i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Available online at www.sciencedirect.com

ScienceDirect

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

Review Article

Research progress and applications of nickel-based

catalysts for electrooxidation of urea

Jinqi Li a, Jie Zhang b,**, Jing-He Yang a,*

a
School of Chemistry Engineering, Zhengzhou University, Zhengzhou 450001, China
b
School of Ecology and Environment, Zhengzhou University, Zhengzhou 450001, China

highlights graphical abstract

Nickel is confirmed as an effective

catalytic component for urea
oxidation.

Various typical nickel-based cata-
lysts in alkaline media are
summarized.

The applications of nickel-based
catalysts in urea oxidation are
introduced.

article info abstract

Article history: The combination of wastewater treatment and energy production is a hot issue that meets
Received 19 October 2021 the current requirements of sustainable development. The direct discharge of large
Received in revised form amounts of urea-rich wastewater without treatment will pose a serious threat to the
6 December 2021 environment and human health. Urea electrooxidation can realize wastewater restoration
Accepted 9 December 2021 and transform energy at the same time. However, due to the 6e transfer process of the
Available online 31 December 2021 urea oxidation reaction, the kinetics is sluggish, and exploring efficient catalysts for urea
electrooxidation brooks no delay to improve. Nickel is considered to be an effective cata-
Keywords: lytic component of urea oxidation reaction, with low cost and good catalytic activity. This
Urea electrooxidation article reviews the recent research progress of nickel-based urea electrooxidation catalysts
Nickel and makes a detailed comment on the four applications of wastewater remediation,
Electrocatalyst hydrogen production, fuel cells, and urea sensors. Moreover, the development prospects
Wastewater remediation and challenges faced by nickel-based catalysts and their practical applications are
Hydrogen production discussed.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author.
E-mail addresses: zhangjie630@zzu.edu.cn (J. Zhang), jhyang@zzu.edu.cn (J.-H. Yang).
https://doi.org/10.1016/j.ijhydene.2021.12.099
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
7694 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7694
Mechanism of nickel-based catalysts for urea electrolysis under alkaline conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7695
The nickel-based catalyst for electrooxidation of urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7697
Mono-metallic Ni and its alloy catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7697
Nickel-based hydroxides and oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7697
Ni(OH)2-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7697
NiO-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7698
Novel nickel-based catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7700
Application of nickel-based catalysts for urea electrooxidation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7702
Wastewater remediation and energy conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7702
Wastewater remediation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7702
Hydrogen production by electrolysis of urea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7702
Direct urea fuel cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7703
Urea electrochemical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7704
Conclusion and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7708
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7709
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7709
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7709

electrolytic urea under standard conditions requires only

Introduction
Urea is one of the main products of protein metabolism in
mammals. It can be used as a neutral and quick-acting fer-
tilizer, which is easy to store and easy to use. Its derivatives
are widely used in medicine, textiles, cosmetics, and other
fields [1]. If the resulting large amount of urea-rich wastewater
flows directly into the environment, it will further decompose
and lead to the release of toxic ammonia, which will cause
serious pollution to groundwater and air, and even endanger
human health [2,3]. As an effective method to decompose
urea, electrooxidation of urea has received more and more
attention. The electrochemical process purifies the waste-
water and produces nitrogen, carbon dioxide, and hydrogen
[4]. The overall reaction is given by
CO(NH2)2 (aq) þ H2O (l) / N2 (g) þ 3H2 (g) þ CO2 (g)
As environmentally friendly and clean energy, hydrogen is
considered to be the most potential energy carrier in the 21st
century (33.6KWH Kg1) [5,6]. Hydrogen production by elec-
trolysis of water has the advantages of simple operation,
strong controllability, no pollution, and high purity of
hydrogen production, but it is limited by high energy con-
sumption and low efficiency [7]. Some hydrogen carriers can
be used instead of electrolyzing water to produce hydrogen,
including methanol [8,9], ethanol [10,11], ammonia [12,13],
and urea, etc. Among them, Urea has obvious advantages
because of its abundant source and low cost.
Urea is rich in hydrogen (6.7 wt%) and has a high energy
density (16.9 MJ L1). Urea is very stable under environmental
conditions and is neither toxic nor flammable, making it
easy to store and transport [14]. The thermodynamics of
0.37 V electrolytic cell potential, which is far lower than the
1.23 V battery voltage required for water electrolysis under
standard conditions. More importantly, urea has low energy
costs, which is more conducive to large-scale applications
[15,16]. Besides, urea can be used as a solid fuel for direct urea
fuel cells (DUFCs), and it can also be used to prepare enzyme-
free urea sensors (Scheme 1). The DUFC system produces ni-
trogen and carbonate after electrooxidation. It is inexpensive,
non-toxic, and is a promising clean energy device [17]. The
non-enzymatic urea electrochemical sensor is based on non-
biological substances, which can effectively avoid the influ-
ence of environmental factors such as temperature, air, acid,
and alkali, and help improve the activity, stability, and
orientation selectivity of the sensor [18].
However, urea electrolysis involves six electron transfer
processes, and the kinetics of the anode reaction is very
(1) sluggish. The electrochemical performance of the catalyst
directly affects the efficiency of urea electrolysis. How to
improve the kinetics of urea electrooxidation to promote urea
electrolysis is the key to solving the problem [19]. Most
precious metals and their oxides have high conductivity and
excellent electrocatalytic activity (such as platinum [20,21],
rhodium [22,23], and iridium dioxide [24]), but they are difficult
to be applied in practice due to their scarcity, high price, and
low mechanical strength [25]. Therefore, looking for non-
precious metal catalysts with low prices and high electro-
catalytic activity has become the focus of research.
As a non-precious metal, nickel has low cost and corrosion
resistance, and research has found that nickel catalysts
exhibit higher electrocatalytic activity in alkaline media than
precious metals such as Pt, Ir, Rh, etc [4]. The catalysis of
urease can explain this characteristic of the nickel-based
catalyst [27]. Musculus obtained the first urease from
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
decaying urine in 1874, and it was proposed by Miquel and
named urease in 1890 [28]. As shown in Fig. 1, Urease, con-
sisting of two Ni(II) and bridging hydroxides attached to two
water molecules, can be used in either free or stationary form
to catalyze urea hydrolysis [26]. Sua
rez et al. [29] analyzed the
catalysis of urease on urea by quantum chemical calculation,
and found that nickel and hydroxyl were the active sites
for the dissociation of urea molecules. The activity of the
enzyme depends on the structure of the binuclear nickel
active center [26,28].
Based on this, in recent years, metal nickel and its alloys,
oxides, hydroxides, and related composite material catalysts
have been widely used in urea electrooxidation. Improving the
activity and service life of catalysts based on reducing costs
has become a research hotspot in this field [9,30]. Further-
more, it is worth mentioning that the improvement of urea
electrooxidation kinetics is also of great significance to urea
electrochemical sensors and fuel cells. The enhanced dy-
namics can make the urea sensors more selective and sensi-
tive so that the urea sensors work more efficiently and
accurately, and it can also make the fuel cells operate at a
lower cost due to cheaper hydrogen supply [16].
Within this context, this article focuses on the nickel-based
catalyst used for the urea oxidation reaction (UOR), and to
explore the reaction process in-depth, the catalytic mecha-
nism of the nickel-based catalyst is briefly introduced. In
addition, based on the detailed research progress of various
nickel-based catalysts, the applications in wastewater treat-
ment, hydrogen production, fuel cells, and urea sensors are
reviewed.
Mechanism of nickel-based catalysts for urea
electrolysis under alkaline conditions
Urea electrolysis is an effective technology that directly con-
verts urea into hydrogen and benign nitrogen. Studying and
understanding its reaction mechanism is very important for
the development of technology. Wright et al. [31] studied the
electrolysis mechanism of urea for the first time, determined
that N2, O2, CO2, and H2 were the main electrolysis products.
Urea can be electrochemically oxidized in supporting elec-
trolytes with different pH values, and its adsorbents and re-
action products have a strong dependence on pH [32].
However, nickel-based catalysts are vulnerable to acid
corrosion and unstable, so they are not suitable for use in
acidic media. In the neutral electrolyte, the catalysts are less
corroded, which is expected to increase its service life, but
they will produce corrosive ion Hþ, precious metals are
generally used. In addition, Cl2 and active chlorine produced
during the reaction are toxic, and the standard electrode po-
tential of Cl2 evolution is 1.36 V, which is higher than 1.23 V of
water electrolysis [27]. In comparison, there are more studies
on the electrolysis of urea in alkaline electrolytes. And elec-
trooxidation of urea under alkaline conditions is usually
catalyzed in nickel-based systems largely because of the sta-
bility of Ni at high pH values and high ionic conductivity.
Importantly, non-toxic gases are produced in the reactions,
which effectively addresses the shortcomings of acidic and
neutral media.
7695
In alkaline media, urea electrooxidation has two oxidation
paths, including (I) direct oxidation; (II) indirect oxidation/
catalyst regeneration. Boggs et al. [4] studied the experimental
process of directly converting urine and urea into pure
hydrogen under the action of a cheap nickel catalyst, and
proposed a direct oxidation method of UOR in an alkaline
medium, that is, Ni(OH)2 becomes NiOOH through one step of
electrochemical oxidation. Then NiOOH catalyzes the oxida-
tion of urea into nitrogen, carbon dioxide, and water mole-
cules. The anode reaction mechanism of this method is as
follows:
6Ni(OH)2 (s) þ 6OH (l) 4 6NiOOH (s) þ 6H2O (l) þ 6e (2a)
CO(NH2)2 (aq) þ6OH (l) / N2 (g) þ CO2 (g) þ 5H2O (l) þ 6e(2b)
Subsequently, to better understand the electrochemical
oxidation process of urea on nickel in alkaline medium, the
electrocatalytic behavior of urea oxidation on nickel electrode
in alkaline medium was investigated by cyclic voltammetry
(CV), linear sweep voltammetry (LSV), and rotating disc elec-
trode (RDE) voltammetry [33] (Fig. 2a and b). Based on the CV
data, a possible alternative oxidation process, known as the
indirect oxidation mechanism or catalyst regeneration
mechanism, has been proposed [33]. The anode reactions of
this method are as follows:
6Ni(OH)2 (s) þ 6OH (l) 4 6NiOOH (s) þ 6H2O (l) þ 6e (3a)
CO(NH2)2 (aq) þ 6NiOOH (s) / N2 (g) þ CO2 (g) þ 6Ni(OH)2 (s)(3b)
Different from direct oxidation, in the indirect oxidation
process, Ni(OH)2 is oxidized to NiOOH in one step and then
NiOOH is reduced to Ni(OH)2 by urea, while the urea itself is
oxidized to CO2 and N2 [33]. It was found that the electro-
catalytic oxidation of urea occurred after the formation of a
certain amount of Ni(III) on the electrode surface. The oxida-
tion reaction of low concentration urea was mainly controlled
by diffusion, while the oxidation reaction of high concentra-
tion urea was mainly controlled by kinetics.
The mechanisms proposed above are based on data ob-
tained from electrochemical measurements. However, due to
the lack of identification of the species involved in the
response, it is not possible to conclude the mechanism, and
further analysis by techniques such as in situ surface char-
acterization is needed to distinguish between the two
different hypothesized mechanisms [34]. Lots of methods
have been employed to study the reaction mechanism such as
density functional theory (DFT) calculations [35,36], in-situ X-
ray diffraction (XRD) measurements [14], and in-situ surface-
enhanced Raman (SER) spectroscopy [34].
Firstly, Daramola et al. [35] used DFT to study the adsorp-
tion competition between hydroxide ions and urea molecules
on the NiOOH catalyst surface. In the dissociation of urea, the
desorption of carbon dioxide is the rate-limiting step, which is
thought to be the reason for the experimentally observed
decrease in reaction rates with time. In addition, the surface
charge state caused by the specific structure of the catalyst
also affects the decomposition of urea [36]. Wang et al. [14]
combined in situ XRD measurement and electrochemical
7696 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Scheme 1 e Introduction and applications of electrooxidation of urea. The influx of urea-containing wastewater into the
environment mainly comes from industrial production, mammalian protein metabolites, and field fertilizers.

