water splitting applica-
multiple elements, such as the development of new types of anion
tions using transition metal oxide-based electrocatalysts are
and cation doping, in-situ characterization techniques for tracking
explored. These current examples may help with the logical devel-
doping variations, and confirmation of the relationship between
opment of an effective catalyst for certain electrocatalytic
the electrocatalytic performance and doping concentration.
applications.

7. Metal and non-metal-doped transition metal oxide
electrocatalysts: Synthesis and catalytic performance
In recent days, heteroatom-doping is a feature adjusting
approach that refers to the intentional insertion of a heteroato-
m into the parent crystal structure with the goal of modifying
the intrinsic properties. The band structure of the doped semicon-
12
7.1. Metal (cation)-doped transition metal oxide electrocatalysts
Metal oxides comprised of an appropriate mixture of transition
metal oxides can sometimes outperform their single metal coun-
terparts in terms of the catalytic performance. Metal-doping is a
simple and effective method of introducing second metals [2,55].
Doping transition metal compounds with heteroatoms has the
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
potential to change the structural, optical, and electronic proper-
ties, increase the electrical conductivity to improve the hydrogen
adsorption energy, and increase the number of active sites
[197,198]. As a result, the cation exchange approach substantially
increases the intrinsic and apparent activity of electrocatalysts
which has great potential in terms of designing novel energy con-
version devices, such as total water splitting apparatus and metal-
air batteries. Metal (cation)-doping can provide a fresh insights and
possibilities for the logical design of a new generation electrocata-
lysts [77]. The metal (cation)-doping method has been suggested
as an encouraging method for increasing the intrinsic catalytic
activity of the active sites, which may not only improve the Schot-
tky barrier for electron transfer during electrocatalysis, but also
can tune the electronic structure of the catalysts by lowering the
HER or OER reaction energy barrier. Because, kinetic variables such
as the activation barrier play a key part in specifying the viability of
this reaction, the progress of the cation-doping process may differ
considerably from a thermodynamic viewpoint [78]. The major
focus is on the metal (cation)-doping approach, which is a strong
tool for finely adjusting the electron structure of the catalyst via
surface faceting, heteroatom-doping, defect creation, and strain
modulation. The electronic structure can be successfully adjusted
upon appropriate atomic structure engineering, which improves
the electronic conductivity and makes the adsorption/desorption
of reaction intermediates easier for metal oxide electrocatalysts
[85,199]. Many metal dopants have been demonstrated to operate
as electrocatalytic activity boosters for transition metal oxides,
which is attributed to their capacity to alter the electronic struc-
ture of the host material and therefore, increase the intrinsic activ-
ity [200]. Doping with first row non-noble metals, such as Ni, Mo,
and Fe, has been shown to enhance the catalytic performance of
transition metal oxides in alkaline and acidic media. Furthermore,
the doping levels of their related cations are critical to improving
the electrochemical performance, but this has been rarely investi-
gated. In order to build effective and stable electrocatalysts for
total water splitting, the direct development of nanostructured
electroactive species on three-dimensional (3D) porous and con-
ductive current collectors has become a more straightforward
and desirable technique. Another broad method for improving
the intrinsic activity of electrocatalysts is defect engineering. As a
result, metal (cation)-doping is a handy way to introduce defects
into the nanocrystalline host for metal oxide electrocatalysts.
According to density functional theory (DFT) simulations, nanoma-
terials containing cationic doping may decrease the energy barriers
for the precursors and accelerate the release of the produced oxy-
gen [72]. The doping method substantially increases the intrinsic
and apparent activities of metal oxide electrocatalysts and shows
a lot of promise for the creation of novel energy conversion devices,
such as water splitting, metal-air batteries, supercapacitors, and
gas sensors [74]. Moreover cation-doping provides fresh insights
and possibilities for the logical design of a new generation of
TMO-based electrocatalysts. Metal heteroatom-doped transition
metal oxide-based catalysts can be divided into the following
major classes based on the dopants reported i.e. Fe, Co, Ni, M,
etc. In this regard, focus on noble metal-doped transition metal
oxide-based electrocatalysts has been elucidated.
7.1.1. Fe-doped transition metal oxide-based electrocatalysts
Heterogeneous atomic-doping is an inexpensive method to
increase the intrinsic conductivity of metal oxide electrocatalysts
to enhance the water splitting activity. Because, the transition
and central metals have identical effective ionic radii, ionic
charges, and crystal field environments, transition metals can also
be chosen as dopants. As iron has a lot of d-band electrons, it may
be used to control the electronic structure of the parent metal
oxide electrocatalyst. Most of the research work on Fe-transition
13
Coordination Chemistry Reviews 474 (2023) 214864
metal oxide-based electrocatalysts has so far concentrated on sub-
stituting Fe for host metal atoms with similar electronic structures
and atomic radii, such as Co, Ni, and Cu. During the synthesis, the
desired quantity of iron salt is generally added as the Fe dopant
precursor. In general, the improved electrocatalytic activity
observed upon Fe-doping is ascribed to the modified local electron
structure and therefore, hydrogen adsorption frequency. In fact,
iron affects the catalytic efficiency and overpotential of the overall
water splitting reaction with a reversed volcanic pattern, which is
remarkable. Transition metal oxides can be made more electrically
active and conductive in a variety of ways. It is a good approach to
make composite metal materials because the HER and OER activity
of composite metal materials outperform that of their single coun-
terparts. Dong et al. synthesized fascinating 2D Fe-doped NiO
nanosheets (NiFexO) using a facile solvothermal process, which
can be converted into 2D Fe-doped NiO with a granule border
defect using a low-temperature oxidation process in which the
grain boundary defect in the 2D NiFe0.1O nanosheets showed supe-
rior OER efficiency with a low overpotential of 274 mV at a current
density of 10 mA cm
2 in a 1.0 M KOH electrolyte [201]. More
importantly, the doped Fe changed the atomic and electronic struc-
ture of NiO by activating the Ni centers via an Fe-induced partial
charge transfer mechanism, which improved the electrocatalytic
performance of (oxide) hydroxides for overall water splitting elec-
trocatalysts [202,203]. Recently, Wu et al. reported synthesis of Fe-
doped NiO mesoporous nanosheets array successfully on bickel-
foam (NF or NiF) via an eco-friendly solvothermal approach, fol-
lowed by an annealing process. The Fe11%-NiO/NF electrode
showed superior OER performance with an ultra-small overpoten-
tial of 206 mV and ultra-low Tafel slope of 49.4 mV dec–1 required
to reach 10 mA cm
2 with robust stability over 20 h [204]. More
importantly, it also exhibited superb HER activity with an ultra-
small overpotential of 88 mV and ultra-low Tafel slope of
49.7 mV dec–1 required to reach 10 mA cm
2 with robust stability
over 20 h. A two-electrode alkaline electrolyzer utilizing Fe11%-
NiO/NF for total water splitting only required a cell voltage of
1.579 V to reach 10 mA cm
2, suggesting Fe11%-NiO/NF is a promis-
ing electrocatalyst for total water splitting. Raman spectroscopy
measurement confirmed that the Fe ions were integrated into
the NiO lattice. The field emission scanning electron microscopy
(FESEM) images of Fe11%-NiO/NF revealed that the product retained
the structure of the nanosheets array precursor. As a result, the dis-
sociation of water may be aided by a huge number of exposed
active edge sites. The transmission electron microscopy (TEM)
images showed that adding Fe atoms to a mesoporous nanosheet
may efficiently control the size of the component nanoparticles.
By optimizing the structure and composition it is possible to
increase the HER and OER efficiency of Fe-doped Ni-based cata-
lysts. Creating a free standing 3D porous nanostructures on a con-
ductive substrate used as the electrode can supply a large number
of exposed active sites, while buffering the volume changes
observed during the reversible redox process. Furthermore, by
doping Fe3+ ions and adjusting the electronic structure, the HER
and OER catalytic performance of NiO catalysts can be significantly
enhanced.
Fe-doping can increase the number of active sites while improv-
ing the electrical and ionic conductivity. The direct development of
an active phase on porous NiF eliminates the need for a binder and
has been proven to be more efficient in terms of its electrical con-
ductivity and robustness [59,205]. Fe-doping results in an
enhanced electrochemical surface area, improved water adsorption
capacity which optimizes the hydrogen adsorption energy and oxi-
dation of the metal oxide for better HER and OER performance
[206]. Surprisingly, one of the most effective ways to improve
the catalytic performance can be regulated and selective doping.
There have been various publications on doped electrocatalytic
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
systems. For example, Chen et al. suggested a new approach to
metal ion-doping and the formation of heteroatom structures that
may be suitable for transition metal oxides used for water splitting
process [199]. Here, a rational, easy, and eco-friendly hydrothermal
method was utilized to construct an allocation of Fe-doped MoO2/
MoO3 sheets with abundant oxygen vacancies and interfacial
heterojunctions made on etched nickel-foam (ENF) (Fig. 5a). Scan-
ning electron microscope (SEM) image was used to analyze the
morphology of the bare NF as illustrated in (Fig. 5b); when the
smooth surface of NF was etched for 24 h, visible irregular cracks
emerged on the surface and the cracks on these surfaces may
increase the materials adherence. After hydrothermal treatment
for 24 h, the SEM images of the Fe-Mo precursor/NF revealed that
the electrode surface is evolved with a vertical alignment (Fig. 5c).
The huge number of vertically scattered membranous structures
may significantly enhance the interfacial interactions formed
between the material’s surface and solution, enhancing the active
sites on the surface of the catalyst by increasing the Schottky bar-
rier and electron transport. The surface morphology of the Fe-
MoO2/MoO3/ENF samples did not alter considerably after hydrogen
reduction (Fig. 5d). As a result, Fe-MoO2/MoO3/ENF can be
regarded as a superior catalytic electrode for water splitting appli-
cation. The proposed hydrothermal process has a number of
advantages in terms of its simplicity, low cost, low-temperature,
and ease of scale-up, all of which are beneficial for real water split-
ting activity. TEM revealed the microscopic structure of the Fe-
MoO2/MoO3/ENF catalyst. The crystalline structures of Fe-MoO2/
MoO3/ENF, MoO2/MoO3/NF, and Fe-MoO3/ENF were studied with
the help of X-ray diffraction (XRD) patterns. The MoO2/MoO3/ENF
exhibited an ultra-low overpotential of 36 mV with a Tafel slope
Fig. 5. a) A schematic representation of the synthesis of Fe-MoO2/MoO3/NF. SEM images of (b) NF, (c) Fe-Mo precursor/NF, and (d) Fe-MoO2/MoO3/NF. Reproduced with
permission from ref. [199] Copyright Ó 2020, Elsevier.
14
Coordination Chemistry Reviews 474 (2023) 214864
of 84.2 mV dec
1 at 10 mA cm
2 and superior stability over 95 h
for the HER, which are smaller and better than those obtained with
platinum (Pt)/carbon (C) (Fig. 6a–f). The results obtained for MoO2/
MoO3/ENF demonstrated excellent overpotential of 310 mV at
100 mA cm
2 with a Tafel slope of 31.7 mV dec
1 over 120 h at
a current density of 10 mA cm
2 for the OER, which were smaller
and better than those obtained with Pt/C. Accordingly, for both
cathode and anode catalysts, the heterogeneous interface of Fe-
MoO2/MoO3/NF exhibited an ultra-small overpotential of 1.57 V
at 10 mA cm
2 in 1 M KOH. DFT calculations confirmed that Fe-
doped MoO2/MoO3 heterojunctions decrease the band gap of the
electrode, increasing the rate of electron transfer and decrease
the potential barrier for water splitting. The distinctive peaks of
Fe-MoO2/MoO3/ENF moved to lower diffraction angles when com-
pared to MoO2/MoO3/ENF, indicating that the inclusion of Fe
affects the lattice constants of the material, which was also found
for other doped materials. The electrode hydrolytic kinetic activity
is represented by the potential barrier for hydrogen adsorption
energy and oxidation of the metal by incorporating Fe into the lat-
tice [207]. In addition, doping is a popular approach to fine-tune
the electronic structure and increase the number of active sites
for electrochemical water splitting. However, the high cost of noble
metals limits their potential applications. Due to its good stability,
superior overpotential, and inexpensive cost, metal-doping with Fe
for metal oxide electrocatalytic applications is also useful to
enhancing their catalytic performance. Fe-doped metal oxide
nanocomposites have potential applications in supercapacitors,
photocatalysts, and gas sensors [208]. For example, Fominykh
et al. fabricated Fe-doped NiO nanoparticles (NPs) with Fe contents
of >20 mol.% using tert-butanol (tBuOH) via a facile solvothermal
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 6. (a) HER polarization curves obtained for Fe-MoO2/MoO3/NF, MoO2/MoO3/NF, Fe-MoO3/NF and Pt/C with IR compensation in 1 M KOH, (b) corresponding Tafel plots, (c)
double-layer capacitance (Cdl) at 0.423 V (V vs. RHE), (d) EIS spectra for the electrocatalysts with amplitudes of 5 mV at 100 mV (V vs. RHE), and (f) corresponding TOFs, and
stability test of Fe-MoO2/MoO3/NF in 1 M KOH at a static overpotential of 105 mV for 95 h. Reproduced with permission from ref. [199] Copyright Ó 2020, Elsevier.
process. The results obtained for 10% Fe (III) showed a TOF of
1.9 s
1 and a small overpotential of 300 mV required to obtain a
current density of 10 mA cm
2 and Tafel slope of 37 V dec–1. The
unusual crystalline FexNi1-xO NPs demonstrated great potential
as catalysts for the OER due to their high electrocatalytic efficiency,
ease of manufacture, tremendous flexibility, and low cost. X-ray
absorption spectra (XPS), and Mossbauer spectroscopy measure-
ments indicated the existence of iron as Fe (III) and nickel as Ni
(II) on the surface and within the NPs. As a result of the singular
properties of Fe-doped NiO nanocrystals have potential applica-
tions in electrochemical water splitting as well as use as competi-
tive anode materials. In addition, the doped elements may
influence the geometry and/or electrical properties of the host
materials, resulting in the improved electrocatalytic activity of
doped metal oxides over their non-doped equivalents. For instance,
Meng et al. prepared Fe2+-doped NiFe (II, III)-LDH under hydrother-
mal conditions on NF with an ultra-small overpotential of 140 and
113 mV for the OER and HER, respectively at a current density of
10 mA cm
2 in 1 M KOH electrolyte for total water splitting in a
two electrode system where an ultra-low voltage cell of 1.54 V
to achieve a current density of 10 mA cm
2 reported. Both XPS
and Raman spectroscopy measurements were used to examine
the surface composition of the pure and doped catalysts. These
findings suggested that Ni ions with a high valence play a crucial
role in accelerating the OER and HER [57]. Zhang et al. synthesized
a series of hierarchical cross-channeled hollow NPs with ultra-thin
Co3O4 hierarchical nanoplates using an
etching
coordination
reorganization hydrothermal reaction.
The material was doped with thirteen different metal atoms. The
zeolitic imidazolate framework-67 (ZIF-67) hierarchical hollow
nanoplates were uniform with an average side length
of  900 nm and thickness of  160 nm. TEM images were used
15
Coordination Chemistry Reviews 474 (2023) 214864
to investigate the structure of the Fe-Co3O4 NPs, revealing the hier-
archically porous structure with orthogonal channels and
nanosheet subunits. The presence of perpendicular channels in
each NP was verified by TEM images. A limited quantity of Fe spe-
cies was absorbed onto the as-formed cross-channeled ZIF-67 NPs,
according to energy-dispersive X-ray (EDX) spectroscopy. EDX
analysis showed the presence of Fe, Co, and O in the sample. The
surface chemical states of the Fe-Co3O4 NPs were further validated
using XPS [209] measurement. Min et al. prepared oxygen-
deficient Fe-doped Co3O4 NPs using a simple self-templating
approach for the electrocatalytic OER activity. The defect-rich Fe-
doped Co3O4 NPs demonstrated outstanding electrocatalytic per-
formance in the OER with an ultra-small onset overpotential of
318 mV at 10 mA cm
2, low Tafel slope of 76.8 mV dec–1, and
TOF of 0.1553 s
1 at a small overpotential of 370 mV with excellent
stability in 1.0 M KOH [60]. The Fe-doped spinel Co3O4 NPs with
abundant oxygen vacancies were effectively absorbed onto the
N-doped carbon framework. The synergistic effect between the
Fe dopants, oxygen vacancies, and N-doped carbon matrix in the
FCO-Vo@NC catalysts played a favorable role in improving the
OER activity, implying incorporation of Fe and producing oxygen
vacancies can significantly boost the electrochemical performance.
Yan et al. synthesized ternarymixedmetal spinel oxides comprised
of FexNi1–xCo3O4 (x = 0, 0.1, 0.25, 0.5, 0.75, and 0.9) nanowires
using NF as the substrate utilizing a simple solvothermal method
followed simple annealing step with improved electrocatalytic
activity in the OER (i.e. overpotential of 350 mV at a current den-
sity of 10 mA cm–2and ultra-small Tafel slope of 27 mV dec_1)
when compared to samples prepared with various Fe/Ni ratios
[210]. Swaminathan et al. also obtained Fe
Co3O4 nanosheets via
a solvothermal reaction [211]. A variety of materials with regu-
lated doping levels were examined. Regulated iron incorporation
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
into Co3O4 resulted in an apparent improvement in the OER perfor-
mance, which was represented by a 160 mV reduction in the over-
potential to achieve a current density of 10 mAcm
2. DFT
calculations revealed the enhanced catalytic activity in terms of
the electron density delocalization and changed adsorption energy
for the reaction intermediates that occurred upon adding Fe ions
into the structure. More significantly, the presence of Fe ions with
differing valences causes electron delocalization, which may signif-
icantly increase the conductivity. The production of large and thin
nanosheets was confirmed using the SEM images obtained for the
Co3O4 and Fe-Co3O4-4.5 % nanoflake samples. Oxygen vacancies
were created that increased the catalytic activity by promoting
the adsorption of oxygen-containing species throughout the reac-
tion. Iron-doping is a key for metal oxide OER activity. These find-
ings pointed out a realistic method for the improvement and
design of extremely effective electrocatalyst materials that can
be adjusted upon varying the quality and amount of dopants used.
In addition, doping with heterogeneous metal oxides does not only
represent the specific properties of the diverse components, but
also boost the catalytic performance by its synergistic effects,
including the electrical design and interface effects [87,196]. These
findings increased the burden of validating the active species in
water oxidation and rigorous control studies should be carried
out to rule out the potential of pollution influencing the electrocat-
alytic activity of water oxidation electrocatalysts [204].
Overall, the electronic structures of Fe-doped transition metal
oxide-based catalysts can be changed for better the HER and OER
performance, suggesting importance of iron as one of the best dop-
ing elements. It is inferred that Fe-doping reduces the overpoten-
tial and increases the stability of transition metal oxide-based
electrocatalysts by modulating the surface morphology, tuning
the structural, optical, and electronic properties, enhancing the
electrical conductivity of the electrocatalysts, and thus optimizing
the intrinsic activity of nanomaterials. Despite the efficiency of Fe-
doping in various transition metal oxide-based catalysts in the HER
and OER, systematic research on the relationship between the dop-
ing levels, local doping morphology, and catalytic activity of tran-
sition metal oxides is still lacking. However, further in-depth and
broad investigations on these issues are required to increase the
number of intrinsic active sites and understand the electronic
structure as well as surface reconstruction in order to enhance
their overall catalytic properties.
7.1.2. Co-doped transition metal oxide electrocatalysts
Transition metals doped with non-noble metals such as Ni, Fe,
and Co, and their compounds i.e. oxides, carbides, sulfides, and
phosphides have gained considerable interest as non-precious
metal electrocatalysts among the other electrocatalyst materials
reported to date. Doping transition metals with non-noble metal
compounds and heteroatoms has the potential to change the elec-
tronic structure, increase electrical conductivity, improve the
hydrogen adsorption energy, and increase the number of active
sites. Due to a low H-bonding energy Co has been considered a
viable HER and OER catalyst. The electronic structure of these cat-
alysts can be successfully changed by implanting small amounts of
Co into the crystal lattice. The catalytic performance is highly influ-
enced by the Co doping level, and a correct doping level increases
the intrinsic conductivity and decreases the Gibbs free energy of H*
adsorption (DGH*), which can act as more efficient catalytic sites
with much stronger catalytic activity [28,63]. Very recently, Co-
doping produced crystal defects and turned inactive basal planes
into active sites in transition metal oxide electrocatalysts. Li et al.
synthesized a Co-doped MoO2 nanorod (NR)-type catalyst using a
simple wet chemistry approach that endowed an ultra-low overpo-
tential of 26 mV at a current density of 10 mA cm
2 and an ultra-
small Tafel slope of 30.9 mV dec
1 in 0.5 M H2SO4 electrolyte. This
16
Coordination Chemistry Reviews 474 (2023) 214864
was excellent when compared to the pure MoO2 NR and commer-
cial Pt/C catalysts over 12 h stability. Furthermore, the Co–MoO2-
NRs also showed outstanding electrochemical stability and
superior robust structural durability after long-term use. The phase
composition and elemental chemical states of the Co-MoO2 cata-
lyst were not changed after cycling. A comparison of the XRD
and XPS analyses strongly suggested that the phase composition
and elemental chemical states of the Co-MoO2 catalyst were not
changed, sugegsting the Co-MoO2 NRs have a stable structure,
composition, cycle stability and durability. This indicates that Co-
doping improves the active surface area of the MoO2 catalyst,
resulting in more active sites being exposed on the catalyst surface
following Co-doping by accelerating the development of additional
oxygen vacancies, which activate the nearby O atoms as active
sites with significantly enhanced catalytic activity, all of which
improve the HER activity of the Co-MoO2 catalyst. This was a viable
method for producing additional metal oxide-based catalysts to
use in the energy conversion field by rational defect engineering
strategies [212]. Yang et al. developed a three-dimensional (3D)
hybrid heterostructure comprised of a Ni0.82Co0.18O@C/NF
nanocomposite catalyst using the combination of ultra-thin Co-
doped NiO (Ni0.82Co0.18O nanosheets) and carbon on NF with syn-
ergism between their geometric structures and electronic proper-
ties using a simple and low-cost immersion-adsorption-pyrolysis
strategy with bifunctional performance, (Fig. 7a). The high effi-
ciency of the Ni0.82Co0.18O@C/NF catalyst in total water splitting
was ascribed to the incorporation of Co into NiO along with semi-
conducting carbon forming the hybrid Ni0.82Co0.18O@C/NF compos-
ite enhancing the conductivity and charge transport ability, while
also introducing additional defect active sites for intrinsically high
activity, which is favorable for the reaction kinetics and long-term
electrochemical stability. It is predicted that the combination of a
two-dimensional (2D) porous nickel-based nanostructure with
abundant defects, heteroatom-doping, and conductive carbon can
significantly improve the electrocatalytic activity. After an immer-
sion process, NiCo-layered doublt hydroxide (LDH) nanosheets
were evenly formed on the surface of NF (Fig. 7b). FESEM images
of the resulting product as shown in Fig. 7c–e , revealed that the
catalyst retained the uniform distribution and sheet-like shape of
NiCo-LDH@polydopamine (PDA). The rough surface of the product
was also visible in the magnified FESEM image (Fig. 7e), indicating
the formation of the porous structure during the pyrolysis step.
The ultra-small overpotentials of Ni0.82Co0.18O@C/NF were 62 and
320 mV with a Tafel slope of 98 mV dec
1 at 10 mA cm
2 and
156 mV dec
1 at 50 mA cm
2 for the HER and OER, respectively
(Fig. 8a–f). This enabled a current density of 10 mA cm
2 in 1 M
KOH at a cell voltage of only 1.42 V with long-term (20 h) stability
for total water splitting applications [213].
Meanwhile, Wu et al. obtained a mesoporous Co-doped NiO/
NiFe2O4 nanosheet-type mixed oxide through a facile solvothermal
reaction using methanol as the solvent which inspired the develop-
ment and testing of novel low-cost multi-metal catalysts for
improved OER and HER applications [214]. Tian et al. successfully
prepared Co-doped RuO2 nanorods via a one-step annealing pro-
cess using a Ru-exchange ZIF-67 amorphous composite precursor.
The Co-doped RuO2 nanorods exhibited ultra-high OER efficiency
in acidic medium with an ultra-small overpotential of 169 mV at
10 mA cm
2 and excellent stability over 50 h at 10 mA cm
2 in
0.5 M H2SO4 for the OER. This increase in the OER performance
was assigned to the increased charge depletion on the oxygen
vacancies and greater energy shift toward the Fermi level of the
p-band center. They used XPS spectrum to determine the surface
chemical states of Co-RuO2 and TEM to determine the shape and
structure of the Co-doped RuO2. In many circumstances, oxygen
vacancies can greatly improve the OER activity by dramatically
increasing the electrical conductivity, resulting in the production
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 7. (a) Synthesis of Ni0.82Co0.18O@C/NF nanosheets, (b) FESEM image of NF, and (c–e) FESEM images of Ni0.82Co0.18O@C/NF. Reproduced with permission from ref. [213]
Copyright Ó 2019, Elsevier.

