Small Science - 2021 - Chen - Electrocatalytic C N Coupling For Urea Synthesis

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Electrocatalytic C–N Coupling for Urea Synthesis

Chen Chen,* Nihan He, and Shuangyin Wang*
or carbon monoxide only yields products

The industrial urea synthesis consists of two consecutive processes, nitrogen with limited bond structure, whereas the
þ hydrogen ! ammonia followed by ammonia þ carbon dioxide ! urea. The synthesis of valuable chemicals containing
electrocatalytic coupling of carbon source (carbon dioxide) and nitrogen source special bonds (such as C─N bond) still suf-
fers from the drawbacks of rigorous reac-
(nitrogen, nitrite, nitrate) by skipping the ammonia synthetic process might be a
tion conditions.
promising alternative to achieve the efficient urea synthesis; in this case, two To this end, Jiao and collaborators crea-
industrial steps with high energy consumption and high pollution are optimized tively introduced ammonia as another reac-
into one renewable energy-driving electrocatalytic process. Herein, the progress tant into the electrocatalytic reduction of
of green urea synthesis is summarized, focusing on the electrocatalytic coupling carbon monoxide (Figure 1). The formation
of C─N bond arises from the nucleophilic
of carbon source and nitrogen source for direct urea synthesis under ambient
attack of ammonia to the *C═C═O inter-
conditions. The mechanism researches for urea synthesis are also reviewed, and mediate, resulting in the production of
the future development directions of electrocatalytic urea synthesis are pro- acetamide with nearly 40% efficiency.[5]
spected. The electrocatalytic C–N coupling reaction realizes the efficient resource This strategy of combining electrocatalytic
utilization and provides guidance and reference for molecular coupling reactions. processes with organic reactions has
been adopted to broaden the application
of C─N bond coupling, which can be dated
back to the year of 1963. Rapson and Bird
1. Introduction demonstrated the electrosynthesis of glycine from the electrore-
duction of oxalic acid and nitric acid in the same cell.[6] The inter-
The industrial synthesis of chemicals usually operates under action between the electrochemically generated glyoxylic acid and
harsh conditions with high energy consumption, aggravating hydroxylamine realizes the C–N coupling and desirable yield of
energy crisis and environmental concerns.[1] Driven by renew- glycine. By expanding the substrates, Fukushima and Yamauchi
able electricity, the electrocatalysis can reduce the energy barrier achieved the efficient synthesis of a series of amino acids via con-
of the reaction to achieve the efficient and green synthesis of ducting the electrolysis of α-keto acids with ammonia/hydroxyl-
chemicals under milder conditions.[2] The realization of the amine.[7] As an important building block for valuable chemicals,
resource utilization of abundant gaseous molecules through elec- methylamine is always produced from high temperature and
trocatalytic activation and fixation is the focus of electrocatalysis pressure reaction of methanol and ammonia. Very recently,
research nowadays.[3] Among them, the electrocatalytic conver- Wang et al. achieved the direct electrosynthesis of methylamine
sion of carbon dioxide can achieve the electrosynthesis of liquid from coelectrolysis of carbon dioxide and nitrate via the conden-
fuels with high energy density, which not only alleviates the sation of hydroxylamine from nitrate reduction and formalde-
energy shortage, but also contributes to progress toward the hyde from carbon dioxide reduction,[8] as shown in Figure 1.
carbon-neutral goal.[3b] As the key intermediate for electrocata- It is a feasible and effective strategy to realize the C─N bond
lytic carbon dioxide reduction, the direct electrolysis of carbon formation and amines generation by coelectrolysis of carbon-
monoxide could be an efficient alternative approach to achieve containing and nitrogen-containing feedstocks.[5–8] As one of
the synthesis of multicarbon products with promoted carbon– the important amines in the fields of agriculture and industry,
carbon coupling.[4] However, the electrolysis of carbon dioxide the conventional synthesis of urea includes two consecutive pro-
cesses.[9] Nitrogen reacts with hydrogen to form ammonia and
ammonia reacts with carbon dioxide to form urea, both operating
C. Chen, N. He, S. Wang
at high temperature and high pressure (scenario A in Figure 2).