analysis to identify the structural changes of the nickel cata-
lyst. Ni(OH)2 was electrochemically oxidized to NiOOH at cell
voltages from 1.2 to 1.6 V. When urea was present in an
alkaline solution, the electrochemically generated NiOOH
reacted with the urea molecule and was reduced to Ni(OH)2,
while the urea was oxidized and converted into nitrogen and
hydrogen. Vedharathinam et al. [34] proposed for the first time
that the electrooxidation of urea on the surface of NiOOH
catalyst in an alkaline medium is an indirect or catalyst
regeneration mechanism by in situ SER spectroscopy. In the
presence of urea, the time-resolved Raman spectra of the
NiOOH catalyst surface showed the disappearance of the
NiOOH double peak, confirming the chemical reduction of the
active NiOOH by urea to the inactive Ni(OH)2.
Subsequently, in another work by Vedharathinam and
Botte [37], for the first time, they observed the potential
oscillation during the electrochemical oxidation of urea on a
nickel catalyst. The variation in NiOOH bimodal intensity
obtained from the in-situ time-resolved SER spectrum sug-
gests that the periodic formation and consumption of the
active catalyst NiOOH may be responsible for the oscillation
mechanism (Fig. 2c). In the oscillation mechanism, even after
the electrode rotates at a speed of 2000 rpm, the potential
oscillation continues, which shows that the oscillation is not
caused by mass transfer, that is, the mass transfer may not be
the main effect.
With b-Ni(OH)2 as the model catalyst, the complex pro-
cess of UOR can be analyzed more directly. Recently, Wang
and his team [38] used b-Ni(OH)2 to reveal the mechanisms of
electrocatalytic action and urea molecular transformation
during the electrochemical oxidation of urea. They proposed
a possible UOR mechanism, that is, the spontaneous proton-
coupled electron transfer (PCET) process was driven by
electrogenic hydrogen defects generated by b-Ni(OH)2 at
oxidized potential, forming a dynamic cycle of hydrogen
defects. In the PCET process, two amino groups in a urea
molecule lose four protons and electrons in turn, and the
rapid rearrangement reaction leads to the spontaneous for-
mation of NeN bonds in the intermediate of urea dehydro-
genation. This intermediate will spontaneously and rapidly
generate water and form water and intermediate. Water and
intermediates undergo two more PCET processes and rear-
rangement reactions and eventually degrade to nitrogen and
carbon dioxide (Fig. 2d).

Fig. 1 e Crystal structure of K. aerogenes urease [26]. Copyright (2019), MDPI.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
The nickel-based catalyst for electrooxidation of
urea
With simple operation and large processing capacity, urea
electrooxidation shows the dual advantages of energy saving
and environmental protection. The study of catalysts is a key
link in determining the efficiency of urea oxidation and its
application prospects. Non-precious metal nickel has high
electrochemical activity and low price, which shows excellent
competitiveness. A series of different types of nickel-based
catalysts will be reviewed below, which are summarized in
Table 1.
Mono-metallic Ni and its alloy catalysts
Nickel is a transition metal with good plasticity and corrosion
resistance, and its structure and morphology are crucial to the
catalytic performance of the material. Low-dimensional
nanostructures are formed by a small number of atoms or
molecules, whose integration of small size effect and surface
effect can effectively increase the specific surface area of the
catalyst and provide more reactive sites.
Lan et al. [58] found that nano-nickel is a key material to
improve the performance of urea and urine fuel cells. Using
KBH4, they successfully synthesized hexagonal nanocrystal-
line nickel with a primary particle size of 2 ~ 3 nm by reduc-
tion, which greatly increased the active surface area. Yan et al.
[39] developed a one-dimensional nickel nanowire electro-
catalyst (NNE) using AAO template-assisted electrodeposition
method to enhance the electrocatalytic oxidation of urea.
Through calculation, the electroactive surface area of the
nickel nanowire catalyst was 79.1 cm2 mg1, which was
greatly improved compared with the massive nickel film cat-
alyst's 18.6 cm2 mg1. Moreover, some materials with high
specific surface area and excellent electrical conductivity are
often introduced to solve the problem of high oxidation
overpotential of single metal nickel and unstable oxidation
current caused by rapid degradation of the catalyst. Bian et al.
[40] synthesized monodisperse Ni nanoparticles using OAm as
a reducing agent, and uniformly dispersed Ni nanoparticles on
MWCNTs by ultrasound. The electrooxidation activity and
stability of the catalyst were investigated by CV and chro-
noamperometry respectively. The results showed that the
80% Ni/MWCNT catalyst has higher catalytic activity
(1866 mA cm2 mg1), which is better than most nickel-based
catalysts.
Polymetallic catalysts tend to be more active than mono-
metallic catalysts, which can be explained by metallic syn-
ergies that promote the kinetics or thermodynamics of elec-
trochemical reactions in the form of increased activity,
stability, or toxicity resistance [15,59]. Co, Mo, Mn, Fe, Se, and
other metals can be blended with Ni to form alloys, which can
effectively catalyze the oxidation activity of urea [60,61].
Botte's research group tried to dope precious metals and pre-
pared Rh/Ni electrodes by electroplating on a nickel foil sub-
strate by potentiostatic method [23]. The synergistic effect of
rhodium and nickel can reduce the surface clogging, reduce
the electrooxidation overpotential of urea, and improve the
stability of the catalyst [62]. Ni-co bimetallic catalyst has low
7697
cost and high current density in electrooxidation of urea
[41,63,64]. However, the current density of the reaction may
decrease to a large extent due to the introduction of inactive
factors in NieCo alloying [42]. Feng's research group proved
that nickel-molybdenum oxide was an effective catalyst for
the electrooxidation of urea [65]. The Ni/Mo oxides synthe-
sized by them have fast kinetics, low charge transfer resis-
tance, and low Tafel slope. In addition, Mn, Fe, Se generally
can enhance the oxidation activity of Ni and facilitate the
removal of toxic intermediates from the catalyst surface
[61,66e68]. Among these, Mn has a significant effect. The
nanofibers prepared by Alajami et al. in electrospinning so-
lution containing 10% manganese acetate showed the best
performance in terms of initial potential and current density,
which were 430 mV and 79 mA cm2, respectively [69].
Nickel-based hydroxides and oxides
Ni(OH)2-based catalysts
Nickel hydroxide has a special layered structure, its structure
and chemical composition are easy to be adjusted. The elec-
trochemical properties of nickel hydroxide can be optimized
employing surface modification and self-assembly. Nickel
hydroxide mainly has two polycrystalline forms: a and b [70].
Previous studies have shown that many a-rich and porous
nanostructured hydroxides are more effective for UOR than b-
Ni(OH)2, which may be due to the disordered a-Ni(OH)2 having
better conductivity and Mass transfer capacity.
Ji et al. [44] reported the preparation of open-ended a-
Ni(OH)2 nanotubes grown on a three-dimensional nickel
skeleton by electrochemical deposition using hexagonal zinc
oxide as a template. The open-ended nanotubes increase the
effective surface area of the urea electrolyte, allowing more
active sites to be exposed to the electrolyte. When the
applied potential was greater than 0.64 V, the current density
of the three-dimensional Ni skeleton attached to the Ni(OH)2
nanotube array reached 215 mA cm2, which was much
higher than that of the attached Ni(OH)2 thin film. A Ni(OH)2/
CNT/CF composite electrode was developed by Liu et al. [45],
and the kinetics of the electrode was studied to improve the
performance of its UOR. The composite electrode combines
the advantages of a-Ni(OH)2 catalyst, CNT conductive
network, and CF collector. Compared with a-Ni(OH)2/CF or CF
electrodes, a-Ni(OH)2/CNT/CF electrode has lower charge
transfer resistance, which improves the performance of
UOR, and is beneficial to alleviate urea contamination and
produce hydrogen.
For layered materials, doping is another important
modification method [71e73]. Using the hydrothermal one-
step method to directly grow Ni-M double hydroxide
(M ¼ Cr, Mn, Fe, Co, Cu, Zn) on carbon fiber cloth and
foamed nickel electrodes, Xu et al. [46] investigated several
catalysts for electrooxidation of urea. The NiFe double hy-
droxide (DH) exhibited the highest activity, with a specific
current density of ~95 mA cm2 mg1, which was about 10
times larger than that of Ni(OH)2. Similarly, Xie et al. [74]
investigated the use of iron-incorporated a-Ni(OH)2 frac-
tional nanosheet arrays. The unique single-crystalline belt-
on-sheet hierarchical nanostructure of the catalyst gener-
ates more active sites for UOR. Due to the synergistic merits
7698 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Fig. 2 e (a) Cyclic voltammogram of nickel electrode in 5 M KOH solution containing 0.33 M urea; (b)Voltammograms of
nickel electrode using a rotating disk electrode [33]. Copyright (2012) Elsevier Ltd. (c) Potential oscillations observed for the
UOR on NiOOH in 5 M KOH and 0.33 M urea [37]. Copyright (2014), American Chemical Society. (d) The UOR mechanism on
the b-Ni(OH)2 electrode [38]. Copyright (2020), Wiley-VCH GmbH.

of the increased surface areas, improved charge transfer NiO-based catalysts

behavior, favorable reaction kinetics as well as excellent
structural stability, the a-Ni(OH)2/NF self-supported catalyst
incorporated with 1% Fe displays significantly improved
UOR performance.
Recently, our group reported a controlled synthesis strat-
egy for preparing CuOeNi(OH)2-d nanosheets using selective
S2O2
3 as the coordinating etchant [75]. The CuOeNi(OH)2-
d nanosheets exhibited high UOR activities at 1.41 V vs. RHE to
achieve the current density of 10 mA cm2. In addition, the
current density of CuOeNi(OH)2-d nanosheets was
21.5 mA cm2 at 1.52 V, which was much higher than that of
commercial Ni(OH)2 and CuOeNi(OH)2. And it still shows good
stability after the 36 h I-T test, the current density does not
decrease significantly compared with the initial current den-
sity (Fig. 3). This study provides a new strategy for the design
of advanced electrode materials and provides promising ap-
plications in urea-rich wastewater treatment, hydrogen pro-
duction, and fuel cells.
Among the nickel-based oxides, NiO is a classic catalyst ma-
terial with a simple structure, which can be modified by a
variety of means [76,77]. Wu et al. [47] grew vertically arranged
ordered mesoporous NiO (OM-NiO) nanosheets on three-
dimensional nickel foam by simple hydrothermal synthesis
and heat treatment. The oxidation current density of the OM-
NiO nanosheet electrode at 0.52 V was as high as
330 mA cm2 mg1, which was mainly due to its vertically
aligned structure, three-dimensional macroporous frame-
work, and the large open space between the nanosheet and
macropores.
However, pure nickel oxide is easily deactivated under
strong catalytic conditions, which leads to its limited appli-
cation range. Doping metal to change its structure is a choice
to optimize its performance. The Schottky catalyst formed by
the contact between metal and semiconductor is a new type of
electrocatalyst. The existence of its unique heterogeneous
interface can effectively regulate the electronic structure of
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2 7699

Table 1 e Performance parameters for UOR based on various catalysts.