Fig. 8. (a) LSV polarization curves obtained at a scan rate of 5 mV s
1 with 95% iR compensation for bare NF, Pt/C/NF, Ni0.82Co0.18O @C/NF, NiO@C/NF, and Ni0.82Co0.18O/NF
during the HER, (b) corresponding Tafel plots of Pt/C/NF, Ni0.82Co0.18O @C/NF, NiO@C/NF and Ni0.82Co0.18O /NF, and (c) I-t curve obtained for Ni0.82Co0.18O @C/NF over 20 h at a
constant potential of –0.066 V (vs. RHE) during the HER.(d) LSV polarization curves obtained for bare NF, IrO2/NF, Ni0.82Co0.18O @C/NF, NiO@C/NF, and Ni0.82Co0.18O /NF during
the OER, (e) corresponding Tafel plots, and (f) I-t curve obtained for Ni0.82Co0.18O@C/NF over 20 h at a constant potential of 1.49 V (vs. RHE) during the OER. Reproduced with
permission from ref. [213] Copyright Ó 2019, Elsevier.

of additional active sites. This suggests that doped RuO2-based cat-
alysts can be used to overcome the limitations of the acidic OER
[215]. Jia et al. reduced Co-doped MnO2 nanowires by using a
NaBH4 solution at room-temperature to form MnCo2O4.5
nanosheets with more oxygen vacancies and active sites. The as-
prepared hierarchical Co-doped-MnO2@MnCo2O4.5 nanowire/-
nanosheet nanocomposite exhibited greater catalytic activity than
pristine Co-doped MnO2 nanowires and revealed an ultra-small
overpotential of 250 mV at a current density of 10 mA cm
2 in
1.0 M KOH electrolyte. According to the reduction approach at
overpotential of 300 mV, the estimated TOF of Co-doped-
MnO2@MnCo2O4.5 was 0.034 s
1, i.e. 136 times greater than that
of Co-doped-MnO2. The outstanding OER activity was attributed to
the synergistic effect of the increased number of oxygen vacancies

17
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
and active sites over the hierarchical nanowire-nanosheet struc-
ture [72]. CuOx is electrocatalytically inert and oxidatively stable,
which is a significant advantage over carbon-based systems. When
compared to nickel and iron, cobalt has a significantly stronger
synergism [216]. The optimum Co-dopant concentration in CuOx
nanocrystals is advantageous for electron transfer, adsorption,
and desorption of the OER intermediates. The XRD observations
indicated that there is a link between the OER activity and CuO
content during OER cycling tests, which was in good agreement
with the electrical and chemical measurements. XPS confirmed
that Co, Cu, and O coexist on the surface of Co0.30CuOx. Further-
more, the small size of the CuOx nanocrystals led to a high electro-
chemically active surface area, allowing the electrolyte to have
access to abundant Co active sites. Furthermore, oxygen vacancies
in metal oxides have been found to improve the catalytic perfor-
mance because they may affect the geometrical and electronic
structures as well as the chemical characteristics of metal oxides,
in addition to serving as active sites [217]. This indicates that
CuO can function as a possible host oxide material that is both
affordable and practical, thereby, Co-doping transforms it into a
very powerful OER catalysts [218,219]. Metallic cobalt has been
proven to be important for the production of long and ultra-thin
MnO2 nanostructures during the redox process. Moreover, cobalt
ions doped into MnO2 nanostructures greatly improve their cat-
alytic efficiency. Co-MnO2|OV composite materials have outstand-
ing catalytic performance and robust durability for
electrochemical water oxidation due to the combined benefits of
the doping technique, rapid charge transfer kinetics, and strong
synergistic effects. As the reaction progressed, the Raman spectra
revealed the increased intensity of the peaks corresponding to
the vibration of the M
O (M = Mn, Co) bonds and the decreased
intensity of the peaks corresponding to carbon. The elemental
compositions of the products acquired at successive phases were
identical, according to XPS measurement (C, O, Mn, and Co). The
production of nanosheets on the Co/NCNFs surface was verified
using TEM of the Co-MnO2|OV, which revealed nanomaterials
of  800 nm in size. Furthermore, Co-doping and oxygen vacancies
could alter the electronic structure of the nanosheets with
increased conductivity for an improved catalytic performance. As
a result of these synergistic effects, multifunctional active sites
are created, allowing a maximum catalytic activity to be achieved.
Consequently, Co-MnO2|OV outperformed most MnO2-based cata-
lysts in terms of its catalytic activity toward the OER. DFT simula-
tions also showed that the surface oxygen vacancies in Co-doped
MnO2 could improve the conductivity, reduce the uphill free
energy gap, and shift the rate-determining step of the OER from
*OH and *O (pure MnO2) to the production of an adsorbed *OH
intermediate. The ultra-thin (Co-MnO2) nanosheets demonstrated
superior catalytic performance and robust durability with an
ultra-low overpotential of 279 mV at 10 mA cm
2 and outstanding
stability 12 h in 1 M KOH solution during the OER due to the com-
bined benefits of the doping technique, rapid charge transfer kinet-
ics, and strong synergistic effects. Consequently, cobalt doping
enhances the composites conductivity and catalytic properties.
The improved catalytic performance of VO-MnO2-NF was attribu-
ted to; (a) a larger surface area provided by the reassembled
nanosheets and nanoflowers with porous structures, (b) abundant
oxygen vacancies generated in the electro-oxidation step, which
improve the kinetics of the OER, and (c) the increased number of
Mn3+ active sites induced by the treatment having a positive effect
on the catalytic performance. This research has shown that fabri-
cating an efficient OER catalyst is achievable and electron donation
and bandgap engineering techniques may be useful in the future
for designing improved metal oxides in practical water-splitting
devices [219]. Lu et al. developed and produced Co-doped NixPy
on the Co3O4/NF [220] which showed extraordinary catalytic per-
18
Coordination Chemistry Reviews 474 (2023) 214864
formance and ascribed to its plentiful active sites, controlled elec-
tronic arrangement, and synergistic impacts between metal atoms
and thereby, identified as a potential bifunctional electrocatalyst
for improving overall water splitting performance. Moreover, the
catalytic performance of transition metal oxides can significantly
be enhanced after metal doping. The creation of oxygen vacancies
in transition metal oxides may be enhanced by metal-doping as
well as changing the electronic structure and boosting the electric
conductivity of transition metal oxide-based catalysts. Therefore,
Co-doped TMOs can increase the catalytic properties and perfor-
mance in water electrolysis. It should be emphasized that, in addi-
tion to Co dopants, the type of substrate used also plays an
important role in increasing the catalytic activity of TMOs for total
water splitting application. It has been proven to be a major and
effective method for improving the intrinsic properties of a cata-
lysts, despite the fact that significant research has been carried
out for developing transition metal oxide-based electrocatalysts
of high surface areas, enhanced electrical conductivity, and distinc-
tive facet structures. The related HER and OER activities are not as
desirable as envisaged and must be further developed.
7.1.3. Ni-doped transition metal oxide electrocatalysts
Transition metal oxides are currently being extensively
explored because their intriguing physical characteristics and
potential applications in a diverse range of technological fields.
Nonetheless, researchers resort to doping various types of metals,
particularly transition metals, in order to obtain physical proper-
ties for a particular application. Doping is a successful method used
to enhance the performance of important electrocatalysts. Because
their 3d-electrons can be easily modified, non-noble metals such as
Ni and Fe are interesting candidates as HER and OER electrocata-
lysts, but their HER and OER performance still need to be increased.
The two most effective strategies used to enhance the HER and OER
performance of catalysts are to increase the number of effective
reaction sites and optimize the intrinsic activity of transition metal
oxide-based electrocatalysts [74]. Nanostructure engineering is
commonly utilized to increase number of active sites by enlarging
the active surface area. Transition metals with high oxidation
states, particularly Ni, demonstrate inherent activity. Ni2+ is the
most frequent ion found in the nickel salts, which can be used to
make Ni catalysts by oxidizing Ni2+ to Ni3+ or even Ni4+ and stabi-
lizing these species under mild conditions. However, extreme con-
ditions, such as high pressure and an oxidizing atmosphere, are
often needed. As a result, simpler and more cost-effective methods
for preparing high-valence Ni suitable for electrocatalytic applica-
tions are needed. Ni atoms are also good water dissociation centers
and oxide group active adsorption sites. Ni metal is found near the
crater in the well-known volcano-type HER and OER curves, sug-
gesting that Ni may efficiently modify the Gibbs free energy of
H* adsorption (DGH*) for favorable HER and OER catalysis. Ni2+
has also activated the HO-H bond for speeding up the dissociation
of H2O into protons [50]. There has recently been a surge in interest
in Ni-doped electrocatalysts for water reduction. In comparison to
Co– and Fe-doped catalysts, electrocatalysts with Ni-doping need
to be further developed. In general, Ni-doping is accomplished by
incorporating the nickel salt into the raw materials during the
preparation process [63]. The Cu, Fe, Mn, Co, Ni, and other doped
elements are among them. The physical and electrochemical
behaviors of pristine NiO are linked to the dopant effect. Several
doping elements have been introduced into NiO using various syn-
thetic methods in recent years to improve the optical and electrical
properties of nickel oxide-based products. According to the pub-
lished literature, researchers have recommended that the electro-
chemical and electrical conductivities of metal oxide can be
improved by doping metal ions, which may adjust its electronic
structure [221]. Furthermore, due to its high structural stability,
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
good reversibility of oxygen adsorption, and strong interactions
between Mn and Ni species in these materials, the Ni-MnO2 cata-
lyst demonstrated excellent catalytic stability and water resistance
[222]. Because of their low cost, nontoxicity, and chemical stability,
molybdenum oxides have been considered attractive non-noble
metal electrocatalysts for water splitting process [223]. Moreover,
Ni-doping significantly improved the redox characteristics, oxygen
mobility, and toluene adsorption of the MnO2 catalyst, resulting in
its improved catalytic performance. They not only constructed a
Ni-MnO2 catalyst with excellent activity and stability for toluene
removal, but also paved the way for heteroatom-doping to create
extremely efficient catalysts [222]. The development of active Ni-
doped metal oxide based-electrocatalysts is largely due to the
alteration in their electronic structures upon the introduction of
Ni atoms to obtain a reduced DGH* as well as a lower energy barrier
for the OER. The incorporation of Ni in CuOx-based catalysts has
obtained a more suitable energy barrier for OER [224].
NiF is a common material used in catalysts because of its large
surface area, open structure, strong chemical attraction, and high
electric conductivity. Very recently, other high-performance HER
and OER catalysts have been manufactured using the proposed
design strategy. For example, Zeng et al. used a conventional
method involving a facile one-pot chemical bath deposition pro-
cess under low temperature (90 °C) and atmospheric conditions
to synthesize a Ni-doped metal oxide electrocatalyst comprised
of Co3O4 3D interconnected nanosheets array on NiF (Ni-Co3O4
NS\NiF) via in-situ etching of H+ from the hydrolysis of cobalt chlo-
ride. The interconnected nanosheet array (Ni-Co3O4 NS\NF) was
used as a large-sized electrode material that exhibited small over-
potentials of 170 and 310 mV at 10 mA cm
2 with ultra-low Tafel
slopes of 76.9 and 91.8 mV dec
1 for the HER and OER in 1.0 M
KOH solution, respectively [225]. Subsequently, full water electrol-
ysis was achieved using Ni-Co3O4 NS\NiF that allowed a current
density of 90.8 mA cm
2 with ultra-long stability over 10 h under
Fig. 9. (a) Polarization curves obtained for Pt plate, Ni-Co3O4 NS\NiF, Co3O4 NS\NF, Ni(OH)2 NS\NiF, and NiF with iR correction. (b) The corresponding Tafel plots obtained for
(a). (c) The overpotential and exchange current density obtained at 10 mA cm
2 from (b). (d) Nyquist plots and equivalent circuit for the Ni-Co3O4 NS\NiF electrode with
different overpotentials. (e) Chronoamperometric response for Ni-Co3O4 NS\NF at different overpotentials. (f) The polarization curves obtained before and after i–t testing.
Inset of (f):; The SEM image of Ni-Co3O4 NS\NiF after i–t testing. Reproduced with permission from ref. [225] Copyright Ó 2018, American Chemical Society.
19
Coordination Chemistry Reviews 474 (2023) 214864
a cell voltage of 2.0 V, which was about five times higher than
industrial NiF (Fig. 9a–f). The XRD result revealed that the
nanosheets produced on NiF were Ni-Co3O4. The SEM image
revealed the consistently developed Co3O4 nanosheets on the sur-
face of NiF. The 2D shape and ultra-thin thickness were clearly
seen in the TEM images of the as-prepared Co3O4 nanosheets.
The smooth sheet documented an average thickness of 3.2 nm
according to atomic force microscopy (AFM) used for the elemental
mapping of Ni-Co3O4 NS\NiF. This method provided significant
advantages of simplicity, low-cost, low-temperature operation,
and simple scale-up, all of which are beneficial for industrial water
splitting performance. Li et al. reported the synthesis of Ni-doped
Co3O4 porous nanoplates via a hydrothermal process. The results
showed that the electrochemical stability in the HER and OER of
the 4 wt.% Ni-doped Co3O4 was greatly improved with an ultra-
small overpotential of 240 mV required at a high current density
of 10 mA cm
2 for the OER and 120 mV for the HER in 1 M KOH
electrolyte over the pure Co3O4 and other Ni-doped Co3O4 cata-
lysts. Therefore, it was discovered that Ni-doped Co3O4 porous
nanoplates have the following characteristics; (a) they can be pre-
pared using non-toxic and low-cost raw materials via simple and
inexpensive synthetic method, (b) their porous morphology pro-
vides a greater number of active sites due to the modification of
their surface as well as superb catalytic performance, and (c) mate-
rials with ultra-low doping levels have significantly promoted
activity for the overall splitting of water in alkaline medium. These
findings suggest that transition metal oxides doped at low concen-
trations have great potential for the rational design and synthesis
of other highly active catalysts used for overall water splitting
[226,227].
The higher OER performance of CeO2x–FeNi was attributed to
the strong intrinsic activity of Ni with high valence states and
the increased electronic conductivity caused by Ni-doping into
ceria. Yu et al. prepared Ni-doped ceria (CeO2
x-FeNi), decorated
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
with FeOOH nanosheet arrays, using a facile one-step method uti-
lizing oxygen vacancy-rich CeO2
x on carbon cloth as the substrate.
The corner stone to their method was transition metal-doping of
oxygen-vacancy-rich ceria with Ni, which was then oxidized to
higher valence states by H+ formed via the hydrolysis of Fe3+. The
obtained results demonstrated the high intrinsic OER activity of
Ni3+/Ni4+ coupled with FeOOH that led to an ultra-small overpoten-
tial of 195 mV cm
2 to reach a current density of 10 mA cm
2 and
ultra-high TOF of 0.99 s
1 in 1 M KOH. This excellent OER perfor-
mance was similar to other well-known OER catalysts. They found
that CeO2
x was uniformly doped by Ni without the formation of
pure Ni-based phases. The proposed technique for manufacturing
and distributing high-valence transition metal ions, which are
required to efficiently catalyze the OER and other oxidation reac-
tions, appears promising for sustainable energy storage applica-
tions. Ceria (CeO2) is a substance that is not stoichiometric. If Ce-
containing hybrid catalysts are developed for this purpose, the easy
transition between Ce4+ and Ce3+ should boost electron transport
between CeO2 and the other components. When CeO2 converts to
CeO2x, electron transport is further improved. Both experimental
studies and DFT simulations showed that Ni-doping significantly
can increase the electrocatalytic activity of Co3O4 in the OER.
Because of its distinctive 3d electronic structures, Ni is said to have
an appropriate chemical binding strength with the intermediates
of the reaction [228]. Due to the different accessibility for solution
species, face-selective etching should encourage the further appli-
cation of the morphology-controlled production of porous materi-
als. Wu et al. prepared NixCoyRu1
x
yO2 catalysts using a
hydrothermal reaction method [229]. Co-doped RuO2 prepared
with a Co/Ni ratio of 1.5 achieved an ultra-small Tafel slope of
32 mV dec
1 in 0.1 M HClO4, which was significantly lower than
that observed for pure RuO2 (64 mV dec
1). The improved oxygen
vacancies and higher valence of the Ru sites causes the host metal
to change. Upon changing the molar ratio (Co/Ni) from 1 to 1.5 this
considerable effect led to an increase in the OER activity. Further-
more, the residual Ni metal gives a direct pathway for electron
transfer and guaranteed the catalyst’s good electrical conductivity,
which encouraged the reaction kinetics by releasing the gaseous
products. Furthermore, the hierarchically porous structure offers
an abundant number of open channels for gas release, which can
further boost the direct contact between the active sites and solu-
tion [230]. Moreover, for the design of catalysts that can meet a
variety of needs, an understanding of the relationship between
the catalytic properties and reaction performance is required.
7.1.4. Mn-doped transition metal oxide electrocatalysts
Surface engineering via etching and the effective doping of
metal oxides with heteroatoms such as Ni, Mn, Fe, Cu, and others
are thought to be useful methods for manipulating the intrinsic
characteristic of nanomaterials in terms of their electrical conduc-
tivity and catalytic activity. The partial cationic replacement of
transition metals, especially Mn, via doping has a significant
impact on the OER and HER performance. Importantly, the modi-
fied electronic structure and adsorption energy following doping
with Mn-based materials further improves the catalytic efficiency
[231]. The electronic arrangement of Mn makes it a better dopant
than other transition metals. The enhanced catalytic activity can be
attributed to the disordered structure with defects and oxygen
vacancies formed at the surface of metal oxides, as well as the
broad tuning of the electronic structure of the electrocatalyst due
to effective doping, which is a topic of debate in several recent
research papers. Mn is basically a valuable dopant for activating
the catalytic performance of transition metal oxide-based electro-
catalysts with lower DGH* [63]. On the other hand, manganese
dioxide (MnO2) and its derivatives are appealing materials for
water splitting process because of their excellent stability, small
20
Coordination Chemistry Reviews 474 (2023) 214864
Tafel slope, ultra-low overpotential, ultra-high activity, and dura-
bility. Liu et al. reported the successful adjustment of the electronic
structure of NiO sheets via Mn-doping, which employed a small
amount of Mn (Mn/Ni atomic ratio of 0.030). The catalyst produced
styrene oxide (STO) in 75% yield under the optimized reaction con-
ditions was used for the styrene oxidation reaction. The results
suggested that Mn-doping enhanced the catalytic performance
for the selective oxidation of styrene [232]. Furthermore, the reac-
tion performance was maintained even after five reaction cycles,
indicating the possibility of industrial application. Numerous Ni
(II) species, redox couples, and oxygen vacancies are responsible
for this good catalytic performance. In another work, Chan-
drasekaran et al. obtained Mn-doped WO3 using a facile hydrother-
mal process that showed outstanding catalytic performance with a
small overpotential of 38 mV required to achieve 10 mA cm
2 and
a Tafel slope equal to 41 mV dec–1 in a 0.5 M H2SO4 electrolyte
[233]. DFT calculations suggested that; a) Mn-doping in the WO3
system results in a low concentration of metallic dopants that
cause the optical band gap to decrease in WO3, b) multivalent V
bonding with the terminal oxygen atom in the WO3 lattice leads
to localized covalent bonds and a boost in the HER activity when
compared to Mn-doping, and c) if the dopant concentration is high,
they are likely to damage the semiconductor. Furthermore, WO3
doped with Mn is a degenerate semiconductor with potential to
become a remarkably low-cost and abundant HER catalyst. As a
result, the mechanism of the interfacial catalyst was illustrated
in the study using both empirical and theoretical analyses, indicat-
ing a promising interface engineering strategy to produce more
effective and active non-precious (transition metal-free) electro/
photocatalysts for sustainable energy and various other applica-
tions. In another work, Ma et al. successfully synthesized MnxCo3-
xO4 nanostructures on NiF via tuning an eco-friendly hydrothermal
method that exhibited an outstanding ultra-low overpotential of
218 mV at 10 mA cm
2 and small Tafel slope of 92 mVdec
1 in
0.1 M KOH for the OER. This exceptional electrocatalytic perfor-
mance was attributed to the special design, highly dispersed active
sites, and huge surface roughness formed during the alkalization
process, making it a possible candidate for the electrocatalytic
OER [234]. Raj et al. developed Co(OH)2 nanosheets using a facile
ammonia evaporation and Mn-doping strategy to improve the
electrocatalytic OER performance [235]. The Mn-doped Co3O4
showed an overpotential of 436 mV at a current density of
50 mA cm
2 and ultra-low Tafel slope of 60 mV dec
1 in 1 M
KOH. The hexagonal phase of Co(OH)2 was closely matched with
the XRD pattern of the as-deposited sample on NiF. The SEM
images of the as-deposited Co (OH)2 nanoflakes and Mn-doping-
induced Co3O4 conversion on NiF were examined. The morpholog-
ical characteristics of the Mn-doped Co3O4 nanoflakes placed on
NiF prior to the heat treatment step were examined using TEM
analysis. XPS was carried out to establish the chemical composition
of the Mn-doped Co3O4 nanoflakes. Apart from exhibiting excep-
tional catalytic activity, the electrode material showed a high level
of stability over a long period of time. Mn-doping significantly
reduces the charge transfer resistance, while improving the OER
kinetics, resulting in high electrocatalytic performance. The exis-
tence of metallic Mn, as well as Mn2+ species, and the subsequent
strain formed during Mn-doping can be used to explain this spec-
tacular performance. According to theoretical analysis and the
experimental results, the outstanding electrocatalytic activity of
transition metal oxides for total water splitting can be ascribed
to various characteristics;: a) the huge number of accessible active
sites formed due to the Mn-doped vertical and un aggregated
nanosheet array structure, b) the enhanced intrinsic activity of
the active sites due to Mn-doping, and c) effective electron trans-
port, as well as gas evolution from the active nanosheets on the
3D electrode surface with an open framework. These discoveries
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
may lead to the development and study of novel cost-effective cat-
alyst electrodes based on metal center regulation for realistic water
electrolysis application [236]. Song et al. prepared Ni/Mn-doped
mesoporous cobalt oxides (Co3O4) using a one-step wet-chemical
approach via a reversed micelle process which showed a low over-
potential of 381 mV at 10 mAcm
2 for the OER that was compara-
ble to ultra-high-quality Ir/C electrocatalysts (346 mV for the OER)
and outperformed most cobalt-based electrocatalysts [237]. In
addition to their outstanding activity, the produced catalysts
showed robust durability and negligible activity degradation over
the course of 24 h uninterrupted operations in the OER. Several
characterization methods, including XRD, N2 sorption, TEM, and
SEM, demonstrated successful incorporation of Ni and Mn into
CoNi-(Mn)-O solid solutions with preserved mesoporosity. The
redox activity of Co3+ to Co4+ was critical for the OER activity,
according to XPS, Raman spectroscopy, and O2-temperature-
programmed desorption (O2-TPD). DFT simulations confirmed that
Mn-doping enhances the band gap states around the Fermi level of
the active oxygen sites, facilitating the conversion of OH* to O* and
reducing the energy barrier of the water oxidation reaction [237].
Chen et al. reported the successful synthesis of Mn-doped RuO2
nanocrystals using spray pyrolysis that exhibited an ultra-small
overpotential of 158 mV at 10 mA cm
2 and 254 mV at
100 mA cm
2 with an ultra-low Tafel slope of 42.94 mV dec–1 at
10 mA cm
2 and robust durability over 10 h in 0.5 M H2SO4
[238]. These findings demonstrated that controlling the electronic
structure of RuO2 may effectively increase its intrinsic activity,
resulting in unparalleled good performance and providing a direc-
tion for the development of optimal acidic water splitting catalysts.
Moreover, Mn-doping improves the catalytic performance for the
selective oxidation of the metal oxide to gain a thorough grasp of
the catalytic behavior, and the effects of the doping contents and
other reaction parameters on the reaction performances were care-
fully explored. Mn-doping decreases the free energy of hydrogen
adsorption in some situations, resulting in favorable HER and
OER activity across the pH range studied. However, there are still
some difficulties to be resolved; a) the effect of phase segregation
caused by Mn-doping into TMOs is difficult to rule out, and b) the
relationship between the doping-level structure and electrocat-
Fig. 10. A schematic representation of the fabrication of Mo-doped Co3O4. Reproduced with permission from ref. [240] Copyright Ó 2021, Elsevier.
21
Coordination Chemistry Reviews 474 (2023) 214864
alytic properties in Mn-doped TMO catalysts is still unknown.
The underlying structural origin of the TMOs catalytic activity pro-
vided by Mn dopants needs more research to overcome.
7.1.5. Mo-doped transition metal oxide electrocatalysts
Heteroatom doping is a potential strategy for achieving con-
trolled manipulation of crystal phase and electrical structures of
materials for water splitting application [239]. Non-noble metal
such as Mo may significantly boosts the water splitting activity
of transition metal oxides/hydroxides due to its variable valence
states [28]. Mo is on the right side of the curve in the ‘‘volcano
charts.” It is possible to change the hydrogen adsorption energy
and oxidation of metals by incorporating Mo into the lattice hold-
ing the metal on the left of the ‘‘volcano plot”. In this scenario,
modest transition metal oxide-based catalysts may be sufficient
to provide positive HER and OER activity [63].
Xiong et al. obtained Mo-doped Co3O4 ultra-thin nanosheets
using an eco-friendly solvothermal method which were in air at
350℃ (Fig. 10). The SEM image was used to study the morphology
of Co3O4 doped with varying amounts of Mo. Fig. 11a shows that
the thickness of the nanosheets steadily becomes thinner as the
amount of Mo-doping increases. EDS elemental mapping (Fig. 11-
b-c) image endowed presence of evenly distributed Mo, Co, O,
and C on the 2D nanosheets, indicating that Mo has successfully
been introduced into the Co3O4 nanosheets. TEM images revealed
that Mo has evenly distributed across the nanosheets, indicating
that Mo had been effectively doped into Co3O4 (Fig. 11d–f). HRTEM
images of 0.4Mo-Co3O4 and elemental mapping (using HRTEM)
confirmed that Mo was effectively absorbed into the Co3O4 lattice
(Fig. 11g). The SAED pattern was obtained at different regions
(Fig. 11h) corresponding to Fig. 11f. The XRD patterns obtained
for several Mo-doped Co3O4 catalysts indicated that the addition
of Mo had no effect on the crystal phase of Co3O4. The effective
doping of the Mo-Co3O4 nanosheets was further confirmed using
Raman spectroscopy analysis. The effect of doping on the electro-
chemical activity was studied by changing the amount of doped
metal ions [240]. The OER and HER performance of Mo-Co3O4
demonstrated an ultra-low Tafel slope of 83.7 and 98 mV dec–1,
respectively, benefiting from their interesting ultra-thin properties
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 11. (a) SEM image of 0.4 Mo-Co3O4, (b, c) EDS mapping of 0.4 Mo-Co3O4, (d-f) TEM and (g) HRTEM images of 0.4 Mo-Co3O4, and (h) SAED pattern corresponding to (f).
Reproduced with permission from ref. [240] Copyright Ó 2021, Elsevier.

and conductivity at 10 mA cm
2. The current density revealed a 10 mA cm
2. (Fig. 12a–f), showing the electrocatalytic performance
small onset overpotential of 315 and 79 mV, as well as significant of the Mo-doped Co3O4 electrodes in the OER. Because of its shape
durability even after 12 h of continuous electrolysis. The water and structure, the resulting Mo-Co3O4 electrode material exhibited
electrolysis device required a potential of 1.64 V to reach high electrocatalytic performance. In addition ultrathin nanosheets

Fig. 12. Electrocatalytic performance of Mo-doped Co3O4 electrodes in the OER. (a) LSV curves obtained for Mo-doped Co3O4 and Co3O4 at a scan rate of 2 mV s
1, (b) a
comparison of the Mo content and electrocatalytic performance, (c) Nyquist plots, and (d) linear fitting of the capacitive currents of Mo-doped Co3O4 and Co3O4 vs. the scan
rate. (e) chronopotentiometry (CP) curves obtained for 0.4Mo-Co3O4over 22 h at various current densities from 10 to 100 mA cm
2. (f) LSV curves obtained for 0.4Mo-Co3O4
before and after 3000 CV cycles at a scan rate of 100 mV s
1; the inset shows the time-dependent potential at a current density of 10 mA cm
2 over 18 h. Reproduced with
permission from ref. [240] Copyright Ó 2021, Elsevier.

