Advanced Sensor and Energy Materials 2 (2023) 100055

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Advanced Sensor and Energy Materials

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Review

Recent progress of Ni-based catalysts for methanol electrooxidation reaction

in alkaline media
Chunru Liu a, Fulin Yang a, Alex Schechter b, Ligang Feng a, *
a
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, PR China
b
Department of Chemical Science, Ariel University, Ariel, 40700, Israel

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

Keywords: Methanol as an important hydrogen-rich fuel has received increasing attention in energy storage and conversion
Ni-based catalyst techniques, and energy release can be realized in the methanol oxidation reaction (MOR) process. Note that highly
Electrocatalysis efficient catalysts are still required to drive methanol oxidation, and the Ni-based catalysts have received intensive
Methanol oxidation reaction
attention due to their facile active site generation based on the electrochemical-chemical oxidation mechanisms. In
Promotion principle
light of the significant advances made recently, herein, we reviewed the recent advances of Ni-based catalysts for
methanol oxidation in the alkaline medium. The fundamental of methanol oxidation in the alkaline medium was
first presented, and then the catalyst design principles including synergistic effect, electronic effect, defect con-
struction, doping effect, as well as surface reconstruction were presented; and the advances of various Ni-based
catalysts for MOR are summarized and discussed by combining with some typical examples. The problems and
challenges were also concluded for the Ni-based catalyst fabrication, the performance evaluation, and their
application. We believe that the summary of this review will be helpful in the design of nickel-based catalysts and
understanding the catalysis mechanism of nickel-based materials in alcohol fuel electrochemical reactions.

1. Introduction the hydrogen production by methanol electro-reforming, which is very

The rapid development of the economy driven by the large consum-
mation of traditional fossil fuels is not sustainable, and global attention is
shifted to the utilization of renewable energy sources, and biomass fuels
[1,2]. Methanol is considered a good biomass fuel to realize energy
storage and conversion, which is convenient for storage and trans-
portation; more importantly, it is much safer than other fuels such as
gasoline, diesel, and natural gas [3,4]. In addition, it can be prepared
with wide sources in low-cost and environmentally friendly approaches
[5]. Especially, methanol is one of the target products of CO2 reduction
that plays an important role in the carbon cycle [6]. Therefore, it is
chosen as a competitive fuel in new energy, since it has a very high en-
ergy density, even much higher than that of lithium-ion batteries [7].
As an important hydrogen-rich fuel, the energy release and conver-
sion of methanol can be realized in a methanol oxidation reaction, which
is a key half-reaction for methanol-reforming of hydrogen production
and direct methanol fuel cells (DMFCs) [8,9]. The theoretical oxidation
potential of MOR is 0.016 V vs. RHE [10,11], which is much lower than
that of the water oxidation; therefore, compared with the traditional
electrochemical water electrolysis, the overpotential is greatly reduced in
helpful for the hydrogen release and circulation [12]. In the DMFCs
technique, which is not controlled by the Carnot cycle, the high power
generation efficiency can be realized with the advantages of environ-
mental friendliness and high specific energy [13]. The MOR is also
involved in some of the electro-oxidation processes for many organic
materials [14]. Therefore, the study of MOR is of great significance to the
basic research of simulating the electrocatalytic process of various or-
ganics. In addition, the development of MOR has important implications
for transforming methanol into value-added products such as formate
[15,16]. Thus, MOR is a significant reaction in the carbon cycle, energy
conversion, and chemical industry [17,18]. Note that the inherently slow
kinetics of MOR is not favored in these methanol-based techniques, and
highly efficient catalysts are required to drive MOR [19].
The noble metal-based materials of Pt and Pd are the most common
catalysts for MOR, while the high cost of noble metal catalysts cannot
support the commercial application on a large scale [20]. More impor-
tantly, the poisoning effect during the process of MOR is adverse to the
noble catalyst, as some intermediate products generated will strongly
occupy the active sites, making it difficult for the catalytic reaction to
continue [21,22]. The MOR can be done in acid and alkaline electrolytes

* Corresponding author.
E-mail addresses: ligang.feng@yzu.edu.cn, fenglg11@gmail.com (L. Feng).

https://doi.org/10.1016/j.asems.2023.100055
Received 9 January 2023; Received in revised form 22 February 2023; Accepted 21 March 2023
Available online 24 March 2023
2773-045X/© 2023 The Author(s). Published by Elsevier B.V. on behalf of Changchun Institute of Applied Chemistry, CAS. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
C. Liu et al.
[23]. Although MOR in acidic media is much easier to start than that in
alkaline media, it has a strong dependence on noble metal-based catalysts
[24], because non-noble metal catalysts are less stable in chemical prop-
erties resulting in their easy dissolution in acidic media [25]. The MOR in
an alkaline medium has the advantages of a less toxic effect, easy polari-
zation at low anode overpotential, and much better oxidation kinetics than
that in an acidic medium [26]. Moreover, the deprotonation kinetics of
methanol in an alkaline medium is favourable, which makes it possible for
the application using non-noble metal-based catalysts as catalysts [27].
Among the non-noble catalyst, nickel has attracted much attention due to
its good catalytic activity and anti-poisoning ability [28,29]. The easy
conversion of Ni, Ni2þ, and Ni3þ redox centres could facile promote the
active species formation, thus, speeding up the MOR in the alkaline me-
dium [30]. As early as 1955, porous nickel and porous nickel silver were
used as an anode and cathode to catalyze methanol oxidation in an alkaline
medium [31–33]. In the 1970s, the electrochemical oxidation of some
organic compounds in alkaline solutions was systematically evaluated
using nickel anodes by Fleischmann et al. [34], and they found that the
oxidation of Ni(OH)2 to NiOOH was much faster than methanol oxidation
catalyzed by NiOOH on Ni-based materials [35]. Since then, Ni-based
catalyst for MOR has been developed including Ni(OH)2 [36,37], Ni
complexes [38,39], and various Ni alloys [40], as well as the
carbon-supported Ni catalysts [41]. For example, due to the inhibition of
the α-Ni(OH)2 phase by Cu, NiCu-based noble metal-free catalysts have
been developed [42–44]. The oxophilicity of Ni has a good adsorption and
oxidation effect on CO, hybrid materials of Ni and noble metal-based cat-
alysts have also been developed [45,46]. In the past ten years, the newly
developed Ni-based catalysts have become more and more complicated
with varied structures but high catalytic performance such as core-shell
structures [47,48], heterostructures [49], and composite hybrid Ni-based
catalysts [50]. In 2019, a review of ethanol oxidation catalyzed by
Ni-based materials in alkaline media was done [51]; the review progress of
Pt-based and Pd-based, or the progress of MOR catalysts catalyzed by
non-noble catalysts has been overviewed from time to time [28,52,53]. The
metal-based electrocatalysts of noble metals and non-noble metals for
methanol oxidation in direct methanol fuel cells technique were also
revised recently [23]. While to the best of our knowledge, a comprehensive
understanding of the progress of recent advances for MOR catalyzed by Ni
in alkaline electrolytes is rare, especially considering the MOR-assisted
water splitting for hydrogen generation.
Making a critical review of these achievements would be helpful in the
new catalyst development, thus, an effort is highly required in this field.
Considering the different properties of the Ni-based hybrid catalyst for the
catalytic reactions, herein, the advances of the catalyst were displayed as
Ni-based catalysts with noble metals and Ni-based catalysts without noble
metals in the system. The reason is that the MOR catalyzed by Ni-based
catalysts without noble metals required much higher potentials, higher
than the potentials for oxygen reduction reaction, which makes it cannot be
used in the DMFC technique but suitable for the methanol electrolysis for
hydrogen generation and methanol oxidation in catalysis; while low po-
tentials for MOR can be realized for the Ni-based catalysts with noble
metals so that they can be employed in the fuel cell technique. In this re-
view, the general mechanism of methanol oxidation was first introduced,
and the catalysis effect of Ni-based material on MOR as well as their
structure evolution involving the catalysis process in an alkaline medium
was clarified. And then, the reasons why Ni-based materials can enhance
MOR are introduced from four aspects: synergistic effect, electronic effect,
defect structure, and surface reconstruction. Subsequently, the research
progress of various Ni-based materials for MOR including Ni-based alloys,
Ni-based compounds, and Ni-based composite hybrid catalysts in an alka-
line medium was classified and discussed. Finally, the problems and chal-
lenges of nickel-based catalysts for methanol oxidation in alkaline media
are summarized. We believe this summary helps readers understand the
catalytic mechanism for MOR catalyzed by Ni-based catalysts, and it will be
instructive to design and develop novel nickel-based catalysts for methanol
oxidation in the alkaline electrolyte.
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Advanced Sensor and Energy Materials 2 (2023) 100055
2. Mechanism of methanol oxidation
2.1. Catalytic mechanism
The reaction equation of MOR in the alkaline electrolyte is presented
as follows [10,26]:
Anode: CH3OH þ 6OH ⇾ CO2 þ 6e þ 5H2O (Ea ¼ 0.81 V vs.
SHE at 1 bar, 298.15 K)
Cathode: 3/2O2 þ 6e þ 3H2O⇾ 6OH (Ec ¼ 0.40 V vs. SHE at 1 bar, 298.15 K)
Overall: CH3OH þ 3/2O2 ⇾ CO2 þ 2H2O (Ecell ¼ 1.21 V at 1 bar, 298.15 K)
It can be seen that the high coverage of OHads at low potentials in
alkaline media could promote MOR [53]. In the process of methanol
oxidation, carbon dioxide will be generated and react with the alkaline
medium, and the electrolyte solution will be carbonated, resulting in the
reduction of OHads in the solution [31,54]. This will also result in a
decrease in pH and cause carbonate precipitation around the electrodes
to retard the progress of MOR [55].
For the Ni-based catalysts hybrid with noble metals, the active sites
for MOR are generally considered to be noble metals (Pt, Pd, etc.) [52,
56]. The presence of Ni in the system makes the noble metals less
poisoned by COads as the oxidation of COads is accelerated after Ni acti-
vation which can offer more oxygen-containing species at lower poten-
tials via the bifunctional catalytic mechanisms as shown below (Fig. 1a)
[57], resulting in better performance [58]. To be specific, noble metals
(M) provide adsorption sites to transfer methanol to adsorbed CO, and Ni
provides OH adsorption sites; this suggests that Ni-based catalysts hybrid
with noble metals possess both CO and OH adsorption sites that can lead
to improved performance for MOR. The first step is the dehydrogenation
of methanol to form COads as the following equation:
M-CH3OH þ 4OH → M-COads þ 4H2O þ 4e (1)
The subsequent oxidative removal of COads adsorbed on the noble
metal active sites occurs with the assistance of OH species [59]. Under
alkaline conditions, the oxidative removal of COads can proceed via two
approaches. Free OH in alkaline electrolytes directly participate in the
reaction via the Eley-Rideal mechanism and sequentially remove COads
from the surface of the catalyst as shown in equation (2) [60]. The ac-
tivity is mainly affected by the bonding strength of COads, and the binding
energy of COads can be regulated by the electronic effect.
M-COads þ 2OH → M þ CO2 þ H2O þ 2e (2)
Alternatively, OHads can be generated either on or around noble sites,
and COads could react with absorbed OHads via the Langmuir-
Hinshelwood mechanism as shown in the below equation (3) [61]. In
this mechanism, a bifunctional catalyst with both CO and OH adsorption
sites is preferred, that can synergistically realize the catalysis reactions.
M-COads þ 2OHads → M þ CO2 þ H2O (3)
The noble metals and NiOOH as dual active sites for MOR were also
proposed recently [62,63], while these discussions have not been widely
accepted for the time being. Due to the high catalytic ability of these
noble metals for MOR, these kinds of catalysts were generally employed
for MOR in the fuel cell technique. Pure Ni-based materials were difficult
to provide low overpotentials for MOR, so it is not easy to employ noble
metal-free catalyst materials in fuel cells.
When noble metal-free Ni-based materials are used as MOR catalysts,
the nickel surface in contact with the alkaline aqueous solution is
oxidized to form Ni(OH)2 layer. Ni(OH)2 will be transformed into other
phases during the reaction [64]. Barakat et al. found that the oxidation of
methanol over nickel-based catalysts can be realized without the for-
mation of the NiOOH layer [65]. They proposed that the nickel hy-
droxide layer automatically formed over the catalyst surface upon
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

Fig. 1. (a) Bifunctional mechanism of Ni-based materials to accelerate COads catalysis [57]. (b) Transformation mechanism of Ni-based materials in methanol
oxidation [65]. Reproduced from Ref. [57] with permission from Springer Nature, copyright 2018. Reproduced from Ref. [65] with permission from Elsevier,
copyright 2018.

contacting the alkaline solutions can already oxidize methanol, and the
formation of the NiOOH driven by high potentials is more active for the
MOR, which follows the conventional catalytic mechanism. Therefore,
the methanol oxidation processes take place continuously by two suc-
cessive mechanisms in a cyclic (Fig. 1b). While most of the research re-
sults still well supported the convention mechanism, where NiOOH is
regarded as the active phase for catalytic methanol oxidation. The
transformation process is usually as follows [64]:
Ni(OH)2⇾NiOOH þ Hþ þ e
 
Ni(OH)2 þ OH ⇾Ni(OH)3 þ e
Ni(OH)3⇾NiOOH þ H2O
NiOOH þ (CH3OH)ads⇾(CH3O)ads þ Ni(OH)2
 
NiOOH þ (CH3O )ads⇾(CH2O )ads þ Ni(OH)2
 
NiOOH þ (CH2O )ads⇾(CHO )ads þ Ni(OH)2

NiOOH þ (CHO )ads⇾(CO)ads þ Ni(OH)2
can be obtained by analyzing the peak position, heights, and shapes [73].
FTIR has been used to study MOR on nickel-based materials as early as
the last century [74], the intermediates in the oxidation process of
methanol were observed and analyzed, and correspondingly, the reaction
pathway of methanol oxidation was proposed [75]. For example, the
periodically arranged four-six-coordinated nickel hydroxide nanobelt
structure (NR-Ni(OH)2) was studied for MOR by FTIR [68]. Residual
intermediates of CH3O* (* is an active site) and COOH* were detected
upon one CV scan, and the presence of CH3O* and COOH* as residual
(4) intermediates suggested that the reaction mechanism of MOR catalyzed
by NR-Ni(OH)2 is different from that of Pt/C, in which CO* and COOH*
(5)
are usually the residual intermediates. Based on this FTIR characteriza-
(6) tion, a MOR pathway was proposed as CH3OH* → CH3O* → CH2O* →
CHO* → CO* → COOH* → CO2*. The catalytic products of MOR were
(7)
also analyzed using FTIR characterization on the NiPd alloy catalyst [76].
The findings indicated that Pd/C-catalyzed MOR led to the formation of
(8)
formate and formaldehyde as the primary products, whereas Pd4Ni/C--
(9) catalyzed MOR resulted in the production of not only formate and
(10) formaldehyde but also carbonate.