Materials Method Solution Peak current Eonset/Reference Ref.
density (mA cm2) electrode (V)
KOH (M) Urea (M)
Ni nanowires AAO templates 1 0.33 ~7 0.46/(Hg/HgO) [39]
80 wt% Ni/MWCNT OAm reduction 1 0.33 1866 mA cm2 mg1 e [40]
NieCo nanowires AAO templates 1 0.33 ~6 0.39/(Hg/HgO) [41]
Ni electro-deposition and alkaline 5 0.33 22 0.43/(Hg/HgO) [42]
NieZn leaching 67 0.39/(Hg/HgO)
NieZneCo 24 0.35/(Hg/HgO)
NiCoMo 811 one-pot co-precipitation method 1 0.33 69.8 0.30/(Ag/AgCl) [43]
NiCoMo 90,505 48.3 0.33/(Ag/AgCl)
NiCoMo 71,515 39.6 0.28/(Ag/AgCl)
Ni(OH)2 nanotubes electro-deposition and alkaline 1 0.33 215 0.300/(SCE) [44]
leaching
a-Ni(OH)2/CNT/CF electrophoretic co-deposition and 1 0.33 407 e [45]
hydrothermal
Ni(OH)2/CFC one-step hydrothermal 1 0.33 ~8 mA cm2 mg1 0.42/(Ag/AgCl) [46]
NiFe DH/CFC ~95 mA cm2 mg1 ~0.35/(Ag/AgCl)
SS/OM-NiO Hydrothermal 1 0.33 103 mA cm2 mg1 0.28/(Hg/HgO) [47]
nanosheets
NF/OM-NiO 330 mA cm2 mg1 0.25/(Hg/HgO)
nanosheets
NiCO2O4 Chemical deposition and post- 1 0.33 136 0.46/(Hg/HgO) [48]
annealing
Ni1.5Mn1.5O4 template-free hydrothermal 1 0.33 6.9 0.29/(Ag/AgCl) [49]
r-NiMoO4/NF defect engineering 1 0.33 249.5 0.6/(Ag/AgCl) [50]
Ni2P nanoflower@ Ni Hydrothermal and phosphating 5 0.6 750 0.24/(Ag/AgCl) [51]
foam
Ni(OH)2 @ Ni foam Hydrothermal 450 0.27/(Ag/AgCl)
C@Ni2P NRs-peapod Hydrothermal and surface 1 0.33 e 0.25/(Hg/HgO) [52]
engineering
Ni2PeC Hydrothermal 1 0.33 70.4 e [53]
Ni2P/C-Yolk shell Hydrothermal and phosphating 1 0.33 252.5 1.35/(RHE) [54]
NiCoP nanosheets/ Hydrothermal and phosphating 1 0.33 112 0.3 (vs.Hg/HgO) [55]
carbon cloth
NiF2/Ni2P Hydrothermal, fluoride and 1 0.33 157.35 1.31/(RHE) [56]
phosphating
Ni2P/Ni Phosphating 1 0.33 103.6 1.223/(RHE) [57]

*AAO ¼ anodic aluminum oxide; Eonset ¼ onset oxidation potential; MWCNT ¼ multi-walled carbon nanotube; CF ¼ carbon fiber; SS ¼ stainless
steel; GC/PANI/LNO-GO ¼ graphene oxide/poly/lanthanum nickel oxide-graphene oxide.

the material, which is beneficial to the UOR process [78]. Ji
et al. designed and prepared two-dimensional Ni/NiO nano-
sheets coated with N-doped carbon layers, and established a
Schottky heterogeneous interface on them (Fig. 4a and b) [79].
As shown in Fig. 4b, Ni/NiO@NC400 only needs a 1.40 V over-
potential to reach the current density of 50 mA cm2. On the
one hand, the self-driven charge redistribution at the het-
erogeneous interface promotes the decomposition of urea, on
the other hand, the 2-D Ni/NiO coupling effect of the N-doped
carbon layer inhibits the inactivation of the active sites in the
alkaline solution. Combined with these two advantages, the
catalyst can improve the efficiency of urea oxidation while
maintaining long-term stability.
Polymetallic oxides with many geometric sites (such as
Spinel or Perovskite catalyst) are also an area of research
[60,80,81]. Adopting a simple chemical deposition method and
post-annealing process, Ding et al. synthesized Mesoporous
spinel nickel cobaltite (NiCo2O4) nanostructures and carried
out a detailed examination of its physical and chemical
properties and electrocatalytic activity [48]. The material had a
high specific surface area (190.1 m2 g1) and a high mesopore
volume (0.943 cm3 g1). In 1 M KOH and 0.33 M urea electrolyte,
the current density of the electrode at 0.7 V (vs. Hg/HgO) was
136 mA cm2 mg1. Spinel nickel-manganese oxides are also
used in urea electrooxidation. NieMn oxide-based catalysts
with different Ni: Mn atomic ratios were prepared by Peri-
yasamy et al. [49]. The study found that the differences in
redox behavior and catalytic activity of the studied nickel
manganese oxide were mainly attributed to the different
phases in the samples. Ni1.5Mn1.5O4 has a good stability of
electrocatalytic activity and resistance to the electrooxidation
of urea. The current density was 6.9 mA cm2 when the urea
was oxidized at 0.29 V vs Ag/AgCl.
In addition, defect engineering, especially the oxygen va-
cancy of 2-D transition metal oxide (TMO) materials, is
considered to be an effective strategy to regulate the catalytic
active sites and adsorption energy of active components of
their electronic structures [82]. Tong et al. designed NiMoO4
nanosheets with oxygen-rich vacancies using defect engi-
neering strategies and studied the relationship between O
7700 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
vacancies and UOR activity [50]. At 0.6 V, oxygen-enriched
NiMoO4 could achieve a very high current density of
249.5 mA cm2, which was 1.9 times that of ordinary NiMoO4
material (Fig. 4c and d). Thanks to abundant O vacancies,
higher exposed active sites, faster electron transfer, and lower
adsorption energy of urea molecules are successfully brought.
Novel nickel-based catalyst
The efficiency of urea electrolysis mainly depends on the
mass transfer capacity and the number of active sites of cat-
alysts. Recently, novel nickel-based materials containing
heteroatom (N, P, S) have attracted the attention of re-
searchers because of their unique molecular structure, rich
active sites, high stability, and excellent electrochemical ac-
tivity [30,83,84].
Nickel sulfide has abundant and active NieS and NieNi
bonds, which not only facilitate the formation of UOR in-
termediates (OOH*), but also promote the recombination of
adsorbed hydrogen radicals (H*) into H2 [36]. Yousef's group
prepared a sol-gel solution containing nickel acetate tetrahy-
drate and ammonium sulfide by electrostatic spinning [85]. A
superior urea electro-oxidation current density and favored
stability were attained. Feng et al. vulcanized NiMoO4 nano-
rods to obtain NiS2eMoS2 and realized the mixing of single
metal sulfide at the nanometer scale with sufficient nano-
interface. The current density of the catalyst is
103.41 mA cm2 at 1.54 V, 10 and 78 times higher than pure
NiS2 and MoS2 electrodes, respectively [86]. Barakat et al.
found that nitride nickel could favor the NiOOH formation on
the surface of nickel particles and then exhibit good UOR
electrooxidation activity [87]. Hu et al. successfully synthe-
sized a new MOF-derived nickel nitride over a nickel foam
catalyst at different temperatures. And its current density can
be maintained for at least 24 h, showing its potential for
practical applications [88].
In addition, Nickel phosphide-based catalysts have excellent
electrocatalytic ability and high resistance to poisoning. There
are two main reasons for this. Firstly, the non-metallic P doping
into the metal lattice effectively regulates the nickel electronic
structure, followed by the change in d electron density caused
by the polymerization effect produced by the combination of P
and Ni, resulting in more reactive sites [3,89]. Therefore, nickel
phosphide shows similar properties to precious metals in some
aspects and has excellent electrocatalytic performance [90,91].
As the most active mono-metal phosphide, nickel phosphide
exists in a series of different phases, such as Ni3P, Ni12P5, Ni2P,
Ni5P4, NiP2, etc [92]. And nickel-rich phosphates are good con-
ductors of electricity and heat, with high hardness, strength,
thermal stability, and chemical stability, among which Ni2P is
the model [93]. By combining DFT calculations with experi-
ments, Hansen et al. studied the (10 1ð一Þ 0), (1ð一Þ1ð一Þ 20), (11
2ð一Þ 0), (11 2ð一Þ 1), and (0001) facets of hexagonal Ni2P (Fig. 5d)
[94]. They found that the superior activity of Ni2P depends on its
abundant and active sites.
One of the most effective ways to improve the conductivity
of electrode materials is to control the nanostructure through
carbon coating. To increase the active surface area of the
catalyst, Yang et al. prepared the Ni2PeC catalyst by a facile
hydrothermal method and characterized its morphology to
verify the structure of the hexagonal Ni2P crystal [53]. The
corresponding electrochemical test results showed that the
current density at 0.5 V was about 70.4 mA cm2, which was
2.7 times that of the reference commercial nickel oxide cata-
lyst. Zhang et al. obtained Ni2P nanocrystals by in-situ growth
on a plain carbon fiber cloth (Ni2P/CFC) using a simple vapor
phase hydrothermal (VPH) method [95]. The current density of
10 mA cm2 could reach 0.09 V and 1.42 V as UOR and
hydrogen evolution reaction (HER) electrodes, respectively.
Fig. 5aec shows the electrochemical hydrogen production
process of Ni2P/CFC as a bifunctional catalyst in the overall
water decomposition system and its excellent performance.
Further considering the influence of structure on catalyst
efficiency, Khalafallah et al. prepared carbon-doped hetero-
structure Ni2P (C@Ni2P) nanocomposites by one-step hydro-
thermal method using peapod-assisted surface engineering of
nanorods (NRS-Peapod) [52]. In terms of specific surface area
and Tafel slope, the NRS-Peapod (266.15 m2 g1,74.28 mV
dec1) had a complete advantage over nanoparticles NPs
(180.40 m2 g1,128.90 mV dec1). In another work, Zhang et al.
[54] synthesized a novel yolk-shell nanostructured Ni2P/C
composite material (Ni2P/C-YS) (Fig. 6aed). The doped carbon
nanoparticles make it possible to achieve rapid electron
transfer and thus have high conductivity, and the optimized
crystallinity and in-situ constructed hollow yolk-shell struc-
ture provide more active sites for the catalytic process. In the
alkaline electrolyte, when the current density was
50 mA cm2, its electric potential was only 1.366 V, and it
showed good durability after 23 h. In addition, this study
provided a profound perspective for the rational design and
preparation of non-noble metal/carbon hybrid materials in
the form of hollow yolk and shell.
As above, it is clear that bimetallic catalysts generally have
better catalytic activity than mono-metallic catalysts [64].
Based on this, Xie et al. prepared bimetallic NiCoP nanosheet
arrays on carbon cloth (NiCoP NS/CC) for high-performance
urea electrooxidation [55]. In 1.0 M KOH and 0.33 M urea so-
lution, a current density of 50 mA cm2 required a potential of
0.455 V (vs. Hg/HgO). Using hydrothermal, fluorination, and
phosphating processes, Liu et al. synthesized the NiF2/Ni2P
hybrid catalyst with covalent bonds and ionic bonds for the
first time [56]. At 1.53 V, the maximum current density of urea
electrooxidation could reach 157.35 mA cm2, which was
much higher than NiF2 (23.55 mA cm2) and Ni2P
(102.72 mA cm2). The author believes that the excellent
performance of the catalyst is mainly due to the synergistic
effect of covalent bonds and ionic bonds in the catalyst system
and the unique flower-like skeleton which exposed more
active sites, increasing the transport and diffusion of ions in
the electrolyte. More recently, Li et al. synthesized porous rod-
shaped Ni2P/Ni composites through precise control of phos-
phating time and temperature [57], and 330  C, phosphating
for 1 h were important conditions for the reaction. Based on
morphology analysis and DFT calculations, it was found that
compared with NiO/Ni, Ni2P/Ni fully embodied the small size
effect of nanomaterials. While the material exhibited high
stability, it also promoted the full contact of the alkaline sys-
tem reaction medium, making the surface easier to be acti-
vated, and greatly improving its electrical conductivity and
electrocatalytic performance (Fig. 6e).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2 7701