22
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
reveal, a) higher specific area and electroactive surface area due to
the complete interaction of the electrolyte with the active material,
b) reduce the volume expansion induced by charging and discharg-
ing, the space between the loose nanosheets can be employed as a
container for electrolyte ions, and c) does not modify the crystal
structure of the original Co3O4 on appropriate Mo doping but it
increases the charge density around the Co atoms causing defects,
enhancing the conductivity and accelerating charge transport. This
outstanding rate performance can be traced to a shift in the elec-
tronic structure surrounding Co produced by an appropriate
amount of the Mo dopant. Furthermore, ultra-thin nanosheets
have a larger specific surface area and greater number of electroac-
tive sites for metal ion redox reactions and the porous structure
can operate as an ion buffer, thus reducing the ion diffusion route
and volume expansion. Moreover, the Mo dopant is beneficial for
the catalytic activity and robustness of the multifunctional elec-
trode materials for sustainable energy production and conversion
[240]. Therefore, Mo-doping can expose an abundant number of
catalytically active sites, which contribute to the enhanced electro-
catalytic performance [241].
Moreover, an appropriate amount of Mo-doping and edge engi-
neering can help to adjust the intrinsic electronic structure of the
active sites, which is required for the OER and HER. For example,
Pei et al. obtained Co1Fe1Mo1.8O@NiF through a simple hydrother-
mal synthesis method, which produced an excellent OER catalyst
with an ultra-small overpotential of 210 mV and HER activity with
an ultra-low overpotential of 157 mV required to obtain a current
density of 10 mA cm
2 and a long-term cycle durability of 24 h.
Importantly, as a bifunctional electrode, Co1Fe1Mo1.8O showed an
ultra-small potential of 1.68 V to reach 10 mA cm
2 coupled with
robust durability in a 1 M KOH electrolyte. Based on XRD, XPS,
SEM, and TEM measurements, the morphology and chemical com-
position of the Co1Fe1Mo1.8O was proved to be retained after the
OER and HER process, which contributed to the excellent stability
of the catalyst [242]. The catalytic performance of Mo, like that of
other transition metal oxide dopants, is linked to the quantity of
the Mo dopant used. An appropriate doping dosage should be con-
sidered throughout the catalyst design. Furthermore, Mo-doping
had an important effect on the shape of the original TMO based-
catalysts, resulting in a catalyst with a high specific surface area.
However, if the Mo concentration is too high, phase separation
may occur, jeopardizing the performance of the transition metal
oxide electrocatalyst. As a result, precisely regulating the degree
of Mo-doping to achieve a homogeneous dispersion with high con-
centrations of the dopant is extremely difficult. However, further
work is needed to understand the electrical structure surface of
Mo-doped transition metal oxide-based-electrocatalysts to further
improve the efficiency of their total water splitting applications.
7.1.6. Cu-doped transition metal oxide electrocatalysts
Recent studies have shown that non-noble metal dopants are
very efficient in enhancing the performance of HER and OER cata-
lysts [28]. Copper is a low-cost metal with a lower environmental
impact and more accessible oxidation states than other elements,
such as cobalt and nickel. Because copper complexes have a poor
H* absorption ability and are unstable, catalytic water splitting
with copper-based electrocatalysts has not been widely investi-
gated. Copper, being a transition element and non-precious metal,
has exceptional electrical conductivity and is earth abundant. To
improve the structure and performance of important electrochem-
ical catalysts, normally copper ions are added as dopants [243]. Cu
and Co atoms are quite similar in terms of their atomic size, elec-
tronegativity, and bonding states [63]. Cu-doping causes deforma-
tion of the metal lattice and produces additional defects, resulting
in an increase in the number of active sites, suggesting that Cu can
be used as a possible dopant to increase the HER and OER perfor-
23
Coordination Chemistry Reviews 474 (2023) 214864
mance of electrocatalysts. Copper, in particular, is an excellent can-
didate for doping since it has the second greatest electrical
conductivity of all metals. The high-valence Cu active species in
CuOx are useful to increase the overall water splitting activity
and they have long been known to be effective HER and OER active
sites. This phenomenon has sparked a lot of interest in exploiting
the energy produced from ultra-high-valence active Cu species
and boosting their quantities in order to improve the electrocat-
alytic performance in the HER and OER. For many years, RuO2
has been investigated as a superior OER catalyst in a vast number
of studies. In an alkaline environment, Ru exhibits higher HER cat-
alytic activity than Pt. As a result, Ru plays a significant role in alka-
line water electrolysis. On the other hand, researchers have
inferred that the OER is kinetically slow and causes a significant
overpotential and energy loss in the water splitting process. In
the Norskov volcano hypothesis, RuO2 is closest to the top of the
volcano among a wide variety of oxides, yet there is still room
between RuO2 and the vertices, enabling one to synthesize better
catalysts for the OER [244]. Yang et al. synthesized an ultra-low
Ru/Cu-doped RuO2 using a metal–organic frameworks (MOFs)
template method as a very active electrocatalyst for total water
splitting. The results showed outstanding OER activity with a cell
voltage of 1.47 and 1.67 V acquired at a current density of 10
and 100 mA cm
2 in 1 M KOH solution, respectively [55]. They
revealed that the Cu-based dopant can efficiently tailor the d-
band modifying the electronic structure of the Ru active sites on
the RuO2 (1 1 0) plane to enhance the OER activity. Upon the appli-
cation of the selective dissolving method used to form binary tran-
sition metal oxides, this novel approach to Cu-doped/MnO2-like
oxides can provide new options for the design of novel MnO2-
based catalysts as efficient catalysts used for the oxidation of vola-
tile organic compounds (VOC) [245]. Niu et al. prepared Cu-doped
Mn3O4 nanopolyhedra and Cu-doped Mn2O3 hollow nanospheres
with a 20% ratio of copper incorporated into their structures using
an easy one-step solvothermal method upon adjusting the H2O2
content, which revealed high specific surface areas (60.48 and
76.24 m2/g, respectively) and chemical stability over 24 h [246].
Cu-doped MnOx displayed the best performance for the oxidation
of CO when compared to unmixed MnOx, suggesting that the Cu-
doped MnOx products are favorable catalysts for CO oxidation.
Time gradient studies were carried out using TEM to analyze the
temporal morphology of the catalyst crystals; it was found that
the formation of Cu-doped MnOx involved a precipitation-dissolu
tion-re-precipitation process. Cu-doping may effectively alter the
electronic characteristics of Co3O4 allowing more efficient charge
transfer and reaction kinetics. This is advantageous to improve
the catalytic activity and long-term stability, indicating their future
use in water oxidation [247]. Recently, Feng et al. designed and
prepared a Cu-doped RuO2 electrocatalysts by calcination of amor-
phous Ru-Cu sample for OER in acidic medium and the results of
Cu-RuO2 demonstrated an highly low overpotential of 189 mV at
10 mA cm
2 [248]. Tian et al. prepared Cu-doped Co3O4 porous
nanosheet arrays on NiF using a simple one-step pyrolysis method
utilizing bimetallic organic framework precursors, in which the Cu-
Co3O4 NAs/NF electrode nanoarchitecture demonstrated excellent
efficiency a low overpotential of 230 mV for the OER and 125 mV
for the HER to reach a current density of 10 mA cm
2 which
showed a low cell voltage of 1.58 V with good stability and robust
durability over 20 h for total water splitting in 1 M KOH. This
opened up new possibilities for the development of sophisticated
and cost-effective electrocatalysts using high valence Co3+ and
3D porous structures for a variety of catalytic and energy-related
applications [249]. The as-obtained SEM images revealed the sur-
face structures of the Cu, Co-MOF nanoarrays varied with leaf-
like 2D structures and solid and smooth surfaces uniformly cover-
ing the NiF surface. According to the XPS data, the surface anion
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
decoration increased the total Co valence state (Co3+ cations) for
Co3O4, a state of cobalt that has been linked to the improved oxida-
tion potential of adsorption active oxygen species and, as a result,
increased the Co cation activity for the OER. The following factors
contributed to the good catalytic performance of Cu-Co3O4 /NiF
in the OER and HER; a) the synergistic effects of the Co and Cu com-
ponents led to the high electrical conductivity of Cu-doped Co3O4,
allowing for easy charge transfer during the electrocatalytic pro-
cess, b) the porous nanosheet structure, and c) the strong 3D elec-
trode structure, which not only allows electrolyte penetration and
mass diffusion for quick reaction kinetics, but also assures a strong
mechanical connection between the active materials and conduc-
tive substrates for long-term mechanical durability. The superb
properties and enhancement of the HER are assigned to Cu-
doping, which can cause structural distortions as well as changes
in the electronic configuration, which results in; morphological
change, an increase in the number of electrochemical active sites,
and the stronger inherent activity of the catalyst itself, which are
beneficial for lowering the intermediate hydrogen (H*) adsorption
free energy.
7.1.7. Ru-doped transition metal oxide-based electrocatalysts
Ruthenium (Ru) is a 4d transition metal; however it is only 5%
the price of Pt. Because of the 65 kcal mol
1 hydrogen bond energy,
similar to Pt-H, Ru is a theoretically viable replacement to Pt. Ru-
based catalysts are being utilized in several essential industrial
processes, such as hydrogenation, ammonia synthesis, and CO oxi-
dation, as well as some classical electrochemical reactions, such as
the OER and HER [5,46]. Heteroatom-doping has been viewed as a
possible way to significantly improve the catalytic activity in the
HER, OER, and total water splitting reaction by altering the elec-
tronic structure. Ru-doping has sparked exploratory research
among several metals. Ru, which has similar metal-hydrogen bond
strength to Pt and good water-dissociation properties, may be used
as an alternate water splitting catalyst. According to theoretical
analysis and practical observations, Ru has good adsorption capac-
ities toward both hydrogen and oxygen-containing intermediates.
In addition, the cost of Ru ($195.00 per troy ounce) is less than that
of Pt ($974.00 per troy ounce). The insertion of Ru species into
bimetallic oxides may produce strong electron contacts, optimize
GH*, and improve the adsorption free energy of water, endowing
enhanced intrinsic activity and the anchoring individual single
Ru atoms with the maximum atomic efficiency. In order to
enhance the HER performance of metal oxide/hydroxide-based
electrocatalysts, two approaches have been investigated; a) the
synthesis of various nanostructured materials with various mor-
phologies, such as films, nanowires, nanosheets, and nanotubes,
which expose more reactive lattice planes, and b) optimization of
the electronic structure of the catalysts, such as doping, forming
deficiencies, and boosting the electrical conductivity and catalytic
ability of each reactive site [250,251]. Doping with valuable Ru
metal can also improve the HER performance by enhancing the
intrinsic activity of the catalytic material and the density of the
active sites [252–254]. Doping the catalyst with transition metals
can further reduce the cost of the catalyst leading to improvements
in the electronic environment of the core metal, resulting in inex-
pensive active metal catalysts for the electrolysis of water. Further-
more, taking advantage of the multi-metal synergetic effect
between the transition metal oxide and other materials (metal, sul-
fide/metal, carbides/metal, and phosphides) is an encouraging
strategy to increase the catalytic performance of transition metal
oxide-based compounds via the regulation of the energy barriers
of the essential intermediate species. The reaction kinetics of the
OER is mostly obtainedby the simplicity of the adsorption and des-
orption of the intermediates. As a result, changing the chemical
properties of the catalyst upon doping with transition metals to
24
Coordination Chemistry Reviews 474 (2023) 214864
modify its morphology is an efficient way to enhance its perfor-
mance and durability. In general, the electrochemical performance
of a catalyst is connected to the binding ability of the catalytic sur-
face with the intermediate species. One effective method to
increase the efficiency of water electrolysis is to modify the
adsorption capacity via doping with heterogeneous atoms, which
increases the inherent activity of the electrocatalyst. Doping het-
eroatoms or positive inclusion of the active site have been shown
to be useful methods for controlling the electronic structure of
the catalyst and enriching the catalytic sites. Ruthenium has been
recently shown to have adequate adsorption energies for adsorbed
hydrogen and oxygen as the cheapest platinum group metal with
copious d-orbital electrons, allowing the HER and OER efficiency
to be improved. Furthermore, establishing heterogeneous nanoint-
erfaces has lately been acknowledged as an effective strategy to
boost the catalytic activity by exerting interfacial synergy and
changing the valence electron states of the active sites. As an
example, Wang et al. reported the fabrication of a single
heterostructured inter-doped ruthenium-cobalt oxide ((Ru-Co)Ox)
hollow nanosheet array on carbon cloth (CC) via changing the Co
MOF nanoarrays using a simple ion-exchange method coupled
with drying in air (Fig. 13a). The (Ru-Co) Ox nanoarraysshow dra-
matically increased bifunctional electrocatalytic activity due to
their favorable composition and structural benefits of increase
number of revealed active sites, improved electronic structure,
and interfacial synergistic effect.
Subsequent annealing of the Ru-Co MOF derived nanoarrays in
air resulted in their transition into hollow (Ru-Co)Ox nanosheet
arrays, and the morphology of the hollow nanosheets were well
preserved even after in-situ SEM measurement, as illustrated in
(Fig. 13b-c). The XRD pattern as seen in Fig. 13d exhibited broad
diffraction peaks relating to rutile RuO2 with modest shifts to
higher angle sides, as well as broad diffraction peaks corresponding
to Co3O4 with slight shift to lower angle sides. This finding revealed
that Co and Ru were integrated into the RuO2 and Co3O4 lattices,
respectively, indicating the creation of an inter-doped heterostruc-
ture composed of Co-doped RuO2 (Co-RuO2) and Ru-doped Co3O4
(Ru-Co3O4) nanocrystals.
The (Ru-Co)Ox electrocatalyst showed extraordinary activity in
the HER with an ultra-low overpotential of 44.1 mV at 10 mA cm
2
and an ultra-small Tafel slope of 23.5 mV dec–1 (Fig. 14a–c), as well
as a remarkable OER performance with an ultra-small overpoten-
tial of 171.2 mV at 10 mA cm
2 and Tafel slope of 60.8 mV dec–1
to reach 10 mA cm
2 in 1 M KOH (Fig. 14d–f). Moreover, a cell volt-
age of 1.488 V was required for total water splitting with superior
long-term stability over 10 h at 10 mA cm
2. The optimal chemical
composition and structural properties of the hollow (Ru-Co)Ox
nanosheet arrays toward the HER and OER were ascribed to their
superior electrocatalytic activity, (Fig. 14g). These findings indi-
cate; a) the innovative hollow nanosheet arrays result in faster
mass/charge transfer, larger electrochemical active regions, and
more interaction with the electrolyte ions, and b) electronic
manipulation of (Ru-Co)Ox due to heteroatom-doping and the for-
mation of a heterogeneous nanointerface will optimize the Ru sites
to reduce Hads adsorption and enhance Oads adsorption. Finally, the
Co sites in Ru-Co3O4 and the produced Co(OH)2 are likely to
increase water dissociation of the Ru sites for enhanced HER activ-
ity. The surface oxidized (oxy)hydroxides and Co sites in Co-RuO2
can enhance the oxygen binding energy of the Ru sites for pro-
moted OER activity which is assigned to the potential induced
interfacial synergistic effect [163]. For one thing, the Ru doping
into the CoOx could significantly moderate its electronic structure
to optimize the binding strength with oxygen-containing interme-
diates [255]. Incorporation of elemental Ru into CoOx/NF con-
tributed enhanced electrochemical kinetics [256]. Li et al.
prepared Ru-incorporated oxygen-vacancy-enriched MoO2
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 13. (a) A schematic representation showing the fabrication of hollow (Ru-Co)Ox nanosheet arrays on carbon cloth. (b, c) SEM images of the (Ru-Co)Ox nanoarrays; the
inset in (b) is a low-magnification image and the inset in (c) shows a broken hollow nanosheets. c) XRD pattern obtained for (Ru-Co) Ox; the inset in (d) shows the enlarged
scan range of 27.5–37.5°. Reproduced with permission from ref. [163] Copyright Ó 2020, John Wiley and Sons.
nanosheets (Ru/MoO2
x) successfully by using hydrothermal pro-
cess [183] that recorded an ultra low overpotential of 29 mV at a
small current density of 10 mA cm
2, with a small Tafel slope of
22 mV dec
1 in 1 M KOH electrolyte solution as a HER catalyst.
That’s why incorporating Ru into MoO2 can lower the energy bar-
rier for H2O dissociation and promote desorption of intermediate
hydrogen atoms (H*) from water. To ensure an optimal HER perfor-
mance, significant research efforts have been undertaken to control
the size, shape, electronic structure, and delicate local chemical
environment of Ru-based electrocatalysts. Furthermore, Ru-based
materials have shown outstanding OER performance. The unique
features of Ru, including its large surface area, well-defined poros-
ity, and self-supporting qualities, make it the perfect foundation
for creating electrocatalysts that match the requirements outlined
above [257]. Doping noble metals, such as Pd, Ru, and Ni, in layered
metal oxides is also regarded as one of the most successful meth-
ods of activating the metal oxide basal planes. Interestingly, Ru
may be viewed as a possible alternative dopant as its cost is almost
order of magnitude lower than Pt and Au. Furthermore, this may
result in defects and sufficient oxygen vacancies, considerably
increasing the electrochemical performance of the metal oxide in
the water-splitting process. The addition of Ru to NiFe–LDH may
enhance its sluggish reaction kinetics and alter its electronic struc-
ture, opening the door to the development of a bifunctional elec-
trocatalyst for total water splitting application. Ye et al. reported
a FeNi-LDH and self-supporting binder-free bifunctional electro-
catalyst using a one-step oil bath etching process, which was fab-
ricated in- situ and grown on the surface of iron-foam (named Ru–
Fe3O4@FeNi–LDH/IF) (Fig. 15) [258].
TEM image was used to examine the morphology of Ru–Fe3-
O4@FeNi–LDH/IF in order to confirm its core–shell structure
(Fig. 16a–d). SAED pattern indicated the two inconspicuous con-
centric rings which were ascribed to the (0 1 2) and (1 1 3) crystal
planes of FeNi–LDH (Fig. 16e). At the same time, weak lattice
fringes were visible in the HRTEM image, which may be attributed
to the poor crystallinity of FeNi–LDHs (Fig. 16f). Furthermore,
25
Coordination Chemistry Reviews 474 (2023) 214864
STEM-EDS mapping image revealed the four elements which were
evenly distributed in the sample (Fig. 16g). These findings further
indicated that during the reaction, the Ru–Fe3O4 nanoparticle core
could be generated first, followed by the formation of the LDH shell
on the surface of the core.
Ru–Fe3O4@FeNi–LDH/IF showed superior electrocatalytic activ-
ity under alkaline conditions and exhibited ultra-low overpoten-
tials for the HER of 104, 173, and 212 mV at current densities of
10, 50,and 100 mA cm
2 respectively with a Tafel slope of
86.5 mV dec
1 at 10 mA cm
2; for the OER, overpotentials of
189, 214, and 226 mV were required to provide current densities
of 10, 50, and 100 mA cm
2, respectively with a Tafel slope of
34.3 mV dec
1 at 10 mA cm
2 in 1 M KOH electrolyte (Fig. 17a–
f). A cell voltage of 1.52 V was needed for total water splitting to
achieve a current density of 10 mA cm
2, which showed robust sta-
bility over 36 h [258]. The surface of Ru–Fe3O4/IF was covered with
NPs of uniform size, suggesting Ru-doping may lead to the creation
of NPs. XPS showed that the presence of Ru can dramatically
change the electronic structure of the catalyst. The improved
HER, OER, and total water splitting activity of Ru–Fe3O4@FeNi–
LDH/IF under alkaline conditions may benefit due to; a) the unique
3D microflower-like structure composed of 2D ultra-thin
nanosheets provide a greater electrochemically active surface area
with extra accessible active sites, b) doping Ru into Fe3O4@FeNi–
LDH allows strong interactions between Ru, Fe, and Ni, which
changes the electronic structure and enhances the efficiency of
the HER and OER, and c) the in-situ growth of Ru–Fe3O4@FeNi–
LDH on the surface of 3D porous foam improves the structural
durability and long-term stability by providing channels for rapid
electron transport and gas bubble release. The Ru-Co3O4-NiO-NF
electrode showed noticeable overpotentials of 44 and 115 mV at
current densities of 10 and 100 mA cm
2, respectively for the elec-
trocatalytic HER in 1 M KOH. The optimized Ru-Co3O4-NiO-NF
electrocatalyst was more active than commercial Pt/C (20 wt.%).
The improved self-supported electrode material maintained its
electrocatalytic efficiency at 100 mA cm
2 for >60 h without sub-
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 14. a) HER polarization curves, b) comparison of the overpotentials, and c) Tafel plots obtained for(Ru-Co)Ox, Pt/C, RuO2, Co3O4 and bare CC. d) OER polarization curves, e)
comparison of the overpotentials, and f) OER EIS Nyquist plots obtained for(Ru-Co)Ox, RuO2, Co3O4 and bare CC with the equivalent circuit (inset). g) A schematic
representation of the mechanism of enhanced water splitting on the hollow (Ru-Co)Ox nanosheet arrays. Reproduced with permission from ref. [163] Copyright Ó 2020, John
Wiley and Sons.

stantial degradation, opening up a new avenue for developing
improved MOF-derived alkaline HER self-supported catalysts for
sustainable energy applications via synergistic tailoring of the mor-
phology and electronic structure. Elemental mapping operated
using HRTEM and high angle annular dark field scanning transmis-
sion electron microscopy (HAADF-STEM) images confirmed that Ru
was effectively absorbed into the Co3O4 and NiO lattices. In nut-
shell, the Ru-doping and hetero-interfaces derived from Co3O4
and NiO can effectively control the electronic states of the Ni and
Co active sites by increasing the conductivity, boosting H2O
adsorption/dissociation and improving hydrogen adsorption
[259]. The inclusion of a transition metal phase is anticipated to
provide extended spacing, extra active sites, plentiful edge sites,
and active edges.
7.1.8. W, Zn, Ag, and Ce-doped transition metal oxide-based
electrocatalysts
In addition to the commonly utilized transition metal dopants
used to increase the HER and OER performance of transition metal
oxide-based catalysts, other non-noble metals, such as V, Sn, Cr,
and W, Zn, have been examined to tune the electronic structure
of the host materials by adding extra active sites to improve the
electrocatalytic efficiency [63,260]. Metal-doping into transition
metal oxides can also increase the conductivity, which is advanta-
geous for obtaining improved performance. The catalytic proper-
ties of transition metal oxides are being improved by the
addition of dopants, such as tungsten, chromium, iron, and nickel,
and hence improve the catalytic performance in the HER and OER
via precise structural control and defect engineering [72]. In addi-
tion, the dependability of high-valence-cation doping, such as
tungsten, has been verified, indicating that it is a viable strategy
to improve the HER efficiency. On the other hand, the doping strat-
egy can control the overall water splitting efficiency of a
heterostructure by tuning the bonding strength between hydrogen
and the electrocatalyst at certain places. For example, Li et al.
reported a unique hetero-electrocatalyst comprised of a W-doped
MoO2/CNT composite on carbon nanotube-foam prepared via a
one-step, simultaneous sulfurization and doping strategy to use
in the HER. According to DFT simulations, the high-
valencecation-doping strategy can improve the catalytic activity
of MoO2, particularly at the edge locations where W-doping was
present [261]. The W-doped MoO2/CNT hetero-electrocatalyst

26
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 15. A schematic representation of the formation of Ru–Fe3O4/IF, FeNi–LDH/IF and Ru–Fe3O4@FeNi–LDH/IF. Reproduced with permission from ref. [258] Copyright Ó
2021, Dalton Transactions.