NiOOH þ (CO)ads⇾CO2 þ Ni(OH)2 (11)
Though the standard redox potential of methanol oxidation is 0.016 V
vs. RHE [10,11], much lower than that of 1.23 V vs. RHE for water
oxidation [66], the practical MOR in the alkaline electrolyte happens at
very high potentials, even higher than 1.23 V. This is because when NiOOH
services the active center, the redox potential of Ni(II)/Ni(III) in alkaline
media is around 1.35 V vs. RHE [67–69]. Therefore, the potential window
shared by NiOOH-catalyzed MOR with oxygen evolution reaction (OER) is
likely to lead to unfavourable competition [27,70]. When judging the MOR
performance of nickel-based catalysts in alkaline media by cyclic voltam-
metry (CV), it is necessary to compare the performance of the catalysts in
alkaline solutions with and without methanol to determine whether its
catalysis comes from MOR or OER. At present, many kinds of research are
targeted at Ni-based material with noble metal free as anode catalysts for
DMFCs, while these studies are currently difficult to be applied in DMFCs
[71,72]. The noble metals involved in a catalyst for MOR can occur much
lower than 1.23 V, while the reaction potential of Ni-based catalysts
without noble metal is usually above 1.35 V, which cannot successfully
construct the fuel cells because it will have a much higher onset potential
for MOR than the cathode oxygen reduction reaction.
2.2. Spectroscopic analysis of MOR products
2.2.1. Fourier transform infrared spectroscopy (FTIR)
FTIR is a non-destructive analytical method that can provide unique,
label-free information on molecular composition; this technique can
transform the vibrational and rotational information of chemical bonds
in the molecules into visual wavenumbers, and the structural information
2.2.2. X-ray absorption fine structure spectroscopy (XAFS)
XAFS is powerful to reveal the element type, valence state, and coor-
dination environment of atoms [77,78], and it reflects the relationship
between the incident light energy and the light absorption coefficient of the
substance to be measured [79,80]; As structural characterization spectrum
induced by electronic transitions at excited core levels, this technique has
the characters of element-dependent, short-range structural sensitivity, and
high-sensitivity. XAFS was reported to monitor the oxidation state and local
environmental changes of catalysts at different potentials [81]. For
example, the electronic states and the coordination environments of Pt
species in single-nickel-atom-alloyed platinum hexagonal nanocrystals
(NiPtSAA/GDY) during the MOR process were studied by XAFS [82].
Fig. 2a displays the Pt-L3 edge X-ray absorption near-edge structure curves
of NiPtSAA/GDY, illustrating the Pt metallic state at different applied po-
tentials of 0.60, 0.28, and 0.10 V vs. RHE. The commercial Pt/C was
used as a comparison at the same conditions. The normalized white-line
intensities (μnorm) of NiPtSAA/GDY and commercial Pt/C at the Pt-L3
edge were used to evaluate the chemisorption of the catalysts' surface
oxygenated species. At 0.28 V, the NiPtSAA/GDY exhibited the highest
normalized white-line intensities than 0.10 and 0.60 V, probably
because of the stronger adsorption of CO* or other oxygenated species. The
μnorm of NiPtSAA/GDY showed at the initial potential of 0.10 V was
similar to that for the potential 0.60 V and much lower than that of
0.28 V; which can be due to the dynamic balance between CH3OH mo-
lecular adsorption and CO* oxidation and the subsequent CO intermediates
desorption. The easy poisoning of Pt/C as compared to NiPtSAA/GDY was
shown by the Δμnorm [Δμnorm (0.1_0.28 V) ¼ μnorm (0.1 V) μnorm
(0.28 V)], which was much higher for Pt/C at 0.10 V than that obtained
at  0.28 V (Fig. 2b and c). Wavelet transform of NiPtSAA/GDY at space

3
C. Liu et al.
Fig. 2. (a) In-situ Pt-L3edge XANES spectrum of NiPtSAA/GDY, magnified regions are marked with black squares [82]. (b) In-situ Pt-L3edge XANES spectrum of 20%
Pt/C, magnified regions are marked with black squares [82]. (c) Δμ-XANES spectra of NiPtSAA/GDY and 20%Pt/C [82]. (d) WT plots of NiPtSAA/GDY at  0.1,
0.28, and 0.60 V, respectively [82]. (e) In-situ Pt EXAFS fitting results of NiPtSAA/GDY, compared with PtO2 and Pt foil under different potentials [82].
Reproduced from Ref. [82] with permission from Elsevier, copyright 2022.
showed a negative shift (Fig. 2d), which indicated the increased light ele-
ments (e.g., H*, COOH*, COH* and CO*) and probably because of the
chemisorption of the oxygen-containing group in NiPtSAA/GDY. The
in-situ XAFS results also revealed that the excellent MOR activity and
durability of NiPtSAA/GDY may originate from the increased chemisorp-
tion of the oxygen-containing group compared with commercial Pt/C
(Fig. 2e). To unveil the superior MOR activity exhibited by the alternating
four-six-coordinated NR-Ni(OH)2, the electronic structure was further
examined using near-edge X-ray absorption fine structure (NEXAFS) [68].
It was found that all Ni atoms in NR-Ni(OH)2 were arranged in NiO6 oc-
tahedron and the unique electronic states of the four-coordinated Ni atoms
resulted in the lower-Hubbard band delocalization, thus, efficient MOR was
realized by electron delocalization in nickel hydroxide nanoribbons. X-ray
absorption near-edge structure (XANES) spectra analysis was employed to
investigate the influence of the interaction between the components of
platinum-nickel hydroxide-graphene on MOR catalysis [83]. The results
reflected that electron transfer from rGO to Ni(OH)2 or Pt through their
interactions resulted in more C 2pπ unoccupied states and the covalent
coupling between rGO and Ni(OH)2 or Pt via C–O–Ni or C–O–Pt bonds,
respectively. Therefore, the three components of the hybrid materials
achieved impressive MOR activity and durability. EXAFS characterization
was used to analyze the coordination environment of Ni2þ in the Ni-MOF
(Ni–Ni-2), which was synthesized directionally using a nickel hydroxide
template for MOR [84]. The blue-shifted peaks of Ni–Ni-2 (1.65 Å)
compared with its precursor suggested a binding interaction between its
components. This interaction provided a facile ion diffusion path that
enhanced the MOR catalytic performance.
2.3. Catalytic promotion principle
The enhancement of catalysts mainly comes from two aspects:
increasing the number of active sites on the electrode surface or
enhancing the intrinsic activity of electrocatalysts [85]. Herein, the
design strategies for enhancing Ni-based catalytic MOR from four aspects
were displayed in terms of the synergistic effect, electronic effect, defect
engineering, and surface reconstruction. Note that these effects might be
involved in a specific catalyst system, namely, they cannot be
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Advanced Sensor and Energy Materials 2 (2023) 100055
distinguished individually, and the combined effect would account for
the promoted catalytic ability.
2.3.1. Synergistic effect
The synergistic effect means that when two or more components are
combined or integrated, the effect on the catalytic performance is greater
than the sum of the effects of the individual components. The compo-
nents can be various crystal planes, dopants, morphologies, structures,
supports, and so on [86]. The combinations of multiple components can
compensate for the shortcomings of a single active site species, and
realize a largely increasing catalytic ability [87]. The synergistic effect
may be generated by the proton-donating sites or the electronic structure
change caused by the surface topography change of the catalyst. The
advantages of each crystal plane can be integrated by designing specific
exposed crystal planes [88]. The catalytic performance can also be
altered by involving the morphology and structure of different compo-
nents [89], e.g., it is believed that porous metals shorten the pathway of
ion and electron transport [90,91]. The metal-support interaction also
significantly affects the performance of the catalyst, and the interaction
generated by the synergistic effect from the support and the supported
active metals can improve the catalytic performance [92]. For example,
the nickel oxide nanospheres (NiO) composited with biomass-derived
activated carbon (AC) nanosheets and polypyrrole (PPy) were studied
to catalyze methanol oxidation, and high catalytic performance was
observed that can be attributed to the synergistic effect of NiO with AC
and PPy [93]. To be specific, the conversion of NiO to NI(III) provided the
electrocatalytic active sites for MOR, PPy contributed to the chemical
stability of the electrode, and the presence of AC improved the electrical
conductivity of the catalyst system. The synergism of the metals like Ni,
Cu, and Mo was realized in the multi-walled carbon nanotubes supported
catalysts [94]. The Ni/Cu/Mo trimetallic composite can significantly
enhance the electrocatalytic activity through the synergism of the Ni–Cu
and Ni–Mo interfaces; it was found that the catalytic performance of the
system with the mass ratio of Ni, Cu, and Mo as 8:1:1 showed the best
catalytic performance due to the combined synergistic effect of the
co-catalyst and the conductive support. In a report on the ultrafine
Ni/WC hybrid for MOR [95], tungsten carbide and nickel oxyhydroxide
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

(derived from Ni) species were reported to activate the functional groups
of methanol, and the synergistic effect of WC and Ni species could
effectively enhance the catalytic performance for MOR. The synergistic
effect of noble metal Pt and non-noble metal Ni was also reported for a
Pt–Ni/C catalyst prepared by in-situ loading Pt nanoparticles with a low
ratio of 9.4 wt% onto the Ni-based MOF-derived Ni/C support [96]. To be
specific, the Pt–Ni/C exhibited high catalytic performance for MOR, with
nearly 2-fold performance improvement than the reference catalyst
without Ni addition (Fig. 3a). Therefore, the synergistic effect of the
hybridization of multiple species can compensate for the shortcomings of
the active site of a single species and improve the catalytic performance.
2.3.2. Electronic effect
The electronic effect always plays an important role in improving the
catalytic performance of the hybrid catalyst, and the chemical environ-
ment changes of the active sites will affect the electronic structure and
their distribution [97]. The difference in the Fermi level (EF) between the
metal and the adjacent metal would cause the electronic effect (Fig. 3b);
because to balance the EF at the interface, electron transfer will happen,
resulting in a strong interaction between the different components [98].
It can occur between different components such as alloys [99], compo-
nents with different electronegativity [100], central atoms and ligands
[101], hetero-structured catalysts and the supported catalyst, etc. [102,
103]. The redistribution of electron density modulates the binding en-
ergies of reaction intermediates, thereby enhancing the catalytic per-
formance of the active center. The ligand effect is one of the electronic
effects, which is often used to explain the enhanced electrocatalytic
performance of alloys [104,105]. The origin of the ligand effect is due to
the electron transfer between the adjacent metal atoms, where the
electrons will transfer from the more electronegative metal to the less
electronegative one [106]. This electron transfer would generate the shift
in the d-band center, thereby, changing the catalytic performance.
The hybridization of Ni with Pt can enhance the anti-poisoning ability
of Pt to COads due to the electronic effects [58,107]. For example, NiPt-
SAA/GDY showed enhanced MOR activity and resistance to CO
poisoning compared with platinum hexagonal nanocrystals

Fig. 3. (a) CV curves of various catalysts for MOR in 0.1 M KOH þ 1 M CH3OH at a scan rate of 10 mV s1 [96]. (b) Metal-support interaction: electronic effect [98].
(c) Computed reaction coordinate of MOR on F–Ni-G and Ni-G catalysts [109]. (d) Types of vacancies in electrocatalysts [118]. (e) Typical Ni2P crystalline structure
with Mo doping [124]. (f) CV curves of Mo–Ni2P/NF and other electrocatalysts for MOR in 1 M KOH þ 1 M CH3OH [124]. (g) CV curves of Ni-CNFs with different
nitrogen contents for MOR in 1 M KOH þ 3 M CH3OH at a scan rate of 50 mV s1 [128]. Reproduced from Ref. [96] with permission from American Chemical Society,
copyright 2021. Reproduced from Ref. [98] with permission from Multidisciplinary Digital Publishing Institute 2018. Reproduced from Ref. [118] with permission
from Wiley, copyright 2018. Reproduced from Refs. [109,124,128] with permission from Elsevier, copyright 2021,2021, 2014.