Fig. 3 e (a) A schematic diagram of the preparation of CuOeNi(OH)2-d nanosheets; (b) CVs of electrocatalytic oxidation by
different materials in 0.33 M Urea þ1 M KOH electrolyte solution; (c) Amperometric i-t curve of the CuOeNi(OH)2-d supported
on FTO at 0.6 V in 1 M KOH and 0.33 M urea [75]. Copyright (2021), Elsevier B.V.

Fig. 4 e (a) LSV curves of Ni/NiO@NC400 and reference samples in 1.0 M KOH solution containing 0.33 M urea; (b) The
schematic UOR catalytic mechanism based on Ni/NiO Schottky synergistic effects [79]. Copyright (2020), Wiley-VCH. (c) Cdl
linear fitting and calculation of different materials; (d) Histogram of the current density of different materials [50]. Copyright
(2018), American Chemical Society.
7702 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
Application of nickel-based catalysts for urea
electrooxidation
Timely and scientific management of urea is very important
and urea electrolysis is simple and efficient, which has grad-
ually become the most attractive management method.
Nickel is considered to be an effective catalytic component for
urea electrooxidation. In addition, urea electrooxidation has
shown great application prospects, including the remediation
of urea-rich wastewater, hydrogen production, fuel cells, and
sensors. While avoiding the hazards caused by the natural
decomposition of urea, the use-value of “turning waste
into treasure” is also deeply explored, which has the dual
significance of protecting the environment and saving
energy [16,30].
Wastewater remediation and energy conversion
Wastewater remediation
The influx of urea-containing wastewater into the environ-
ment mainly comes from industrial production, field fertil-
izers, and mammalian protein metabolites. Untreated urea
will naturally decompose into ammonia and other derived
nitrogen pollutants [1]. There are many treatment methods
for urea-rich wastewater, such as electrochemical oxidation,
hydrolysis [96], enzymatic decomposition [28], catalytic
decomposition [97], adsorption [98], and biological treatment.
Each method has its unique technological characteristics,
and electrochemical oxidation is currently a more advanced
one, which produces less waste, has a low impact on the
environment, and can be followed-up processing and utiliza-
tion [1,99]. Lu et al. applied microbial and electrolysis methods
to urea hydrolysis. Ions migration driven by the self-generated
electric field was used to recover nutrients from the waste-
water. The removal rates of urea and COD are as high as 99%
and 97%, respectively. In addition, the removal rates of SO2 4 nanoporous NiFe-based catalyst. The catalyst showed the best
and PO34 can also reach 98e99% [100].
In addition, the combination of wastewater treatment and
energy production is a hot topic of sustainable development. A
recent study found that 2000 tons of urea-containing waste-
water are produced every day in industrial production, and
human urine is more than 120 times that number [30,101]. For
these large amounts of urea-rich wastewater or urine, not
only can they be used for wastewater repair through electro-
chemical treatment to protect the environment, but they can
also be treated as the original carrier of energy for recycling or
utilization, such as hydrogen production by electrolysis and
direct urea/urine fuel cells. And they will be introduced in
detail later.
Hydrogen production by electrolysis of urea
In today's increasingly serious energy shortage, as the clean-
est energy source, the development of hydrogen energy pro-
duction and application technology has attracted much
attention. Compared with electrolyzed water, the electrolysis
of urea to produce hydrogen is more economical and more
energy-saving [5,6]. UOR is the anode reaction of urea elec-
trolysis, which generates nitrogen, carbon dioxide, and water
in alkaline electrolytes. At the same time, HER occurs at the
cathode side of urea electrolysis to produce hydrogen (Fig. 7a).
The overall urea electrolysis reaction equations are as follows:
Anode: CO(NH2)2 (aq) þ 6OH / N2 (g) þ CO2 (g) þ 5H2O
(l) þ 6e (4a)
Cathode: 6H2O (l) þ 6e / 3H2 (g) þ 6OH (aq) (4b)
Overall Reaction: CO(NH2)2 (aq) þ H2O (l) / N2 (g) þ3H2 (g)
þCO2 (g) (4c)
Compared with UOR, the application of metallic nickel in
HER is earlier. Researchers have focused on the optimization
of nickel's catalytic performance to achieve its dual functions
of urea oxidation and high-efficiency hydrogen production.
These materials are summarized in Table 2.
Wang et al. [102] synthesized porous pomegranate-like Ni/
C in a multi-element metal-organic framework. The author
speculates that its excellent performance comes from the
introduction of Zn in Ni-MOF. The evaporated Zn left pores
and then forms an open channel, which effectively increased
the specific surface area and abundant active sites of the
catalyst. A two-electrode urea electrolyzer was constructed
with Ni/C as both the cathode and anode electrocatalyst,
under the same conditions, its hydrogen production
(3.36 L h1) was 52 times that of the water electrolyzer
(0.064 L h1). Cao et al. [103] synthesized 3D hierarchical NiMo-
based composite microrod arrays on nickel foam using a urea-
assisted method with ZnO as the core and support. When the
current density reached 10 mA cm2, the overpotential of HER
and UOR only needed 110 mV and 1.405 V, respectively.
Adopting it to a two-electrode cell, the voltage for overall urea
electrolysis dropped from 1.718 V to 1.549 V at 10 mA cm2
after substituting the oxygen evolution reactions (OER) with
UOR, and the potential remained stable within 24 h. Similarly,
Cao et al. [104] chose to dope another metal Fe to synthesize a
performance towards both HER and UOR when the ratio of Ni
to Fe is 7:3. And the voltage of the as-prepared NP-Ni0.70Fe0.30
for overall urea electrolysis was 1.55 V to attain a current
density of 10 mA cm2. Meanwhile, it also provided some
references for wastewater treatment.
Doping with non-metallic elements is also an optimization
strategy. Wang et al. [105] synthesized NiTe2 and NiTe simply
by recombining NF-assisted NiTe with reduced graphene
oxide, which showed superior activity for both HER and UOR.
Importantly, the technology can be extended to the practical
use of human urine, as well as to achieve sustainable waste-
water treatment and hydrogen production. A method for the
synthesis of nickel sulfide and multi-walled carbon nanotube
composites on nickel foam (Ni3S2/MWCNTs/NF) was proposed
by Zhao et al. [106]. The integration of Ni3S2 reduced graphene
oxide and MWCNTs optimized the electrochemical charac-
teristics of the composite electrode. HER and UOR showed low
overpotentials, which were 104 mV and 1.338 V at the current
density of 10 mA cm2, respectively. And the Ni3S2/MWCNTs/
NF||Ni3S2/MWCNTs/NF electrodes provided a current density
of 10 mA cm2 at a voltage of 1.509 V, which exhibited its
commercial viability in energy-efficient hydrogen production
(Fig. 7cef). Recently, Fei et al. [107] directly used low-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2 7703

Fig. 5 e (a) Schematic diagram of Ni2P/CFC as electrodes for two-electrode urea electrolysis system; (b) The urea electrolysis
and full water-spitting voltages at 10 mA cm¡2 of different electrodes; (c) H2 production amount as a function of water-
splitting time in the presence and absence of 0.33 M urea powered [95]. Copyright (2017), Elsevier Ltd. (d) The Ni2P unit cell
and top views of the low index surfaces used in this study [94]. Copyright (2015), the Owner Societies.