Fig. 16. (a–d) TEM images of Ru–Fe3O4@FeNi–LDH/IF and (e) corresponding SAED pattern. (f) HRTEM image of Ru–Fe3O4@FeNi–LDH/IF and (g) EDX elemental mapping
images of Ru–Fe3O4@FeNi–LDH/IF. Reproduced with permission from ref. [258] Copyright Ó 2021, Dalton Transactions.

showed an ultra-low Tafel slope of 44 mV dec–1 with an ultra-small
overpotential of 62 mV (vs. RHE) at a current density of 10 mA cm
2
in 0.5 M H2SO4. Physical characterization, including XPS, confirmed
doping of W in the material and clarified the quantities and chem-
ical states of each element. Consequently, the theoretical explana-
tion of the HER activity of W-doped MoO2 stated that the
enhancement in the hetero-electrocatalyst HER efficiency was
mostly due to the synergistic impact of the intrinsic HER activity
and electrical conductivity of MoO2. Wang et al. prepared W-
doped NiO/NiS2 interfaced nanosheets directly on carbon sheets
via a hydrothermal method as water-splitting catalysts that
showed superior electrocatalytic performance with an ultra-low
overpotentials of 116 mV (HER) and 263 mV (OER) at 10 mA cm
2
with robust durability over 24 h in 1 M KOH solution. An extraor-

27
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 17. The OER performance of different samples in 1 M KOH at a scan rate of 1 mV s
1. (a) LSV polarization curves, (b) a comparison of the required overpotential of several
catalysts at various current densities, (c) their corresponding Tafel plots, (d) Nyquist plots obtained for different samples, (e) the capacitance current corresponding to
different scanning rates in the synthesized catalysts, and (f) chronopotentiometry curves obtained for Ru–Fe3O4@FeNi–LDH/IF at a current density of 10 mA cm
2.
Reproduced with permission from ref. [258] Copyright Ó 2021, Dalton Transactions.
dinary performance in the total water splitting process was noticed
with a cell voltage of 1.614 V observed at 10 mA cm
2 for the
bifunctional electrode [262]. An excellent electrocatalytic perfor-
mance was assigned to its nanosheet structure, rich active sites
at the nanointerface, and modified electronic states. The following
merits can be attributed to the remarkable catalytic performance;
a) the addition of W may efficiently change the electron density of
the Ni center, increasing the intrinsic activity, b) the rich nanoint-
erfaces formed between NiO and NiS2 may cause significant elec-
tron contact, increasing the rate of charge transfer, and c) by
building the catalysts directly on a robust and conductive sub-
strate, the electrical connection and mechanical strength may be
improved, which is superior to those made using organic binders.
Rani et al. developed nanocluster morphology of pristine 10% Zn
and 20% Zn-doped NiO electrocatalysts by employing a facile and
low cost solvothermal route. The electrochemical OER activity
showed ultra-small overpotential and ultra-low Tafel slope of
75 mV dec-1 and excellent stability of over 12 h at 10 mA cm
2
[263]. Huang et al. prepared Ce-MnCo2O4 nanomaterials using a
facile oxalate co-precipitation method in which the electrode pre-
pared with 1.49 wt.% Ce-doping demonstrated efficient OER activ-
ity with an ultra-small overpotential of 390 mV at 10 mAcm
2 and
ultra-small Tafel slope of 125 mV dec
1 as well as high HER activity
with a noticeable overpotential of 389 mV at 10 mA cm
2 and
ultra-small Tafel slope of 96 mV dec
1, which adduced a low volt-
age cell of 1.56 V with superior stability over 12 h at 10 mA cm
2 in
an 1.0 M KOH electrolyte [264]. Because the HER and OER pro-
cesses are linked to the surface oxygen vacancies, oxygen adsorp-
tion, and oxygen transfer ability, the lower energy needed for
surface oxygen removal typically indicates an improved oxygen
transfer ability and higher OER activity. Yan et al. reported a facile
electrodeposition-hydrothermal method to synthesize meso-
porous Ag-doped Co3O4 nanowire arrays on a flourine-tin-oxide
glass substrate for water oxidation in 0.5 M H2SO4, which dis-
played outstanding OER activity with an ultra-low potential of
28
Coordination Chemistry Reviews 474 (2023) 214864
1.6 V at the current density of 10 mA cm
2 and an overpotential
of 370 mV [265]. Ag-Co demonstrated robust durability at a nearly
constant overpotential of 370 mV over 10 h in 0.5 M H2SO4 for the
OER. As a result, Ag-doping has significantly improved the conduc-
tivity as well as the stability of electrocatalysts under acidic condi-
tions. Furthermore, Ni-doping in Ag-Co3O4 had no favorable
influence on the OER activity. As a result, earth-abundant meso-
porous Ag-doped TMOs may be promising OER electrocatalysts
under acidic conditions. Chromium has also been utilized in HER
and OER catalysts as a dopant. Cr3+ cations form unique electrical
structures that facilitate electron capture and charge transfer. Dop-
ing Cr3+ cations into Ni or Co oxides boosts the conductivity [266].
Moreover, metal-doped earth-abundant metal oxides need to be
further widely studied and expanded to additional metal oxide
composites used for various sustainable electrochemical energy
storage and water splitting applications [267,268].
Furthermore, a good electrocatalyst must meet two main
requirements in order to construct an efficient electrolysis cell;
a) for electrochemical reactions at the electrodes, the electrocata-
lyst must be extremely active with minimal overpotentials, and
b) the electrocatalyst must be sufficiently stable and exhibit robust
durability to support its performance for an extended period of
time, making it an appropriate for commercial applications.
The findings of the studies reviewed here are comparatively
summarized in (Table 1). In addition, electronic structure regula-
tion through doping of transition metal oxides with metals such
as Fe, Co, Ni and Cu might be a promising route to improving
OER activity, whereas other transition metal elements, such as
Ru, Mo and W, can also act as effective doping elements to improve
the HER electrocatalytic performance of the TMOs. Furthermore,
the doped TMO catalysts showed a smaller Tafel slopes, charge
transfer resistances, and higher ECSAs, in comparison with the
undoped TMOs. Among various non-noble metal materials Co3O4
has drawn much attention as a promising electrocatalyst for HER
and OER. Generally, it is probably the most advanced electrode
 A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Table 1
Summary of metal-doped transition metal oxide electrocatalysts reported recently for the HER and OER.

Catalyst Electrolyte Overpotential for HER at Overpotential for OER Tafel slope for Tafel slope for Overall voltage at Stability Stability Method Reference
j (mV@mA cm
2) at j (mV@mA cm
2) HER (mV OER (mV j (V@mA cm
2) for HER for OER
dec
1) dec
1) (h) (h)
Fe-MoO2/MoO3 1 M KOH 36 mV at 10 mA cm
2 310 mV at 100 mA cm
2 84.2 31.7 1.57 V at 10 mA cm
2 95 h 120 h Hydrothermal 199
2D NiFexO 1 M KOH – 274 mV at 10 mA cm
2 – 79.1 – – – Solvothermal 201
Fe-NiO 1 M KOH – 300 mV at 10 mA cm
2 – 37 – – – Solvothermal 208
Fe2+-NiFe (II, III)- 1 M KOH – 140 mV at 10 mA cm
2 113 1.54 V at 10 mA cm
2 – – Hydrothermal 87
LDH
Fe-Co3O4 1 M KOH – 262 mV at 10 mA cm
2 – 43 – – 50 h Hydrothermal 209
Fe-Co3O4 1.0 M KOH – 318 mV at 10 mA cm
2 – 76.8 – – 35 h Self-templating 54
Fe-Co3O4 0.1 M KOH – 160 mV at 10 mA cm
2 – – – – – Solvothermal 211
nanosheets
Fe-Ni(OH)2 1 M KOH – 220 mV at 10 mA cm
2 – 48.3 1.57 V at 10 mA cm
2 – 600 h Autologous chemical oxidation 203
Fe-NiO 1 M KOH 88 mV at 10 mA cm
2 206 mV at 10 mA cm
2 49.7 49.4 1.579 V at 10 mA 20 h 20 h Solvothermal 204
Fe–NiO 1 M NaOH 183 mV at 10 mA cm
2 336 mV at 100 mA cm
2 105.5 65.3 1.636 V at 10 mA cm
2 12 h 12 h Chemical bath deposition 202
Ni-doped Co3O4 1 M KOH 120 mV at 10 mA cm
2 240 mV at 10 mA cm
2 62 64.2 1.636 V at 10 mA cm
2 16 h 16 h Hydrothermal 226
Fe–NiO 1 M KOH – 245 at 10 mA cm
2 – 43.4 1.475 V at 10 mA cm
2 – 24 h In-situ anodic Oxidation 207
Co-MnO2 1 M KOH – 279 mV 10 mA cm
2 – 75 1.5 V at 10 mA cm
2 – 12 h Spontaneous redox reaction 217
Co-CuO 1 M KOH – 120 mV at 10 mA cm
2 – 118 1.43 V at 10 mA cm
2 – 10 h Solvothermal 219
Co-CuO 1 M KOH – 299 mV at 50 mA cm
2 & – 134 1.5 V at 50 mA cm
2 – 15 h Cation exchange 218
330 mV at 100 mA cm
2
Co-CuOx 1.0 M KOH – 290 m V at 10 mA cm
2 – 57 1.52 V at 10 mA cm
2& – 25 h Spray pyrolysis 216
1.62 V at 10 mA cm
2
(Ru-Co)Ox 1 M KOH – 350 mV at 10 mA cm
2 – 60 1.57 V at 10 mA cm
2 – 20 h Ion-exchange 255
Mn-RuO2 0.5 M – 158 mV at 10 mA cm
2 & – 42.94 – – 10 h Spray Pyrolysis 238
H2SO4 254 mV at 100 mA cm
2
Ni-MoO3 1 M KOH 234 mV at 10 mA cm
2 – 171 –
0.4 V at 10 mA cm
2
24 h – Thermal treatment 223
29

Co-MoO2 0.5 M 26 mV at 10 mA cm
2 – 30.9 – – 12 h – Wet chemical 212

H2SO4
Co– NiO 1.0 M KOH 62 mV at 10 mA cm
2 320 mV at 50 mA cm
2 98 156 1.42 V at 10 mA cm
2 20 h 20 h Pyrolysis 213
Co– NiO/NiFe2O4 1 M KOH 84 mV at 10 mA cm
2 186 mV at 10 mA cm
2 53.6 38.5 1.583 V at 10 mA cm
2 12 h 12 h Solvothermal 214
Co-RuO2 0.5 M – 169 mV at 10 mA cm
2 – 350 – – 50 h – 215
H2SO4
Ni
Co3O4 1.0 M KOH 170 mV at 10 mA cm
2 310 mV at 10 mA cm
2 76.9 91.8 1.643 V at 10 mA cm
2 10 h 10 h Chemical bath deposition 225
Ni- (CeO2
x- 1 M KOH – 195 mV cm
2 at – 43 1.45 V at 10 mA cm
2 – 48 h Simultaneous in-situ formation 228
FeNi) 10 mA cm
2
Ni- CuOx 1 M KOH – 305 mV at 10 mA cm
2 – 72 1.50 V at 10 mA cm
2 – 120 h Galvanic displacement 268
NixCoyRu1
x
yO2 0.1 M – – – 32 1.7 V at 10 mA cm
2 – 6h Hydrothermal 229
HClO4
MnxCo3
xO4 0.1 M KOH – 218 mV at 10 mA cm
2 – 92 – –
50 h Hydrothermal 234

Coordination Chemistry Reviews 474 (2023) 214864

Mn-Co3O4 1 M KOH – 436 mV at 50 mA cm
2 – 60 1.7 V at 50 mA cm
2 – 16 h Ammonia evaporation 235
techniques
Ni-/Mn-cobalt 0.1 M KOH – 381 mV at 10 mA cm
2 – 74 1.615 V at 10 mA cm
2 – 24 h Wet chemical 237
oxides

2
2
2
Co1 Fe1Mo1.8O 1 M KOH 157 mV at 10 mA cm 210 mV at 10 mA cm 112 32 1.68 V at 10 mA cm 24 h 24 h Hydrothermal 242
Mo-Co3O4 3 M KOH 79 mV at 10 mA cm
2 315 at 10 mA cm
2 98 83.7 1.64 V at 10 mA cm
2 18 h 12 h Solvothermal 240
W-doped MoS2/ 0.5 M 62 mV at 10 mA cm
2 – 44 – – 17 h – One-step simultaneous 261
MoO2 H2SO4 sulfurization
Cu-Co3O4 1.0 M KOH 125 mV at 10 mA cm
2 230 mV at 10 mA cm
2 66 86 1.58 V at 10 mA cm
2 20 h 20 h Pyrolysis 249
Cr-Co3O4 3 M KOH – 146 mV at 10 mA cm
2 – 57.7 1.561 at 10 mA cm
2 – 36 h Hydrothermal 266
Zn-NiO 1 M KOH – 345 mV at 10 mA cm
2 – 75 – – 12 h Solvothermal 263
Ce-MnCo2O4 1 M KOH 389 mV at 10 mA cm
2 390 mV at 10 mA cm
2 96 125 1.56 V at 10 mA cm
2 12 h 12 h Co-precipitation 264
Ag- Co3O4 0.5 M 370 mV at 10 mA cm
2 – 219 1.6 V at 10 mA cm
2 – 10 h Electrodeposition and 265
H2SO4 hydrothermal
(Ru-Co)Ox 1 M KOH 44.1 mV at 10 mA cm
2 171.2 mV at 10 mA cm
2 23.5 60.8 1.488 V at 10 mA cm
2 10 h 10 h Ion-exchange 163
Ru-Fe3O4@FeNi– 1 M KOH 104 mV at 10 mA cm
2 189 mV at 10 mA cm-2 86.5 34.3 1.52 V at 10 mA cm
2 25 h 25 h Oil bath etching 258
LDH

(continued on next page)

A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

material because the Co3þ in Co3O4 possesses many dangling

Reference

bonds as active sites for H2O dissociation. Therefore, in view of

the physicochemical properties, advantageous and multiple syn-
259

256

148

174

244

175
221
142
254

146

147
thesis methods, cheap but efficient metal doped TMO electrocata-
lysts would be the best candidates to replace noble metals for
electrocatalysis reactions. It is inferred that metal-doping reduces

Coordination-assisted etching
Carburization of Rumodified
the overpotential and increases the stability of transition metal

Mo–MOF under an inert

Thermal decomposition
oxide-based electrocatalysts by modulating the surface morphol-

Chemical precipitation
ogy, tuning the structural, optical, and electronic properties, espe-
Pyrolysis strategy

cially around the active centers, enhancing the electrical

Co-precipitation
In-situ growth

Hydrothermal

Hydrothermal
Wet chemical

conductivity of the electrocatalysts, and thus optimizing the intrin-

Selenization
atmosphere

sic activity of nanomaterials.

Method

To summarize the effect of transition metal oxide-doping on the

HER/OER activity of several transition metal-based electrocatalysts
metal cation-doping has been extensively explored which is an
Stability
for OER

efficient and easy method for enhancing the intrinsic electrical

100 h

100 h

24 h
50 h

50 h

conductivity, cycle stability, and electrochemical capacitance of

8h
(h)
–

–
transition metal oxides. Moreover, doping cations such as Fe, Co,
Stability
for HER

Ni, Cu, Mn, Mo, and W into transition metal oxides has been used
100 h

h
60 h

20 h

to alter the electronic structure of materials, improving the electri-

(h)

12

25
50

50
–

cal conductivity and electrocatalytic efficiency even further, which

is promising for non-precious metal electrocatalysts. Although,
2.2 V at 1000 mA cm
2

1.529 V at 10 mA cm
2

2

1.49 V at 10 mA cm
2
1.53 V at 10 mA cm

some metallic transition metal-doped transition metal oxides have

Overall voltage at

shown considerable potential as overall water splitting electrocat-

j (V@mA cm
2)

alysts, theoretical studies suggest that their catalytic properties are

not thermodynamically high. As a result of these designs, the cat-
alytic activity can be harnessed based on which a wider range of
applications can be predicted. It is important to uncover the under-
–

lying modified electronic structure-catalytic activity relationships

Tafel slope for

in both the transition metal oxide and host catalysts for the HER
and OER. Performing thorough research on the effectiveness of
OER (mV

metal-doped transition metal oxides in the HER and OER, revealing

dec
1)

43.96
61.2

86.9
134

the activity as well as performance order of the various dopants is

62

38
–

of considerable scientific interest. As a result, it is proposed that

extensive work needs be dedicated to elemental doping in transi-
Tafel slope for

tion metal oxides in order to further improve the efficiency of their

HER (mV

total water splitting applications.

dec
1)
53.9

63.1
93.8
28

44

72
35

37
–

7.2. Non-metal (anion)-doped transition metal oxide electrocatalysts

2

2
188 mV at 10 mA cm
2

175 mV at 10 mA cm
2

304 mVat 10 mA cm
2

164 mV at 10 mA cm

Overpotential for OER

Recently, heteroatom-doping, particularly using anions in

308 mV at 50 mA cm
at j (mV@mA cm
2)

carbon-based materials with ultra-small radii and large elec-

1000 mA cm
2

tronegativity, have displayed remarkable benefits in terms of their

accuracy, variety, and performance in modifying the electronic
370 mV at

structure of the electrocatalytically active sites in transition metal

oxides, and have accomplished full water splitting efficiencies
–

comparable to Pt and Ru. Heteroatom-doping lowers the energy

required to produce an oxygen vacancy in the material and is a
252 mV at 1000 mA cm
2
Overpotential for HER at

good way to create vacancy defects in transition metals [269]. In

29 mV at 10 mA cm
2

2

mV at 10 mA cm
2
mV at 10 mA cm
2

43 mV at 10 mA cm
2
44 mV and 115 mV at

mV at 10 mA cm

metal oxides, the non-metal dopants produce tension within the

j (mV@mA cm
2)

10 mA cm
2 and

and 48 mV @

structure, reducing the optical band gaps and shifting the absorp-
100 mA cm
2

tion toward lower energy side, resulting in enhanced electrocat-

mA cm
2

alytic activity. [270]. Controlling the electrical structure and

improving the intrinsic properties of the nanomaterial in the cata-
lyst one can obtain heteroatom-doping. The reaction kinetics, nota-
56
72
98
22
10
–

bly the functional processes of the hetero-dopants in the catalyst,

1 M KOH &
Electrolyte

remains unknown [59]. To improve these catalysts, a variety of

1 M KOH

1 M KOH

1 M KOH

1 M KOH
1 M KOH
1 M KOH

1 M KOH

ways have been devised, including expanding the surface area,

H2SO4

H2SO4

H2SO4

H2SO4
0.5 M

0.5 M

0.5 M

0.5 M

generating distinctive facet structures, and boosting the conductiv-

ity. Among these enhancements, fabricating defects on electrocat-
alysts is a viable and efficient method for accelerating the reaction
Table 1 (continued)