5
C. Liu et al.
(HPtNs/GDY) [82]. After the introduction of nickel species, the binding
energy of the Pt 4f peak was negatively shifted due to the interaction
between Pt and Ni, which meant the charge could be transferred from Ni
to Pt, weakening the d-band center of Pt, and then reducing the CO
adsorption energy. Therefore, this electronic effect helps remove the
toxic intermediates of COads adsorbed on the Pt surface, thereby
enhancing the efficiency of MOR. The strong electronegativity of fluorine
will pull the electrons and change the polarity of the system for
increasing highly active species [108]. For example, surface fluorinated
nickel-graphene nanocomposites (F–Ni-G) were reported for MOR [109],
and the increased activity and kinetics for MOR were observed due to the
surface fluorination induced the formation of high-valent nickel species.
Specifically, the modified fluorine in graphene caused the decreased
reaction energy barrier from *CO to *COOH step in MOR, because the
strong electronegativity of the F atom promoted the intermediates much
easier to attract OH groups and repel protons, which is conducive to
decreasing the reaction energy barrier for MOR (Fig. 3c).
2.3.3. Defect construction
The physical and chemical properties of a material can be effectively
changed by introducing defects inside the material structure [110]. De-
fects are generally generated by the differences between ideal and actual
structures, including vacancies, dislocations, voids, and disorder, among
others [111]. The presence of defects disturbs the regular arrangement of
the crystal lattice and leads to the redistribution of atoms or electrons.
Therefore, the formation of defect structures leads to some new physical
and chemical properties, which will affect the properties of activity,
selectivity, conductivity, etc. [112]. Defect engineering is one of the most
effective strategies to enhance the catalyst activity for electrocatalysts.
Introduced defects can generate more active sites [113]; the catalytic
activity can also be improved due to the surface electronic structure
modification and adsorption energy of reaction intermediates optimiza-
tion [114].
The vacancy is one of the most typical defects referring to the defects
caused by the absence of atoms at lattice sites [115,116]. Defects caused by
vacancies exist in almost all materials, and the presence of vacancies will
change the entropy and enthalpy of the system [117]. The vacancies are
usually located at metal sites (cations) or non-metal sites (anions), while the
existence of cationic and anionic vacancies was reported in the same ma-
terial system [118]. According to the different sites of defects, the vacancies
can be divided into anionic vacancies, cationic vacancies, and multi va-
cancies (Fig. 3d). Among the anion vacancies, oxygen vacancies are the
most common type of vacancies, which greatly facilitate the adsorption of
methanol molecules for MOR, and effectively increase the exposed active
sites. For example, a boron-doped NiCo2O4 (B/NiCo2O4) with abundant
oxygen vacancies was developed for methanol oxidation, and the
maximum current density was found much higher than that of the pristine
nickel-cobalt oxide (NiCo2O4) and Pt/C composite [119]. The high cata-
lytic activity and selectivity towards the generation of formate were
attributed to the accessibility of methanol molecules on the catalyst surface
via B-doping-induced oxygen vacancies.
2.3.4. Doping effect
Heteroatom doping is an effective strategy to enhance the intrinsic
activity of catalysts [120]. The microstructure engineering of the elec-
tronic and crystal structures can be modified by doping exogenous ele-
ments into the bulk catalysts [121]. Because of the different atomic radii
for the heteroatoms, the dislocations in the original lattice and the local
electron redistribution will change the adsorption and desorption ca-
pacities of the reaction intermediates, as a result, the catalytic perfor-
mance can be modified effectively [120,122]. For example, Ni aerogels
doped by the oxophilic Bi showed a largely improved catalytic perfor-
mance for MOR compared to the original catalysts [123]. The trace
amounts of Bi atomically dispersed on the surface down-shifted the
d-band center of Ni; as a result, the Bi-doped Ni aerogel showed a
6
Advanced Sensor and Energy Materials 2 (2023) 100055
performance of 7.2 times higher than that of Ni aerogel for MOR. The
crystal structure and electronic configuration of Ni2P were modified by
Mo-doping approach to investigate the role of the promotion of trace Mo
on Ni for MOR (Fig. 3e) [124]. Compared with the d-band center of Ni for
the pristine Ni2P (2.812 eV), the d-band center of Ni for the Mo–Ni2P
(2.416 eV) is transformed, which implied the decreased occupancies of
the anti-bonding states and the increased binding energy of adsorbed
oxygen intermediates, which can contribute to higher electrocatalytic
performance.
The doped high-valent Mo species also promoted the nickel with a
higher oxidation state for better adsorption of oxygen intermediates, and
then high catalytic performance for MOR was observed compared to the
undoped Ni2P (Fig. 3f). The high oxidation state of Ni driven by Mn-doped
Ni(OH)2 with well-shaped and uniform nanosheets was reported for MOR
[125]. The X-ray photoelectron spectroscopy (XPS) characterization
revealed that the binding energy of the Ni 2p3/2 peak in Mn-doped
Ni(OH)2 shifted to a higher value (855.6 eV) compared to that of
Ni(OH)2 nanosheets (855.2 eV). This observation suggested that the
introduction of Mn promoted the higher oxidation state in Ni of Mn-doped
Ni(OH)2. The catalyst had more active site exposure due to the hollow
structure and increased conductivity by the Mn-doped structure. The peak
current density could reach 16.4 A g1 for MOR, and the current density
remained above 90% of the initial value after the 1000 s stability test.
Besides, nitrogen-doped carbon nanostructures as support would also
influence the catalytic ability of the supported Ni-based catalysts [126].
The interaction between the supported metal and the doped carbon
support can be increased due to the increased surface nucleation sites,
which are conducive to the anchoring and dispersion of the metal site
[127]. Furthermore, N-doping could enhance the durability of the sup-
ported catalysts due to enhanced π-bonding and the electron-donor
ability of nitrogen. For example, the influence of N-doping on the cata-
lytic activity of Ni-incorporated carbon nanofiber was evaluated for MOR
[128]. The highest current density of 198.5 mA cm2 was obtained for
MOR when the nitrogen content was 4 wt% (Fig. 3g). Nitrogen-doped
carbon nanofiber-supported nickel oxide nanocomposite (N-CNF/NiO)
prepared by the electrospinning method also exhibited good alkaline
methanol oxidation performance [129]. In the other case, nickel dis-
elenide with N-doped carbon (NiSe2/NC-450) also exhibited good cata-
lytic activity for MOR with a high current density of 164.68 mA cm2 at
1.7 V vs. RHE [130].
2.3.5. Surface reconstruction
Surface reconstruction generally refers to the process by which the
surface composition, crystal phase, or atoms at the surface of a catalyst
are reconstructed to form a new crystal phase, or surface structure
compared to the bulk catalyst [131]. As can be seen in the mechanism,
the high valent Ni species are the active phase for the MOR [132], and the
phase transformation will occur during the reaction on all the Ni-based
catalysts, which can be called pre-catalysts. Many efforts have been
done to rationalize the design of the Ni-based catalyst to promote active
Ni species formation [42,43]. Ni(III) is generally regarded as one of the
real active phases for Ni-based materials to catalyze methanol oxidation
in alkaline media, and the conversion of Ni-based materials to NiOOH in
the process of anodic MOR has been mentioned elsewhere [65]. It has
been reported that four phases, β-Ni(OH)2, α-Ni(OH)2, β-NiOOH, and
γ-NiOOH, are generated during the lifetime of the nickel hydroxide
electrode for catalysis reactions [133,134]. The well-known Bode dia-
gram identifies the phase transitions during normal cycling, and the
formation of the γ-NiOOH phase is related to the swelling or volume
expansion of the nickel film electrodes [133]. Compared with the
γ-NiOOH phase, the β-NiOOH phase has much better electrochemical
performance for catalyzing MOR in an alkaline solution [42,43]. The
formation of β-NiOOH and γ-NiOOH were competitive with each other
[135,136], and the addition of copper hydroxide to the nickel oxide
species could effectively suppress the formation of the γ-NiOOH phase
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

[43]. The catalytic efficiency of these electrodes can thus be increased
when the active phase was in-situ generated during the catalysis process
[137]. This process was also found on the newly developed catalyst
materials like NixT(T ¼ P, S, Se) [16], which can be activated by cyclic
voltammetry in KOH solution to form NixT-R, and NixT-R was further
activated in the process of MOR to form NiOOH coordinated by oxy-
anions. Furthermore, the coordinated oxyanion effectively tailored the
d-band center of the Ni sites and increased the Ni–O covalency, thereby,
MOR catalytic activity was improved. A Ni3S2 grown on carbon
(Ni3S2-CNFs) nanofibers could generate sulfate ion coordinated NiOOH
during the activation process [138]. The in-situ generated NiOOH and
SOx species showed a synergistic effect, which effectively modulated the
d-band center of Ni3S2 in Ni3S2-CNFs nano heterostructure to promote
the oxidation of methanol.
3. Research progress on Ni-based catalysts
Pure nickel is not active enough for MOR in alkaline media like that of
pure platinum, therefore, it is seldom reported for MOR. The use of nickel
as a catalyst usually requires the coordination of multiple metals or the
oxidation of nickel [139]. The preparation of a single nickel as an alka-
line MOR catalyst usually combines nickel with ligands to obtain a large
electrochemically active area, thereby enhancing the catalytic perfor-
mance [140]. And on this basis, the morphology is controlled and carbon
materials are added for better performance improvement. For example,
Ni-MOF-74 synthesized by the solvothermal method was reported to
possess high electrochemical stability and performance for methanol
oxidation [141]. Three-dimensional flower-like Ni-MOFs grown on
multi-walled carbon nanotubes (Ni-MOF@CNT) by microwave synthesis

Fig. 4. (a) Schematic illustration of the synthesis of Ni-MOF on CNT [142]. (b) The square root of scan rate of Ni-MOF and Ni-MOF@CNT in 1 M KOH solution [142].
(c) Field-emission scanning electron microscopy image of hierarchically structured Ni0.75Cu0.25 alloy [148]. (d) Illustration of the formation of highly branched Ni–Cu
alloys [148]. (e) CV curves of different catalysts for MOR in 1 M KOH þ 1 M CH3OH at a scan rate of 10 mV s1 and the corresponding SEM images of catalysts treated
with different alkali concentrations [170]. (f) Schematic illustration of the in situ synthesis of Ni–Ni hetero-composites from hydrangea-shaped Ni [84]. (g) SEM image
of NiS/Ni(OH)2@PPy/GO [67]. (h) CV curves of different catalysts for MOR in 1 M KOH þ 0.5 M CH3OH at a scan rate of 10 mV s1 [176]. Reproduced from Refs. [67,
142] with permission from Elsevier, copyright 2021,2019. Reproduced from Refs. [148,170] with permission from Wiley, copyright 2017,2021. Reproduced from
Ref. [84] with permission from American Chemical Society, copyright 2021. Reproduced from Ref. [176] with permission from The Royal Society of Chemistry,
copyright 2017.

7
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

protocol were evaluated for methanol oxidation reaction (Fig. 4a) [142].
A diffusion-controlled process was indicated by the linear plotting of the
anodic/cathodic peak current densities versus the square root of the scan
rates (Fig. 4b). The higher electrochemical active surface area of
Ni-MOF@CNT (494.3 cm2) compared to the pristine Ni-MOF (203.5 cm2)
electrocatalyst resulted from the availability of large active sites in the
Ni-MOF@CNT to catalyze MOR. As a result, in the MOR, the onset po-
tential of the electrolyte with methanol added was 0.2 V lower than that
without methanol added. A catalyst of reduced graphene oxide (rGO)
supported nickel-2-aminoterephthalic acid MOF (NiNH2BDC) composite
was prepared for MOR in an alkaline environment [143]. The optimal
catalyst showed a current density of 267.7 mA cm2 at 0.699 V vs.
Hg/HgO, much higher than some platinum-based electrocatalysts.
However, due to the low catalytic activity and the less value for the
low-performance improvement, it was not worth putting effort into the
single or pure Ni for MOR. Attention is thus paid to the various Ni-based
catalysts with different hybrid structures as will be discussed in the
following section. As mentioned in the above section, the advances of the
catalysts for MOR will be displayed as Ni based catalyst with noble metals
and Ni-based catalysts without noble metals in the system.
3.1. Ni-based catalyst without noble metals
Ni-based catalysts without noble metals generally are difficulty
providing low overpotentials to drive fuel cells but they are good at the
application of methanol-assisted water-splitting reactions for hydrogen
generation. Herein, according to the different components, the form of Ni
species, and the structures, the relevant contents were discussed corre-
spondingly in the following sub-sections. For easy comparison, the MOR
performance of the nickel-based catalysts without noble metals discussed
in this work was also summarized in Table 1.
3.1.1. Nickel alloy
Multi-metallic catalysts tend to be more active than the monometallic
catalyst due to the electronic effect [144], the synergistic effect [145],
and the ligand effect [144,146], etc., which facilitates the kinetics or
thermodynamics of electrochemical reactions in the form of increased
activity, stability, or resistance to toxicity, as a result, the oxidation of
methanol was effectively improved. Research on alloy catalysts mainly
focuses on the synergistic electrocatalytic benefiting from the alloy
components optimization and novel structure design, which has good
anti-corrosion ability in alkaline media [147–149]. For noble metal-free
nickel-based alloy catalysts, Ni(III) is the active site for MOR, and the
main purpose of alloy formation is to promote the catalytic ability of Ni
by the generation of high valent Ni species [148,150]. Moreover, the
poor electrical conductivity of Ni-based catalysts can be improved by
coupling with the conductive carbon materials [151].
Mn is favored to induce Ni(III) formation in the NiMn alloy for MOR due
to its strong oxidizing properties. Ni and NiMn alloy-modified graphite
electrodes (G/Ni and G/NiMn) were examined for the oxidation of meth-
anol in alkaline solutions [152]. The formation of high-valent Ni induced
by Mn improved the MOR performance. The faster MOR response at the
G/NiMn electrode was found due to the pre-adsorption of methanol mol-
ecules at Mn sites. NiSn is also a potentially excellent candidate for MOR,
the bimetallic NiSn alloy nanoparticles with tuned composition were
fabricated by co-reduction of the two metals in the presence of appropriate
surfactants [153], and they exhibited excellent performance for MOR in an
alkaline solution. The most Ni-rich alloy exhibited the best performance for
MOR with a mass current density of 820 mA mg1 at 0.70 V vs. Hg/HgO.
The authors attributed the high performance to the collaborative oxidation
of the byproducts from methanol which poisons the Ni surface.
Since nickel and cobalt have similar crystal structures and similar
lattice parameters, nickel and cobalt were ready to form solid solution

Table 1
Summary of MOR performance in alkaline electrolytes for nickel-based catalysts without noble metals discussed in this review.
Catalysts Electrolyte Scan rate (mV s1) Spike potential Peak current Ref.