temperature phosphating nickel foam to synthesize a three-
dimensional self-supporting nickel phosphide/foam nickel
electrode with high catalytic activity. And the PeNF||PeNF
electrodes required only 1.37 V to reach 10 mA cm2 with
excellent prolonged durability for at least 100 h.
Direct urea fuel cells
An efficient and green energy system is an important form to
solve the energy crisis. Fuel cells are considered as promising
energy sources for their high energy density (103 Wh kg1 or
Wh L1) [101,108], which directly convert chemical energy into
electric energy. DUFC is the advanced representative among
them, the anode fuel is mainly derived from artificial urea
wastewater and mammalian urine [19,27], which exhibits
high energy density and solubility [61]. The diagram is illus-
trated in Fig. 7b and the specific equations are as follows:
Anode: CO(NH2)2 (aq) þ 6OH / N2 (g) þ CO2 (g) þ 5H2O
(l) þ 6e (5a)
Cathode: O2 (g) þ 2H2O (l) þ 4e / 4OH (l)
Overall Reaction: 2CO(NH2)2 (aq) þ 3O2 (g) / 2N2 (g) þ 2CO2
(g) þ 4H2O (g) (5c)
Compared to hydrogen production by electrolysis, it is
more efficient to directly use urine or wastewater for power
generation. Nickel-based chemical catalysts are very stable at
high pH values, which means that an increase in pH does not
limit the current density, and these catalysts are summarized
in Table 3.
Urea is directly electrically oxidized into N2 to generate
electricity, which is easy to operate and has a high power
density [101]. For the first time, a direct urea/urine fuel cell has
been developed to generate electricity directly from urea or
urine by Lan et al. [109]. Using low-cost alkaline membrane
electrolytes and non-precious metal catalysts such as nickel,
silver, and manganese dioxide, they turned fertilizers and
waste into energy sources, which aroused the interest of re-
searchers in this direction. In addition, the authors believe
that to obtain good performance, the small particle size of the
catalyst is essential, so they had further optimized and syn-
thesized nano-sized nickel with the primary particle size of
2e3 nm, which effectively improved the activity of the catalyst
[58]. The peak power density of 14.2 and 4.23 mW cm2 were
obtained in the urea fuel cell and urine fuel cell, respectively.
The core-shell nanostructure of bifunctional cobalt oxide
(Co3O4) was synthesized by Senthilkumar et al. on carbon
cloth fibers modified by nickel oxide and manganese dioxide
[17], which exhibited excellent UOR properties. A direct urea/
urea fuel cell was constructed with Co3O4@NiO/CC as the
(5b) anode and Co3O4@MnO2/CC as the cathode. The maximum
power densities of 33.8 mW cm2 and 23.2 mW cm2 were
obtained at 60  C, with OCV of 0.992 V and 0.978 V,
respectively.
In another work, Basumatary et al. [110] used a two-step
hydrothermal method to load NieCu alloy nanoparticles on
ZnO-coated MWCNTs, and synthesized the NieCu/
ZnO@MWCNT catalyst, which was applied to DUFCs. The
experiment also explored the influence of urea concentration
and operating temperature on fuel cell performance. The re-
sults found that when the KOH concentration was fixed at 3 M,
7704 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Fig. 6 e (a) Unique hollow York shell structure schematic of a novel Ni2P/C-YS composite; (b) FESEM image of Ni2P/C-YS-350;
(c, d) LSV curves with iR compensation and Tafel slope curves of Ni2P/C-YS [54]; Copyright (2020), Elsevier. (e) Density of
states of rod-like Ni2P and NiO [57]. Copyright (2020), Springer Nature.

the urea concentration was 0.7 M and the temperature was
50  C. The cell showed the best performance, which was
represented by a power density of 44.36 mW cm2 and an OCV
of 0.91 V (Fig. 8aed). The author believes that its outstanding
electrocatalytic performance mainly depends on the following
factors: (ⅰ) the strong electron interaction between the carrier
and the metal; (ⅱ) the uniform coating of ZnO nanoparticles on
MWCNTs; (ⅲ) the high dispersion of NieCu alloy
nanoparticles.
In addition to using wet air as an oxidant, the researchers
also tried to use H2O2 as an oxidant, and the theoretical OCV of
the cell was increased to 2.51 V from 1.15 V (CO(NH2)2-
þ 3H2O2 þ 3H2SO4 þ 8KOH / K2CO3 þ 3K2SO4 þ N2 þ 12H2O).
Guo et al. [111] investigated a nickel-cobalt nanowire array
electrode (Co/Ni ¼ 10%) using a one-step constant current
electrodeposition method, and then applied it to construct a
single direct urea/hydrogen peroxide, which had an OCV of
0.92 V and a maximum power density of 7.4 mW cm2 at room
temperature (Fig. 8e). At about the same time, the authors also
synthesized a bimetallic three-dimensional porous catalyst
with a Co/Ni molar ratio of 80% on foamed nickel and applied
it to a direct urea-hydrogen peroxide fuel cell (DUHPFC) [112].
The OCV of the cell was 0.83 V, and its maximum power
densities were 17.4, 19.1, and 31.5 mW cm2 at 20  C, 40  C, and
70  C, respectively.
Urea electrochemical sensors
As one of the main products of protein degradation and
metabolism of nitrogen-containing compounds, the content
of urea in human blood and urine has become an important
parameter for evaluating human organs such as the liver and
kidney [113]. Under normal circumstances, the content of urea
in urine is between 7e20 mg dL1, and its abnormal level may
be a sign of renal failure, heart failure, or liver disease, so it is
very important to monitor the urea content in the human
body [114,115].
Compared with the high-cost and easily deactivated
enzyme sensors, the nickel-based electrooxidation catalyst of
urea has a good application prospect in non-enzyme bio-
sensors. The related catalysts mentioned in this paper are
listed in Table 4. Tran et al. synthesized a porous composite
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2 7705

Fig. 7 e (a) An illustration of a typical urea electrolytic cell and its corresponding UOR and HER at anode and cathode,
respectively; (b) A schematic of a typical urea fuel cell with UOR at anode and ORR at the cathode [19] Copyright (2020),
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (c) Schematic diagram of Ni3S2/MWCNTs/NF. (d) SEM of Ni3S2/MWCNTs/
NF. (e) LSVs of water electrolysis and water-urea electrolysis. (f) LSVs of different electrodes [106]. Copyright (2020), The
Electrochemical Society.

Table 2 e Parameters of hydrogen production by urea electrolysis on various catalysts.

Anode/Cathode Potential at 10 mA cm2 Electrolytes Cell Voltage at 10 mA cm2 Stability (h) Ref.
HER (mV) UOR (V) KOH (M) Urea (M)
Ni/C 40 1.33 1 0.33 1.6 12 [102]
NiMo@ZnO/NF 110 1.405 1 0.33 1.549 24 [103]
NP-Ni0.70Fe0.30 e 1.33 1 0.33 1.55 10 [104]
NiTe/rGO/NF 174 1.374a 1 0.33 1.50 ~14 [105]
NiTe2/NF 184 1.394a 1 0.33 1.56 ~14
Ni3S2/MWCNTs/NF 104 1.338 1 0.5 1.509 26 [106]
3D P/NF 213b 1.32 1 0.33 1.37 100 [107]

*a ¼ @50 mA cm2; b ¼ @20 mA cm2

catalyst combining nickel metal-organic framework and
multi-walled carbon nanotubes and then coated it with in-
dium tin oxide glass as a new urea electrochemical sensor
with a sensitivity of 685 mA mM1 cm2 [116]. Moreover, the
detection limit of this sensor was 3 mM and the response time
was 10 s, with good stability within 30 days without loss of
activity. Bao et al. also prepared ultra-thin nickel metal-
organic framework nanobelts and successfully used them in
the preparation of non-enzymatic urea sensors [117], which
exhibited a high sensitivity of 118.77 mA mM1 cm2 and a low
 7706
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
Table 3 e Performance parameters for DUFCs based on various catalysts.
Catalyst Membrane Fuel OCV (V) Peak Power density (mW cm2) Temp. ( C) Ref.
Anode Cathode
Pt/C Pt/C AERePVA Urea 1 M 0.5 0.55 Room temp. Room temp. [109]
Urea 5 M 0.4 0.2
AdBlue 0.57 0.3
Ni/C Ag/C AERePVA Urea 1 M 0.29 0.14
Ni/C MnO2/C AERePVA Urea 1 M 0.62 1.7 50
Nanosized Ni/C MnO2/C AERePVA Urea 1 M 0.83 14.2 60 [58]
Urine 0.67 4.23
AdBlue 0.75 8.65
Co3O4@NiO/CC Co3O4@MnO2/CC AEM (AMI-7001) Urea 50 mM 0.992 33.8 60 [17]
Urine 50 mM 0.978 23.2
NieCu@MWCNT Pt/C AEM Urea 0.7 M/KOH 3 M 0.91 22.11 50 [110]
NieCu/ZnO@MWCNT Pt/C AEM Urea 0.7 M/KOH 3 M 0.91 44.36
NieCo NWAs Pd/carbon fiber cloth Nafion 115 Urea 0.33 M/KOH 5 M 0.83 5.03 25 [111]
Urea 0.33 M/KOH 9 M 0.92 7.4
NieCo/Ni foam Pd/CFC Nafion 115 Urea 0.5 M/7 M KOH 0.83 17.4 20 [112]
0.85 19.1 40
0.88 31.5 70
Fresh human urine 0.8 7.5 20
human urine after 24 h' standing 0.83 4.7 20

*OCV: open circuit voltage; AER-PVA: anion exchange resin-polyvinyl alcohol; AdBlue: a commercial 32.5% urea; RH: relative humidity; AEM: anion exchange membrane.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2 7707

Fig. 8 e Unit cell performance with different urea concentrations: (a) Current density vs. voltage curves. Influence of the
temperature on the cell performance using (b) NieCu/ZnO@MWCNT, and (c) NieCu/MWCNT catalysts as anodes. (d)
Mechanism of the urea electrooxidation on the surface of the NieCu/ZnO@MWCNT catalyst [110]. Copyright (2017), Elsevier
Ltd. (e) Schematic representation of direct urea/H2O2 fuel cell configuration [111]. Copyright (2017), WILEY-VCH Verlag GmbH
& Co. KGaA, Weinheim.

detection limit of 2.23 mM (S/N ¼ 3). The experiment also
applied the sensor to the recovery test of three real urine
samples, and the recovery rate was in the range of
92.0e115.0%, which verified the applicability of the developed
enzyme-free urea sensor in real urine samples.
Nickel-based oxides have also been used in non-enzymatic
urea sensors. Nguyen et al. prepared NiCo2O4/3D graphene/
ITO electrodes [118] and NiO/cellulose/CNT electrodes [119]
based on NiCo2O4 and NiO, respectively. The response time of
the NiCo2O4/3D graphene/ITO sensor was only about 1.0 s, and
the sensitivity was 166 mA mM1 cm2. The NiO/cellulose/CNT
sensor had a longer response time of 4 s, but the sensitivity
could reach 371 mA mM1 cm2. To verify the feasibility of the
urea sensor in practical applications, recovery tests in urine
were carried out, and all showed good recovery and
repeatability.
But from another point of view, nickel-based catalysts are
mainly suitable for alkaline environments and have limita-
tions in detecting urine or serum. A method for preparing Ag/
NiOOH nanorod composite catalyst by using CV to process the
Ni(OH)2 precursor and sputtering and depositing Ag in a
neutral environment was proposed by Yoon et al. [120].
Additionally, the Ag/NiOOH/C nanorod electrode had a high
sensitivity of 233.7 mA mM1 cm2, with a comprehensive
linear detection ranging from 0.2 to 26.0 mM and an excellent
LOD of 5.0 mM for urea detection, which provided ideas for the
actual monitoring of urea (Fig. 9).
Like the previous chapter, Novel nickel-based catalysts
such as Ni2P also have outstanding activity in the field of
urea non-enzyme sensors. Zheng et al. synthesized NieP
nanomaterials with different morphologies on cellulose
paper by adjusting the pH and concentration of the elec-
troless plating solution [121]. Comparing the electro-
chemical performance of catalysts with different
morphologies, the order of their electrocatalytic activities is
as follows: nanoflowers > nanosheets > nanowire
microspheres > microspheres. The NieP nanoflower paper
electrode showed the best electrochemical performance
with the highest sensitivity of 1140 mA mM1 cm2, the
lowest detection limit of 12 mM, the shortest response time
7708 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2

Table 4 e Comparison of analysis performance of urea sensors.