WCoSe/WCo3O4

Fe-incorporated
Cu-doped RuO2

MoNi@Mo-NiO
Ru-Co3O4-NiO

Ru–Cu–MoO2

rate [250]. Doping with non-metals has been employed in the

NixMo1
xO2
Ru3MoCeOx

Ru–MoO2

design of the metal oxide-based electrocatalysts. Carbon and nitro-

Ru-CoOx
Catalyst

CoO
Ni/NiO

gen are the primary non-metal dopants used in metal oxides. In

brief, doping transition metal oxides with non-metal heteroatoms,
such as N, F, P, and S, can be effective way to improve their HER and
30
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
OER efficiency under both acidic and alkaline conditions. The fol-
lowing are the essential causes and positive advantages for choos-
ing non-metal atom doping; a) simple operation without a time-
consuming fabrication process, b) producing oxygen vacancies as
the HER and OER active sites, and c) improving the electronic con-
ductivity for better charge transfer process. Furthermore, hetero-
anion-doping has been shown to be an important method for fab-
ricating transition metal oxides with strong activity toward elec-
trocatalytic water splitting. In general, adding hetero-anions to
transition metal oxides increases the number of intrinsic active
sites, improves active site of utilization, improves the conductivity,
and induces charge reallocation in the host materials, modulating
the electronic structure to enhance the adsorption free energy of
the reaction mediator, and lowering the overall reaction energy
barrier for electrochemical water splitting [45,85,271]. Studies car-
ried out to produce more active sites and facilitate charge transport
in order to achieve enhanced OER or even HER activity include the
formation of heteroatom-doping and mixing with carbon materials
to form self-standing conductive skeletons [25]. Anion regulation
in transition metal oxides includes oxygen and sulfur selenium,
nitrogen, phosphorus, and fluorine-doping. Many transition metal
oxides, including MnO2, Co3O4, Fe2O3, CoFe2O4, MnCo2O4, CaMnO3,
La1-xSrxCoO3, and Pr0.5Ba0.5MnO3, have reported that anion regula-
tion has an important effect on the electronic structure, con-
veyance properties, and absorption/desorption of reactants and
reaction mediator for obtaining improved OER and HER activity.
In this section, we will briefly focus on non-metal-doped transition
metal oxide based-electrocatalysts.
7.2.1. N-doped transition metal oxide-based electrocatalysts
Doping is another effective method to improve the overall
water splitting performance of metal-based catalysts.
Heteroatom-doping is predicted to boost both the number of cat-
alytic active sites and the electrical conductivity on the catalyst
surface. Recently, one effective strategy for composition engineer-
ing is to substitute another transition metal with a similar atomic
radius and electron configuration into the cubic or orthorhombic
structure of the transition metal oxide without changing the lat-
tice, thereby enriching the structural deficiencies and vacancies,
regulating the catalytic active sites on an atomic scale.
Transition-metal oxides, hydroxides, selenides, sulfides, nitrides,
and phosphides and other transition-metal compounds have been
extensively studied. Due to their advantages of rich abundance,
structural diversity, and stability under alkaline conditions,
transition-metal oxide, such as Co3O4, is considered as the most
suitable choice for the OER. Despite the fact that significant
research has been carried out for developing Co3O4-based catalysts
with high surface area, enhanced electrical conductivity, and dis-
tinctive facet structures, their related OER activities are not as
desirable as envisaged and must be further developed [272]. For
instance, N-doped Co3O4 catalysts outperform than their N-free
counterparts in terms of the HER and OER performance, indicating
that N-doping can provide efficient catalytic sites for total water
splitting. The N atom valence electron layer includes three elec-
trons and a single match of electrons, giving it a variety of bonding
types. Because nitrogen has a small atomic radius, it may be easily
implanted in the interstitial sites of the catalyst without altering
the overall electrical conductivity. Furthermore, nitrogen has
strong electronegativity and can easily polarize the atoms in its
vicinity, changing the catalytic activity. Using nitrogen as a modu-
lator to tune the electron densities and d-band centers of the active
sites one can improve the HER and OER activity. In general, electro-
catalysts can be prepared by doping nitrogen into the lattice of the
host using; a) ammonization, i.e., high-temperature treatment
with NH3, and b) solid-state reaction with nitrogenous reagents,
such as urea [63]. The doping approach is a simple and effective
31
Coordination Chemistry Reviews 474 (2023) 214864
way to increase the electrochemical active surface area and
improve the electron conductivity. As an example, Wang et al. pre-
pared N-doped NiO nanosheet arrays (N-NiO) on NiF as an interest-
ing electrocatalyst for the HER in alkaline media using a simple
hydrothermal and nitrogen-doping method. The catalyst displayed
noteworthy electrocatalytic performance in the HER with robust
durability and superior stability in a 1 M KOH electrolyte. A notable
overpotential of 154 mV at 10 mA cm
2 and ultra-low Tafel slope
of 90 mV dec–1 over 10 h of continuous operation were reported.
Raman spectroscopy measurement confirmed that the N-doped
NiO was successfully synthesized. As a result, the N-doping tech-
nique plays an important role to increasing the HER electrocat-
alytic activity [273]. Dai et al. reported the synthesis of Co/CoO
firmly attached on an N-doped carbon layer covered on carbon
cloth (Co/CoO@NC@CC) using an easy self-assembly-
carbonization method. The Co/CoO@NC@CC electrode exhibited
excellent electrochemical activity toward the OER with an ultra-
low overpotential of 284 mV and ultra-small Tafel slop of 80 mV
dec–1observed at 10 mA cm
2; for the HER an ultralow overpoten-
tial of 152 mV and ultra-low Tafel slope of 80 mV dec–1 at
10 mA cm
2 were achieved and the catalyst showed robust dura-
bility over 25 h. More significantly, the Co/CoO@NC@CC electrocat-
alyst only required a small potential of 1.66 V for total water
splitting to gain a current density of 10 mA cm
2 in a 1.0 M KOH
electrolyte [274]. Furthermore, Co/CoO@NC@CC exhibited excel-
lent stability over 25 h of continuous operation, which leads to a
novel way of making bifunctional electrocatalysts. The XRD analy-
sis showed that Co and CoO were converted from ZIF-67 and Co
(NO3)2, respectively. The SEM image was used to study the mor-
phology and microstructure of the intermediate, Co/CoO@NC@CC,
Co@NC@CC, and CoO@NC@CC. The Co and CoO nanoparticles were
encased in the graphitic carbon layer, which was formed from the
catalytic impact of the Co species during the graphitization of
amorphous carbon in the carbonization step. The discrete lattice
fringes with 0.34 nm d-spacing correspond to the (0 0 2) plane of
graphitic carbon has demonstrated the excellent reliability of
XRD. Furthermore, HRTEM images (as well as fast Fourier transfor-
mation (FFT) and inverse Fourier transformation (IFFT) imaging)
indicated the well-maintained crystallinity of Co/CoO@NC@CC
and the coexistence of Co and CoO. According to the above-
mentioned experimental findings and analyses, the remarkable
improvement in the electrocatalytic capabilities of Co/
CoO@NC@CC toward both the OER and HER could be a result of
three factors; a) due to their affinity, the presence of Co and CoO
can enhance the water splitting process, b) the hierarchical porous
structure may not only extend the accessible ECSA, allowing the
preferential exposure and exploitation of active sites, but also
enrich the electron/ion diffusion pathways, allowing for quicker
charge transfer in the electrocatalyst, and c) the self-supported
open design, which is free of binders, accelerates ion transport
and mass transfer, while allowing gas bubbles to escape, which is
beneficial for the reaction dynamics and long-term electrochemical
durability. These characteristics combine to give Co/CoO@NC@CC
significantly increased electrocatalytic activity. Xu et al. fabricated
N-doped Co3O4 nanosheets as an OER electrocatalyst with oxygen
vacancies using N2 plasma treatment, which exhibited a small cell
voltage of 1.54 V to achieve a current density of 10 mA cm
2 and a
lower Tafel slope of 59 mV dec–1 than pristine Co3O4 nanosheets
(234 mV dec-1) [275]. Jin et al. fabricated Co-CoO/N-doped carbon
sheets hybrids (CoOx@CN) comprised of CoO and Co3O4 utilizing
a facile, scalable, inexpensive, and effective one-pot annealing
method. The CoOx@CN electrode exhibited noticeable overpoten-
tial of 85 mV for the OER and a small HER overpotential of
235 mV to achieve a current density of 10 mA cm
2 in a 1 M
KOH electrolyte. More significantly, the corresponding alkaline
electrolyzer reached  20 mA cm
2 at a voltage of 1.55 V [276].
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Using the correct amount of N-doping to generate oxygen vacan-
cies is a good approach to boost the catalytic efficiency of electro-
catalysts. For example, Wang et al. obtained a defect-rich N-Co3O4
nanoparticles/nitrogen doped carbon framework (N-Co3O4@NC)
using a highly controllable N-doping strategy and ZIF-67 made
using a standard room-temperature technique (Fig. 18a) to boost
OER related bifunctional electrocatalysis [277]. The XRD patterns
of Co3O4@NC and N-Co3O4@NC-2 are shown in Fig. 18b. The mor-
phology of the as-synthesized material was investigated using
FESEM. ZIF-67 has uniform cube-like morphology with a smooth
surface. On the other hand, Co3O4@NC retains its polyhedral shape,
but has multiple mesopores, producing a 3D porous structure
(Fig. 18c). With the exception for the N-Co3O4@NC-4 sample, the
N-doped samples retained the Co3O4@NC after the N-doping proce-
dure (Fig. 18d). TEM images revealed that N-Co3O4@NC-2 had a
homogeneous nanocube-like morphology with a porous and rough
surface (Fig. 18e). These open areas were intended to make the cat-
alytically active sites more accessible by providing numerous mass
transfer pathways. The porous and carbon-containing structure of
N-Co3O4@NC-2 is shown in (Fig. 18f-g) confirmed the uniform dis-
tribution of Co, O, and NthroughouttheN-Co3O4@NC-2 composite
(the uniform distribution of C element is not shown) with N con-
tent of 3.48%. Experimental and computational studies have shown
that introducing zero-dimensional point defects (oxygen vacan-
cies) and two-dimensional planar defects (crystal defects) into
transition metal oxides can provide; functionalities to adjust the
electronic structure, enhance electrical conductivity, and optimize
the adsorption energy and oxidation of the reactants and interme-
diates. Excellent OER catalytic activity and stability were achieved
with an overpotential of only 266 mV at a current density of
10 mA cm
2 and ultra-small Tafel slope of 54.9 mV dec–1
(Fig. 19a–d). Due to N-doping, the electrode surface hydrophilicity
was enhanced which could be assigned to the fact that nitrogen
Fig. 18. a) A schematic representation of the preparation of N-Co3O4@NC. b) XRD patterns obtained for Co3O4@NC and N-Co3O4@NC-2. FESEM images of c) Co3O4@NC and d)
N-Co3O4@NC-2. TEM e) and HRTEM f) images of N-Co3O4@NC-2. HAADF-STEM and elemental mapping images g) of the resultant N-Co3O4@NC-2 samples. Reproduced with
permission from ref. [277] Copyright Ó 2019, John Wiley and Sons.
32
Coordination Chemistry Reviews 474 (2023) 214864
functional groups are hydrophilic, allowing for easier interaction
between the electrolyte ions and the electrodes.
To conclude, N-doping not only preserves the host catalysts
metal characteristics, but also increases the electric conductivity
in some circumstances, allowing for enhanced charge transfer. Fur-
thermore, N-doping can alter the surface crystal structure and gen-
erate more active sites, while lowering the hydrogen adsorption
force, allowing for improved HER and OER reaction rates. As a
result of the structural features offered via N-doping, the electro-
catalytic HER and OER activity may be significantly increased.
The empty orbitals of N atoms, in essence, offer intermediate char-
acteristics for the Tafel and Volmer reactions, resulting in promis-
ing catalytic activity for hydrogen production. As a result, it is
argued that N-doping is a viable strategy for increasing the HER
and OER efficiency of transition metal oxide-based electrocatalysts.
Furthermore, the significance of N-doping in metal oxides, particu-
larly its impact on the atomic structure and surface electron states
near the metal sites, is still unclear and requires further
investigation.
7.2.2. P-doped transition metal oxide-based electrocatalysts
Non-noble-metal electrocatalyst advancements for sustainable
water splitting application have had a substantial influence on
renewable clean energy generation (H2) [278]. Doping is an
approach used to improve the activity of electrocatalysts by boost-
ing the electrical conductivity, increasing the active surface area,
and lowering the energy barrier for the transition state, among
other things. Phosphorus -doping is projected to change the elec-
tronic structure of transition metal catalysts, resulting in funda-
mentally increased water electrolysis activity [28]. P is an
attractive dopant for improving the electrocatalytic activity via
modifying the electronic structure of electrocatalyst due to its
greater atomic size and better electron-donating capacity. To
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 19. a) LSV curves obtained for ZIF-67, Co3O4@NC, N-Co3O4@NC-1, N-Co3O4@NC-2, N-Co3O4@NC-3, and RuO2 during the OER. b) Tafel plots obtained for Co3O4@ NC, N-
Co3O4@NC-1, N-Co3O4@NC-2, N-Co3O4@NC-3, and RuO2. c) The LSV curves obtained before and after 2000 accelerated CV scans at a scan rate of 100 mV s
1. d) The
chronopotentiometry (i–t) curve obtained for N-Co3O4@NC-2 at a potential of 1.51 V (vs. RHE) over 30 h (without iR correction). The mass loading was 0.70 mg cm
2 for all
catalysts. Reproduced with permission from ref. [277] Copyright Ó 2019, John Wiley and Sons.

increase the intrinsic activity and speed up the reaction kinetics, P-
doping may transfer the local charge density and optimize the sur-
face charge states, as well as provide an abundant number of active
surface sites and surface reactions [29,279,280]. Moreover, P-
doping is a more beneficial technique for improving the catalytic
performance than transition metal-doping because it takes advan-
tage of the in-situ manipulation of the electronic structure using P
atoms without affecting the intrinsic characteristics of the host
material. P-doping has been used in a variety of materials to date,
including carbon materials, semiconductors, metal compounds,
and their derivatives, such as oxides [281,282]. It is worth noting
that adding phosphorus to metal oxide nanostructures has been
shown to improve the electrocatalytic efficiency of oxygen-
deficient catalysts in general water splitting experiments
[283,284]. Phosphate is expected to perform a dual role in improv-
ing the electrocatalytic properties of ferrite; it promotes high Ni
oxidation states via facilitating proton transfer [285]. Phosphorous
has a larger atomic radius and greater ability to donate electrons
than N. Therefore, it has a greater influence on the control of the
surface charge states. The electronic states of the metal compo-
nents can be changed by adding phosphorous to transition metal
oxide-based catalysts in order to improve their catalytic properties.
Phosphorous-doping can be created using NaH2PO2 as a precursor
[63]. Despite the fact that enhanced catalytic behavior has been
achieved, the following issues still exist; a) it is challenging to pro-
duce an accurately regulated doping quantity during heteroge-
neous gas–solid processes when employing NaH2PO2 as the
precursor, b) achieving a high level of P-doping is difficult to over-
come, c) the connection between the doped structure and TMOs
activity is still unknown, d) for large-scale manufacturing, the dop-
ing procedure is currently complicated, and e) the P precursors are
prohibitively expensive. The introduction of phosphorous, in gen-
eral, necessitates a phosphatization reaction. According to the dop-
ing hypothesis, P and S atoms have comparable atomic radii,
making them simple to substitute for one another. On the other
hand; P has one fewer valence electron than S. The new non-
metallic-P bonds can offer additional active sites and reduce the
Gibbs free energy for the HER and OER after doping. Active phos-
phorus compounds react with transition metal oxide-based mate-
rials throughout the process, resulting in a decrease in the oxide
contaminants present on the catalyst surface. Firstly, the catalyst
may be doped by replacing N atoms with P [286]. The addition of
P to the 3p-orbital with lone-pair electrons and unoccupied 3d-
orbitals may shift the local charge density and optimize the surface
charge states to increase the intrinsic activity and reaction kinetics.
Under alkaline conditions, the hydrophilic metal oxide may
enhance the conductivity, while also having a beneficial effect on
water molecule absorption and dissociation. Thus, phosphorous
is one of the most interesting dopants due to the reaction condi-
tions used for P-doping being less severe than those used for N-
doping; the electrocatalytic durability of P-doped Co3O4 is greater
than that of S-doped Co3O4 [287]. Co3O4 has sparked a lot of inter-
est as an OER and HER catalyst. However, its performance is lim-
ited due to its poor electrical conductivity and small number of
accessible active sites. The electronic states and surface area of
Co3O4 determine its electrocatalytic activity. Heteroatom-doping,
facet control, and oxygen vacancies can all be used to alter the
electronic states of Co3O4. Non-metal doping is one of these strate-
gies and is thought to be the best method to enhance the electro-
chemical efficiency of Co3O4. For example, Wang et al. developed a
P-doped Co3O4 nanowire arrays (P-Co3O4/NF) using a facile
method, in which NaH2PO2 was used as the P source. P-Co3O4/NF
exhibited OER activity in 1.0 M KOH with a small overpotential
of 260 mV used to obtain a current density of 20 mA cm
2 at

33
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
around 1.7 V with a low Tafel slope 60 mV dec–1 and favorable sta-
bility [288]. The P8.6-Co3O4/NF-based total water splitting device
achieved a current density of 10 mA cm
2 at 1.63 V for the poten-
tial deciding step of the OER. DFT simulations revealed a smaller
free energy change than pure Co3O4. XPS showed that P was effec-
tively doped into Co3O4, resulting in a decrease in the electron den-
sity around Co and an increase in the number of Co3+ species,
which can provide enriched unoccupied d-orbitals to aid OH*
group and H atom adsorption. As a result of the enhanced OH*
adsorption and H* binding, the kinetics of the OH* adsorption
and Volmer steps in the HER process were enhanced, and the Tafel
slopes of the OER and HER processes on P-doped Co3O4 were
reduced, respectively. Wang et al. developed a defect-rich,
highly-ordered microporous phosphorus-doped cobalt oxide cata-
lyst (Co: Pi/CoOx/CP) on carbon plate (CP) via phosphorus modifica-
tion using a microwave-induced plasma method [289]. The as-
obtained 3D Co:Pi/CoOx/CP exhibited improved electrocatalytic
performance and robust durability with a cell potential of 1.65 V
at 10 mA cm
2 observed over 100 h of total water splitting in 1
M KOH. Surface defects and cobalt phosphate production produced
by microwave-induced plasma were revealed using in-situ Raman
spectroscopy and ex-situ spectroscopic and microscopic tech-
niques, which have substantial influence on the superior electro-
catalytic activity of 3D Co:Pi/CoOx/CP. The as-obtained electrodes
have many advantages; a) the binder-free cobalt carbon electrode
has good electrical conductivity and durability, allowing active
charge transport, b) the abundant defects in the cobalt phosphate/-
cobalt oxide catalyst that significantly improve the intrinsic elec-
trochemical performance, c) the 3D ordered porous design
provides a large surface area and interconnected open channels,
allowing a significant number of accessible catalytic sites and dis-
persion of the generated gases bubbles (O2/H2). It is predicted that
replacing transition metal oxides in the host electrocatalyst with P
from various groups will result in a more significant improvement
in the catalytic performance. Li et al. successfully prepared the 3D
porous ‘‘celosia” heterogeneous interface engineering of LDH and
P-doped molybdenum oxide on MXene-modified NF substrate (de-
noted as P-MoO3 FCL MXene/NF by a facile eco-friendly hydrother-
mal method where an ultra low overpotential of 1.53 V was
sufficient to reach a current density of 10 mA cm
2 in a two-
electrode system which was superior remarkably to another elec-
trocatalysts used in overall water splitting activity [290]. The DFT
simulations and experimental results indicated that P-doping
causes spontaneous hydrogen adsorption on the neighboring metal
oxide atoms, resulting in a nearly thermo-neutral DGH*. In-situ P-
doping also changes the valence state of metal oxides, helping to
stabilize the oxygen vacancies, which are one of the most common
active sites for the HER and OER, and improves the materials elec-
trocatalytic activity. Significantly, the P-doped TMOsaresuitable-
candidate materials for total water splitting performance.
Moreover, phosphorous, like sulphur, has one valence electron
than oxygen, which must result in comparable electrical structural
changes in P-doped sulphides. However, further work is needed to
understand the electrical structure surface of P-doped transition
metal oxide-based electrocatalysts for water splitting process.
7.2.3. B-doped transition metal oxide-based electrocatalysts
Due to having only three valence electrons, boron is an
electron-deficient element which is less electronegative than phos-
phorous although the electronegativity of boron is 2.04. As a result,
boron is more likely to interact with a single electron from oxygen
in H2O, allowing for a quick proton release during the HER and
OER. Zhang et al. obtained CoO nanowires with oxygen vacancies
using a pyrolysis strategy via B-doping [291]. The inclusion of
boron was predicted to favor the formation of oxygen vacancies
in transition metal oxides using DFT simulations. The B-doped
34
Coordination Chemistry Reviews 474 (2023) 214864
CoO-Ov demonstrated superior OER activity with a low onset over-
potential of 280 mV required achieving a current density of
10 mA cm
2 and a small Tafel slope of 71 mV dec
1 in 1.0 m
KOH, suggesting the heteroatom-doping method may be used to
efficiently produce an abundant number of oxygen vacancies for
extremely efficient electrocatalysis. The oxygen vacancies were
formed when the local structure was disordered upon B-doping.
The efficient integration of oxygen vacancies via B-doping in CoO
was ascribed to the disordered local structure, resulting in high
OER performance. According to DFT simulations, the inclusion of
boron in transition metal oxides encourages the formation of oxy-
gen vacancies. The DFT calculations further revealed that the oxi-
dation of *OOH was the rate-limiting step for oxygen vacancy-
enriched CoO. In addition, the presence of oxygen vacancies may
effectively decrease the reaction barrier for breaking the Co-O
bond, resulting in improved OER kinetics. Furthermore, the link
between atomic deficiency and electrocatalytic characteristics
may serve as a theoretical framework for the improvement of
extremely efficient electrocatalysts for sustainable energy and con-
version. Yuan et al. presented self-supported B-doped Co3O4 (VOB-
Co3O4/NF) nanowire architectures with controlled oxygen vacan-
cies on NF via alternate Co salt and hydrolysis using an alkaline
NaBH4 solution for total water splitting, which exhibited overpo-
tentials of 184 and 315 mV at a current density of 50 mA cm
2
for the HER and OER, respectively in 1.0 M KOH. For total water-
splitting, a potential of 1.67 V was required to achieve a current
density of 10 mA cm
2 with robust durability over 20 h. This work
may open up new insights on the use of monolithically incorpo-
rated transition metal oxide nanoarchitectures prepared using
simple defect engineering technique as low-cost, highly-efficient,
and robust multi-functional catalysts for hydrogen production
[292]. After alternating the Co salt and NaBH4 treatment, SEM
image revealed that the oxygen vacancies and boron-doping were
successfully achieved on the Co3O4 nanowires. Due to the creation
of oxygen vacancies, the band gap of Co3O4 was reduced, which
aids the electrical transition from the valence band to the conduc-
tion band. Engineered boron and oxygen defects in Co3O4 nano-
wires could efficiently change their electronic structure, resulting
in improved electrical conductivity and a high number of elec-
troactive sites. Ahn et al. reported that B-doping into nickel–iron
LDH (B:NiFe LDH) can be successfully achieved using a two-step
hydrothermal method and galvanostatic oxidization process,
which is useful for improving the OER activity showing an ultra-
low overpotential of 229 mV at 10 mA cm
2 with a Tafel slope of
57 mV dec-1 and robust durability over 100 h at 10 mA cm
2 in
1 M KOH [293]. It was verified that B-doping kinetically enhanced
the electrocatalyst due to the reduced charge-transfer resistance
observed using EIS of each electrocatalytic electrode. Boron-
doping causes LDH to amorphize, resulting in an oxygen vacancy.
The generated vacancy has an effect on the charge transfer capabil-
ity. When these findings were compared to those of prior studies, it
is clear that B-doping improves the catalytic properties. Due to B-
doping, the degree of graphitization and wettability between the
electrolyte and the electrode can be enhanced, potentially increas-
ing the electrical conductivity [23]. What’s more, borate=doped
transition metal oxides have a localized enhancement electron
density which is great advantageous for splitting of water perfor-
mance. Furthermore, how to doped boron into the lattice of non-
noble metal oxides and the mechanisms of B-doping must be
investigated further [28].
7.2.4. S-doped transition metal oxide-based electrocatalysts
Anchoring heteroatoms such as phosphorous, nitrogen, boron,
and sulphur into metal oxide composites results in an increased
active surface area, good electrical conductivity, outstanding elec-
trochemical performance, durability, and chemical stability, as well
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
as a high rate of oxygen release. In particular, S- and N-doped metal
oxides can be employed as effective water splitting catalysts [294].
Affordable non-noble metal-based oxides, which benefit from low
cost as well as high performance, present new choices for the man-
ufacture of unique water spitting electrocatalysts, but they are lim-
ited by their poor conductivity followed active sites. Sulfur-doping
has the potential to successfully address these issues [28]. Conse-
quently, sulfur-doping has been utilized as a foreign element to
enhance the electrochemical performance of transition metal oxi-
des. Using spatial confinement and electron donor–acceptor inter-
actions, researchers have found that sulphur-doping may improve
the stability of metal NPs [23]. A sulfidation process has been used
to introduce S atoms, a common chalcogen element, as dopants
into the lattice of host catalysts. The S-doping technique used
can considerably increase the catalytic efficiency and durability
in both acidic and alkaline water electrolysis, and also serves as
an effective overall water splitting catalyst. Due to its semiconduc-
tor nature, copper oxide has been commonly utilized as a photo-
electrochemical catalyst. Cu2O is generally inactive in both the
OER and HER process because of its inadequate crystal structure,
low conductivity, and low band gap, limiting its application in
the water splitting process. Zhang et al. synthesized self-
supported nanoporous S-doped copper oxide (Cu2OxS1–x) on Cu-
foam using an electrochemical method [295]. Cu2OxS1-x/Cu
demonstrated outstanding electrocatalytic performance towards
the HER with an ultra-small overpotential of 40 mV at a current
density of 10 mA cm
2 and a small Tafel slope of 68 mV dec-1
which showed ultra-high stability in 1.0 M KOH solution. The S-
doping method substantially enhanced the catalytic properties
and stability under both acidic and alkaline conditions, which also
served as an effective overall water splitting catalyst. The Cu2OxS1–
x/Cu catalysts show strong HER activity that could be attributed to;
a) the intrinsic HER catalytic activity of Cu2OxS1–x being greatly
improved by S-doping, and b) the HER kinetics being improved
by the fast electron transfer between the catalytic active sites of
Cu2OxS1–x. The specific nanoporous structure can expose a larger
active surface area to provide more active sites for the HER. Porous
nanostructures reveal intriguing qualities, such as large specific
surface area and quick electrolyte diffusion, which are advanta-
geous for high HER activity. Furthermore, sulphur atoms have high
electrical conductivity and can accelerate electron transport [296].
On modifying the S-doping ratio, the shape of the transition metal
oxide can be changed from nanorods to nanosheets, the defect oxy-
gen density is changed, and the electrical state can be manipulated
by adjusting with doping time. The change in the electrical state
was found to be the most important, but morphological and defect
oxygen changes also have a role in the improved OER performance.
Li et al. used S-doped carbon materials to build catalysts used for
energy-conversion electrocatalysis because of their distinctive
physical and chemical structures [297]. On the other hand, S-
doping is thought to be more difficult than N-doping because of
the larger atomic size and lower charge transfer of sulphur. As a
result, there is a significant need for the creation of a new precur-
sor that can simultaneously introduce N and S as co-dopants into a
carbon matrix. Geng et al. synthesized S-doped MoO2 nanosheets
as a highly efficient and stable HER catalyst using a facile two-
step strategy involving a hydrothermal reaction with P123 used as
a reducing agent, followed by a sulphuration process. Doping sul-
phur atoms into MoO2 nanosheets resulted in an initial small over-
potential of 120 mV and an ultra-small overpotential of 176 mV at
a current density of 10 mA cm
2, which was reduced to 166 mV
when compared to that of the pristine MoO2 nanosheets, and an
ultra-small Tafel slope of 57 mV in 0.5 M H2SO4 electrolyte [298].
Hao et al., constructed Fe2O3 nanosheet arrays on IF via sulfur dop-
ing (S-Fe2O3/IF) for high efficient HER performance. The results
convinced ultralow Tafel slope of 76 mV dec–1 and small overpo-
35
Coordination Chemistry Reviews 474 (2023) 214864
tential of 134 mV to reach a small current density of 10 mA cm
2
and strong stability for 50 h without any decay [299]. However, S-
doping boosted the active sites by producing structural instability
and a larger degree of the amorphous state, as well as introducing
partial metal-S bonding species into the structure, facilitating elec-
tron transport [300]. Moreover, the use of sulphur atoms as
dopants has been shown to benefit the two aforementioned
aspects. In addition, tuning the concentration of doping process
is still needed to improve the HER and OER activity and better
understand the intrinsic promotion mechanism of S-doped TMOs.
7.2.5. Se-doped transition metal oxide-based electrocatalysts
Selenium (Se) is another chalcogen element of VIA group, as
well as in the same oxygen family, with a comparable valence elec-
tron structure, although it has poor reactivity and lower vapor
pressure, which requires a higher reaction temperature for its -
doping. The inclusion of selenium has been proven to change the
surface electronic structure of the catalyst, hence to improve the
intrinsic activity of catalysts. In particular, polarization-induced
partial negative charges localized on Se centers are more efficient
than those of phosphides and sulphides. They can bind to protons
by providing basic sites to enhance the HER [301]. Du et al. pre-
pared Se-doped Co3O4@CeO2 nanoparticle-dotted nanoneedle
arrays using a hydrothermal method, followed air calcination and
selective selenation. The outstanding HER and OER activity of
SCCN–1 results in an increased number of oxygen vacancies as well
heteroatom-doping level. The ultra-low overpotentials at various
specific current densities are; 48 mV@10 mA cm
2 and
175 mV@50 mA cm
2 for the HER, and 188 mV@20 mA cm
2
and 293 mV@50 mA cm
2 for the OER. Moreover, the SCCN–1/
SCCN–1 electrode required a small cell voltage of 1.49 V to deliver
a current density of 10 mA cm
2 in a 1.0 M KOH electrolyte over a
12 h period to improve the total water splitting performance [302].
DFT studies revealed that Se-doped Co3O4 had higher water
adsorption energy than CeO2 and adding CeO2 enhanced the elec-
trical conductivity of the composite, proving that Se-doped Co3O4
is a genuine reactive center. Furthermore, the SCCN–1 composite
design concept and methodology may be used to enhance the
HER activity of transition metal oxides and used in the catalytic
water splitting process. To summarize, both CeO2 and Se-doping
can increase the water adsorption energy and electronic distribu-
tion of Co3O4. As a result, Se-doping improved the performance
of Co3O4, while partially changing its structure. These two methods
have been tuned and matched to produce the optimum electro-
chemical catalytic activity of SCCN–1 for HER and OER. Therefore,
Se; a) induces the formation of more oxygen vacancies as OH–
adsorption sites, b) increases the ratio of Co2/Co3 on the surface
of the catalyst, accelerating electron transport, and c) increases
charge transfer efficiency in the OER process. Furthermore, Se-
doping boosts the surface ratio of Co2+/Co3+ and accelerates elec-
tron transport, which promotes the electrochemical performance
[303,304]. These findings suggest that incorporating Se into
Co3O4 is a good effective method for increasing OER activity. How-
over, a selective Se-doping method may be used to increase the
HER and OER efficiency of transition metal oxides and even cat-
alyzes water splitting applications.
7.2.6. Carbon-doped transition metal oxide electrocatalysts
Carbon-doped Co3O4 electrocatalysts exhibit low overpotential
and good stability for both the HER and OER under alkaline condi-
tions, pavinge the way for a novel approach to designing highly
active bi-functional electrocatalysts by engineering the electronic
structure of metal oxides because the electrocatalytic activity is
highly dependent on the arrangement of the surface atoms [305].
Furthermore, carbon-based materials offer several possibilities to
experiment with the shape and surface chemistry, both of which
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
play important roles in revealing and maintaining active sites for
effective electrocatalysis [306]. Due to their comparatively low
coordination number, the single-crystal electrochemistry of pre-
cious metal catalysts has revealed a high index surface with open
atom structure with high activity. Defect engineering is therefore
crucial for modulating the surface atom arrangement. Defects can
fine-tune the electronic structure and surface characteristics of cat-
alysts, which can significantly affect their electrochemical perfor-
mance. The development of oxygen vacancies in Co3O4 can
greatly improve the OER activity, whereas the production of a
Co-C bond in Co3O4 can provide optimum HER activity. Point
defects, such as heteroatom-doping, vacancies, and interstitial
atoms, are widely known. Some defect locations, such as edges,
voids, or poorly coordinated steps, can function as active sites
among multiple defects. On the other hand, some defects affect
the electrical characteristics of nanomaterials. The defect chem-
istry of nanomaterials has been widely studied in order to improve
their performance for a range of diverse applications. However,
achieving carbon-doped metal oxides without generating amor-
phous or graphitic carbon is extremely difficult. Yan et al. prepared
defect-rich carbon-doped Co3O4 nanosheets using an efficient one-
step room-temperature (25 oC) CH4 plasma treatment method
[305]. The solution contained both doped heteroatoms and vacan-
cies as point defects, and the results confirmed a low overpotential
of 163 mV at 10 mA cm
2 with a small Tafel slope 89 mV dec–1 at
10 mA cm
2 for the HER and a low overpotential of 250 mV at
10 mA cm
2 with an ultra-small Tafel slope of 54 mV dec–1 at
10 mA cm
2 for the OER in 1 M KOH, suggesting importance of
the electronic structure of metal oxides to create highly effective
bifunctional electrocatalysts. Physical measurements revealed an
uniform distribution of C across the nanosheets, indicating that it
had been effectively doped into Co3O4. Combining these findings,
we may conclude that plasma defect engineering can not only
achieve C doping, but also etch and disorder the material [5,23].
The deformed structure of C-Co3O4 was in accordance to vacancies
(oxygen or cobalt) formed in the lattice as a result of carbon-
doping and plasma etching. The active sites for the electrocatalytic
reactions could be these defect sites. Metal oxides with
heteroatom-doped carbon can be beneficial for the production of
highly active and low-cost overall water splitting catalysts [307].
Doping graphene with heteroatoms, such as nitrogen, has been
shown to effectively modify the electron and chemical characteris-
tics in both theoretical and experimental studies.
7.2.7. F-doped transition metal oxide electrocatalysts
It is worth noting that fluorine can generate a range of unique
features in fluorine-containing molecules/materials due to its high
electronegativity and ultra-low electric polarizability. F-doping
may be a viable method to modify the electrical structure since F
has stronger electronegativity (3.98) than phosphorus (2.19), sul-
phur (2.58), and nitrogen (3.04). Efficient F-doping can be achieved
by employing NH4F as a reactant [63]. Wu et al. obtained a series of
noble-metal-free NiCo2O4 catalysts doped with NiO and CoF2 using
a facile solvothermal method [308]. F-doping and O-vacancies can
breach the energy barrier limit of the water separation step syner-
gistically to make the generation of hydrogen free radicals (H*) in
the alkaline HER, according to DFT calculations and kinetic studies.
Zhang et al. synthesized F-Co3O4-x nanoarrays using a gas-phase
fluorination method used to develop a dual-defective Co3O4
nanoarray (F-Co3O4-x) electrocatalyst with a well-modulated elec-
tronic structure of Co-centers for higher overall water splitting per-
formance [309]. F-Co3O4-x showed ultra-small overpotentials of 77
and 192 mV at 10 and 100 mA cm
2, and 253 mV at 10 mA cm
2
and 338 mV at 100 mA cm
2 with a Tafel slope of 72.9 and 37.3 mV
dec-1 at 10 mA cm
2 for the HER and OER, respectively. The cell
voltage required for full water splitting was 1.56 V at 10 mA cm
2
36
Coordination Chemistry Reviews 474 (2023) 214864
with robust durability over 120 h. Furthermore, F-induced surface
self-reconstruction can be observed during the OER when numer-
ous critical intermediates (OOH*) were generated via F-leaching.
Subsequently, a gas-phase fluorination technique was used to cre-
ate F-Co3O4–x nanosheet arrays with extensive F-doping and O-
vacancy defects. F-Co3O4–x has a nanosheet array structure with
uniform size and thickness, similar to Co3O4, demonstrating the
logical design of multiple-defect electrocatalysts suitable for
high-performance overall water splitting applications. Fan et al.
synthesized a RuO2 on fluorine-doped graphene (F-graphene)
(RuO2/F-graphene) catalyst with silicon nanowires using a sacrifi-
cial template to reduce the Si–H bonds to decrease Ru3+ and gra-
phene oxide [309], where the content of Ru in the optimal
electrocatalyst was determined to be 6.9 wt.% for the HER and
OER. The catalytic efficiency was better than those of RuO2/-
graphene, commercial RuO2, and 20% Pt/C. Suitable overpotentials
at 10 mA cm
2 were observed for RuO2/F-graphene for total water
splitting in 1 M KOH. Zhu et al. suggested that appropriate non-
metallic doping at the oxygen sites of the metal oxide can generate
many favorable features to catalyze the HER and OER, such as
abundant oxygen vacancies, improved electrical conductivity, and
enhanced metal oxide covalency, as a proof-of-concept [310]. Fur-
thermore, the inclusion of highly electronegative fluorine
improved the electrical conductivity and stability of RuO2/F-
graphene. Moreover, F-doped transition metal oxides endowed
superior electrocatalytic activity for water splitting due to two
important affect; a) inducing abundant oxygen vacancies, and b)
enhancing the electronegativity of the transition metal oxide,
which is advantageous to exposing the active sites [311]. The reg-
ulated manufacture of non-metal-doped transition metal oxide-
based electrocatalysts is significantly more complex than the dop-
ing of metallic heteroatomic dopants. This group of catalysts also
includes non-metal (anion) doping multi-transition metal
(MTM)-based catalysts, which have gained popularity due to their
outstanding electron transport characteristics, robust durability,
and unique synergistic influence induced by many metal elements.
Even today, achieving high-level doping and the highly uniform
diffusion of dopants is a significant problem. Low-temperature
pyrolysis, sulfidation/phosphorylation/nitrogenization, and other
methods are often used to achieve non-metal doping. It’s worth
noting that most manufacturing processes use high temperatures,
which can lead to changes in the general surface and morphology
of the electrocatalyst, as well as the induction of disordered struc-
tures, many defects, or increased exposed lines at which the sur-
face ends. Table 2 summarizes the effect of transition metal-
oxide doping on the HER/OER activity of several non-metal-
doped transition metal-based electrocatalysts.
Briefly, doping anion such as N, P, F, S, Se, C, and so on, into non-
noble transition metal oxide electrocatalysts is a straightforward
and effective way to improve the overall water splitting efficiency
in both acidic and alkaline electrolytes. The following are the fun-
damental causes and advantageous for choosing non-metal atom
dopants; a) simple operation without a time-consuming manufac-
turing procedure, b) producing oxygen vacancies as total water
splitting active sites, c) improving electrical conductivity for opti-
mum charge transfer, and d) adjusting the electronic structure
and regulating the reactant. The modified electronic structure of
the transition metal oxide can optimize the free-energy change
(DGH*) for total water splitting performance under acidic and alka-
line conditions. Under alkaline conditions, the surface charge dis-
tribution following non-metal element modification not only
enables DGH*, but also increases early water adsorption and disso-
ciation and DGOH*, effectively accelerating the alkaline HER and
OER. Due to the tunable charge distribution, the doping strategy
will be an active solution to regulate the adsorption and increase
the electrocatalytic efficiency. In the future, these criteria will be
 A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Table 2
Summary of the non-metal doped transition metal oxide electrocatalysts recently reported for the HER and OER.