NiSn 0.5 M KOH þ0.5 M CH3OH 50 0.7 V vs.Hg/HgO 820 mA mg1 [153]
Co0.2Ni0.2-Gr 1 M KOH þ 3 M CH3OH 50 1 V vs.Ag/AgCl 230 mA cm2 [150]
Co1–Ni4/G 1 M KOH þ 1 M CH3OH 50 0.4 V vs.Ag/AgCl 22.5 mA cm2 [156]
Cu1Ni1 NWs/C 1 M NaOH þ 0.5 M CH3OH 50 1 V vs.SCE 425 mA mg1 [132]
Ni–Cu/RCQDs/GCE 0.5 M KOH þ 0.5 M CH3OH 50 0.72 V vs.Ag/AgCl 90.41 mA cm2 [158]
Ni60Cr10Ta10P16B4 1 M NaOH þ 1 M CH3OH 20 0.75 V vs.Ag/AgCl 17.1 mA cm2 [90]
Ni2.5Co0.5Sn2 1 M KOH þ 2 M CH3OH 50 0.6 V vs.Hg/HgO 65 mA cm2 [164]
Ni(OH)2–0.25 1 M KOH þ 1 M CH3OH 10 1.5 V vs.RHE 171.8 mA cm2 [170]
Ni–NiCu-3 0.1 M KOH þ 1 M CH3OH 50 0.85 V vs.Hg/HgO 28 mA cm2 [84]
Ni/Al LDH 1 M KOH þ 2 M CH3OH 100 0.55 V vs.SCE 25 mA cm2 [174]
Ni/Fe LDH 1 M KOH þ 2 M CH3OH 100 0.55 V vs.SCE 40 mA cm2 [174]
SS/rGO/P–CoNi LDHs 1 M KOH þ 0.5 M CH3OH 10 0.6 V vs.Hg/HgO 78 mA mg1 [176]
NiO/CNT-400 1 M KOH þ 0.5 M CH3OH 50 0.6 V vs.Ag/AgCl 140 mA cm2 [180]
VO-rich NiO 1 M KOH þ 0.5 M CH3OH 50 0.7 V vs.Ag/AgCl 85.3 mA cm2 [184]
Ni/NiO/CNTs 1 M KOH þ 1 M CH3OH 50 0.58 V vs.Hg/HgO 2094 mA mg1 [187]
4 wt% rGO-FeO/NiO MOF 1 M NaOH þ 3 M CH3OH 50 0.85 V vs.Ag/AgCl 486.14 mA cm2 [181]
Cu–Ni/CuO–NiO 1 M KOH þ 0.5 M CH3OH 50 0.78 V vs.Hg/HgO 152 mA cm2 (3563 mA mg1) [189]
NiCo2O4/rGO 1 M KOH þ 0.5 M CH3OH 50 0.6 V vs.Ag/AgCl 78 mA cm2 [193]
MOF derived NixCo3-xO4-y 1 M KOH þ 1 M CH3OH 50 0.6 V vs.Hg/HgO 300 mA mg1 [194]
NiCo2O4-450-Vo 1 M KOH þ 1 M CH3OH 50 1.75 V vs.RHE 209.3 mA cm2 (592.4 mA mg1) [183]
Co0.5Ni0.5MoO4 1 M KOH þ 1 M CH3OH 50 0.7 V vs.SCE 164.5 mA cm2 [195]
NiS/CA 1 M KOH þ 0.5 M CH3OH 50 0.8 V vs.Ag/AgCl 42.6 mA cm2 (263 mA mg1) [204]
Co–Ni–S 1 M KOH þ 0.5 M CH3OH 50 0.65 V vs.Hg/HgO 55.6 mA cm2 [207]
Co3O4–Ni3S4-rGO 1 M KOH þ 0.3 M CH3OH 10 0.4 V vs.Ag/AgCl 52.9 mA cm2 [208]
Ni12P5 1 M NaOH þ 1 M CH3OH 10 1.72 V vs.RHE 210 mA cm2 [213]
Ni2P-L 1 M KOH þ 0.5 M CH3OH 50 1.74 V vs.RHE 427 mA mg1 [214]
NiCo-MOF-P 1 M KOH þ 0.5 M CH3OH 10 1.54 V vs.RHE 170 mA cm2 [215]
Si(0.3)-NiPO-2 0.1 M NaOH þ 1 M CH3OH 50 0.6 V vs.SCE 43 mA cm2 [224]
NiCoPO-2 0.5 M KOH þ 1 M CH3OH 50 0.8 V vs.SCE 39.9 mA cm2 (1567 mA mg1) [225]
CNB/NF 6 M KOH þ 0.5 M CH3OH 20 0.55 V vs.Hg/HgO 62 mA mg1 [228]
NiB-400 1 M KOH þ 1 M CH3OH 20 1.51 V vs.RHE 100 mA cm2 [49]
Ni–B–Co0.05 1 M NaOH þ 1 M CH3OH 10 0.75 V vs.Hg/HgO 978.48 mA mg1 [231]
NiSe/RGO-550 1 M KOH þ 0.5CH3OH 50 1.7 V vs.RHE 59.84 mA cm2 [236]
NiSe/Ni 1 M KOH þ 0.5CH3OH 10 0.5 V vs.SCE 132 mA cm2 [237]
Ni0.75Fe0.25Se2 1 M KOH þ 1 M CH3OH 50 1.5 V vs.RHE 53.5 mA cm2 (2200 mA mg1) [238]

8
C. Liu et al.
alloys [154]. When Ni–Co alloys were used to catalyze MOR, cobalt can
promote the adsorption of OH at low potentials [155], and at the same
time, promote the formation of NiOOH active sites. Therefore, NiCo al-
loys were highly efficient electrocatalysts for MOR [150,155,156]. For
example, the electrocatalytic activity of Nix-Coy/graphene with different
nickel-cobalt ratios was investigated for methanol oxidation in an alka-
line medium [156], and the electrocatalytic activity could be improved
by increasing the content of nickel in the catalyst system. In another
work, the CoxNiy-decorated graphene also showed largely improved
performance for MOR [150]. The electronic structure was tuned by the
alloy composition which influences the catalytic performance, and
Co0.2Ni0.2 alloy nanoparticles revealed the best performance while
Co0.1Ni0.3 showed the worst activity for MOR.
As mentioned previously, the presence of Cu could promote the
conversion of Ni to β-NiOOH, which was generally considered the real
active phase for MOR [43]. Moreover, the lower affinity of CO to the Cu
than that to the Pd or Pt noble metals makes it suitable for anti-poisoning
electrocatalysts construction [157]. For example, hierarchically struc-
tured Ni–Cu alloys composed of 3D network-like microscopic branches
with nanoscopic dendritic feelers on each branch (Fig. 4c) were prepared
by an electrodeposition approach for MOR [148]. Ni2þ and Cu2þ ions in
the solution were electrochemically reduced into the isolated Ni–Cu alloy
nuclei on the Ti substrate (Fig. 4d). As the deposition time increases, the
isolated nuclei develop into Ni–Cu alloy nano-nodules and serve as
growth points or seeds. Thereby, anisotropic growth was promoted to
generate branching, and finally, grow into a hierarchically structured
Ni–Cu alloy. Among the Ni–Cu alloys with different Ni/Cu ratios, the
Ni0.75Cu0.25 electrode exhibited the largest peak current density of
140 mA cm2 at 0.83 V vs. Ag/AgCl toward methanol oxidation. The
enhanced performance of Ni0.75Cu0.25 electrocatalyst can be attributed to
its alloyed structure with the proper Ni/Cu ratio and a large number of
active sites on the surface of hierarchical structures. It was reported that
the thermal-induced phase engineering of Cu–Ni nanowires could
improve the electrochemical activity and stability of MOR under alkaline
conditions [132]. The optimized catalyst could deliver an unprecedented
mass activity of 425 mA mg1, which was 4.3 times higher than that of
the untreated one. Detailed analysis suggested the improved perfor-
mance came from the large active surface area, the increased number of
NiOOH, and fast methanol electrooxidation kinetics. A similar study was
done by loading CuNi bimetallic nanoparticles onto reduced carbon
quantum dots, and a much lower onset potential of methanol electro-
oxidation was also obtained [158], and the peak current density was as
high as 90.41 mA cm2, about three times higher than that of the
Ni–Cu/GCE catalyst. The effect of the co-deposition of Ni60Cr10Ta10P16B4
amorphous metallic glass powder on the morphology and electrocatalytic
properties of Ni–Co coatings was evaluated for MOR [90]. Among them,
nickel acted as an active site to catalyze MOR, and the addition of cobalt
improved the surface coverage of redox species and tuned CH3OH
adsorption. It should be noted that some Ni alloys are not easy to prepare.
For example, NiCu alloys with high phase compatibility are difficult to
prepare due to the easy formation of oxides [159,160], and manganese is
difficult to form a zero-valent alloy due to its strong oxidizing properties
[161].
Compared to binary alloys, multi-component alloys have unique ad-
vantages that allow the formation of new and customizable active sites in
multiple elements adjacent to each other, and the interaction can be
tailored by rational selection of elemental configuration and composition
[162,163]. For example, compared with binary Ni3Sn2 nanoparticles,
Ni3-xCoxSn2 exhibited much better catalytic performance for MOR in an
alkaline medium [164]. The introduction of small amounts of Co into the
structure improved the electrocatalytic performance, while the cycling
performance was slightly decreased. In addition, Sn played a more sig-
nificant role in improving the catalyst stability concerning Ni NPs,
though a slow desolvation was observed in the KOH electrolyte. The
theory calculations showed the more effective sites for CO and CH3OH
adsorption could be formed by the incorporation of Co within the Ni3Sn2
9
Advanced Sensor and Energy Materials 2 (2023) 100055
structure. They also pointed out that the relatively lower stability was not
related to CO or CH3OH poisoning effect. Due to the combined advan-
tages of the special structure and electronic effects of Ni and transition
metal alloys, the obtained Ni-based catalysts generally exhibited high
catalytic activity, fast kinetics, and high stability.
3.1.2. Nickel hydroxide
Since Ni(OH)2 is easily converted to NiOOH during the catalysis re-
action, thus, it is a potential catalyst for methanol oxidation [165,166].
Ni(OH)2 has two well-characterized polymorphs, α and β structures. The
α structure consists of Ni(OH)2 layers with intercalated anions or water,
and the β form adopts a hexagonal close-packed structure with Ni2þ and
OH ions [167,168]. In the presence of water, the α structure typically
recrystallizes to the β form [169]. Hierarchical Ni(OH)2 nanostructures
with high porosity and excellent electrochemical performance from
Ni-MOF were prepared through an ex-situ wet chemical transformation
method with alkali treatment at room temperature [170]. The structure
and electrocatalytic properties of Ni(OH)2 nanostructured flowers were
dependent on the alkali concentrations (Fig. 4e), since the formation of
Ni(OH)2 was accompanied by the disconnection of the coordination bond
between Ni and ligands to form defects. The Ni(OH)2 obtained from
Ni-MOF treated with 0.25 M NaOH showed the best performance for
MOR (Fig. 4e). Ni(OH)2 nanosheet arrays were prepared on nickel foam
by ultrasonication in HCl solution and the subsequent drying procedures
[15]. The nanostructures assembled by the interconnected nanosheet
arrays provided abundant active centres, which were favourable for MOR
with a low potential of only 1.36 V vs. RHE to drive 100 mA cm2.
By combining different components, the conductivity and chemical
stability of the heterostructures can be regulated to enhance electro-
catalyst performance [171]. For example, heterogeneous Ni–Ni com-
posites as Ni-MOF on the Ni(OH)2 composite were prepared by a nickel
hydroxide template-directed in situ synthesis method (Fig. 4f), which can
promote the electrochemical MOR [84]. The unique hierarchical struc-
ture and synergistic effect of the composite afford favourable perfor-
mance for MOR, which showed a peak current density of 24.6 mA cm2.
A two-dimensional layered NiS/Ni(OH)2 with an average thickness of
less than 10 nm was uniformly distributed on the surface of PPy/GO
nanosheets due to the coordination interaction between the Ni2þ and
–NH– segments in the PPy chain (Fig. 4g) [67]. The as-prepared NiS/-
Ni(OH)2@PPy/GO nanosheets exhibited excellent performance in
methanol oxidation due to the synergistic effect of layered GO, conduc-
tive polypyrrole, highly active Ni(OH)2, and NiS.
Layered double hydroxides (LDHs) consisting of stacked brucite-type
octahedral layers with anions and water molecules occupying the inter-
layer spaces have attracted growing interest in electrocatalysis [172]. For
example, Ni/Al LDHs electrodeposited on the glassy carbon (GC) elec-
trodes were studied in detail by cyclic voltammetry and chro-
noamperometry for MOR and they showed much higher electrocatalytic
activity and stability than that of the Ni(OH)2/GC [173]. Ni/Al and Ni/Fe
LDHs were compared for MOR [174]. The XPS analysis demonstrated
that when Fe was present in the Ni/Fe LDH, a larger proportion of Ni3þ
was obtained compared to Ni/Al LDH. The percentage of Ni active sites
for Ni/Fe LDH was much higher than that of Ni/Al LDH, which showed
high performance for MOR for the current recorded at any potential
values. Heteroatom-doped LDHs were further developed for methanol
oxidation. S-doped Co–Ni layered double hydroxides (S-LDHs) using
thiourea as the sulfur source were evaluated for MOR [175]. The
charge-transfer resistance was reduced by S-doping due to the formation
of highly conductive sulfides during the S-doping, which facilitates
electron transfer. P doping and coupling with reduced graphene oxide
were adopted to adjust the MOR activity of CoNi-layered double hy-
droxides (SS/rGO/P–CoNi LDHs) [176]. The synergistic contributions
from both nickel and cobalt ions offered much richer redox reactions and
higher conductivity than the two corresponding single-component hy-
droxides. Therefore, the methanol oxidation performance of
SS/rGO/P–CoNi LDHs is higher than that of the two corresponding
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