Electrode Sensitivity (mA mM1 cm2) Limit of detection (mM) Linear range (mM) Response time (s) Ref.
Ni-MOF/MWCNTs/ITO 685 3 0.01e1.12 10 [116]
Ni-MOF/Nafion/GCE 118.77 2.719 0.01e7 e [117]
NiCO2O4/3D graphene/ITO 166 5 0.06e0.3 1 [118]
NiO/cellulose/CNT 371 7 0.01e1.4 4 [119]
Ag/NiOOH/C nanorod 233.7 5 0.2e26.0 3 [120]
NieP nanoflower 1140 12 0.05e11 3 [121]
NieP nanosheet 924 15 0.05e11 5
NieP nanowire microsphere 875.4 10 0.05e12 5
NieP microsphere 531.78 15 0.05e12 5

Fig. 9 e Schematic illustration of Ag/NiOOH/C formation; Illustration shows the electrocatalytic urea oxidation performance
of different electrodes in a 0.1 M PBS solution with 0 mM and 50 mM urea [120]. Copyright (2020), American Chemical
Society.

of 3 s, which may owe to the highest surface area of the
NieP nanoflower structure.
Conclusion and outlook
Urea management has always been a major environmental
and health problem. Urea electrooxidation is an environ-
mentally friendly, controllable, and energy conversion
method. This article summarized the research progress of
nickel-based from the aspects of mono-metallic nickel and
its alloys, nickel-based hydroxides and oxides, and
novel nickel-based catalysts. Among them, nickel-based
composite functionalized materials can integrate the ad-
vantages of materials, thus effectively improving the
current density and stability of catalysts and enhancing
their competitiveness in practical applications, which are
the main development direction at present. Finally, the
application prospects of urea electrooxidation, including
urea removal/decomposition, hydrogen production, fuel
cells, and sensors, were also described in detail.
However, there are still some problems in the field of urea
electrooxidation. Firstly, there is still a lack of a more detailed
and direct interpretation of the mechanism of internal reac-
tion and optimization. Secondly, nickel-based catalysts still
suffer from obstacles such as fast catalyst degradation, un-
stable oxidation current, and insufficient resistance to CO
poisoning, which will lead to poor circulation or serious po-
larization. Additionally, nickel-based catalysts also have high
catalytic activity for OER, which will reduce the UOR efficiency
to a certain extent. Finally, the actual wastewater usually has
complex composition and properties, and the nickel-based
catalysts mainly have good activity in the alkaline environ-
ment, which cannot meet the actual requirements well, and it
is difficult to achieve large-scale applications.
Based on this, we propose some directions for improvement:
1. Deeply explore the internal mechanism of the UOR at the
atomic/molecular level; It is an effective method to carry out
in-depth exploration with modern analytical techniques
including Raman, X-ray photoelectron spectroscopy, elec-
tron microscope technology, isotope labeling, etc.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
2. Optimize the preparation method; The current fabrication
of catalysts mostly uses heat treatment-related methods,
which are costly and have certain risks. Researchers can try
to simplify the synthesis method to reduce the cost and risk
factors. In addition, the side reactions can be inhibited by
corresponding measures to improve the reaction efficiency.
3. Design targeted catalysts and develop new types of high-
activity carriers; At present, most catalysts are aimed at
HER and OER, and there are few studies based only on UOR.
Researchers can explore new carriers to optimize the
structure of catalysts to the actual conditions of different
applications to meet different needs and maximize their
potential.
4. Doped functional materials; The combination of materials
will form an advantage integration. Complex nickel-based
composites with a specific structure, high electrical con-
ductivity, and abundant active sites will be the develop-
ment trend of nickel-based catalysts.
5. Control costs and realize “chemical amplification”; Reali-
zation of real-world applications is one of the ultimate
goals of scientific research, cost and efficiency are two key
factors. It is the main direction of the current development
to realize the leap from laboratory scale production to in-
dustrial production by making full use of advantages and
circumventing disadvantages.
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.
Acknowledgements
This study is supported by the National Natural Science
Foundation of China (Grant No. 21706241, U1404503,
21403053), China Post-doctoral Science Foundation
(2020M672305, 2018M642791), and Key Scientific and Techno-
logical Project of Henan Province (202102210042).
references
[1] Urban
czyk E, Sowa M, Simka W. Urea removal from
aqueous solutionsda review. J Appl Electrochem
2016;46:1011e29.
[2] Song X, Gao L, Li Y, Chen W, Mao L, Yang J-H. Nickel
phosphate-based materials with excellent durability for
urea electro-oxidation. Electrochim Acta 2017;251:284e92.
[3] Sun X, Ding R. Recent progress with electrocatalysts for
urea electrolysis in alkaline media for energy-saving
hydrogen production. Catal Sci Technol 2020;10:1567e81.
[4] Boggs BK, King RL, Botte GG. Urea electrolysis: direct
hydrogen production from urine. Chem Commun
2009:4859e61.
[5] Pan Y, Zhang C, Lin Y, Liu Z, Wang M, Chen C.
Electrocatalyst engineering and structure-activity
relationship in hydrogen evolution reaction: from
7709
nanostructures to single atoms. Sci China Mater
2020;63:921e48.
[6] Yang W, Chen S. Recent progress in electrode fabrication for
electrocatalytic hydrogen evolution reaction: a mini review.
Chem Eng J 2020;393:124726.
[7] Zhou J, Dou Y, Zhou A, Guo R-M, Zhao M-J, Li J-R. MOF
template-directed fabrication of hierarchically structured
electrocatalysts for efficient oxygen evolution reaction. Adv
Energy Mater 2017;7:1602643.
[8] Song X, Sun Q, Gao L, Chen W, Wu Y, Li Y, Mao L, Yang J-H.
Nickel phosphate as advanced promising electrochemical
catalyst for the electro-oxidation of methanol. Int J
Hydrogen Energy 2018;43:12091e102.
[9] Yang J-H, Song X, Zhao X, Wang Y, Yang Y, Gao L. Nickel
phosphate materials regulated by doping cobalt for urea
and methanol electro-oxidation. Int J Hydrogen Energy
2019;44:16305e14.
[10] Ashok A, Kumar A, Bhosale R, Saleh Saad MA, AlMomani F,
Tarlochan F. Study of ethanol dehydrogenation reaction
mechanism for hydrogen production on combustion
synthesized cobalt catalyst. Int J Hydrogen Energy
2017;42:23464e73.
[11] Mohd-Nasir NS, Osazuwa OU, Zainal Abidin S. Synergistic
catalysis of bi-metals in the reforming of biomass-derived
hydrocarbons: a review. Int J Hydrogen Energy
2021;46:31000e23.
[12] Lan R, Irvine JTS, Tao S. Ammonia and related chemicals as
potential indirect hydrogen storage materials. Int J
Hydrogen Energy 2012;37:1482e94.
[13] Sun H-Y, Xu G-R, Li F-M, Hong Q-L, Jin P-J, Chen P, Chen Y.
Hydrogen generation from ammonia electrolysis on
bifunctional platinum nanocubes electrocatalysts. J Energy
Chem 2020;47:234e40.
[14] Wang D, Botte GG. In situ X-Ray diffraction study of urea
electrolysis on nickel catalysts. ECS Electrochem Lett
2014;3:H29e32.
[15] King RL, Botte GG. Investigation of multi-metal catalysts for
stable hydrogen production via urea electrolysis. J Power
Sources 2011;196:9579e84.
[16] Yan W. Nickel-based catalysts for urea electro-oxidation.
Ohio University; 2014.
[17] Senthilkumar N, Gnana kumar G, Manthiram A. 3D
hierarchical core-shell nanostructured arrays on carbon
fibers as catalysts for direct urea fuel cells. Adv Energy
Mater 2018;8:1702207.
[18] Xie A, Du J, Zhang J, Xiong Z, Shao F, Luo S. A high-
performance nonenzymatic urea sensor based on
graphene-NiO-polyaniline. J Electrochem Soc
2019;166:B456e63.
[19] Zhu B, Liang Z, Zou R. Designing advanced catalysts for
energy conversion based on urea oxidation reaction. Small
2020;16:1906133.
[20] Bai J, Jia N, Jin P, Chen P, Jiang J-X, Zeng J-H, Chen Y. Metal-
organic interface engineering for boosting the
electroactivity of Pt nanodendrites for hydrogen
production. J Energy Chem 2020;51:105e12.
[21] Wang T-J, Sun H-Y, Xue Q, Zhong M-J, Li F-M, Tian X,
Chen P, Yin S-B, Chen Y. Holey platinum nanotubes for
ethanol electrochemical reforming in aqueous solution. Sci
Bull 2021;66:2079e89.
[22] Camposeco R, Hinojosa-Reyes M, Zanella R. Highly efficient
photocatalytic hydrogen evolution by using Rh as co-
catalyst in the Cu/TiO2 system. Int J Hydrogen Energy
2021;46:26074e86.
[23] Miller AT, Hassler BL, Botte GG. Rhodium electrodeposition
on nickel electrodes used for urea electrolysis. J Appl
Electrochem 2012;42:925e34.
7710 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
[24] Amstutz V, Katsaounis A, Kapalka A, Comninellis C,
Udert KM. Effects of carbonate on the electrolytic removal
of ammonia and urea from urine with thermally prepared
IrO2 electrodes. J Appl Electrochem 2012;42:787e95.
[25] Reier T, Oezaslan M, Strasser P. Electrocatalytic oxygen
evolution reaction (OER) on Ru, Ir, and Pt catalysts: a
comparative study of nanoparticles and bulk materials. ACS
Catal 2012;2:1765e72.