Catalyst Electrolyte Overpotential for HER at Overpotential for OER at j Tafel slope for Tafel slope for Overall voltage at Stability Stability Method Reference
j (mV@mA cm
2) (mV@mA cm
2) HER (mV dec
1 OER (mV dec
1) j (V@mA cm
2) for HER h for OER h
Co/CoO 1 M KOH 152 mV at 10 mA cm
2 284 mV at 10 mA cm
2 80 76 1.66 V at 25 h 25 h Self-assembly-carbonization 274
10 mA cm
2
CoOx 1 M KOH 235 mV at 10 mA cm
2 85 mV at 10 mA cm
2 – – 1.55 V at – – Thermal treatment 276
10 mA cm
2
P-Co3O4 1 M KOH 97 mV at 10 mA cm
2 260 mV at 20 mA cm
2 86 60 1.63 V at 25 h 25 h Hydrothermal 288
10 mA cm
2

2
3D Co:Pi/CoOx 1 M KOH 243 mV at 373 mV at 100 mA cm 60 78 1.65 V at 100 h 100 h Colloidal templating 289
100 mA cm
2. 10 mA cm
2

2
B-doped CoO-Ov 1 M KOH 280 mV at 10 mA cm – 71 1.516 V at – 40 h Spray pyrolysis 291
10 mA cm
2
VOB-Co3O4 1.0 M KOH 184 mV at 50 mA cm
2. 315 mV at 50 mA cm
2 60.7 112 1.67 V at 20 h 20 h Alternate Co salt and NaBH4 292
10 mA cm
2 treatment
B:NiFe LDH 1.0 M KOH 229 mV at 10 mA cm
2 57 – 100 h Hydrothermal 293
37

Cu2OxS1-x 1.0 M KOH 40 mV at 10 mA cm
2 68 1.56 V at – – Wet chemical 295

10 mA cm
2
S- CoO/Co3O4 1.0 MKOH 181 mV at 10 mA cm
2 275 mV at 10 mA cm
2 64 92 1.6 V at 20 h 20 h Solution-combustion 303
10 mA cm
2
Se- Co3O4@CeO2 1 M KOH 48 mV@10 mA cm
2 188 mV@20 mA cm
2 and 46.32 68.49 1.49 V at 12 h 12 h Hydrothermal, air calcination 302
&175 mV@50 mA cm- 2 293 mV@50 mA cm
2 10 mA cm
2 and selective selenation
C-Co3O4 1 M KOH 163 mV at 10 mA cm
2 250 mV at 10 mA cm
2 89 54 – – – CH4 plasma 305
P–NiO 1 M KOH – 286 mV at 10 mA cm
2 – 70.6 – – 10 h Hydrothermal 156
Ru/C–MoO2 1 M PBS and 46 and 36 mV mV at – 69 and 32 – – 100 h – Solid-phase reaction 307
0.5 M H2SO4 10 mA cm
2
F-CoO 1 M KOH 52.8 mV at 10 mA cm
2 237.7 mV at 10 mA cm
2 65 68 1.53 V at 60 h 60 h Hydrothermal 166
10 mA cm
2
P-CoMoO4 1 M KOH 44 mV at 10 mA cm
2 260 mV at 20 mA cm
2 66 74 1.54 V at 72 h 72 h Hydrothermal 282

Coordination Chemistry Reviews 474 (2023) 214864

10 mA cm
2

2
P-NiO/NiCo2O4 1 M KOH 290 mV at 10 mA cm – 49.6 – – 20 h Thermal oxidation and 284
phosphorization

2
CoO–F/Co 1 M KOH 15 mV at 10 mA cm – 50.9 – – 97 h – Electro-deposition method 165
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
critical for the improvement of low-cost, high performance overall
water splitting applications. To summarize, non-metal heteroatom
doping has a beneficial impact on the catalytic performance as well
as activity. The charge transfer produced by electronegativity mis-
match between the non-metal dopant atoms and host atoms sig-
nificantly alters the electronic structure of the original catalyst.
Non-metal heteroatoms are more flexible in terms of modifying
the surface lattice structure, introducing new active sites, improv-
ing the electrical conductivity and hydrophilicity, and adjusting the
DGH* to thermal neutrality. The principle for regulating the elec-
tronic structure of non-metal elements as dopants is to create a dif-
ference in electronegativity. In general, non-metal-doped
transition metal oxide electrocatalysts affect the increased local
charge as the electronegativity gap between foreign and host
atoms grows. Moreover, non-metal-doped transition metal oxide-
based electrocatalysts using S, P, N, F, C, and Se have been shown
to be critical for both the HER and the OER. However, only a few
attempts have been reported in this field, because their fabrication
require high annealing temperature and thereby high cost which is
not realistic. In view of this context, to solve and develop this, sci-
entists should pay more attention on developing; a) novel in-situ
doping strategy without annealing and low-cost, and b) high effi-
ciency and accurate content of heteroatom in the host materials.
Future studies will mainly focus on modifying the contents of these
dopants in orders to maximize the TMOs for overall water splitting
activity and understand their processes in considerable depth.
7.3. Anion
cation dual-doped transition metal oxide electrocatalysts
Doping is a crucial technique for enhancing catalyst activity.
Due to the synergistic impact of various dopants, recent investiga-
tions have demonstrated that suitable anion-cation-dual doping
can be more advanced method to increase the number of active
sites in transition metal oxides as well as improve their perfor-
mance as overall water splitting catalysts. A low-cost and environ-
mentally friendly synthesis of various transition metal oxides is
very important for bifunctional water splitting applications.
Researchers have investigated overall water-splitting catalysts
with distinct valence state metals as both cations and anions.
Appropriate anion-cation-dual doping may significantly enhance
the activity of total water splitting electrocatalysts due to the syn-
ergistic effect of the dopants. As a result, improving the catalyst
design for a range of electrocatalytic applications by regulating
the crystallinity and surface structure of the active metal compo-
nent in hybrid systems at an atomic level, e.g., inserting vacancies
can open up new possibilities [94]. Moreover, incorporating appro-
priate heteroatoms into the structure of catalysts has also been
shown to improve their activity in electrocatalytic reactions, such
as the HER, ORR, and OER [82,227,312]. Designing highly efficient
HER and OER electrocatalysts prepared using easy and green syn-
thesis technique with abundant porosity, high specific surface area,
and an increased number of active sites are critical. It will be espe-
cially significant if a variety of electrocatalysts of different catalytic
functionalities can be made in a single step, one-pot procedure.
Active metal ion doping has been used to successfully assist the
electrocatalytic activities of metal oxide electrocatalysts. More-
over, co-doping in the design and construction of OER electrocata-
lysts offers good OER characteristics [313]. In this situation, the
simultaneously insertion of two foreign heteroatoms can be more
successful approach in controlling the morphology and electronic
configuration, leading to improved electrocatalysis [28]. The metal
and non-metal dual-doping technique is fascinating due to the
changes in the electronic structure, adsorption energy, and electri-
cal conductivity observed. The intrinsic activity of metal oxides is
highly affected by their elemental composition. Furthermore, the
amorphous phase of metal oxides contains an abundance of oxy-
38
Coordination Chemistry Reviews 474 (2023) 214864
gen vacancies and active sites due to the large number of defect
sites, which explains the higher intrinsic active surface area and
enhanced ionic conductivity. Furthermore, during electrocatalysis,
the oxygen vacancies and dangling bonds present in the amor-
phous phase can react quickly with gas molecules, resulting in
the improved electrochemical characteristics of amorphous metal
oxide catalysts [27]. In addition, anion–cation co-doping was
shown to be critical for the OER activity which may be used as a
technique for developing transition metal oxide-based nanomate-
rials [314]. Yin et al. developed Fe-borate (Bi)-doped NiO using
solvothermal and self-templating strategies. The highly active
OER catalysts with hollow bipyramid prism-like structure exhib-
ited exceptional efficiency with an ultra-low overpotential of
261 mV at 10 mA cm
2 with an ultra-small Tafel slope of 46 mV
dec–1 which was ascribed to the high intrinsic activity and strong
durability, shortened mass transfer pathway, tunable electronic
structure via Fe-doping, high number of accessible electroactive
sites generated by oxygen vacancies via borate doping, and the cre-
ation of BO33-OH- to speed up the dissociation of OHads. Overall,
alkaline water splitting utilizing Fe/Bi-Ni/NF as an anode yielded
minimal cell voltages of 1.50 and 1.63 V at 10 and 100 mA cm
2,
respectively, and operated consistently at the high current density
of 100 mA cm
2 for 55 h without any degradation. This work
demonstrated the importance of anion-cation co-doping in the
OER, which provides an accurate approach for the creation of tran-
sition metal oxide-based materials [315]. Sun et al. reported the
high OER activity of an oxygen vacancy-rich vanadium-doped
Co3O4 (V-Ov-Co3O4) catalyst synthesized via a vanadium ion
implantation approach, which exhibited an ultra-small overpoten-
tial of 329 mV to obtain a current density of 10 mA cm
2 and ultra-
small Tafel slope of 74.5 mV dec–1. The charge density of the Co
atom increased and the reaction barrier of the chemical transfor-
mation from O* to HOO* reduced [316]. Hai et al. produced Fe,
Ni-dual-doped W18O49/NF using a facile solvothermal process,
which demonstrated enhanced catalytic activity and achieved an
ultra-low decay voltage of 1.58 V at 10 mA cm
2, as well as robust
durability in 1 M KOH solution [317]. Bhanja et al. prepared micro-
porous nickel phosphonate derived heteroatom-doped nickel oxide
and nickel phosphide NP/NiO using a hydrothermal reaction
method and non-templated reaction pathway. Among the three
catalysts prepared, NP/NiO showed the highest electrocatalytic
performance for the electrochemical OER with a relatively small
overpotential of 332 mV required to obtain a current density of
10 mA cm
2 and a small Tafel slope of 65.6 mV dec
1 in 1.0 M
KOH with superior stability over 15 h [318]. Lu et al. prepared an
amorphous CoNiSx nanostructure via the sulfurization of a CoN-
iCHH precursor at room-temperature as a new HER electrocatalyst
[319]. Li et al. used an easy and scalable hydrothermal method as a
novel strategy to obtain phosphorus and aluminum co-doped
nickel oxide (PA-NiO) nanosheets utilizing LDH as precursor
(Fig. 20a), which displayed a superior catalytic activity for total
water splitting application in an alkaline electrolyte. The morphol-
ogy and content of the samples were analyzed using SEM and TEM,
as shown in (Fig. 20b–f). A current density of 100 mA cm
2 was
noted at a low overpotential of 310 mV with a Tafel slope of
36 mV dec
1 at 10 mA cm
2 and ultra-long stability over 7 h in
1 M KOH (Fig. 21a–f). In addition, the results for the HER showed
a superb ultra-small overpotential of 138 mV and ultra-low Tafel
slope of 81 mV dec
1 at 10 mA cm
2 and ultra-long stability over
7 h with a small potential of 1.56 V needed to drive a current den-
sity of 10 mA cm
2 in 1 M KOH (Fig. 22a–f) [320].
The high performance of PA-NiO was obtained due to P and Al
co-doping, which can enhance the intrinsic electron transfer, sta-
bility, and porous structure of the nanomaterials where sufficient
active sites were exposed with supported mass-transfer proper-
ties [320]. Electrocatalytic activity for both the HER and OER
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 20. (a) A schematic representation of the synthesis of an NF-supported porous PA-NiO electrocatalyst. (b) SEM images of NF supported porous PA-NiO at low
magnification and the corresponding high magnification image (inset). TEM pictures of (c) AlNi-LDH and (d) PA-NiO. (e) HRTEM image of PA-NiO showing the local structure
from panel (d) and the lattice fringe (inset). (f) EDS elemental mapping of PA-NiO. Reproduced with permission from ref. [320] Copyright Ó 2018, American Chemical Society.
should be present in the same electrolytes in dual-functional elec-
trocatalysts for total water splitting [321]. The Se/Ni-Co3O4 on the
microtube structure of Ni-Co3O4 provides additional active sites
with oxygen vacancies after thermal salinization to catalyze the
OER. A low potential, small Tafel slope, and robust durability in
alkaline solution were a result of the production of highly active
Co(IV) species. Furthermore, electrochemical studies revealed that
appropriate anion-cation double doping can limit the possibility
for the creation of high valence Co(IV) species by promoting the
OER catalytic activity. More significantly, anion-cation dual adjust-
ments may pave avenues for developing highly active electrocata-
lysts for the OER. Li et al. produced a flexible anion
cation double
doped flower-like Co3O4 (Se/Ni-Co3O4) electrocatalyst with a sin-
gular microtube architecture as an OER electrocatalyst via the com-
bination of a template-free solvothermal method and calcination
under an air-atmosphere to obtain the Co-based oxides [322].
The as-obtained Se/Ni-Co3O4 electrocatalyst provided perfect OER
catalytic activity with a potential of 1.52 V over 10 h and low Tafel
slope of 62.9 mV dec
1 to reach 10 mA cm
2 as well as superior
stability under alkaline conditions when compared to that
acquired for the benchmark RuO2 catalyst. This means that effec-
tive doping can encourage the production of high valence Co as
OER active sites; i.e., the faster the active sites of Co(IV) are gener-
ated, the simpler the OER process, and the more negative the
potential value of the redox reaction occurs (lower OER onset
potential). As a result, the improved OER was attributed to the fol-
lowing factors; a) anion-cation double doping can effectively
enhance the transition between Co(III)/Co(IV) with a reduced
potential to create high valence Co active sites, b) after reasonable
39
Coordination Chemistry Reviews 474 (2023) 214864
doping, abundant oxygen vacancies, and mesoporous structures
can reveal more active sites on the surface of the electrocatalyst,
and c) Se and Ni-doping improves the electrical conductivity.
One-dimensional conductive substrates prepared using the Co-
doping technique have a lot of potential in heterogeneous catalysis.
This concept is appealing for a broad range of heterogeneous cat-
alytic activity. Kim et al. produced rich defect sites and oxygen
vacancies in an amorphous phase with ample surface area due to
the formation of a hollow nanocage structure, as well as the
‘ensemble effect’ induced by N and S-doping, which account for
the remarkable OER performance [323]. Many studies have been
carried out to produce more active sites and facilitate charge trans-
port in order to achieve higher OER activity or HER activity with
NiO, involving the formation of defects, heteroatoms-doping,
employing unique nanoarchitectures, mixing with carbon materi-
als to form self-standing conductive skeletons. Tahir et al. obtained
a NiO/Co3O4@NC hybrid catalyst via thermal annealing of a mix-
ture of melamine, NiCl2, and CoCl2, which possessed an optimized
electronic structure for the OER that revealed a much smaller over-
potential of 240 and 200 mV (@10 mA cm
2) on a glassy carbon
electrode and NiF in 1.0 M KOH, respectively [324]. More signifi-
cantly, the hollow nanomaterials reveal a large number of surface
localized elements and facilitate chemical absorption of the reac-
tants and intermediates, significantly boosting the electrocatalytic
performance. Li et al. developed a novel hollow Co3O4/CeO2
heterostructure, which was implanted in N-doped carbon nanofi-
bers (h-Co3O4/CeO2@N-CNFs) using a simple electrospinning route,
and used as a highly-active electrocatalyst for the OER (Fig. 23a)
[325]. The presence of Co3O4 and CeO2 phases was established
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 21. OER performance of PA-NiO, AlNi-LDH, Ni
P, and RuO2 supported on nickel foam in 1 M KOH: (a) LSV curves, (b) corresponding onset potentials and overpotentials at
t current densities of 60 and 100 mA cm
2, and (c) Tafel plots. (d) Chronoamperometry curve obtained for PA-NiO catalyst at 1.6 V. (e) Comparison studies of the capacitive
current density as a function of the scan rate. (f) EIS of PA-NiO, AlNi-LDH, and Ni
P measured at 1.55 V. Reproduced with permission from ref. [320] Copyright Ó 2018,
American Chemical Society.