single-component hydroxides (Fig. 4h). The Low-electronegative P atom
doping can improve the conductivity and induce a synergistic effect to
increase MOR activity, which was 2 times higher than that of undoped
CoNi LDHs. The Ni-based LDHs showed promising application for MOR
while they suffer from poor conductivity and stability due to their
intrinsic characteristics. The introduction of carbon materials and metal
doping, based on the current findings, are efficient strategies to improve
the intrinsic conductivity of the Ni-based LDH catalysts.
3.1.3. Nickel oxides
Nickel in nature mostly exists in the form of oxides, which has octa-
hedral Ni2þ and O2 sites [177]. Nickel oxides have high specific surface
areas, abundant redox centres, and good stability in alkaline media
[178]. NiO is a classic catalyst material with a simple structure, however,
the charge transport and reaction kinetics for Ni-based oxides are rela-
tively slow [179]; therefore, varied approaches have been employed to
promote the catalytic ability of NiO through structure modification or
composite materials construction [180–182].
Nickel oxide hybrid catalysts loaded on different carbon materials
such as carbon nanotubes, multi-walled carbon nanotubes, and reduced
graphene oxide was evaluated for methanol oxidation due to the good
dispersion and conductivity improvement [129,180]. Highly crystalline
NiO nanoparticles grown on carbon nanotubes (CNTs) by atomic layer
deposition (ALD) were developed (Fig. 5a) and the sizes of the NiO
nanoparticles from 1.5 to 6.3 nm can be precisely controlled at moderate
temperature by varying the number of ALD cycles [180]. The ALD pro-
cess was performed with bis(cyclopentadienyl) nickel (Cp2Ni) and O3 as
the Ni precursor and oxygen source, respectively. Highly dispersed de-
fects and oxygen-containing active sites were generated on the carbon
nanotubes after the first O3 treatment, which became the anchoring sites
for the Ni precursor chemisorption. Upon adsorption, initially, the two
cyclopentadienyl groups of the Cp2Ni molecule will guide the dispersion

Fig. 5. (a) Schematic illustration of the proposed ALD growth initiation of NiO nanoparticles on a CNT [180]. (b) SEM micrographs for the CNF loaded with Ni
hydroxide that was calcined at 500  C [129]. (c) Crystal structure of VO-rich ultrathin NiO nanosheets [184]. (d) The density of states of NiO samples without oxygen
vacancies [184]. (e) The density of states of NiO samples with oxygen vacancies [184]. (f) High-resolution transmission electron microscopy images of Cu–Ni–S [207].
(g) CV curves of Ni–P/CP for MOR in 1 M KOH þ 0.5 M CH3OH at 50 mV s1 [214]. (h) CV curves of NiCoPO catalysts for MOR in 0.5 M KOH þ 1 M CH3OH at
50 mV s1 [225]. Reproduced from Refs. [129,184,207,225] with permission from Elsevier, copyright 2017, 2019, 2022,2016. Reproduced from Ref. [180] with
permission from Wiley, copyright 2012. Reproduced from Ref. [214] with permission from American Chemical Society, copyright 2021.