State Key Laboratory of Chem/Bio-Sensing and Chemometrics
College of Chemistry and Chemical Engineering The ammonia synthesis through Haber–Bosch method con-
Hunan University sumes about 2% of the global energy annually; in addition,
Changsha, P. R. China the feedstock of hydrogen is obtained from reforming of the fos-
E-mail: chenc@hnu.edu.cn; shuangyinwang@hnu.edu.cn sil fuels, belching out hundreds of millions of tons of carbon
The ORCID identification number(s) for the author(s) of this article dioxide annually.[1] The pursuit for the ammonia synthesis under
can be found under https://doi.org/10.1002/smsc.202100070. milder conditions did not stop over the past century.[10] The elec-
© 2021 The Authors. Small Science published by Wiley-VCH GmbH. This trocatalytic process was demonstrated as the promising alterna-
is an open access article under the terms of the Creative Commons tive for its renewable driven force and the protons can be gained
Attribution License, which permits use, distribution and reproduction from water splitting rather than gaseous hydrogen.[2,3] However,
in any medium, provided the original work is properly cited. the electrocatalytic ammonia synthesis is still in its initial stage
DOI: 10.1002/smsc.202100070 with low yield due to high chemical inertness of nitrogen.[2] Urea
Small Sci. 2021, 1, 2100070 2100070 (1 of 9) © 2021 The Authors. Small Science published by Wiley-VCH GmbH
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Figure 1. The progress of C–N coupling reactions for electrocatalytic amine synthesis.
Figure 2. Pathways to urea synthesis. Haber–Bosch method combined with industrial urea synthesis (scenario A) and direct electrocatalytic C–N coupling
process (scenario B).
is the main downstream product of ammonia, the separation and strategies for more efficient urea synthesis have to be explored.
purification of ammonia from aqueous media for subsequent Xiang et al. achieved urea synthesis at atmospheric pressure by
urea synthesis face tremendous challenges as well. the plasma-assisted method.[13] The production of urea arises
Therefore, the exploration of the electrocatalytic process for from the reaction between electronegative ammonia anions
the direct synthesis of urea is needed. In this review, we sum- and carbon dioxide, and the solid product of urea could be
marize the progress of green urea synthesis, focusing on the elec- obtained in the reactor, as shown in Figure 3a. However, the
trocatalytic coupling of carbon source (carbon dioxide) and plasma-assisted synthesis of urea is difficult to overcome the
nitrogen source (nitrogen, nitrite, nitrate) for direct urea synthe- problem of energy consumption for driving the plasma genera-
sis under ambient conditions (scenario B in Figure 2). The mech- tor,[2] and the green manufacture of ammonia has not yet been
anism researches for urea synthesis are also reviewed, and the realized.
future development directions of electrocatalytic urea synthesis The “one-step” conversion of carbon dioxide and nitrogen by
are prospected. skipping the ammonia synthetic process might be a promising
alternative to achieve efficient urea synthesis. Alqasem et al.
demonstrated the electromagnetic field-induced one-step urea
2. Coupling of Carbon Dioxide and Nitrogen for synthesis at ambient conditions but it still suffers from the draw-
Urea Synthesis back of using hydrogen as the feedstock.[14] Utilizing aqueous
solution instead of hydrogen as the proton source would exploit
The gaseous nitrogen is the abundant source of nitrogen, which the advantages of green urea synthesis and it was realized in a pres-
makes up 78% of the atmosphere. Due to high inertness of nitro- surized apparatus, as shown in Figure 3c.[15] In the mixed atmo-
gen, the utilization of nitrogen is dominated by the Haber–Bosch sphere of carbon dioxide (30 bar) and nitrogen (30 bar), the urea
method to synthesize ammonia at high temperature and high formation rate reaches the highest value of 31.8 μg h1 cm2 over
pressure (400–500 C, 200–300 bar).[11] As the main downstream the polypyrrole catalyst at 0.325 V (vs. normal hydrogen electrode
product of ammonia, urea is formed by the reaction of ammonia (NHE)). Shifting the high-pressure working condition to an ambi-
and carbon dioxide along with C─N bond formation, which is ent one would minimize the requirements for synthesis equip-
also conducted at harsh conditions (150–200 C, 150– ment as much as possible. Thus, the green synthesis method
250 bar).[12] Considering the high equipment requirements of carbon dioxide and nitrogen coupling to produce urea under
and complex synthetic processes of the industrial method, ambient temperature and atmospheric pressure arises at the right
Figure 3. Strategies toward efficient urea synthesis. a) Plasma-assisted urea synthesis from carbon dioxide and ammonia under atmospheric pressure.