Fig. 22. HER and full water-splitting activity of PA-NiO, AlNi-LDH, Ni
P, and RuO2//Pt/C (or Pt
C) supported on nickel foam in 1 M KOH: (a) LSV curves, (b) corresponding
onset potentials and overpotentials required at current densities of 10 and 20 mA cm
2, and (c) Tafel plots. (d) Chronoamperometry curve obtained PA-NiO catalyst under a
constant overpotential of 252 mV. (e) LSV curves obtained for the PA-NiO electrode for total water splitting with and without iR compensation at a scan rate of 5 mV s
1. The
inset shown in panel (e) is a comparison of the potential required to obtain a current density of 10 mA cm
2 using different electrodes in a two-electrode configuration. (f)
Chronopotentiometry curves obtained for the PA-NiO electrode carried out at different current densities. Reproduced with permission from ref. [320]. Copyright Ó 2018,
American Chemical Society.

40
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 23. (a) A schematic representation of the synthesis of h-Co3O4/CeO2@N-CNFs. (b) XRD pattern obtained forh-Co3O4/CeO2@N-CNFs, (c) Raman spectrum obtained forh-
Co3O4/CeO2@N-CNFs. (d) Crystal structures of spinel Co3O4 and cubic CeO2, respectively. Reproduced with permission from ref. [325] Copyright Ó 2019, American Chemical
Society.
by two sets of diffraction peaks corresponding to spinel Co3O4 and
cubic CeO2 (Fig. 23b). In addition, Raman spectroscopy was used to
confirm the development of the Co3O4 and CeO2 phases (Fig. 23c).
The crystal structures of Co3O4 and CeO2 are shown in Fig. 23d. The
h-Co3O4/CeO2@N-CNFs demonstrated superior OER performance
with an ultra-small overpotential of 310 mV and ultra-low Tafel
slope of 89 mV dec
1 required to reach a current density of
10 mA cm
2 as well as good electrocatalytic stability over
40000 s in 0.1 M KOH (Fig. 24a–f). Consequently, due to structural
and compositional advantages, h-Co3O4/CeO2@N-CNFs have
demonstrated outstanding OER efficiency (Fig. 24g).
Another technique involves doping noble metals into metal
oxide to improve the number of active sites or develop the inher-
ent activity. Vanadium-doping to transition metals can make the
material’s morphology more regular, which is beneficial to active
site exposure and mass transport. At the same time, V-doping
and the numerous oxygen vacancies that occur can alter the elec-
tronic structure and increase conductivity, which enhances the
electrocatalytic HER performance [326]. Vanadium-doping causes
the development of enriched defect sites in the outer NiO shell,
which improves the electrocatalytic HER and OER performance.
Liu et al. synthesized novel dendritic VNi3S2@NiO/NF core–shell
nanoarrays on NF (V-Ni3S2@NiO/NF) using an easy and template-
free one-pot hydrothermal method [327]. In addition, long-term
durability over 55 h at current density of 10 mA cm
2 was obtained
at a potential of 1.52 V. Liu et al. in another work generated Ni and
NiO hybrids on S- and P-co-doped graphene (SPG) using a simple
hydrothermal approach utilizing sulfuric acid and phytic acid as
the sulfur and phosphorus dopant precursors, respectively, which
showed outstanding HER activity with low impedance (0.48), large
electrochemically active surface area (32.6 m2/g), fast TOF
(0.0051 s
1) as well as a small starting potential (13 mV) and supe-
rior Tafel slope (79 mV dec
1), excellent durability and stable cycle
stability (5000 redox cycles) [328]. The NiO nanosheets were
41
Coordination Chemistry Reviews 474 (2023) 214864
lamellar diffused in three-dimensional doped graphene, presenting
a three-dimensional sponge, and Ni NPs were scattered on the SPG,
sugegsting that the S and P dual-doped graphene has produced
more exposed active sites and surface defects, allowing Ni with
small crystallite sizes to be uniformly dispersed on its surface,
facilitating electron transport. Wang et al. obtained P and W-co-
doped MoO2 nanoflowers on NF using an in-situ hydrothermal
method and phosphorylation [329]. The P and W-co-doped MoO2
nanoflowers exhibited superior catalytic activity with a notable
overpotential of 308 mV to reach 40 mA cm
2 for the OER and
89 mV to reach 10 mA cm
2 for the HER in 1.0 M KOH. A potential
of 1.65 V was required to reach a current density of 30 mA cm
2
with robust stability over 20 h when directly assembled in the
electrolyzer as a catalyst for total water splitting process. The P/
W-MoO2/NF catalyst endowed a blossoming flower-like structure
with plump petals after the phosphorylation step. The transition
of morphology revealed more electrochemically active surface
sites and created a larger contact area with the electrolyte, result-
ing in increased electrocatalytic activity. Furthermore, the close
linkage between the flower clusters can significantly increase the
electron-transport kinetics. However, more research is needed to
confirm the effects of the morphological change. The elemental
mapping images of P/W-MoO2/NF showed a very consistent distri-
bution of Mo, O, P, and W, indicating that P was successfully intro-
duced and W was uniformly doped in the catalyst. In addition, the
morphology of P-MoO2/NF was studied, which revealed a particle-
cluster architecture made up of aggregated particles with edges
and corners when the W-dopant was absent. During the
hydrothermal process, the structure-directing effect of the W spe-
cies on the MoO2 surface caused the morphology to change. The
high HER activity of P/W-MoO2/NF was assigned to the following
factors; a) the blossoming flower-like microarchitecture may pro-
vide more exposed active sites, increasing the catalytic activity as
well as ensure electrolyte accessibility, thereby improving the elec-
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Fig. 24. A comparison of the OER performance of the catalysts: (a) LSV polarization curves obtained in O2-saturated 0.1 M KOH at 1600 rpm,(b) overpotentials at a current
density of 10 mA cm
2 and 1.7 V, (c) Tafel plots, (d) capacitive current densities at 0.99 V as a function of scan rate observed for the electrocatalysts, (e) LSV polarization
curves obtained forh-Co3O4/CeO2@N-CNFs before and after 3000 cycles, (f) i
t responses of h-Co3O4/CeO2@NCNFs and RuO2 at 1.7 V in O2-saturated 0.1 M KOH at 1600 rpm,
and (g) the structure and composition advantages of Co3O4/CeO2@N-CNFs for the OER. Reproduced with permission from ref. [325] Copyright Ó 2019, American Chemical
Society.

trochemical properties, b) heteroatom doping of W/P species may
not only boost conductivity and accelerate charge transfer, but
may also trigger the inherent activity of the catalytic sites and
gas bubble release throughout the whole water splitting process,
c) the charge transfer is accelerated by the 3D porous and conduct-
ing NiF substrate, and d) in-situ growth ensures a strong bond
between the catalyst and substrate, reducing the charge transfer
resistance and ensuring the structural stability in long-term reac-
tions. It is well understood that the development of multi-active
centers in combination with the increased number of active sites
induced by Mo and P-dual doping promotes both the OER and
HER. Zhang et al. reported the synergistic effect originating from
Co and S-doping, which improved the electron transport in
MoO2. Furthermore, heteroatom-doping is considered to be a gen-
eral technique for enhancing the HER performance, which embel-
lishes the surface or electronic structure of the catalyst. Non-
metal elements such as C, N, P, and S have been added to Mo-
based catalysts to boost the HER performance because they may
spin the d-orbitals of the Mo atoms and produce atomic charge
density redistribution. Dopants such as Fe, Co, and Ni are fre-
quently used to enhance the HER efficiency of transition metal
oxide-based electrocatalysts. Dual heteroatom doping of Co and S
is a good way to obtain a synergistic coupling effect that can
change the electronic structure of the catalyst. However, there
have been few instances of dual heteroatom doping between
non-metal and metal elements in MoO2-based HER catalysts
[330]. Co and S co-doped carbon-framework -assisted MoO2
nanosheets (Co-S/MoO2-C) used for the HER display produced
excellent electrochemical activity upon treating MoO2 with ZIF-
67 and S powder due to the increased number of active sites and
high charge transfer rate. As a result, Co-S/MoO2-C showed a small
overpotential (62 mV vs. RHE) and low Tafel slope (98.8 mV dec–1).
LSV was carried out at a scanning rate of 5 mV s
1 in 1.0 M KOH,
which helped to enhance the stability during the HER, suggesting

42
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
that dual heteroatom-doping is an effective way to generate a syn-
ergistic coupling effect that can change the electronic structure of
the catalyst and develop novel active sites upon increasing the
charge transfer rate. Zhang et al. reported the use of hydrother-
mally reduced hierarchical dendrite-like Co0.75Ni0.25 alloy, where
the Co0.75Ni0.25 alloy and CoNi/CoNiO2@ NC-600/CC showed
ultra-long stability with a low cell voltage of 1.51 V required to
achieve a current density of 10 mA cm
2 in 1.0 M KOH [331]. Dinh
et al. improved a simple and sustainable one-step protocol for
preparing bifunctional electrocatalysts consisting of nickel/nickel
oxide NPs and nitrogen-doped activated carbon in which biomass
waste (cauliflower leaves) was fabricated using a pyrolysis method
and used as a natural doped carbon precursor. The Ni/NiO/N-doped
activated carbon obtained at 500 °C showed modest Tafel slopes of
70 and 121 mV dec–1 along with overpotentials of 346 and 180 mV
to reach a current density of 10 mA cm
2 for the OER and HER in a
0.1 M KOH electrolyte, respectively. In a two-electrode elec-
trolyzer, the hybrid bifunctional electrocatalyst required a cell
voltage cell of only 1.688 V to achieve a current density of
10 mA cm
2, exhibiting an excellent rate capability and robust
durability over 20 h with variable current densities of 10 to
30 mA cm
2. This study introduced a sustainable and
environmental-friendly approach for the design of bifunctional
electrocatalysts used to achieve high-performance overall water
splitting [332]. Yuan et al. produced RuO2/N-C using a novel
molecule-supported pyrolysis and subsequent oxidation strategy,
which was an excellent catalyst for total water splitting process
[333]. The RuO2/N-C catalyst exhibited outstanding catalytic per-
formance and robust durability in a 1 M KOH electrolyte achieving
a current density of 10 mA cm
2 at a small overpotential of 40 mV
for the HER and 280 mV for the OER. These remarkable perfor-
mances were assigned to the ultra-small size of the RuO2 NPs
and the synergistic effect of RuO2 and N-C, according to the exper-
imental data and DFT calculations. However, by incorporating trace
amounts of both metallic and nonmetallic-doping into earth-
abundant transition metal-based materials a high performance
water splitting electrocatalyst can be obtained [35]. Balasubrama-
nian et al. produced N-carbon@NiFe2O4 core–shell nanospheres
using a two-step hydrothermal process with accurately controlled
oxygen vacancies to enhance the kinetics of the OER and HERwith
an extraordinarycurrent density of 100 mAcm–2reached at an
ultra-small overpotential of 230 and 200 mV for the OER (Tafel
slope, 42 mV dec
1) and HER (Tafel slope, 59.6 mV dec
1), respec-
tively. In addition, the total water splitting reaction required a very
low cell voltage of 1.47 V at 10 mA cm
2 in 1 M KOH with no sig-
nificant deterioration in the activity observed over 12 h. This
report not only provides a novel route for the construction of accu-
rately oxygen vacancy-engineered metal oxide catalysts to con-
struct N-doped carbon, but also opens a new route for further
study of their prospects as superior dual-functional electrocata-
lysts for over all water splitting [334]. Jang et al. produced Ir-
doped NiCo LDH using a facile atmospheric hydrothermal process
that exhibited extremely high stability for over 200 h when com-
pared to NiCo LDH upon loading of the Ir NPs. For total water split-
ting, a cell voltage of 1.45 V was required for a current density of
10 mA cm
2 in 1.0 M KOH [250].
To summarize, elemental doping may effectively alter the elec-
trical structure of neighboring regions, which further improves
reactant or intermediate adsorption. Furthermore, elemental dop-
ing has a significant impact on the electrical conductivity of elec-
trocatalysts. Thus, rational element doping can significantly
increase the intrinsic activity of electrocatalysts [62,113]. More-
over, using a simple doping method to optimize the structure of
RuO2 can be extremely helpful, resulting in increased electrocat-
alytic performance and higher durability [335]. Furthermore, when
paired with nanostructures and morphological modification,
43
Coordination Chemistry Reviews 474 (2023) 214864
doped-RuO2catalysts have dramatically increased mass efficiency
and high durability, particularly under acidic conditions. In addi-
tion to controlling the electronic microstructure of a catalyst, geo-
metrical engineering is an important technique for governing its
surface characteristics, which is critical for defining the ultimate
catalytic properties toward the OER [336]. Moreover, previous
studies have discovered that manipulating the morphology, such
as creating a porous microstructure, can reveal multiple active
sites and boost the performance of the final electrocatalyst. As a
result, the integration of doping and logical morphological engi-
neering is expected to boost the intrinsic activities of the nanoma-
terials at each electroactive site as well as the number of available
sites on non-noble metal-based materials for total water-splitting
efficiency. Yang et al. produced CoFeRu@C and CoFe-quantum dots
with excellent HER and OER performance using a one-pot
hydrothermal reactor from the upper supernatant and bottom pre-
cipitate, respectively. CoFeRu@C showed superior activity and a
small overpotential of 4 mV for the HER in 1 M KOH, whereas,
the CoFe-CDs demonstrated superior OER efficiency with an
ultra-low overpotential of 320 mV [337]. Due to the synergistic
effect of dual-metal doping, only 1.59 V was required to generate
a total water-splitting current density of 10 mA cm
2. It was deter-
mined that active metal-doping and dual-metal synergistic effects
jointly dominate the enhancement in the electrochemical activity
of the metal oxide, resulting in exceptional overall water electrol-
ysis capabilities. This confirmed the use of a one-step reaction to
synchronize active metal-doping and dual-metal synergistic effects
within two different functional electrocatalysts to synthesize
hybrid electrocatalysts with regulated electrochemical activities
for highly efficient water splitting process. The increased catalytic
activity for energy storage and conversion technologies may be
expected as a result of concurrently introducing an ideal ratio of
P-S dual- doping into transition metal-based materials [338]. Fur-
thermore, advanced XAS, XPS, and Raman analyses indicated the
presence of metal oxide vacancies and a changing the electronic
structure of the heteroatoms causes a considerable difference
before and after doping [339]. Moreover, the cation and anion-
doping in TMO can promote the expose of additional active sites,
improve electronic structure, and increase the charge transport
capabilities, thereby enhancing the HER and OER activity [340].
As a result, dual-metal-doped transition metal oxides may control
the electronic microstructure more effectively than single-metal
doping, leading to a lower water dissociation energy and improved
adsorption energy for diverse chemical intermediates [341]. Lv
et al. successfully prepared a spherical mesoporous W-doped
MoO2/MoC hybrid catalyst with P-doped carbon shells (W-MoO2/
MoC@PC) using ultrasonic spray pyrolysis for higher HER activity
[342]. At a current density of 20 mA cm
2 in 0.5 M H2SO4 and
1 M KOH, the W-MoO2/MoC@PC composite demonstrated a sub-
stantially lower overpotential of 208 mV when compared to
MoO2/MoC@PC without W-doping (317 mV), suggesting that dop-
ing MoO2 significantly improved the HER electrocatalytic perfor-
mance. This process may also be used to synthesize additional
abundant and low-cost transition metals for doping
molybdenum-based catalysts for practical water splitting and
other reactions of interest [343]. It is also possible to accomplish
gram-scale manufacturing by employing this broad method of
dual-site doping [344]. In another work, Meng et al. was fabricated
and developed the Cr-Fe3O4-N/NF nanoarray via a facile induction
treatment followed a calcination approach for efficient water split-
ting. The resultant Cr-Fe3O4-N/NF demonstrated outstanding elec-
troanalytic performance for OER and HER with ultra low
overpotentials of 218 and 95 mV at 10 mA cm
2, respectively.
Moreover, the cell voltage equal 1.53 V with reach a current den-
sity 10 mA cm
2. The synergistic modulation with high perfor-
mance by cation and anion doping of inverse spinel TMOs can
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Fig. 25. (a) The synthesis of Mn-Co3O4/S nanosheet arrays directly on carbon cloth. SEM images of (b, c) Co3O4 and (d, e) Mn-Co3O4/S. (f–h) TEM, (i) HRTEM, and (j)
corresponding element mapping of Mn-Co3O4/S. Reproduced with permission from ref. [361] Copyright Ó 2019, Elsevier.
further enhance the total water splitting catalytic activity, offering
innovative method for Cr and N co-doped metal oxide electrocata-
lysts for high-efficient water splitting [345]. Zhang et al. produced
Fe-S-NiMoO4/MoO3@NF electrode materials using a simple
solvothermal method on NF. The experiment results and DFT sim-
ulations showed that Fe-doping is effective toward controlling the
crystal plane of MoO3, modulating the electronic structure, and
increasing the conductivity. The Fe-S-NiMoO4/MoO3@NF electrode
produced 500 mA cm
2 at overpotential of 271 mV which was
operated continuously for 100 h at 50 °C, meeting the criteria of
industrial water electrolysis. The Fe-doped metal was confirmed
using XPS and EDS. The experiments and DFT simulations revealed
that Fe-doping may simultaneously alter and induce the crystal
plane of MoO3, while also improving the conductivity, resulting
in an increase in the OER activity. Therefore, dual-metal doping
may control the electronic structure more effectively than single-
metal doping, resulting in a lower water dissociation energy and
improved adsorption energy for various chemical intermediates
[346]. Jiang et al. obtained selenium-phosphorus co-doped CoO
on Co foil (CoOSeP@Co foil) using a simple, scalable, and cost-
44
Coordination Chemistry Reviews 474 (2023) 214864
effective approach involving the sequential selenylation and phos-
phorylation of pre-oxidized Co foil. The CoOSeP@Co foil incorpo-
rated electrode exhibited superior electrocatalytic activity and
robust stability requiring a low overpotential of 155 mV for the
HER, 347 mV for the OER, and 510 mV for the overall water split-
ting to achieve a current density of 10 mA cm
2 in alkaline media.
A potential of 1.74 V showed the best long-term durability
over > 30 h of total water splitting. This work not only produced
a new self-supported, binder-free, and bifunctional electrode for
the efficient HER and OER in alkaline media, but also paves the
way to enhance the essential catalytic efficiency of materials via
co-doping with heterostructures for renewable energy storage
and conversion applications [347]. On the other hand, transition
metals with trace amount of metallic and non-metallic dual doping
are not widely known to be a highly effective electrocatalysts for
total water splitting under acidic and alkaline conditions [348].
Even more critically, anion and cation co-doping strategy reduces
the barrier to water-oxidation kinetic energy by optimizing the
free energy of O* production and so speeds up intrinsic electrocat-
alytic activity toward energy conversion [349]. Wang et al. pro-
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
duced 3D N-Mn-Co3O4 electrocatalyst with a cactus-like morphol-
ogy on NF using hydrothermal process and subsequent N2 plasma
treatment [350]. The N-Mn-Co3O4 catalyst showed notable overpo-
tentials of 302 and 320 mV to achieve a current density of 50 and
100 mA cm
2, respectively, and excellent stability over 40 h under
alkaline conditions. For total water splitting, the as-assembled N-
Mn-Co3O4@NF and Pt/C@NF electrolyze provided a current density
of 10 mA cm
2 at an ultra-low potential of 1.55 V with ultra-high
stability over 40 h for the OER in 1 M KOH. The following factors
can be usedtoexplainthe outstanding electrocatalytic activity
observed for the OER; a) the cactus-like nanoarchitecture made
ofinterweaved nanoneedles not only combines the advantages of
the 1D structure for charge transfer and 2D microflakes for struc-
tural durability, but also enables mass transport throughout the
OER reaction, b) the electrocatalytic active sites are exposed due
to the phase transformation-induced nanopores and the abun-
dance of oxygen vacancies caused by heteroatom doping, and c)
doping N and Mn into the Co3O4 lattice may increase the electrical
conductivity and maximize intermediate adsorption free energy.
This approach paves the way for a more logical design and fabrica-
tion of efficient OER systems and promising non-noble electrocat-
alysts by synergistically tailoring the electronic and geometrical
structures for overall water splitting applications. Even though
water splitting kinetics in Transition metals may be controlled by
a synergistically effective cation–anion co-doping approach, it is
critical to discover this strategy’s function in modulating catalytic
activity [351]. Moreover, Mutual substitutions on metal oxide
preferably modify the hydrogen adsorption free energy to increase
water splitting efficiency based on cation and anion doping tech-
niques [352]. In especially, the addition of heteroatoms can directly
and indirectly enhance the interactions between active sites and
intermediates, hence enhancing intrinsic activity of materials. In
terms of electrocatalytic processes, the efficient atomic structure
modification by hetroatoms doping strategy of noble metal-based
electrocatalysts might induce extra active sites, produce rich
defects, and enhance adsorption capacity, therefore promoting
electrocatalytic performance. Furthermore, determining how to
Fig. 26. (a) Polarization curves, (b) the corresponding Tafel slope plots, (c) the Nyquist plots, and (d) current density against scan rates obtained for the obtained samples. (e)
Chronopotentiometry measurements obtained for Mn-Co3O4/S (without iR correction). (f) XRD results obtained for Mn-Co3O4/S after long-term OER tests. Reproduced with
permission from ref. [361] Copyright Ó 2019, Elsevier.
45
Coordination Chemistry Reviews 474 (2023) 214864
regulate the quantity of heteroatoms doping in nanocomposites
and verifying the effects of heteroatoms and heterostructures on
the local electronic structure remains a significant difficulty to
overcome [279,351,353–360].
It may be summarized as follows; most doping engineering is
done by anion and cation doping and the introduction of atoms
of various elements to alter the crystal structure, activate elec-
tronic system modifications, improve electrical conductivity, and
enhance catalytic performance [128]. Mn-doping has been demon-
strated to alter the electronic structure of the Co center, increasing
the inherent activity of the active sites in Co3O4. Meanwhile,
enhancing the electrical conductivity of Co3O4 using sulphur one
can increase the number of S sites available for proton adsorption.
Furthermore, dual-doping with Mn and S can alter the relative
ratio of Co2+/Co3+, resulting in altered adsorption characteristics.
Qi et al. obtained Mn-Co precursor nanosheet arrays on carbon
cloth using a solution method and ion exchange process for the
OER (Fig. 25a) [361]. The SEM images were used to confirm the
morphologies and microstructures of Co3O4, Mn-Co3O4, Co3O4/S,
and Mn-Co3O4/S (Fig. 25b–e). In addition, Fig. 25f–h shows TEM
images of the Mn-Co3O4/S nanosheet arrays. The as-obtained
Mn-Co3O4/S exhibited a nanosheet structure with numerous meso-
porous pores on the surface. The phase was identified using the lat-
tice spacingsi.e. 0.244 and 0.286 nm observed in the HRTEM image
(Fig. 25i), which correspond to the (3 1 1) and (2 2 0) reflection
planes of Co3O4. When comparing the elemental distribution of
Co, Mn, O, and S to theTEM image shown in (Fig. 25j) it was deter-
mined that the Mn and S dopants were uniformly distributed
throughout the nanosheet structure. As a result, Mn-Co3O4/S had
the highest surface area, implying that it contained the most elec-
troactive sites for catalytic processes. Mn and S doping modulated
the electronic structure of the Co centers to boost the inherent
activity and the optimal Mn and S dual-doping Co3O4 arrays pre-
sented ultra-low overpotentials of 330, 407 and 460 mV at reach
a current density of 10, 100, and 300 mA cm
2 for the OER, respec-
tively, and displayed a robust durability after 20 h at current den-
sities of 10 and 50 mA cm
2 during long-term OER testing. The
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al. Coordination Chemistry Reviews 474 (2023) 214864

Table 3
Summary of the metal and non-metal doped transition metal oxide electrocatalysts recently reported for the HER and OER.