10
C. Liu et al.
of the adsorbed molecules. Subsequently, O3 will react with the Ni pre-
cursor to form highly dispersed NiO seeds. The 1D NiO/CNT hybrid
structures can easily form a porous network, which effectively facilitated
ion transport into the modified electrode and significantly increased the
reactive surface area. The stable-state current decay rate of the NiO/CNT
catalysts with an average particle diameter of NiO for 4.9 nm was at least
4 times slower than that of the commercial NiO nanopowder.
Nitrogen-doped carbon nanofiber-supported NiO composite prepared by
electrospinning a sol-gel mixture of graphene and polyaniline followed
by a high-temperature annealing process also demonstrated high cata-
lytic performance towards methanol oxidation [129]. SEM character-
ization of the catalyst obtained at 500  C shows a uniform distribution of
NiO nanoparticles on the carbon nanofibers (Fig. 5b). The MOR peak
current density for the catalyst obtained at 500  C was 0.015 mA cm2 in
6 M KOH þ1 M methanol at 1.3 V vs. SCE. The improved performance
was due to the high N content in the CNF support increased electron
density and the interaction between CNFs and the NiO catalyst. Besides,
the construction of oxygen vacancies in NiO was also one of the effective
ways to improve the MOR [183]. Ultrathin NiO nanosheets with abun-
dant oxygen vacancies were prepared by rapidly heating the Ni-based
ultrathin nanosheet precursors in the air [184]. Taking models of NiO
samples with (Fig. 5c) and without oxygen vacancies as examples,
first-principles calculations based on density functional theory (DFT)
were implemented to investigate the influence of oxygen vacancies on
the electronic structure and properties of NiO catalyst. The adsorption
energy for NiO surface with oxygen vacancies is calculated to be
5.81 eV, lower than that of the perfect surface (3.57 eV), which in-
dicates that the presence of oxygen vacancies can promote the adsorption
of methanol molecules, thus accelerating the catalytic kinetics for MOR.
In addition, as disclosed by the calculated density of states in Fig. 5d and
e, VO-NiO shows a smaller band gap of 1.08 eV with respective to the
pristine NiO (1.6 eV). The introduction of oxygen vacancies endows the
NiO catalyst with a new defect level, which serves as the springboard for
electronic transition from valence band to conduction band. It is greatly
conducive to the excitation of electrons into the conduction band,
thereby achieving enhanced electron transport capacity and better MOR
performance. The obtained VO-rich ultrathin NiO nanosheets showed a
stable and remarkably increased MOR activity with a current density up
to 85.3 mA cm2 at 0.7 V vs. Ag/AgCl, which was roughly 2.3 times and
3.5 times larger than that of the VO-poor ultrathin NiO nanosheets and
bulk NiO samples, respectively.
The single NiO phase cannot afford the satisfied catalytic activity due to
the limited active suites, and the catalytic performance can be improved by
incorporating metal and metal oxide into NiO to form hybrid materials
which can shorten the ion transport path and enable the rapid transfer
between ions and electrons [185,186], for example, Ni/NiO supported on
oxygen-functionalized carbon nanotubes (Ni/NiO/CNTs) with low Ni
loading (3–4 wt%) showed much better OH diffusion properties than
NiO@CNTs and Ni@CNTs [187]. Thus, more electroactive species, such as
NiOOH, were formed on the surface of NiO/Ni@CNTs to catalyze MOR.
The high mass-normalized activity with the peak current density of
2094 mA mg1 at 580 mV was observed for NiO/Ni@CNTs, which was
approximately 1.58 and 2.17 times that of NiO@CNTs (1328 mA mg1)
and Ni@CNTs (966 mA mg1), respectively. Ni/NiO/multi-walled carbon
nanotube hybrid showed a maximum peak current density of
15.94 mA cm2 for methanol oxidation, and the existence of MWCNT was
beneficial to the electrons for catalysis [188]. In addition, hybridizing
nickel oxides with other oxides have also been developed for MOR [72].
Composite of NiO/FeO MOF with different amounts of reduced graphene
oxide were synthesized through a hydrothermal method [181]. The cata-
lysts with 4 wt% rGO in the system showed the highest current density
(486.14 mA cm2, at 0.85 V vs. Ag/AgCl) for MOR. The rGO support
enhanced the conductivity, and the presence of iron promoted the gener-
ation of trivalent nickel active sites, thereby, the performance was
increased. Further research found that the bimetallic nanoparticles could
catalyze MOR through both bifunctional mechanisms and electronic
11
Advanced Sensor and Energy Materials 2 (2023) 100055
effects. The MOR behaviour catalyzed by Cu–Ni/CuO–NiO nanocatalysts
was studied [189], and the mixed Cu/Ni metals and CuO/NiO metal oxides
could efficiently adsorb OH species for further oxidation of CO-like in-
termediates based on the bifunctional mechanism, and the binding energy
of COads on the catalyst surface was decreased due to the electronic effect.
Meanwhile, the electronic effects accelerated the electron transfer between
the metals/metal oxides, as a result, Cu–Ni/CuO–NiO showed a high
electrocatalytic activity of 3563 A g1.
The spinel NiCo2O4 derived from nickel and cobalt is structurally
stable and electrochemically active in electrocatalysis reactions [190].
Due to the easy transformation and the tunable morphology, the elec-
tronic structure of spinel can be optimized to make it have a much better
affinity with oxygen-containing groups [191]. Inspired by these proper-
ties, NiCo2O4 catalyst is expected to be a promising catalyst for methanol
oxidation reaction [192]. Reduced graphene oxide-supported NiCo2O4
(NiCo2O4/rGO) nano-rods were prepared by hydrothermal synthesis, and
the synergistic effect between NiCo2O4 and rGO significantly improved
the electroactivity for MOR due to the formation of mixed-valence cat-
ions of Ni2þ and Co3þ from the octahedral sites [193]. The NiCo2O4/rGO
showed good performance for MOR (78 mA cm2), which was 3.11 folds
higher than the commercial Pt/C (25.08 mA cm2). The MOF-derived
spinel type NixCo3-xO4-y nanocages for methanol oxidation were re-
ported [194]. The number of active redox centres (Ni2þ/Ni3þ and
Co2þ/Co3þ) in NixCo3-xO4-y was increased compared to Co3O4
(Co2þ/Co3þ). The direct electrochemical MOR was facilitated through a
surface intermediate (CH3OH or CO), which is adsorbed on
low-coordinated Ni and Co sites, respectively. As a result, a high current
density of 200 A g1 can be achieved at 1.55 V vs. Hg/HgO. Modification
of the surface properties of spinel oxides could further boost the catalytic
performance. The vacancies or hybridization has been constructed on
spinel NiCo2O4 to promote MOR. For example, a series of controllable
hollow NiCo2O4 nanoparticles with interconnected hierarchically porous
structures and abundant oxygen vacancies were constructed and oxygen
vacancy defect-dependent activity was observed for MOR [183]. The
material annealed in a mixed air/Ar atmosphere at 450  C (NiC-
o2O4-450-Vo) exhibited the best specific activity of 209.3 mA cm2 to-
wards methanol oxidation at 1.75 V vs. RHE in an alkaline medium. The
tri-metal spinel oxides with the mixed molybdates of cobalt and nickel
(Co1-xNixMoO4) were synthesized by substituting nickel for cobalt in
CoMoO4 [195]. Among them, Co0.5Ni0.5MoO4 demonstrated the best
MOR catalytic activity with a current density of 164.5 mA cm2 at 0.7 V
vs. SCE for MOR. The improved electrocatalytic surface properties were
due to the synergistic interaction between Co and Ni.
3.1.4. Nickel sulfide
Nickel sulfide is a compound with the formula NiSx and the simplest
stoichiometry is NiS. In the nickel sulfide, nickel is octahedral, and the
sulfide centres are in trigonal prismatic sites [196,197]. Polysulfide an-
ions can continue to combine with sulfur to form anions with a higher
degree of polymerization or remove sulfur to form anions with a low
degree of polymerization [198,199]. This reversible process of desul-
furization and sulfur addition provides favourable conditions for catal-
ysis such as the excellent absorption for OHads and oxygen-containing
functional groups [200]. Compared to metal oxides, the bond of
metal-S in the transition metal sulfides is more covalent, inhibiting their
corrosion under similar conditions which resulted in better stability
[201].
The cheap nickel sulfide nanoparticles (NiS NPs) (i.e., α-NiS (hexag-
onal, Nickeline phase) or β-NiS (rhombohedral Millerite phase)) have
unique electrochemical properties for the catalysis reactions [202]. For
example, layered flower-like NiS with a high surface area of 26.67 m2 g1
and pore diameters of ~65 nm was synthesized by the solvothermal
method [203]. The hierarchical flower-like NiS exhibited a high elec-
trocatalytic activity and a high tolerance toward the catalyst-poisoning
species during the MOR via the direct electrooxidation of methanol on
the oxidized NiS surface layer. The composite of Nickel sulfide/carbon
C. Liu et al.
aerogel electrodes (NiS/CA) was evaluated for MOR, and the peak cur-
rent density at 0.8 V vs. Ag/AgCl was as high as 43 mA cm2 [204]. The
peak current density of the composite remained 92% of the initial state
after 1000 cycles, and the nickel oxide with low crystallinity was
observed on the surface after the long cycle test. In addition, other phases
of nickel sulfide such as Ni3S2 and Ni3S4 have also been developed for
MOR [205–208]. For example, a Pt-like electrochemical behaviour for
MOR was found for a three-dimensional (3D) self-supported Ni3S2 on
nickel foam [205]. The electronic defects in Ni3S2 might act as active
sites for MOR, and the high performance was attributed to the synergetic
effects between the in-situ formed active NiOx core and Ni3S2 shell
during methanol oxidation. Nanohybrids of multi-walled carbon nano-
tubes and nickel sulfide (Ni3S2) also exhibited superior electrocatalytic
activity for MOR due to the synergistic effects of Ni3S2 and high charge
transporting MWCNTs [206]. The onset potential for MOR was about
0.2 V vs. Ag/AgCl, which provided the possibility for the application of
noble metal-free catalysts in fuel cells. Nickel sulfide nanospheres with
Cu cation-modulated (Cu–Ni–S) were fabricated by a pulsed laser irra-
diation technique, where the Cu–Ni–S sample had a mixed phase of CuS2
and Ni3S2 phases (Fig. 5f) [207]. The Ni–S sample only exhibited Ni2þ
states while Cu–Ni–S sample showed both Ni2þ and Ni3þ states, which
suggested the Cu cation modulation enhanced the oxidation state of Ni
leading to more efficient catalysis of MOR. The bimetallic active sites and
the enriched accessible Cu sites in the Cu–Ni–S sample showed high
methanol electrooxidation activity with a peak current density of
55.6 mA cm2 at 0.65 V vs. Hg/HgO. A three-component nanocatalyst
Co3O4–Ni3S4-rGO (CNR) was reported to have a high exchange current of
8.61  107 mA cm2 in MOR [208]. The synergistic effect of the metal
active sites Co3O4 and Ni3S4, and the conductivity improvement and
increased active sites exposure by adding rGO were key to the perfor-
mance improvement. Generally, the introduction of sulfur into the
Ni-based catalyst could enhance the MOR catalytic activity via promoting
the formation of more Ni hydroxide. However, due to the low intrinsic
stability of metal sulfide, the balance of catalytic activity and stability
should be considered for novel catalyst design.
3.1.5. Nickel phosphide and nickel phosphate
(1) Nickel phosphide
Nickel phosphide has a hexagonal structure with high corrosion
resistance and stability for the catalysis reaction [209,210]; the forma-
tion of Ni–P bond lowed the electron cloud density of Ni, which facili-
tated the formation of high valent Ni(III) [211]. Therefore, the electronic
effect of nickel phosphide and the oxophilic property based on a
bifunctional catalytic mechanism can greatly promote methanol oxida-
tion [212]. The effect of different phases of nickel phosphide for MOR
was done on a comparative study of three different phases of Ni–P
(Ni12P5, Ni2P, and Ni5P4) for MOR [213]. Ni12P5 showed the best cata-
lytic activity for MOR, with a peak current density of 210 mA cm2 at
1.72 V vs. RHE, associated with lower activation energy and a high
number of surface-active sites than the other catalysts. In another work,
nickel phosphide nanospheres with different crystallinity (Ni2P–H,
Ni2P-L, and Ni–P-a) were synthesized by reacting Ni-based MOF and P4
solvothermal for MOR in alkaline media [214]. Ni2P-L showed the
highest current density (Fig. 5g) owing to the abundant electrochemi-
cally active site exposure by forming the amorphous phase and the
electron interaction between Ni and P. In addition, the bimetallic NiCo
phosphides derived from MOF (NiCo-MOF-P) were investigated for
alkaline MOR [215]. A high peak current density of 170 mA cm2 was
observed with remarkable long-term stability at 1.54 V vs. RHE, and the
high electrocatalytic activity towards methanol oxidation was mainly
associated with the synergistic effect of bimetallic element (Ni and Co),
high surface area, and the facilitated charge-transfer due to binder-free
growth on Ni foam. However, the P atoms will largely limit the elec-
tron delocalization of the metal resulting in a gradual decrease in
12
Advanced Sensor and Energy Materials 2 (2023) 100055
electrical conductivity [216]. Therefore, the activation step is required
for the application of the nickel phosphide catalyst in MOR. The incor-
poration of P was proposed to modify the surface electron structure of Ni
and promote Ni2þ to a higher valence state, thus producing fast electron
transport and low reaction resistance. Nickel phosphides with special
morphology offering more active sites are still required to deliver better
catalytic activity and stability.
(2) Nickel phosphate
Nickel phosphate is an inorganic compound with the formula
Ni3(PO4)2, and the octahedral Ni centres are bound to water and phos-
phate [217,218]. Nickel phosphate has been developed to catalyze MOR
due to its excellent structure-induced electron transport properties [219,
220]. For example, porous nickel phosphates modified glassy carbon
electrodes (NiPO-2/GCE) were studied for the electro-oxidation of
methanol in an alkaline medium [221]. The mesoporous NiPO-2/GCE
exhibited much better electrochemical activity and stability than that
of NiO/GCE, benefitting from the large pore space of NiPO-2 for the
diffusion of reactant molecules. Composite nickel phosphate with various
carbon supports can further enhance its catalytic ability [222]. Because
of the strong guest-host interaction between the nickel phosphate and
graphene, the enhancement of the electro-catalytic activity was
observed. The effect of heteroatom doping on nickel phosphate-catalyzed
methanol was also investigated for MOR [223]. Si-incorporated meso-
porous nickel phosphates were evaluated for MOR in an alkaline me-
dium, and good stability was observed at the optimized Si content that
showed the electrochemical activity was increased by a factor of 4
compared to the nickel phosphates [224]. Ni–Co bimetallic phosphates
were also reported for MOR due to the synergistic effect of Ni–Co in
methanol oxidation. The electronic states and texture properties of the
active Ni(III) species in the nickel-cobalt phosphate (NiCoPO) can be
regulated by the introduced Co phosphate. Compared with nickel phos-
phate, the onset potential of NiCoPO with an atomic ratio of 5:5 was
decreased by 132 mV in the MOR process. Besides, a series of Ni–Co–P–O
electrocatalysts were evaluated for methanol oxidation in an alkaline
environment [225]. The chemical composition and surface morphology
of the final composite largely depended on the Co2þ/Ni2þ molar ratios in
the reaction system. The sample with an urchin-like architecture and a
hybrid composition of nano-scaled Ni/Co phosphides and phosphates
was produced at a Co2þ/Ni2þ molar ratio of 0.18. It showed the highest
methanol oxidation current density of ~1567 A g1 (Fig. 5h) at 0.8 V vs.
SCE and good durability (20,000 s) at 0.6 V vs. SCE. The formation of
electron tunneling junctions between the metal phosphides and phos-
phates was proposed to form new channels to accelerate the electron
transfer throughout the composite electrocatalysts.
3.1.6. Nickel boride
Boron is a metalloid element with an intermediate electronegativity
value between metals and non-metals, and the special properties of boron
make nickel boride have a varied crystal structure and compositions, e.g.
Ni3B, Ni2B, Ni7B3 [226]. When alloyed into intermetallic borides, rich
bonding schemes in one compound can be generated, including metallic
bonds, ionic bonds, and covalent bonds [227]. Different combinations
lead to different degrees of electron transfer between boron atoms and
Ni, so borides have been widely used in the field of catalysis. In the
catalysts for MOR, some nickel borides with crystal and amorphous
structures were developed and studied. For example, crystalline Ni3B
nanoparticle agglomerates derived from the solution-produced amor-
phous nickel boride have been compared for MOR [228]. The crystalline
Ni3B/Ni foam (CNB/NF) electrode exhibited a much higher MOR current
density of 62 A g1 at 0.55 V vs. Hg/HgO in a 6 M KOH solution with
0.5 M methanol. A heterostructure of nickel boride/nickel catalyst
(NiB-400) was developed to enable methanol electrooxidation into
formate with a Faradaic efficiency of nearly 100% [49]. Some interfaces
were revealed by high-resolution transmission electron microscopy
C. Liu et al.
(HRTEM) in NiB-400, where the interplanar spacings were assigned to
the crystal planes of face center cubic Ni and orthorhombic Ni3B were
observed (Fig. 6a). It is proposed that the methanol oxidation pathway on
NiB-400 is CH3OH→ *CH3OH → *CH3O → *CH2O → *CHO → *HCOOH
→ HCOOH. The geometric model of Ni(111) and Ni3B(001) was chosen
to demonstrate the pristine Ni and Ni3B materials (Fig. 6b). It can be seen
that the potential-determining step for MOR is all contributed by the
process of *CH3O → *CH2O þ Hþ þ e on the surfaces of Ni3B/Ni
heterostructure, Ni3B and Ni. Among them, Ni3B/Ni heterostructure ex-
hibits the lowest Gibbs energy barrier of 0.57 eV in comparison to 0.74
and 0.70 eV for Ni3B and Ni, respectively, indicating that MOR can occur
most favorably on the Ni3B/Ni surface. As a result, an anodic potential of
ca.1.51 V vs. RHE was required to achieve a current density of
100 mA cm2, and the improved performance was due to the hetero-
structure that can effectively promote the binding of key intermediate
*CH2O and lower the associated energy barrier. In addition to Ni3B, MOR
catalysts with different nickel boride phases have also been developed
[229]. A Ni–Co–B catalyst with different ratios of Ni and Co was syn-
thesized via an electroless deposition method on stainless steel gauze
substrate, and the Ni–Co–B-MR1 (Ni–Co molar ratio of 9:1) exhibited the
best response towards methanol oxidation in alkaline medium with the
current density of about 11.3 mA cm2 at a potential of 0.65 V vs.
Ag/AgCl [229]. The hybrid crystal structures of Ni2B, Ni3B, and Co2B
were found in the system, and the electronic and synergistic effect for the
optimized cobalt content in the catalyst enable nickel to attain its higher
oxidation state during the oxidation process.
The amorphous materials possess more unsaturated atoms as cata-
lytically active sites than highly crystalline ones, their disordered
arrangement and unsaturated coordination structure have received
extensive attention in the field of electrocatalysis [230]. Amorphous
Ni–B nanoparticles doped with cobalt were investigated to reveal the
enhanced mechanism by cobalt for MOR [231]. The Ni–B–Co0.05 nano-
particle with Ni–Co molar ratio of 20:1 showed the peak mass current
density of 978.48 A g1 for methanol oxidation (Fig. 6c). During the
Fig. 6. (a) HRTEM image of the NiB-400 catalyst [49]. (b) Gibbs free energy diagram of MOR occurring on Ni3B(001)/Ni(111) heterostructure [49]. (c) CV curves of
Ni–B4, Ni–B–Co0.02, Ni–B–Co0.05, and Ni–B–Co0.1 nanoparticles for MOR in 1 M NaOH þ 1 M CH3OH at a scan rate of 10 mV s1 [231]. (d) The preparation process for
NiSe/RGO [236]. (e) CV curves of NiSe/Ni, Ni3S2/Ni and NiO/Ni in 1 M KOH þ 0.5 M CH3OH at a scan rate of 10 mV s1 [237]. Reproduced from Ref. [49] with
permission from Springer Nature, copyright 2022. Reproduced from Refs. [231,236] with permission from Elsevier, copyright 2018, 2020. Reproduced from
Ref. [237] with permission from The Royal Society of Chemistry, copyright 2015.
13
Advanced Sensor and Energy Materials 2 (2023) 100055
methanol catalysis, CoOOH was preferentially formed on the surface of
amorphous Ni–B–Co nanoparticles that promoted the generation of
NiOOH to catalyze MOR. Meanwhile, Co could also increase the ab-
sorption ability of Ni 3d orbit towards the methanol and intermediates,
thus improving the catalytic activity for MOR. Actually, the study of Ni–B
in the MOR was not intensive, and much effort can still be done to
develop high-performing catalysts, and understand the structural evo-
lution process.
3.1.7. Nickel selenide
Nickel selenide has the same structure as that of nickel sulfide where
nickel is octahedral and the selenides are in trigonal prismatic sites
[232]. The outermost electron configuration of nickel in nickel selenide
is 3d84s2 with a rich valence and excellent chemical activities [233].
Since the energy levels of Se are close to the 3s and 3p orbitals, the 3d
orbitals of Se might be involved in bonding with metal atoms, which
contributes to more metallic properties of the transition metal selenides
thus improving the electron transport [234,235]. Therefore, nickel sel-
enides have also gained increasing interest in MOR owing to their high
electronic conductivity, structural diversity, and chemical stability. For
example, reduced graphene oxide-supported nickel selenide (NiSe/RGO)
nanoparticles obtained by a simple and universal way of pyrolyzation
and selenylation of Ni on reduced graphene oxide were optimized for the
study MOR (Fig. 6d) [236]. NiSe/RGO-550 prepared at 550  C showed
outstanding performance with a peak current density of
59.84 mA cm2 at 1.7 V vs. RHE, and the improved performance was
because of the increased active sites after selenization and good con-
ductivity. The nickel selenide catalyst synthesized by annealing is highly
dependent on the annealing temperature because the annealing tem-
perature will affect the particle size, active site exposure, and chemical
environment as well as the electrochemically active area [130,236].
Nickel selenide hybridized with other materials was also developed for
MOR [237]. The in-situ growth of NiSe nanowire arrays on nickel foil
(NiSe/Ni) was used for the electro-catalytic oxidation of methanol in
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