Reproduced with permission.[13] Copyright 2012, Springer Nature. b) Electromagnetic field-induced urea production from carbon dioxide, nitrogen, and
hydrogen at ambient conditions. Reproduced with permission.[14] Copyright 2020, Elsevier Ltd. c) Electrocatalytic synthesis of urea from carbon dioxide
and nitrogen in a pressurized reactor. Reproduced with permission.[15] Copyright 2016, Elsevier Ltd. d) Electrocatalytic coupling of carbon dioxide and
nitrogen to synthesize urea under ambient conditions. Reproduced with permission.[12] Copyright 2020, Springer Nature.
moment. Chen et al. demonstrated electrocatalytic urea synthesis redistribution and enhanced molecular adsorption capacity in
on a Pd1Cu1/TiO2-400 catalyst with a urea formation rate of heterostructure, Yuan et al. also demonstrated the perovskite
0.12 mmol g1 h1 and corresponding Faradic efficiency of BiFeO3/BiVO4 hybrids as another efficient electrocatalyst for
0.66% at 0.4 V (vs. reversible hydrogen electrode (RHE)).[12] urea electrochemical synthesis under ambient conditions.[19]
To enhance the electrocatalytic synthesis rate of urea, the Electrocatalytic urea synthesis is a gas consumption reaction
design of electrocatalyst and the optimization of catalytic system and the yield rate of urea is limited by the low solubility of gas,
are needed. Metal alloying can promote the electronic interac- especially nitrogen.[20] Meanwhile, the surface of electrode is dom-
tions between components and provide more active sites for elec- inantly covered by water molecules, which is beneficial for the
trocatalytic reaction,[16] and the electronic interactions would be competitive hydrogen evolution reaction.[21] In addition to the
further enhanced by loading the metal alloy on the defect-rich rational design of the electrocatalyst, the optimization of the cata-
support,[12,17] as confirmed by the shifting of binding energy lytic system is equally important. Figure 5a shows the typical H cell
in Figure 4b,c. The authors demonstrated that the coadsorption with continuous gas bubbling during the electrochemical meas-
of nitrogen and carbon dioxide can be realized on the catalyst, urements. The gaseous feedstocks need to dissolve in the aqueous
which is the prerequisite for urea formation.[12] The strategy solution and then diffuse to the electrode surface for participation
of catalyst design for urea synthesis should focus on the coad- in the reaction,[21] as shown in Figure 5b. The electrochemical flow
sorption and activation of gaseous molecules simultaneously. cell with gas-diffusion layer could construct an efficient three-
Yuan et al. provided a strategy for coactivation and urea synthesis phase reaction interface, allowing the gas and liquid from different
by heterostructure constructing,[18] as shown in Figure 4e. The channels to encounter the solid catalysts for reaction. Moreover,
electron-rich N atom in nitrogen and electron-deficient C atom the hydrophobic layer in Figure 5d blocks most of the water mol-
in carbon dioxide would preferentially adsorb on the electrophilic ecules, only permitting a small number of them to pass through as
and nucleophilic regions in Bi/BiVO4 hybrids, attributed to the a source of protons for urea synthesis.[12,21] Chen et al. tested the
electronic interactions between the reactive molecules and hybrid urea synthesis performance in an H cell and a flow cell, respec-
structure (Figure 4f,g). The urea yield rate of 5.91 mmol g1 h1 tively. The results in Figure 5e show that both the yield rate of urea
and Faradic efficiency of 12.55% are obtained over this catalyst at and the Faradic efficiency are obviously improved due to the abun-
0.4 V (vs. RHE). Due to the accelerated local charge dant gaseous feedstocks and better suppressed competitive
Figure 4. Design of electrocatalysts for coupling of nitrogen and carbon dioxide for urea synthesis. a) High-resolution TEM image of Pd1Cu1/TiO2-400
catalyst. b) Pd 3d XPS spectra of Pd/TiO2, Pd1Cu1/TiO2, and Pd1Cu1/TiO2-400. c) Cu 2p XPS spectra of Cu/TiO2, Pd1Cu1/TiO2, and Pd1Cu1/TiO2-400.
d) Competitive chemisorption of nitrogen and carbon dioxide on TiO2-400 and Pd1Cu1/TiO2-400. a–d) Reproduced with permission.[12] Copyright 2020,
Springer Nature. e) High-resolution TEM image of Bi/BiVO4 hybrid. f ) Electron density isosurface of carbon dioxide and nitrogen molecules. g) The
proposed reaction pathway of urea formation on Bi/BiVO4 hybrid. h) The urea yield rate and i) the corresponding product distribution at various potentials
for Bi/BiVO4 hybrid. e–i) Reproduced with permission.[18] Copyright 2021, Wiley-VCH.