[26] Nim YS, Wong K-B. The maturation pathway of nickel
urease. INORGA 2019;7:85.
[27] Ye K, Wang G, Cao D, Wang G. Recent advances in the
electro-oxidation of urea for direct urea fuel cell and urea
electrolysis. Top Curr Chem 2018;376:42.
[28] Krajewska B. Ureases I. Functional, catalytic and kinetic
properties: a review. J Mol Catal B Enzym 2009;59:9e21.
[29] Sua
rez D, Dı́az N, Merz KM. Ureases: quantum chemical
calculations on cluster models. J Am Chem Soc
2003;125:15324e37.
[30] Hu X, Zhu J, Li J, Wu Q. Urea electrooxidation: current
development and understanding of ni-based catalysts.
Chemelectrochem 2020;7:3211e28.
[31] Wright J, Michaels A, Appleby A. Electrooxidation of urea at
the ruthenium titanium oxide electrode. AlChE J
1986;32:1450e8.
^ de Sa
[32] Bezerra AC,
EL, Nart FC. In situ vibrational study of the
initial steps during urea electrochemical oxidation. J Phys
Chem B 1997;101:6443e9.
[33] Vedharathinam V, Botte GG. Understanding the electro-
catalytic oxidation mechanism of urea on nickel electrodes
in alkaline medium. Electrochim Acta 2012;81:292e300.
[34] Vedharathinam V, Botte GG. Direct evidence of the
mechanism for the electro-oxidation of urea on Ni(OH)2
catalyst in alkaline medium. Electrochim Acta
2013;108:660e5.
[35] Daramola DA, Singh D, Botte GG. Dissociation rates of urea
in the presence of NiOOH catalyst: a DFT analysis. J Phys
Chem 2010;114:11513e21.
[36] Sha L, Liu T, Ye K, Zhu K, Yan J, Yin J, Wang G, Cao D. A
heterogeneous interface on NiS@Ni3S2/NiMoO4
heterostructures for efficient urea electrolysis. J Mater
Chem 2020;8:18055e63.
[37] Vedharathinam V, Botte GG. Experimental investigation of
potential oscillations during the electrocatalytic oxidation
of urea on Ni catalyst in alkaline medium. J Phys Chem C
2014;118:21806e12.
[38] Wang S, Chen W, Xu L, Zhu X, Huang Y-C, Zhou W, Wang D,
Zhou Y, Du S, Li Q. Unveiling the electrooxidation of urea:
the intramolecular coupling of N-N bond. Angew Chem
2020;60:7297. 07.
[39] Yan W, Wang D, Diaz LA, Botte GG. Nickel nanowires as
effective catalysts for urea electro-oxidation. Electrochim
Acta 2014;134:266e71.
[40] Bian L, Du Q, Luo M, Qu L, Li M. Monodisperse nickel
nanoparticles supported on multi-walls carbon nanotubes
as an effective catalyst for the electro-oxidation of urea. Int
J Hydrogen Energy 2017;42:25244e50.
[41] Yan W, Wang D, Botte GG. Template-assisted synthesis of
Ni-Co bimetallic nanowires for urea electrocatalytic
oxidation. J Appl Electrochem 2015;45:1217e22.
[42] Yan W, Wang D, Botte GG. Electrochemical decomposition
of urea with Ni-based catalysts. Appl Catal B Environ
2012;127:221e6.
[43] Shi W, Sun X, Ding R, Ying D, Huang Y, Huang Y, Tan C,
Jia Z, Liu E. Trimetallic NiCoMo/graphene multifunctional
electrocatalysts with moderate structural/electronic effects
for highly efficient alkaline urea oxidation reaction. Chem
Commun 2020;56:6503e6.
[44] Ji R-Y, Chan D-S, Jow J-J, Wu M-S. Formation of open-ended
nickel hydroxide nanotubes on three-dimensional nickel
framework for enhanced urea electrolysis. Electrochem
Commun 2013;29:21e4.
[45] Liu Y-H, Hung C-H, Hsu C-L. Electrochemical fabrication of
carbon fiber-based nickel hydroxide/carbon nanotube
composite electrodes for improved electro-oxidation of the
urea present in alkaline solutions. Separ Purif Technol
2021;258:118002.
[46] Xu W, Du D, Lan R, Humphreys J, Wu Z, Tao S. Highly active
Ni-Fe double hydroxides as anode catalysts for
electrooxidation of urea. New J Chem 2017;41:4190e6.
[47] Wu M-S, Lin G-W, Yang R-S. Hydrothermal growth of
vertically-aligned ordered mesoporous nickel oxide
nanosheets on three-dimensional nickel framework for
electrocatalytic oxidation of urea in alkaline medium. J
Power Sources 2014;272:711e8.
[48] Ding R, Qi L, Jia M, Wang H. Facile synthesis of mesoporous
spinel NiCo2O4 nanostructures as highly efficient
electrocatalysts for urea electro-oxidation. Nanoscale
2014;6:1369e76.
[49] Periyasamy S, Subramanian P, Levi E, Aurbach D,
Gedanken A, Schechter A. Exceptionally active and stable
spinel nickel manganese oxide electrocatalysts for urea
oxidation reaction. ACS Appl Mater Interfaces
2016;8:12176e85.
[50] Tong Y, Chen P, Zhang M, Zhou T, Zhang L, Chu W, Wu C,
Xie Y. Oxygen vacancies confined in nickel molybdenum
oxide porous nanosheets for promoted electrocatalytic urea
oxidation. ACS Catal 2018;8:1e7.
[51] Wang G, Ye K, Shao J, Zhang Y, Zhu K, Cheng K, Yan J,
Wang G, Cao D. Porous Ni2P nanoflower supported on nickel
foam as an efficient three-dimensional electrode for urea
electro-oxidation in alkaline medium. Int J Hydrogen Energy
2018;43:9316e25.
[52] Khalafallah D, Zhi M, Hong Z. Shape-Dependent
electrocatalytic activity of carbon reinforced Ni2P hybrids
toward urea electrocatalysis. Energy Technol
2019;7:1900548.
[53] Yang D, Gu Y, Yu X, Lin Z, Xue H, Feng L. Nanostructured
Ni2P-C as an efficient catalyst for urea electrooxidation.
Chemelectrochem 2018;5:659e64.
[54] Zhang Y, Wang C. Yolk-shell nanostructural Ni2P/C
composites as the high performance electrocatalysts
toward urea oxidation. Chin Chem Lett 2020;32:2222e8.
[55] Xie L, Liu Q, Luo Y, Liu Z, Xu Y, Asiri AM, Sun X, Xie F.
Bimetallic NiCoP nanosheets array for high-performance
urea electro-oxidation and less energy-intensive
electrolytic hydrogen production. ChemistrySelect
2017;2:10285e9.
[56] Liu H, Liu Z, Feng L. Bonding state synergy of the NiF2/Ni2P
hybrid with the co-existence of covalent and ionic bonds
and the application of this hybrid as a robust catalyst for
the energy-relevant electrooxidation of water and urea.
Nanoscale 2019;11:16017e25.
[57] Li Q, Li X, Gu J, Li Y, Tian Z, Pang H. Porous rod-like Ni2P/Ni
assemblies for enhanced urea electrooxidation. Nano Res
2020;14:1405e12.
[58] Lan R, Tao S. Preparation of nano-sized nickel as anode
catalyst for direct urea and urine fuel cells. J Power Sources
2011;196:5021e6.
[59] Hatami E, Toghraei A, Barati Darband G. Electrodeposition
of Ni-Fe micro/nano urchin-like structure as an efficient
electrocatalyst for overall water splitting. Int J Hydrogen
Energy 2021;46:9394e405.
[60] Wang S, Zhu J, Wu X, Feng L. Microwave-assisted
hydrothermal synthesis of NiMoO4 nanorods for high-
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
performance urea electrooxidation. Chin Chem Lett 2021.
https://doi.org/10.1016/j.cclet.2021.08.042. In press.
[61] Sayed ET, Eisa T, Mohamed HO, Abdelkareem MA, Allagui A,
Alawadhi H, Chae K-J. Direct urea fuel cells: challenges and
opportunities. J Power Sources 2019;417:159e75.
[62] Zhao Y, Jia N, Wu X-R, Li F-M, Chen P, Jin P-J, Yin S, Chen Y.
Rhodium phosphide ultrathin nanosheets for hydrazine
oxidation boosted electrochemical water splitting. Appl
Catal B Environ 2020;270:118880.
[63] Wang S, Yang X, Liu Z, Yang D, Feng L. Efficient
nanointerface hybridization in a nickel/cobalt oxide
nanorod bundle structure for urea electrolysis. Nanoscale
2020;12:10827e33.
[64] Sha L, Yin J, Ye K, Wang G, Zhu K, Cheng K, Yan J, Wang G,
Cao D. The construction of self-supported thorny leaf-like
nickel-cobalt bimetal phosphides as efficient bifunctional
electrocatalysts for urea electrolysis. J Mater Chem
2019;7:9078e85.
[65] Yang D, Yang L, Zhong L, Yu X, Feng L. Urea electro-
oxidation efficiently catalyzed by nickel-molybdenum oxide
nanorods. Electrochim Acta 2019;295:524e31.
[66] Gu X, Yang D, Liu Z, Wang S, Feng L. Iron oxide promoted
nickel/nickel oxide rough nanorods for efficient urea
assisted water splitting. Electrochim Acta 2020:353.
[67] Liu Z, Zhang C, Liu H, Feng L. Efficient synergism of NiSe2
nanoparticle/NiO nanosheet for energy-relevant water and
urea electrocatalysis. Appl Catal B Environ 2020;276:119165.
[68] Xu H, Ye K, Yin J, Zhu K, Yan J, Wang G, Cao D. In situ
growth of ZIF67 at the edge of nanosheet transformed into
yolk-shell CoSe2 for high efficiency urea electrolysis. J Power
Sources 2021;491:229592.
[69] Alajami M, A Yassin M, Ghouri ZK, Al-Meer S, Barakat NAM.
Influence of bimetallic nanoparticles composition and
synthesis temperature on the electrocatalytic activity of
NiMn-incorporated carbon nanofibers toward urea
oxidation. Int J Hydrogen Energy 2018;43:5561e75.
[70] Hall DS, Lockwood DJ, Bock C, MacDougall BR. Nickel
hydroxides and related materials: a review of their
structures, synthesis and properties. Proc Math Phys Eng Sci
2015;471:20140792.
[71] Wang H, Lu L, Subramanian P, Ji S, Kannan P. Co, Fe-ions
intercalated Ni(OH)2 network-like nanosheet arrays as
highly efficient non-noble catalyst for electro-oxidation of
urea. Int J Hydrogen Energy 2021;46:34318e32.
[72] Sha L, Ye K, Yin J, Zhu K, Cheng K, Yan J, Wang G, Cao D. In
situ grown 3D hierarchical MnCo2O4.5@Ni(OH)2 nanosheet
arrays on Ni foam for efficient electrocatalytic urea
oxidation. Chem Eng J 2020;381:122603.
[73] Yan X, Hu Q-T, Wang G, Zhang W-D, Liu J, Li T, Gu Z-G. NiCo
layered double hydroxide/hydroxide nanosheet
heterostructures for highly efficient electro-oxidation of
urea. Int J Hydrogen Energy 2020;45:19206e13.
[74] Xie J, Liu W, Lei F, Zhang X, Qu H, Gao L, Hao P, Tang B,