alkaline media [237]. The high electrical conductivity of NiSe favors fast
electron transport along it and the direct growth of NiSe on Ni substrate
ensures an excellent electrical connection between them. Compared with
the NiO/Ni and Ni3S2/Ni electrodes, the NiSe/Ni electrode has a much
higher activity for methanol oxidation (Fig. 6e), which affords
132 mA cm2 at 0.5 V vs. SCE. In addition, some bimetallic selenide
catalysts were also developed for MOR [238]. Ni1xFexSe2 nanorods
catalysts were reported to have a high potential for selective methanol
conversion to formate [238]. The optimized catalyst of Ni0.75Fe0.25Se2
could produce 0.47 mmol cm2 h1 of formate at 50 mA cm2; and the
Faradaic conversion efficiency was as high as 99%, which can continu-
ously work for over 50,000 s with a minimal loss of efficiency. By
introducing Fe into the system, the surface coverage of the active species
(NiOOH) and proton diffusivities can be largely improved.
3.2. Ni-based catalysts hybrid with noble-metals
The high cost and rarity of noble metals such as Pt are not sufficient
for large-scale applications, and from the perspective of basic research,
the poisoning effect caused by the adsorption of intermediates during
methanol oxidation is a thorny issue [239]. Ni-based materials as the
promoter can speed the oxidation of intermediates to enhance MOR by
the electronic effect and the ligand effect resulting from the coupling
effect of the noble Pt and the cheap promoters [240]. Generally speaking,
the electronic effect improves the electrical conductivity and ability to
tune the adsorption/desorption property of intermediates [241]; and the
speeded oxidation of COads through a bifunctional mechanism could
reduce the poisoning issue of noble metals to improve the MOR perfor-
mance [64,242]. The MOR performance of nickel-based catalysts hy-
bridized with noble metals in alkaline electrolytes was summarized in
Table 2.
3.2.1. Alloying with noble-metal catalysts
Noble metals such as Pt or Pd are employed to fabricate alloy catalysts
for MOR in the alkaline electrolyte, especially used in the fuel cells
technique [52,243]. Platinum is widely used due to its high catalytic
activity, while the strong affinity for CO, a by-product generated during
methanol oxidation, can block the active centres and inhibit the reaction
[52,244]. The alloy of PtNi catalysts is highly active for MOR because Ni
helps promote the adsorption of hydroxyl species and remove COads on
adjacent Pt sites [64,242]. This enhancing effect is similar to the
bifunctional mechanism that was often employed to explain Ru
enhancing the MOR activity catalyzed by Pt [245,246]. In addition, the
ligand effect induced by the Pt–Ni alloy could modify the d-band struc-
ture of Pt via the electronic effect by tuning the surface adsorption
property, which increases the catalytic ability [212,247]. The composi-
tion of the Pt and Ni in the alloy has an important effect on the MOR
activity [248]. Specifically, the onset potential for MOR was increased by
increasing the Ni amount for low Pt contents and then dilution of Pt by Ni
caused the performance decrease; For the high content of Pt, the onset
potential for MOR was reduced by increasing Ni amount due to its
assistance for the elimination of COads. PtNi alloy nanoparticles
self-decorated on multiwalled carbon nanotubes with Pt-to-Ni ratio of 1:1
showed high catalytic activity and stability for methanol
electro-oxidation, and the electronic structure characterization showed
the electrons transfer from Ni to Pt suppressed the CO poisoning effect.
From the analysis of density functional theory studies, the electronic
structure of Pt modified by Ni atoms could change the CO adsorption
energy (Eads) [249], and the Eads value of CO over the Pt3Ni (Pt3Ni–CO)
cluster was much lower than that of Pt4–CO cluster (Fig. 7a), which
enhanced mass activity towards MOR and CO oxidation in alkaline media
compared with the Pt/C. The promoting effect of Ni in PtNi alloy for
MOR in alkaline media was further experimentally and theoretically
studied on carbon-supported bimetallic PtmNin electrocatalysts with
different Pt/Ni atomic ratios [58]. The nanoparticles with average di-
ameters of about 3 nm were distributed on carbon supports and the
decreased Pt lattice constants compared with that of pure Pt were indi-
cated by the partial alloy formation for Pt and Ni. Similarly, the electronic
structure of Pt was changed due to the charge transfer from Ni to Pt atoms
in PtmNin clusters, and the weakened CO adsorption in the system could
explain the enhanced MOR activity. The oxygen-functionalized carbon
nanotubes supported(FCNT) PtNi alloy with different Pt: Ni ratios have
been prepared with ethylene glycol as a reducing agent [250]. Phase
separation/restructuring of the catalysts was obtained by heat treatment
at 400  C in N2 atmosphere, where Ni-rich phases close to the FCNTs
were surrounded by a Pt-rich alloy. The catalyst with Pt/Ni ratio of 3
showed the highest catalytic activity due to the proper population of
active Pt sites for methanol adsorption and the high ability for CO
oxidation.
The mechanism of Pd in catalyzing MOR is similar to that of Pt, which
is also affected by COads [53]. While the activity of Pd is much higher in
the alkaline electrolyte than that in the acid electrolyte for MOR, and the
onset potential was generally observed around 0.4 V vs. RHE [251]. The
presence of nickel can further inhibit COads poisoning on Pd active sites
and enhance the catalytic performance [252]. The current density of the
PdNi catalyst was reported to be 3.84 and 1.43 times higher than that of
the Pd/C and Ni/C electrocatalysts, respectively [253]. The role of Ni to
enhance MOR on Pd electrocatalysts was probed by combining experi-
ments and DFT calculations [254]. The catalytic surface coverages based
on cyclic voltammograms and Pourbaix diagrams revealed the oxidation
of the catalyst surface became the more likely process for the Pd–Ni alloy,
and the amount of OHads species was increased on PdNi surface
compared with Pd and Pd3Ni. PdNi alloys proceeded with non-CO routes
where the OHads could easily react to CH2O and CHO via two routes
toward CO2 (Fig. 7b). There was no barrier for the CHO → CO þ Hþ þ e
reaction making the coupling of OHads with CHO less likely for the Pd3Ni
catalyst; the oxidative removal of CO on Pd was more difficult than Pd–Ni
catalyst because the oxophilic property of Ni made highly oxidized

Table 2
Summary of MOR performance in alkaline electrolytes for some of the nickel-based catalysts hybrid with noble metals discussed in this review.
Catalysts Electrolyte Scan rate (mV s1) MOR activity Ref.

Pt3Ni1/C 1 M NaOH þ1 M CH3OH 50 120 mA cm2 [58]

Pd–Ni/C 0.5 M KOH þ 0.6 M CH3OH 10 14.05 mA cm2 [253]
Pd43Ni10Cu27P20 1 M KOH þ 1 M CH3OH 20 9 mA cm2 [256]
Pt/Ni(OH)2/rGO 1 M KOH þ 1 M CH3OH 20 1236 mA mg1
pt [83]
Pt/Ni(OH)2/NG 1 M KOH þ 1 M CH3OH 50 2990 mA mg1
pt [261]
1
PtNi/Ni(OH)2 0.1 M NaOH þ 1 M CH3OH 50 180 mA mg [50]
PtCu/Ni(OH)2/NG 1 M KOH þ 1 M CH3OH 50 2883.75 mA mg1pt [263]
Pt0.54/NiFe-LDH/rGO 1 M KOH þ 1 M CH3OH 50 771.04 mA mg1 [262]
Pt-doped Ni(OH)2/NF 1 M KOH þ 1 M CH3OH 50 1356 mA mg1
pt [266]
Pt/MoS2/Ni3S2-nrs/NF 1 M KOH þ 1 M CH3OH 50 805.4 mA mg1
pt [200]
Pt/CoSe/NiSe-nrs/NF 1 M KOH þ 1 M CH3OH 50 2
256 mA cm (1437.1 mA mg1
pt ) [267]
Ni@Pt/MWCNTs 0.5 M KOH þ 0.2 M CH3OH 50 271.9 mA mg1
pt [275]
1
Ni@Pd/MWCNTs 0.5 M NaOH þ 1 M CH3OH 50 482.2 mA mgpd [278]

14
C. Liu et al. Advanced Sensor and Energy Materials 2 (2023) 100055

Fig. 7. (a) DFT calculations of the structure and CO adsorption energies (Eads) of the CO adsorbed on Pt4 and Pt3Ni clusters [249]. (b) Computed methanol
electro-oxidation reaction pathways on PdNi(111). Red arrows indicate the minimum energy paths, green arrows represent the removal of an H and blue arrows
represent the coupling of an OH [254]. (c) LSV curves in 1 M KOH solution with and without 4 M methanol addition for the NiIr-MOF/NF ||NiIr-MOF/NF system
[258]. (d) Chronoamperograms of Pt/Ni(OH)2/rGO [83]. (e) AFM image of ultrathin Ni(OH)2 nanosheets on a silicon substrate [50]. (f) Schematic diagram of the
formation of Pt/NiFe-LDH/rGO [262]. (g) CV curves of Pt0.54/NiFe-LDH/rGO for MOR in N2-saturated 1 M KOH þ 1 M CH3OH at different cycle numbers at a scan rate
of 50 mV s1 [262]. (h) CV curves of Pt/MoS2/Ni3S2-nrs/NF, Pt/Ni3S2/NF and 10 wt % Pt/C catalysts for MOR in 1 M KOH þ 1 M CH3OH at a scan rate of 50 mV s1
[200]. (i) STEM-HAADF images and EDS-mapping of the Au@Ni-rGO nanocomposites [279]. (j) CV curves of (a) the GO/GCE, (b) the Au@Ni/GCE and (c) the
Au@Ni-rGO/GCE in 0.5 M KOH þ 0.5 M CH3OH at a scan rate of 50 mV s1, the inset is the enlarged part of the three CVs [279]. Reproduced from Refs. [50,249,254,
258,279] with permission from Elsevier, copyright 2010, 2020, 2019, 2022, 2020. Reproduced from Refs. [83,262] with permission from Springer Nature, copyright
2015, 2018. Reproduced from Ref. [200] with permission from American Chemical Society, copyright 2019.

intermediates more likely during MOR. The charge transfer between Pd
and Ni changed the electron density of Pd to enhance the resistance of Pd
to CO poisoning, where the CO binding energy of PdNi(111) was weaker
than that of the Pd(111) surface [255]. Pd43Ni10Cu27P20 bulk metallic
glass (BMG) nanowires were prepared based on PdNi alloy by the nano
molding approach, which exhibited much higher methanol oxidation
activities than that of Pd flat electrodes in alkaline media [256].
Compared with pure Pd, the onset potential of CO oxidation for the
Pd-BMG nanowire was reduced by 300 mV, and the activation energy for
methanol oxidation was 22 kJ mol1, much lower than that of
38 kJ mol1 for the pure Pd. Thus, nickel alloying with noble metals was
an effective strategy to deliver good performance toward alcohol
oxidation at a reasonable price. The alloying of noble metals with more
oxophilic elements can lower electronic binding energy by facilitating
the adsorption of OH at lower potentials and promoting the oxidation of
organic species [257]. In addition, a work of NiIr-MOF nanosheet array
in-situ grown on nickel foam (NiIr MOF/NF) was reported for methanol
electrolysis [258]. The constructed NiIr-MOF/NF ||NiIr-MOF/NF