Catalyst Electrolyte Overpotential for Overpotential Tafel Tafel Overall Stability Stability Method Reference
HER at j for OER at j slope slope voltage at j for HER for OER
(mV@mA cm
2 (mV@mA for HER for HER (V@mA h h
cm
2) (mV (mV cm
2)
dec
1 dec
1
Mn-Co3O4 1 M KOH – 330, 407 and – 68 – – 20 h Solution and ion 361
460 mV at 10, exchange
100 and
300 mA cm
2
Se/Ni-Co3O4 1 M KOH – 300 mV at – 62.9 1.47 V at – 10 h Solvothermal 322
10 mA cm
2 10 mA cm
2
N-Mn-Co3O4 1 M KOH – 302 mV at – – 1.55 V at – 40 h Hydrothermal 350
50 cm -2 and 10 mA cm
2
320 mV at
100 mA cm
2
PA-NiO 1 M KOH 138 mV at 310 mV at 81 36 1.56 V at 7h 7h Hydrothermal 320
10 mA cm
2 10 mA cm
2 10 mA cm
2
NiO/Co3O4 1 M KOH – 200 mV at – 73 1.47 V at – 48 h Thermal 324
10 mA cm
2 10 mA cm
2 annealing
RuO2 1 M KOH 40 mV at 280 mV at 44 56 1.55 V at – – Molecule- 333
10 mA cm
2 10 mA cm
2 10 mA cm
2 assisted pyrolysis
h-Co3O4/CeO2@N- 0.1 M KOH – 310 mV at – 89 1.7 V at – 40 000 s Electrospinning 325
CNFs 10 mA cm
2 10 mA cm
2
NiFeOx 1 M KOH – 195 mV at – 33 1.5 V at – 8.6 h Electrodeposition 360
10 mA cm
2 10 mA cm
2
V-Ni3S2@NiO 1.0 M KOH 112 mV at 170 mV at 69 98.8 1.52 V at 100 h 100 h Hydrothermal 327
10 mA cm
2 10 mA cm
2 10 mA cm
2
Ru-MoS2/CuO 1 M KOH 198 mV at 201 mV at 113 229 1.68 V at 20 h 20 h Hydrothermal 353
10 mA cm
2 10 mA cm
2 10 mA cm
2
F-Co3O4-x 1 M KOH 77 and 192 mV at 253 mV at 72.9 37.3 1.56 V at 100 h 100 h Hydrothermal 309
10 mA cm
2 and 10 mA cm
2 10 mA cm
2 and calcination
100 mA cm
2 and 338 mV at oxidation
respectively 100 mA cm
2
V-Ov-Co3O4 1.0 M KOH – 329 mV at – 74.5 – – – – 316
10 mA cm
2
N-carbon@NiFe2O4 1.0 M KOH 200 mV at 230 mV at 59.6 42 1.47 V at 12 h 12 h Hydrothermal 334
100 mA cm
2 100 mA cm-2 10 mA cm
2
Co, S/MoO2-C 1 M KOH 62 mV at – 98.8 – – 40 h Hydrothermal 330
40 mA cm
2
(P, W)-MoO2 1.0 M KOH 89 mV at 308 mV at 90 286 1.65 V at 20 h 20 h Hydrothermal 329
40 mA cm
2 10 mA cm
2 30 mA cm
2 and
phosphorylation
Co-N-MoO2 0.1 M KOH 69 mV at – 126 – – 10 h – Organic 306
10 mA cm
2
NP/NiO 1.0 M KOH – 332 mV at – 65.6 – – 15 h Hydrothermal 318
10 mA cm
2
Fe/Bi-NiO 1.0 M KOH – 261 mV at – 46 1.50 and – 55 h Solvothermal 315
10 mA cm
2 1.63 V at 10 and self-
and templating
100 mA cm
2 strategy
Ni/NiO/N 0.1 M KOH 121 mV at 70 mV at 180 346 1.688 V at 20 h 20 h Spray Pyrolysis 332
10 mA cm
2 10 mA cm
2 10 mA cm
2
Fe- Co3O4 1 M KOH – 260 mV at 70 1.52 V at – 100 h Co-precipitation 356
20 mA cm
2 20 mA cm
2.
W-MoO2/MoC 0.5 M 209 mV at – 96 – – 16 h Ultrasonic spray 342
H2SO4 &1 20 mA cm
2 pyrolysis
M KOH

SEM and XRD data confirmed no noticeable changes in the mor-
phology or phase of Mn-Co3O4/S, confirming its high durability
(Fig. 26a–f). Moreover, physical characterization studies showed
that adding sulphur to metal oxides can significantly increase their
electronic conductivity, resulting in changed electronic character-
istics, richer electroactive sites, and better electrocatalytic activity
for the OER.
The improved OER performance of Mn-Co3O4/S was attributed
to; a) an increased number of active sites and facilitated mass
transport due to the free-standing arrays formed directly on car-
bon cloth, b) the increased intrinsic conductivity due to the intro-
duction of Mn and S, and c) facilitated four-electron transfer from
the richest Co3+ state. Consequently, the rational fabrication of
ultra-low cost electrocatalysts was accomplished via dual doping
and increasing the high-valence transition metal ions [361].
46
Table 3 summarizes the effect of transition metal oxide-doping
on the HER/OER activity of several dual metal and non-metal-
based electrocatalysts. Metal cation doping is simple to imple-
ment. There is now a large body of work available in the litera-
ture on improving the adsorption and catalytic activity of
transition metal oxides by doping them with different metal
cations. However, due to the severe conditions required, there
are a very few reports on the doping of transition metal oxides
using non-metal anions. On the other hand, greater efforts should
be given to theoretical calculations and modeling approaches in
order to gain a deeper understanding of the doping sites on a
molecular level and the effect of doping on the electronic struc-
ture and reactions energy [325]. As a result, the electrical charac-
teristics of the metal cations on both sites and oxygen anions are
highly correlated [81].
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Overall, doping induces localized amorphization, which offers
more accessible active sites in the local chemical environment than
their completely crystalline structures, which is primarily respon-
sible for the increased catalytic activity. Therefore, the relationship
between amorphization and catalytic activity gives fresh insight
into the improvement of the catalytic activity toward the develop-
ment of low-cost, highly active transition metal oxide electrocata-
lysts. It may be inferred that; a) single-element dopants, such as Fe,
Co, W, N, B, S, P, and metal oxides such as CoOx, NiO, MoOx, MnO2
and other transition metal oxides have high acid and base toler-
ance, and can be utilized in both acidic and basic applications,
and b) carbon supports, such as porous carbon and graphene, can
increase the catalytic efficiency and durability of the loaded cata-
lysts by supplying a high specific surface area, large ordered meso-
porous structure, high electrical conductivity, and high acid and
alkaline resistance. Moreover, dual metal and non-metal doping
is other promising technique for improving the electrochemical
performance transition metal oxides based electrocatalysts.
Because synergetic effect can result in a more important adjust-
ment of the electronic structure, altering the adsorption energy
of the reaction intermediates therefore, the electrical conductivity.
On the other hand, multi-element components used in the fabrica-
tion of transition metal oxide architectures to improve the water
splitting performance have rarely been investigated. Foreign ele-
ments may influence the host geometry or electrical properties,
resulting in the improved electrocatalytic activity of doped metal
oxides when compared to undoped metals and non-metals. As a
result, heteroatom-doping (metals and non-metals) into transition
metal oxides is critical for increasing the electrocatalytic perfor-
mance of some small molecules. On the other hand, research on
heteroatom-doped transition metal oxide catalysts with many
oxygen vacancies and well-defined surface remains a significant
yet unexplored field.
8. Conclusions and outlook
Earth-abundant transition metal oxide electrocatalysts have
unique features and their use in many fields will undoubtedly
increase as a result of significant efforts targeted at replacing the
current expensive state of the art catalysts with inexpensive cata-
lysts. As such, doping engineering is a unique process for improv-
ing the total water splitting of transition metal oxide-based
catalysts. In this article, we have reviewed studies on metal and
non-metal-doped engineering strategies, which affect and control
the electronic structure and physicochemical properties, optimize
reaction processes, lower resistance, and efficiently increase the
reaction rates of the metal oxide electrocatalyst’s phase transition,
and oxygen vacancies to improve the overall water splitting activ-
ity. More importantly, we have discussed the use of non-noble
metals like Fe, Co, Ni, Mn, Mo, W, etc., with a variety of transition
metal oxides to boost their electrocatalytic activity of which metals
like Fe, Ni, and Co have extensively been preferred. In particular,
Fe-doped transition metal oxides reveal outstanding activity for
total water splitting due to the larger d-band centers and Fermi
level of the metal active sites on the surface of the catalyst. In addi-
tion, we have discussed the effect of non-metal (N, C, F, P, S, Se,
etc.) anion-doping on transition metal oxide electrocatalysts in
overall water splitting performance. In particular, sulphur, phos-
phorus, and fluorine-doped transition metal oxides have demon-
strated superior activity for total water splitting due to the
inductive effect on the local charge increasing the electronegativity
gap between the foreign and host atoms grown on the surface lat-
tice structure, introducing new active sites, improving the electri-
cal conductivity and overall water splitting performance. In
addition, we have also discussed how anion and cation dual-
47
Coordination Chemistry Reviews 474 (2023) 214864
doped elements in transition metal oxide electrocatalysts improve
the overall water splitting activity, which may give an effective and
direct way for improving the efficiency of various catalysts in the
future. More importantly, cation-doping has been extensively
investigated and is thought to be an efficient strategy to adjust
the electrocatalytic performance on an atomic level in metal com-
pounds. On the other hand, non-metal anion–doping has only been
observed in a few cases, but it is projected to further enhance the
inherent activity of TMO-based electrocatalysts due to the fine tun-
ing of their electronic structure. We also have briefly described the
techniques of preparation elemental metal and non-metal-doped
transition metal oxide-based electrocatalysts for water splitting
performance. However, more efficient and simple ways of doping
engineering strategies in nanomaterials should be developed
which may speed up the development of metal and non-metal-
doped transition metal oxide electrocatalysts in total water split-
ting process.
In general, elemental doping can increase the active site activity
by generating vacancies and defect sites, boosting the electronic
conductivity, and altering the intrinsic electronic structures of
the catalyst, all of which result in the reduced energy barriers of
transition metal oxide electrocatalysts. This review includes the
unexpected effects on the structural, optical, electrical, and cataly-
sis properties of metal and non-metal-doped transition metal
oxide-based electrocatalysts on the overall water splitting perfor-
mance. Based on the summary of these studies, it is possible to
infer that the catalytic activity of metal and non-metal-doped tran-
sition metal oxide-based electrocatalysts is affected not only by the
hydrogen adsorption energy of the active centers, but also by the
bonding environment and host materials, which affect the local-
ized electronic structure and surface of morphology as well as
the overall catalytic activity of acatalysts under investigation for
their improved performance. Moreover, heteroatom-doping has
been used to increase their electrocatalytic activity. Therefore, in-
situ low doping has great potential for the logical fabrication of
transition metal oxides as extremely efficient electrocatalysis, in
which the rational design of future high active electrocatalysts will
be inspired by transition metal oxides with low concentration dop-
ing for better catalytic performance. Furthermore, an effective dop-
ing method to prevent dopant loss in the catalyst can greatly
increase the reliability and durability in practical applications.
DFT calculations are useful for revealing the electrocatalytic pro-
cess on an atomic level. In addition, theoretical calculations,
advanced in-situ operando characterization strategies and new
materials are important for predicting and explaining the catalytic
activity of newly developed materials, including the effect of metal
and non-metal doping strategies used to prepare transition metal
oxide-based electrocatalysts. Thus, DFT studies need to use ration-
ally designed model for matching and providing a powerful guidi-
ance to developing efficient HER and OER catalysts. A
comprehensive understanding of the effect of metal and non-
metal-doped transition metal oxide-based electrocatalysts on the
total water splitting activity will open the new doors to all these
possibilities. Undoubtedly, creative advances in this promising
field of research as well as energy conversion and storage, and sus-
tainable technology are expected to be obtained in the future.
Despite the many accomplishments described in this review, a
fundamental understanding of the effect of heteroatom-doping
and the unique properties of transition metal oxide-based electro-
catalysts remains a challenge for the improvement of their electro-
chemical performance, particularly in terms of the physiochemical
properties of the electrocatalysts as well as the chemical structures
of the active sites (e. g. functional groups, electronic structure,
atomic size, dopant type, location, and distribution). In summary,
the view points presented in this review may give some clues or
many opportunities for the development of the future generation
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
highly-efficient electrocatalysts, which imply that certain condi-
tions must be fulfilled to gain and improve the functionality and
performance of transition metal oxide-based electrocatalysts,
which include;
(1) increasing the intrinsic properties and number of the active
or steady sites in the nanomaterials which will be achieved
through manipulating the preparation conditions and chemical
properties as well as using in-situ doping and nanostructured tem-
plates to produce catalysts with highly active morphologies. Both
the quantity and high activity of the active sites must be enhanced
using the catalyst design, such as single-atom design. Bubble
behavior and electrolyte effects should also be considered during
the catalyst design due to the complicated nature of water splitting
systems. Furthermore, the use of external fields, such as tension,
optical, electrical, and electromagnetic used to aid electrocatalyst
reactions can be a growing research area. It has been discovered
that the magnetic field-induced effects can speed up the adsorp-
tion of bubbles from the surface of the electrocatalyst. Moreover,
the electromagnetic field effect may affect the spin state of the
electrocatalyst, therefore controlling the intrinsic electronic struc-
ture, which can be advantageous for the construction of high-
performance electrocatalyst nanomaterials.
(2) another important component in total water splitting is the
Schottky barrier for electron transport, which has an effect on the
electrical conductivity of a catalyst. Stronger heteroatomic interac-
tions on the electrocatalyst surface that are equivalent to or better
than that of the benchmark Pt, Ir, Ru have been achieved. The
improvement of several properties of heteroatom-doped transition
metal oxide electrocatalysts remain a challenge due to the low
density of active sites. Consequently, more research efforts are nec-
essary overcome these difficulties.
(3) structure, morphology, composition of the metal and non-
metal doped transition metal oxide catalysts during catalysis
mainly depend on appropriate precursors including metal salt
and non-metal sources used, and the reaction conditions such as
temperature, concentration, reaction time, pressure, pH, solvents,
and so on. It is well-known that the morphology, phase, crys-
tallinity, and structure of transition metal oxide electrocatalysts
can be regulated by varying the pH, temperature, and solvent type.
Therefore, the reaction between TMO-based catalysts and active
gases synthesis method is milder, providing greater control over
the reaction. On the one hand, the introduced metal and non-
metal could greatly enhance the electrocatalytic water splitting
performance by tailoring the electronic properties and adsorption
energy of intermediates, and also increasing the surface active sites
of the electrocatalysts. Structure, morphology, and composition do
not constantly change as like precursor type and temperature.
Since not all TMO dopings are beneficial, and in some cases, they
are harmful too. Most notably, there are still some critical chal-
lenges needed to be resolved. For example, the synthesis of dual
doping TMOs often involves multistep processes, which is ineffi-
cient for scalable applications. Furthermore, the doping levels of
matching anions and cations are critical for obtaining significant
electrochemical performance, but this is rarely explored. Although,
many strategies have been proposed for the synthesis of effective
electrocatalysts with ultralow heteroatom doping, the synthetic
procedures are always complicated and expensive, making the
products expensive as well, which would severely hamper the
large-scale water splitting process. However, the controlled syn-
thesis of such a complex architectures by a facile simple method
is still challengeable owing to the dissimilar growth processes
involved with different microscopic mechanisms and reaction
rates. As a result, no standard synthesis procedure has been pro-
claimed, which is the primary disadvantage of large-scale manu-
facturing and mass applications. Therefore, it is recommended to
develop low-cost and eco-friendly novel methods for realizing
48
Coordination Chemistry Reviews 474 (2023) 214864
metal and non-metal doping into pristine catalysts. However, con-
trolling the structure, morphology, composition of the metal and
non-metal-doped transition metal oxide catalysts during catalysis
is not an easy task in the green synthesis route. Thus, future
research should focus on producing a low-cost, eco-friendly, meet-
ing grad, scale demand, and green synthesis pathway that opti-
mizes all of these aspects.
(4) doping with heteroatoms has been extensively used in tran-
sition metal oxide electrocatalysis. There is still a lack of funda-
mental research and understanding of the doping degradation
mechanisms of transition metal oxide electrocatalysts. However,
recent research in the field of heteroatom-doped heteroatom tran-
sition metal oxide-based nanocomposites still has some new prob-
lems in terms of controlling the doping content in the prepared
materials. The present efficiency, purity, quantity, and pace used
to rationally design and fabricate of transition metal oxides for
extremely effective total water splitting electrocatalysts are still
far from those required for industrial application or promising
potential due to the increase in the doping concentration in transi-
tion metal oxides that will lead to the massive degradation of the
physical, chemical, and electronic properties as well as phase sep-
aration, jeopardizing the performance of transition metal oxide-
based electrocatalysts. Bearing this in mind, low concentration
doping has great potential for the logical fabrication of transition
metal oxides as highly efficient electrocatalysts, which will be a
promising research direction in the future. To obtain high activity
and durability, one should choose a suitable dopant and rigorously
examine the concentrations needed to change the surface mor-
phology for improved electrocatalysis. Furthermore, an effective
doping method to prevent dopant loss during the catalytic reaction
can greatly increase the reliability and durability in their practical
application.
(5) the number of open channels for effective product releases
during doping metal oxide which providing additional strain or
confinement to keep the catalysts in an active non-equilibrium
state, need to be considered which will enhance the surface area
to improve the total number of active sites per gram of catalyst.
(6) superior electrode configuration, which is required to ensure
accessible active sites with low overpotentials for electrochemical
reactions and enhanced transport of the reaction-relevant species
as well as enhance the catalysts stability and durability to maintain
its activity for an extended period of time. Although, several tran-
sition metal oxide electrocatalysts with cation and anion adjust-
ment have been proven to be stable, the effect of the catalyst
composition on their stability has been rarely investigated. This
will increase the conductivity of the catalysts so that more active
sites can be electrically linked to the electrode making it suitable
for commercial applications. Even though several unique ways
for achieving deeper-level temporal dynamics in the electrocata-
lyst have been established, the overall water splitting effi-
ciency and durability of several transition metal oxide-based
electrocatalysis under acidic and alkaline conditions still remain
lower to that of the state of the art RuO2 and IrO2 catalysts used
in full water splitting process. Overcoming these impediments will
therefore accelerate the improvement of energy devices and pro-
vide long-term solutions for renewable energy production and
consumption. The first two tactics are the most vital since the
intrinsic activity of the active sites and their densities are critical
parameters influencing a catalysts activity.
(7) it is critical to uncover the source of electrochemical perfor-
mance and identify the true active sites of an electrocatalyst under
actual working circumstances on an atomic level in order to untan-
gle the underlying electrocatalytic system and create highly effi-
cient catalysts. Although, the dopants in the transition metal
oxide electrocatalysts can remain stable without uninterrupted
operation to the reaction, catalyst evolution is common in many
A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
realistic working circumstances. This is because the dopant atoms
do not only generate new active sites by establishing HER and OER
performance-friendly electronic environments, but they can also
change the electronic state as well as the morphology of the exist-
ing active centers, enhancing their HER and OER performance. This
affects the catalyst’s localized electronic, structural, and optical
properties, as well as the overall catalytic activity, which is advan-
tageous for improved catalytic performance. Furthermore, under
realistic operating circumstances, the voids caused by defect dop-
ing as well as vacancy engineering may be formed or reproduced.
It is well acknowledged that the heteroatom dopants in transition
metals oxide-based electrocatalysts function as the active sites or
centers. An understanding of the effect of heteroatom-doping on
the local states on an atomic level still remains unknown.
(8) it is critical to have a deeper understanding of the underly-
ing reaction processes on heteroatom-doped transition metal oxide
electrocatalysts. Despite our fundamental understanding of the
full water splitting process having improved considerably, the pre-
cise reactions on heteroatom-doped transition metal oxide cata-
lysts remain unknown, particularly for water oxidation under
alkaline conditions.
(9) the shape of heteroatom-doped transition metal oxide elec-
trocatalysts and nanostructured materials, as well as their catalytic
activity, is now the subject of several studies. On the other hand,
the ex-situ mechanism has received little investigation. Some of
the most recent advanced in-situ characterization methods, such
as in-situ XRD, in-situ electron microscopy, in-situ scanning probe
techniques, and in-situ electrochemical cell configurations, could
be useful in exploring the working processes before and after
heteroatom-doping in transition metal oxide electrocatalysts used
for overall water splitting application, which is critical for manu-
facturing new materials and establishing the in-situ electrochemi-
cal reaction mechanisms. They may also reveal additional
important information related to the reaction intermediates and
active sites, as well as the catalyst design. However, significant
information such as the physiochemical properties of the electro-
catalyst as well as the chemical structures of active centers (e.g.,
functional group, electronic structure, atomic size, dopant type,
location, distribution, and crystallinity) and external factors such
as temperature and pressure determined using in situ-operando
studies are not same as those observed experimentally, which is
critical for understanding the working mechanism. Hence to eluci-
date the electrocatalytic properties, further in-situ and operando
characterization methods to explore the active locations and
microstructure of the electrocatalyst surface during the total water
splitting process are needed. Therefore, the mechanism of the elec-
trocatalyst reaction process is the prerequisite for the rational
design of superior electrocatalysts, which should be given great
consideration in future studies.
(10) many ways have been used to produce catalysts with out-
standing electrocatalytic performance for ultra-long stability and
durability in order to meet the aforementioned objectives. Of
course, these are applicable to nearly all types of electrocatalysts
and ought to be further investigated in the near future. However,
experiments and theoretical calculations are needed to back up
the aforementioned objectives.
(11) combining theoretical calculations with advanced experi-
mental characterization techniques should be used to elucidate
the reaction process with the help of machine learning-based
energy-free structure predictions of the morphology and artificial
intelligence. DFT calculations and experimental characterization
can supply and speed up the theoretical basis for the fabrication
and engineering of high performance heteroatom-doped transition
metal oxide-based electrocatalysts in terms of the reaction inter-
mediates and reaction kinetics, and can be used to aid the design
of new materials with catalytic activity in the future. Combining
49
Coordination Chemistry Reviews 474 (2023) 214864
theoretical and experimental data not only helps to understand
the structure–property relationships, but it will also help to
improving transition metal-based catalysts for total water splitting
efficiency in the future.
In conclusion, significant progress has been achieved toward
the development of transition metal-based electrocatalysts over
the last few decades. We anticipate that further development
through in-situ-doping strategy will help revolutionize clean
renewable energy infrastructure and overall applications of
electrocatalysts.
Data availability
Data will be made available on request.
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
Mr. Ahmed H. Al-Naggar is thankful to Indian Council of
Cultural Relations scholarship No. ED2884366507414.
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A.H. Al-Naggar, N.M. Shinde, J.-S. Kim et al.
Ahmed H. Al-Naggar is working for his doctorate
degree at the Center for Nanomaterials & Energy Devi-
ces, School of Physical Sciences, SRTM University, Nan-
ded under the supervision of Prof. Rajaram S. Mane. He
received his Master degree in Physics from the Dr.
Babasaheb Ambedkar Marathwada University, Aur-
angabad, India in 2019. His research focus is the use of
metal oxide/hydroxide/chalcogenide and their com-
posite nanostructures for renewable energy devices like
electro/photocatalysis, fuel cells, and supercapacitors.
Nanasaheb M. Shinde is working as research professor
at Department of Chemical Engineering, Dong-A
University. Dr. Shinde received his M.Sc., in 2010 and
then Ph.D. from the Shivaji University, Kolhapur (India),
in 2014 with Solid state Physics as a specialization
under the guidance of Prof. C. D. Lokhande. He gained
support of the BK21 Plus Early-Career Postdoctoral
Fellowship at Incheon National University in (2014-
2015) and Korea University (2021-2022) South Korea.
He also worked as postdoctoral fellow at Yonsei
University (2015-2016), South Korea followed a Post-
doctoral fellow (2016-2018) and Research Professor
(2019-2020) at Global Frontier Hybrid Interface Mate-
rial, Pusan National University, South Korea. He pub-
lished over 80 research papers (with high citing rate) including 4 review articles
and 3 book chapters. His research interests include chemical synthesis of novel
nanostructures, their in-depth chemical and physical analysis followed laboratory
(small scale) and commercial (industry based) usability in various fields like solar
cells, gas sensors, battery, supercapacitors etc. His current emphasis is to use the
surface modification of cathode materials for lithium-ion batteries.
58
Coordination Chemistry Reviews 474 (2023) 214864
Jeom-Soo Kim is a professor in the Department of
Chemical Engineering, Dong-A University. He received
his M.S. (1997) and Ph.D. (2001), in the Department of
Chemical Engineering at Illinois Institute of Technology
(Chicago, USA). In 2001-2004, he pursued the research
on the high energy cathode materials for lithium-ion
batteries (LIB) as a postdoctoral fellow at Argonne
National Laboratory, USA. (2001-2004). After 5 years of
industrial experience at the Samsung SDI (2004-2009),
he built the career not only as a researcher but also as a
research planner at Korea Electronics Technology Insti-
tute (2009-2014). His research interests include the
synthesis of various positive electrode materials, the
structure-electrochemical relationship of electrode
materials for energy storage systems such as lithium-ion batteries, sodium batteries
and magnesium batteries.
Rajaram S. Mane received his Ph.D. (2000) in Physics
from the Shivaji University, Kolhapur, India and has
worked as a postdoctoral fellow as well as Assist. Pro-
fessor at Hanyang University, Korea during 2004-2008.
He also was on the research faculty of Oxford Univer-
sity, Oxford, UK. Since 2010, he has been a regular
Physics Professor (now Sr. Professor) at S.R.T.M.,
University, Nanded, India and a visiting professor of
Pusan National University (2017-2018), Korea. Pre-
sently, he is a Director of Innovation, Incubation and
Linkages, of S.R.T. M., University, Nanded, India. Prof.
Mane has published nearly 400 research articles with
total h-index 55 and i10- index 261 which received
more than12000 citations. Since 1996, he is actively
engaged in synthesis of nanostructured 2D and 3D metal oxides/chalcogenides/
carbides/nitrides/fluorides for solar cells, electrochemical supercapacitors, chemical
sensors and bioactive applications.