Xie Y. Iron-incorporated alpha-Ni(OH)2 hierarchical
nanosheet arrays for electrocatalytic urea oxidation.
Chemistry 2018;24:18408e12.
[75] Yang J-H, Chen M, Xu X, Jiang S, Zhang Y, Wang Y, Li Y,
Zhang J, Yang D. CuO-Ni(OH)2 nanosheets as
effective electro-catalysts for urea oxidation. Appl Surf Sci
2021:560.
[76] Yan X, Zhang W-D, Hu Q-T, Liu J, Li T, Liu Y, Gu Z-G.
Defects-rich nickel nanoparticles grown on nickel foam as
integrated electrodes for electrocatalytic oxidation of urea.
Int J Hydrogen Energy 2019;44:27664e70.
[77] Wang S, Xu P, Tian J, Liu Z, Feng L. Phase structure tuning of
graphene supported Ni-NiO Nanoparticles for enhanced
urea oxidation performance. Electrochim Acta
2021;370:137755.
7711
[78] Li C, Liu Y, Zhuo Z, Ju H, Li D, Guo Y, Wu X, Li H, Zhai T.
Local charge distribution engineered by Schottky
heterojunctions toward urea electrolysis. Adv Energy Mater
2018;8:1801775.
[79] Ji X, Zhang Y, Ma Z, Qiu Y. Oxygen vacancy-rich Ni/NiO@NC
nanosheets with Schottky heterointerface for efficient urea
oxidation reaction. ChemSusChem 2020;13:5004e14.
[80] Wang D, Vijapur SH, Wang Y, Botte GG. NiCo2O4 nanosheets
grown on current collectors as binder-free electrodes for
hydrogen production via urea electrolysis. Int J Hydrogen
Energy 2017;42:3987e93.
[81] Chen N, Wang Y, Du X, Zhang X. Facile synthesis of Ni
doped CoWO4 nanoarrays grown on nickel foam substrates
for efficient urea oxidation. Int J Hydrogen Energy
2021;46:25114e20.
[82] Lei F, Sun Y, Liu K, Gao S, Liang L, Pan B, Xie Y. Oxygen
vacancies confined in ultrathin indium oxide porous sheets
for promoted visible-light water splitting. J Am Chem Soc
2014;136:6826e9.
[83] Zhao Z, Zhao J, Wang H, Li X, Yang L, Zhao Z, Liu X, Liu Y,
Liu P, Cai Z. Porous flower-like nickel nitride as highly
efficient bifunctional electrocatalysts for less energy-
intensive hydrogen evolution and urea oxidation. Int J
Hydrogen Energy 2020;45:14199e207.
[84] Mai W, Cui Q, Zhang Z, Wen D, Tian L, Hu W. Coaxial
Ni3S2@CoMoS4/NiFeOOH nanorods for energy-saving water
splitting and urea electrolysis. Int J Hydrogen Energy
2021;46:24078e93.
[85] Abdel Hameed RM, Mohamed IMA, Al-Enizi AM, Abutaleb A,
Shaikh SF, Yousef A. Fabrication of electrospun nickel
sulphide nanoparticles onto carbon nanofibers for efficient
urea electro-oxidation in alkaline medium. Int J Hydrogen
Energy 2021;46:12944e60.
[86] Wang S, Zhao L, Li J, Tian X, Wu X, Feng L. High valence
state of Ni and Mo synergism in NiS2-MoS2 hetero-nanorods
catalyst with layered surface structure for urea
electrocatalysis. J Energy Chem 2022;66:483e92.
[87] Barakat NAM, Yassin MA, Yasin AS, Al-Meer S. Influence of
nitrogen doping on the electrocatalytic activity of Ni-
incorporated carbon nanofibers toward urea oxidation. Int J
Hydrogen Energy 2017;42:21741e50.
[88] Hu S, Wang S, Feng C, Wu H, Zhang J, Mei H. Novel MOF-
derived nickel nitride as high-performance bifunctional
electrocatalysts for hydrogen evolution and urea oxidation.
ACS Sustainable Chem Eng 2020;8:7414e22.
[89] Ding R, Li X, Shi W, Xu Q, Wang L, Jiang H, Yang Z, Liu E.
Mesoporous Ni-P nanocatalysts for alkaline urea
electrooxidation. Electrochim Acta 2016;222:455e62.
[90] Lu S, Xu H, Gao B, Ren L. A simple method to freely adjust
the crystalline phase and micro-morphology of NixPy
compounds. New J Chem 2017;41:8497e502.
[91] Stinner C, Prins R, Weber T. Formation, structure, and HDN
activity of unsupported molybdenum phosphide. J Catal
2000;191:438e44.
[92] Callejas JF, Read CG, Roske CW, Lewis NS, Schaak RE.
Synthesis, characterization, and properties of metal
phosphide catalysts for the hydrogen-evolution reaction.
Chem Mater 2016;28:6017e44.
[93] Oyama S, Lee Y. The active site of nickel phosphide
catalysts for the hydrodesulfurization of 4,6-DMDBT. J Catal
2008;258:393e400.
[94] Hansen MH, Stern L-A, Feng L, Rossmeisl J, Hu X. Widely
available active sites on Ni2P for electrochemical hydrogen
evolution-insights from first principles calculations. Phys
Chem Chem Phys 2015;17:10823e9.
[95] Zhang X, Liu Y, Xiong Q, Liu G, Zhao C, Wang G, Zhang Y,
Zhang H, Zhao H. Vapour-phase hydrothermal synthesis of
Ni2P nanocrystallines on carbon fiber cloth for high-
7712 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 7 6 9 3 e7 7 1 2
efficiency H2 production and simultaneous urea
decomposition. Electrochim Acta 2017;254:44e9.
[96] Mahalik K, Sahu JN, Patwardhan AV, Meikap BC. Kinetic
studies on hydrolysis of urea in a semi-batch reactor at
atmospheric pressure for safe use of ammonia in a power
plant for flue gas conditioning. J Hazard Mater
2010;175:629e37.
[97] Shen S, Li M, Li B, Zhao Z. Catalytic hydrolysis of urea from
wastewater using different aluminas by a fixed bed reactor.
Environ Sci Pollut Res Int 2014;21:12563e8.
[98] Xue C, Wilson LD. Kinetic study on urea uptake with
chitosan based sorbent materials. Carbohydr Polym
2016;135:180e6.
[99] Zaher A, Shehata N. Recent advances and challenges in
management of urea wastewater: a mini review. IOP Conf
Ser Mater Sci Eng 2021;1046:012021.
[100] Lu S, Li H, Tan G, Wen F, Flynn MT, Zhu X. Resource
recovery microbial fuel cells for urine-containing
wastewater treatment without external energy
consumption. Chem Eng J 2019;373:1072e80.
[101] Xu W, Wu Z, Tao S. Urea-based fuel cells and
electrocatalysts for urea oxidation. Energy Technol
2016;4:1329e37.
[102] Wang L, Ren L, Wang X, Feng X, Zhou J, Wang B.
Multivariate MOF-templated pomegranate-like Ni/C as
efficient bifunctional electrocatalyst for hydrogen evolution
and urea oxidation. ACS Appl Mater Interfaces
2018;10:4750e6.
[103] Cao J, Li H, Zhu R, Ma L, Zhou K, Wei Q, Luo F. Improved
hydrogen generation via a urea-assisted method over 3D
hierarchical NiMo-based composite microrod arrays. J
Alloys Compd 2020;844:155382.
[104] Cao Z, Zhou T, Ma X, Shen Y, Deng Q, Zhang W, Zhao Y.
Hydrogen production from urea sewage on NiFe-based
porous electrocatalysts. ACS Sustainable Chem Eng
2020;8:11007e15.
[105] Wang Z, Guo P, Liu M, Guo C, Liu H, Wei S, Zhang J, Lu X.
Rational design of metallic NiTex (x ¼ 1 or 2) as bifunctional
electrocatalysts for efficient urea conversion. ACS Appl
Energy Mater 2019;2:3363e72.
[106] Zhao Z, Yang L, Wang Z, Wang L, Guo G, Chen J, Li Y,
Wang C, Zhao J, Cai Z. Ni3S2/MWCNTs/NF hybrid
nanostructure as effective bifunctional electrocatalysts for
urea electrolysis assisted hydrogen evolution. J Electrochem
Soc 2020;167:126514.
[107] Fei L, Sun H, Ran R, Zhou W, Shao Z. Self-supported nickel
phosphide electrode for efficient alkaline water-to-
hydrogen conversion via urea electrolysis. Ind Eng Chem
Res 2021;60:1185e93.
[108] Wang Y, Liu G. Reduced graphene oxide supported nickel
tungstate nano-composite electrocatalyst for anodic urea
oxidation reaction in direct urea fuel cell. Int J Hydrogen
Energy 2020;45:33500e11.
[109] Lan R, Tao S, Irvine JTS. A direct urea fuel cell-power from
fertiliser and waste. Energy Environ Sci 2010;3:438e41.
[110] Basumatary P, Konwar D, Yoon YS. A novel Ni Cu/
ZnO@MWCNT anode employed in urea fuel cell to attain
superior performances. Electrochim Acta 2018;261:78e85.
[111] Guo F, Cheng K, Ye K, Wang G, Cao D. Preparation of nickel-
cobalt nanowire arrays anode electro-catalyst and its
application in direct urea/hydrogen peroxide fuel cell.
Electrochim Acta 2016;199:290e6.
[112] Guo F, Cao D, Du M, Ye K, Wang G, Zhang W, Gao Y,
Cheng K. Enhancement of direct urea-hydrogen peroxide
fuel cell performance by three-dimensional porous nickel-
cobalt anode. J Power Sources 2016;307:697e704.
[113] Yang Y, Yoon SG, Shin C, Jin H, Lee WH, Park J, Kim YS.
Ionovoltaic urea sensor. Nano Energy 2019;57:195e201.
[114] Prats-Alfonso E, Abad L, Casan ~ -Pastor N, Gonzalo-Ruiz J,
Baldrich E. Iridium oxide pH sensor for biomedical
applications. Case urea-urease in real urine samples.
Biosens Bioelectron 2013;39:163e9.
[115] Pundir C, Jakhar S, Narwal V. Determination of urea with
special emphasis on biosensors: a review. Biosens
Bioelectron 2019;123:36e50.
[116] Tran TQN, Das G, Yoon HH. Nickel-metal organic
framework/MWCNT composite electrode for non-
enzymatic urea detection. Sensor Actuator B Chem
2017;243:78e83.
[117] Bao C, Niu Q, Chen Z-A, Cao X, Wang H, Lu W. Ultrathin
nickel-metal-organic framework nanobelt based
electrochemical sensor for the determination of urea in
human body fluids. RSC Adv 2019;9:29474e81.
[118] Nguyen NS, Das G, Yoon HH. Nickel/cobalt oxide-decorated
3D graphene nanocomposite electrode for enhanced
electrochemical detection of urea. Biosens Bioelectron
2016;77:372e7.
[119] Nguyen NS, Yoon HH. Nickel oxide-deposited cellulose/CNT
composite electrode for non-enzymatic urea detection.
Sensor Actuator B Chem 2016;236:304e10.
[120] Yoon J, Yoon YS, Kim D-J. Silver-nanoparticle-decorated
NiOOH nanorods for electrocatalytic urea sensing. ACS Appl
Nano Mater 2020;3:7651e8.
[121] Zheng L, Ma S, Wang Z, Shi Y, Zhang Q, Xu X, Chen Q. Ni-P
nanostructures on flexible paper for morphology effect of
nonenzymatic electrocatalysis for urea. Electrochim Acta
2019;320:134586.