15
C. Liu et al.
two-electrode system could derive a current density of 10 mA cm2 with
a cell voltage of 1.39 V in a methanol-water electrolyte (Fig. 7c). The
electronic structure and coordination environment of nickel are tuned by
a small amount of iridium, which enhanced the intrinsic activity of the
catalyst.
3.2.2. Nickel hydroxide-supported noble metal catalysts
Nickel hydroxide nanostructures play a decisive role in the dissocia-
tion and adsorption of hydroxyl species [259,260], and nickel hydroxide
can effectively remove toxic intermediates from platinum-adjacent sites
[83,261]. According to Sabatier principle, the interaction between
Ni(OH)2 and OH species is neither too strong nor too weak, which is
particularly active for the dissociative adsorption of water molecules to
form OH species [83]. Therefore, nickel hydroxide can weaken the
poisoning effect of CO in MOR, so it is often hybridized with noble metals
as a MOR catalyst [83,261,262]. For example, the incorporation of
Ni(OH)2 in the platinum-nickel hydroxide-graphene ternary hybrid
(Pt/Ni(OH)2/rGO) greatly facilitated the dissociative adsorption of water
molecules and subsequently promoted the oxidative removal of carbo-
naceous poisoning intermediates via the Langmuir–Hinshelwood reac-
tion pathway [83]. Under periodic reactivations, Pt/Ni(OH)2/rGO
showed negligible activity loss for at least 500 000 s at  0.30 V vs. SCE
(Fig. 7d), which was two to three times longer than that of the common
noble metal-based catalysts. Similarly, the improved performance was
also observed for the Pt/Ni(OH)2/nitrogen-doped graphene catalysts
(Pt/Ni(OH)2/NG), which exhibited performance of about 2.8 and 4.8
times higher than that of commercial PtRu/C and Pt/C, respectively
[261]. The crucial factors for the remarkable electrochemical perfor-
mance are attributed to the transfer of electrons promoted by N-doped
graphene carrier materials, abundant OH species provided by Ni(OH)2,
and highly exposed Pt active sites in the ternary compounds.
Further, Ni(OH)2-supported noble metal alloys have been developed
which facilitated the simultaneous working of the bifunctional mechanism
and the electronic effect [50]. Restructured PtNi concave nanocubes sup-
ported on ultrathin Ni(OH)2 nanosheets were prepared through a two-step
hydrothermal method, which showed an open-framework structure with
more active site exposure (Fig. 7e) [50]. The optimal PtNi/Ni(OH)2 showed
the peak current density of 0.18 mA μg1 for MOR due to the synergistic
effect between PtNi to Ni(OH)2 and the electronic effect inside PtNi alloy.
The dendritic PtCu alloys and nickel hydroxide nanostructures were also
found synergistically catalyzing MOR in the PtCu/Ni(OH)2/ni-
trogen-doped graphene ternary hybrid electrocatalysts [263]. In addition,
the layered double hydroxide-supported noble metal-catalyzed MOR has
also been developed for MOR [262,264,265]. Graphene-supported nick-
el-iron layered double hydroxide (NiFe-LDH/rGO) was utilized to immo-
bilize Pt nanoparticles as a catalyst for methanol oxidation (Fig. 7f) [262].
The durability of Pt/NiFe-LDH/rGO was significantly better than that of
Pt/Ni(OH)2/rGO, which maintained 97.6% of its initial catalytic activity
after 600 cycles of CV tests during MOR (Fig. 7g). The introduction of Fe3þ
to partially replace Ni2þ can provide stronger metal-support bonding sites
for the immobilization of Pt nanoparticles. In the system, graphene
increased the electron transfer efficiently and metal hydroxides could
generate oxygen-contained species via water dissociation to accelerate the
removal of poisoning carbonaceous species on adjacent Pt sites. The
self-supported Pt nanoflakes and amorphous Ni(OH)2 on nickel foam with
rich defects were fabricated via a galvanic deposition method [266]. This
composite anode exhibits enhanced activity and stability for methanol
oxidation in alkaline media because of the synergistic effects between Pt
nanoflakes and amorphous Ni(OH)2 on Ni foam substrate and defect en-
gineering. During the MOR catalyzed by Pt-doped Ni(OH)2, the Pt worked
as the active sites, amorphous Ni(OH)2 provides the oxygen containing
species for the poisoning intermediates removal, the good conductivity,
large area, and defects sites offered by Ni foam could maintain the high
activity and stability. While it should be noted that the rigid support of Ni
foam would also contribute some performance for the catalyst, as the Ni is
active for MOR.
16
Advanced Sensor and Energy Materials 2 (2023) 100055
3.2.3. Ni-based chalcogenide-supported noble metal catalysts
Nickel chalcogenides were also reported to assist noble metals in
catalyzing MOR due to their unique structural features and tunable
electronic properties [267]. However, the unstable transition metal sul-
fides in the MOR reaction are likely to generate toxic intermediates such
as SOx, which strongly adsorb and form bonds on the surface of the noble
metal catalyst, then causing the noble metal catalyst poisoning and low
activity [268,269]. Therefore, little work has been done to investigate
sulfides as a promoter although several reports were conducted [200,
270]. For example, PtNiCo/NiCoS nanowires with a metal-metal sulfide
interface can enhance MOR activity and durability [270]. The enhanced
performance can be attributed to the synergistic effect between PtNiCo
and NiCoS, in which the interfaces can effectively remove CO in-
termediates on the Pt surface. Single crystal Ni3S2 nanorods coated with
MoS2 particles grown on nickel foam were used to support low-loading Pt
(0.5 wt %) (Pt/MoS2/Ni3S2-nrs/NF) for MOR [200]. Sufficient Mo–Sx
edge sites facilitated OHads generation from H2O decomposition, which
can react with/eliminate CO-species on MoS2/Ni3S2-nrs attracted from Pt
active sites. As a result, Pt/MoS2/Ni3S2-nrs/NF catalyst exhibited a mass
activity of 805.4 mA mg1 Pt , which was 1.97 times higher than that of
commercial Pt/C (10 wt %) (Fig. 7h). In addition, some nickel com-
pounds (selenides and oxides) supported by noble metal catalysts for
alkaline MOR have been developed [267,271]. For example, cobalt
selenide-coated nickel selenide nanorods grown on nickel foam were
synthesized by a one-pot solvothermal synthesis as a Pt support (Pt/Co-
Se/NiSe-nrs/NFs) [267]. Pt/CoSe/NiSe-nrs/NFs exhibited a much higher
mass activity (1437.1 mA mg1 Pt ) than that of commercial Pt/C (386.2 mA
mg1
Pt ) in alkaline media for MOR, which was ascribed to the effective
OH adsorption on NiOOH/CoOOH to promote the oxidation removal of
poisonous CO.
3.2.4. Noble metal shell and Ni core catalyst
There are many ways to reduce the noble metal loading by adding Ni
without impairing the catalytic ability [272]. One of the effective ap-
proaches is to form core-shell structure by coating the noble metal with
nickel-based materials [273]. This design can not only significantly
decrease the usage of noble metals but also enhance the electrocatalytic
performance by creating the surface strain effect that arises from the
lattice mismatch at the interface between the core and shell by tuning the
shell thickness [274]. Pt and Pd have been widely developed in this way
as excellent active sites for MOR in alkaline media [275,276]. For
example, Ni@Pt (Ni-core, Pt-shell) nanoparticles deposited on the sur-
face of functionalized multi-walled carbon nanotubes (Ni@Pt/MWCNTs)
were prepared by a modified chemical co-reduction protocol for MOR,
which exhibited catalytic activity of a high current density of 271.9 mA
mg1Pt in the alkaline medium [275]. The improved MOR performance
can be interpreted by the bifunctional mechanism for the promoted CO
species oxidation and electronic structure induced by the tensile strain of
the core-shell structure, which modified the adsorption energy of the
intermediates to increase the oxidation ability for poisoning in-
termediates. The Pt-rich shell-coated Ni nanoparticles with the size of
8.9–12.1 nm were synthesized by chemical deposition via successive
reduction of NiCl2 and H2PtCl6, and the higher exposure and utilization
of Pt can be achieved when the thinner Pt shell is deposited on the surface
[276].
In addition to the Pt–Ni core-shell structure, the Pd–Ni core-shell
structure was also intensively studied for alkaline MOR [48,277]. For
example, Ni@Pd core-shell nanoparticles supported over multi-walled
carbon nanotubes (Ni@Pd/MWCNTs) were synthesized using sodium
dodecyl sulfate as structure directing agent a capping material [278]. The
resulting core-shell structure exhibited a diameter in the range of 6–8 nm
with an electrochemical surface area (ECSA) of 176.2 m2 g1. Such high
ECSA enhances the utilization of Pd toward methanol oxidation, and the
peak current density was 770.7 mA mg1, nearly 60% higher than that of
PdNi/Multiwalled carbon nanotube. The bimetallic Au@Ni core-shell
nanoparticles supported on reduced graphene oxide nanocomposites
C. Liu et al.
(Au@Ni-rGO) were also reported for MOR [279]. The formation of
core-shell structure with Au core and Ni shell was displayed by
STEM-HAADF and the EDS-mapping images (Fig. 7i). The Au core acted
as an electron acceptor, which facilitated the electron extraction, and the
electronic changes induced by the Au core and the large specific surface
area helped stabilize Ni at high oxidation levels. A good synergistic effect
exists between Au@Ni core-shell NPs and rGO. Therefore, the catalytic
activity of Ni in Au@Ni-rGO was significantly enhanced with a mass
activity of 1446.7 mA mg1 at ca. 0.7 V vs. Ag/AgCl (Fig. 7j). For the
core-shell structured catalysts, the charge redistribution induced by the
core-shell interaction and the tensile strain modulated the binding
strength of OHads on the surface to remove COads; the core-shell structure
also expand the electrochemical surface area of the catalyst by exposing
more active sites and increasing the noble metal utilization. All these
issues are beneficial to the catalyst performance improvement, and
thereby, constructing a special core-shell structure is improvement to in
the novel catalysis system development.
4. Conclusion and future perspectives
Methanol oxidation as an important reaction for the efficient utili-
zation of methanol has broad application prospects in methanol-
reforming for hydrogen production, direct methanol fuel cells, and the
production of value-added products. Herein, we summarized the
advancement of Ni-based catalysts in methanol oxidation in an alkaline
medium. In specific, the catalytic mechanism of methanol oxidation
catalyzed by catalysts with or without noble metal support in an alkaline
medium was introduced, and attention was given to the catalytic pro-
motion principle and the research progress of nickel-based catalysts for
methanol oxidation in an alkaline medium. For Ni-based catalysts loaded
with precious metals, the active sites are usually precious metals, while
Ni-based catalysts without noble metals require trivalent Ni to participate
in the reaction when catalyzing MOR. Therefore, Ni-based catalysts
without noble metals generally are difficulty providing low over-
potentials to drive fuel cells but they are good at the application of
methanol-assisted water-splitting reactions for hydrogen generation.
Due to the performance limitation of nickel alone, single-metal Ni-
based catalysts have low intrinsic value, poor performance, and weak anti-
poisoning ability. Current attention is focused on hybrid or composite
nickel catalysts with multi-components to expose more catalytically active
sites and to promote mass diffusion utilizing structural modification. Some
approaches have been employed to tune the catalytic activity by facilitating
the reaction between the catalysts and methanol molecules through het-
erostructure construction, electronic structure modulation, defect engi-
neering, and surface functionalization. These methods can enhance the
intrinsic activity of catalysts and achieve multiple orders of magnitude
improvements in catalytic performance. Although conclusions based on
synergistic effects could explain the improved performance of the hybrid
catalyst, the contribution of each component still deserves further explo-
ration which would be instructive to maximize the combination effect.
Therefore, there are still some challenges for Ni-based materials develop-
ment and performance probing.
(1) Catalytic mechanism deciphering for the real catalysts. In a
strongly alkaline medium, the high-valent nickel active centres
can be well regenerated during the catalysis process, while the
study of the catalyst deactivation mechanism and the surface
structure evolution is not enough. Moreover, the surface structure
evolution is closely relevant to the catalyst itself, namely, the
different catalysts would have different active phases or surface
states, thus, more characterization for the catalyst after stability
measurement or the in-situ characterizations to monitor the sur-
face structure evolution are needed to probe micro-surface or local
structure change on the catalyst surface during the reaction.
(2) Methanol-reforming for green hydrogen generation. Currently,
hydrogen production via methanol-reforming technology is a hot
17
Advanced Sensor and Energy Materials 2 (2023) 100055
topic, and this technology can generate clean hydrogen energy
with less energy input. The electrolysis of methanol to produce
value-added products such as format with high selectivity needs to
be further developed. This would be perfectly suited for the Ni-
based catalyst without involving noble metals, which can be
done in the alkaline electrolyte. The combined technique of
hydrogen generation and MOR required highly efficient bi-
functional catalyst, and attention directed to this field might
further inspire novel catalytic system development.
(3) Strategies integration of novel catalysts system. The strategies
such as doping, etching, and surface functionalization have been
used to accelerate the formation of high-valent nickel species, and
the best performance can never be obtained by a single approach.
The combined approaches might compensate for the shortages
and maximize the advantages to further boost the catalytic ability
of Ni species. Moreover, understanding the catalytic mechanisms
from the aspect of single-atom catalysts and developing such a
kind of catalyst might increase the catalytic efficiency, and open
some novel research fields for fundamental research. Combining
multiple discovered methods to develop heterogeneous catalysts
might further promote the active site re-generation during the
catalysis.
(4) In-depth understanding of “synergistic effect”. A synergistic effect
was frequently used to explain the performance improvement for
the hybrid catalyst, while the nature of this effect was still not very
clear, especially for multicomponent catalysts. Exploring the
synergistic effect from a specific bimetallic system to a compli-
cated system, like a ternary, or quaternary system might be
necessary for future study. Methods for visualizing catalytic re-
action routes and catalytic sites while monitoring operational
circumstances (potential, current density, electrolyte, working
electrode, and catalyst loading) could be realized by the current
advanced characterization techniques, like in situ imaging and
spectroscopic characterization. Moreover, understanding the re-
action processes and the activity origin of Ni-based catalysts at the
atomic level, though it is more difficult, might be realized by the
combined spectroscopic measurements and theoretical analysis.
(5) Direct measurements in real devices. Studies on MOR catalysts
lack direct measurements of their practical performance in
methanol-based hydrogen production and fuel cell techniques.
The majority of earlier studies were only carried out in the half-
cell, even though hydrogen production and fuel cells were indi-
cated as the targeted applications in their published works. An
excellent MOR performance does not guarantee equal perfor-
mance in practical applications. The development of uniform and
efficient direct measurement methods might address this issue.
And their application in real devices would be desired to further
probe their promising application property.
(6) Catalyst synthesis in large-scale production. The fabrication
methods of MOR catalysts are limited to lab-scale and limited by
their complex synthetic processes and fabrication methods for the
above-referenced MOR catalysts were not suitable for future mass
production. It may result in a quality drop and performance loss if
the simple expansion of the production scale was only based on
the current lab-scale synthesis methods. Appropriate supports
help disperse and stabilize active sites through metal (oxide)-
support interactions. However, the currently used supports
generally have some problems such as poor conductivity, poor
compatibility, and bad stability during the measurements.
Therefore, Ni-based catalysts with highly conductive supports can
be designed to balance the activity and stability, and further
improve the usability of the catalyst.
In addition, there is still a lack of uniform measurement standards and
procedures for the catalyst, which might be noticed by the community.
There are quite a lot of reports, but they cannot be fairly compared due to
C. Liu et al.
the different measurement conditions, such as the varied catalyst
loading, electrode types, electrolyte environment, and electrode fabri-
cation procedure. Therefore, there is an urgent need to establish widely
accepted criteria for evaluating and comparing the performance of
different MOR catalysts. We hope this review will be helpful for the
general readers to understand the basic knowledge of Ni-based catalysts
for MOR in an alkaline medium.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
L Feng appreciated support from the National Natural Science
Foundation of China (21972124 and 22272148), a project funded by the
Priority Academic Program Development of Jiangsu Higher Education
Institution was also appreciated by the authors.
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