reaction, affording another pathway regarding catalytic system feasibility of this reaction mechanism for urea synthesis on vari-
optimization for urea synthesis.[12] ous electrocatalysts.[18,19]
The electrocatalytic urea production from nitrogen and carbon Urea can be obtained by electrocatalytic coupling of nitrogen
dioxide coupling involves multistep electrochemical processes and carbon dioxide, and the electroxidation of urea usually pro-
and nonelectrochemical processes. Relevant studies are essential duces nitrogen and carbon dioxide as the main products. There is
to clarify the reaction path and mechanism, so as to provide guid- an internal relationship between urea synthesis and oxidation
ance for the design of electrocatalysts.[12,18] The electrochemical process. In terms of urea oxidation, Chen et al. proposed its reac-
urea synthesis at elevated pressure was achieved by Kayan and tion mechanism in Figure 6c based on isotope labeling experi-
collaborators.[15] They proposed that urea production arises from ments and theoretical results.[22] Oxidative dehydrogenation
the chemical reaction between carbon dioxide and ammonia occurs first in the amino groups of urea, followed by the intra-
from nitrogen reduction, and then the generated ammonium molecular coupling of N─N bond. It should be noted that the key
carbamate is converted to urea with one water molecule release. intermediate of *NCON* also forms before the fraction of C─N
However, the driven force and the inherent mechanism for the bond, thus resulting in the high proportion of nitrogen product.
generation of carbamate and urea have not been studied yet. The electrochemical behaviors of urea production and oxidation
Based on the results of theoretical calculations, Chen et al. dem- are tightly related to the particularity of urea molecules with spa-
onstrated that the adsorbed nitrogen molecules would facilitate tial relative positions of nitrogen atoms. According to the previ-
the carbon dioxide reduction process to form carbon monoxide ous results of mechanism studies, the adsorption configuration
and the migrated carbon monoxide species would react with side- of the nitrogen molecules, the reaction paths, and product types
on adsorbed nitrogen.[12] This reaction is exothermic and of carbon dioxide reduction and formation of the key intermedi-
thermodynamically feasible and induces the formation of the ate (*NCON*) play vital roles for the understanding of inherent
key intermediate of *NCON* (Figure 6a,b), serving as the pre- principles toward electrocatalytic urea synthesis from nitrogen
cursor for urea generation. The competition reaction of and carbon dioxide coupling.
*NNH formation is highly endothermic with an energy input
of þ0.90 eV, corresponding to the experimental results with
greatly suppressed release of the side product ammonia. By 3. Coupling of Carbon Dioxide and Nitrite/Nitrate
means of isotope labeling operando electrochemical measure- for Urea Synthesis
ments, the evolution of bond structures in intermediate species
has been tracked and the formation of key C─N bond has been The production and living activities of human beings have a great
confirmed experimentally. Yuan’s work also displayed the impact on the Earth environment, among which, a large number
Figure 5. The optimization of catalytic system for urea synthesis. a) The typical H cell for urea electrocatalytic synthesis. Reproduced with permission.[12]
Copyright 2020, Springer Nature. b) Schematic illustration of solid–liquid interface in H cell. Reproduced with permission.[21] Copyright 2020, American
Chemical Society. c) Electrochemical flow cell for urea synthesis. Reproduced with permission.[12] Copyright 2020, Springer Nature. d) Proposed solid–
liquid–gas interface in a flow cell with gas-diffusion electrodes. Reproduced with permission.[21] Copyright 2020, American Chemical Society.
e) Comparison of electrocatalytic performance in a H cell and a flow cell.
Figure 6. The proposed reaction mechanisms for electrocatalytic urea generation and degradation. a) The schematic diagram for electrocatalytic urea
transformation. b) The proposed mechanism for urea synthesis from nitrogen and carbon dioxide reduction. Reproduced with permission.[12] Copyright
2020, Springer Nature. c) The proposed mechanism for urea oxidation to nitrogen and carbon dioxide. Reproduced with permission.[22] Copyright 2021,
Wiley-VCH.
of nitrogen-containing substances are discharged into the sur- substances has been achieved, however, it cannot realize the
face water in the forms of nitrite and nitrate, threatening human transformation and upgrading of materials and the maximum
health.[23] The conventional approach involves catalytic conver- utilization of energy and waste resources. Subsequent researches
sion of nitrite and nitrate ions into nonpolluting nitrogen are focused on the electrocatalytic reduction of nitrite and nitrate
molecules.[24] Although the harmless treatment of harmful ions into ammonia, also meeting the problem for fabrication of
the downstream product as mentioned earlier.[25] Electrocatalytic electrochemical measurements on the gas-diffusion electrodes
coupling of carbon dioxide and nitrite/nitrate is an effective way with various catalysts were carried out and the maximum
to achieve the above purposes. The expansion of raw material to Faradic efficiency of urea formation on zinc catalysts is 35%
nitrate can not only realize the resource utilization of carbon at 1.75 V.[29] Authors also investigated the electrochemical behav-
dioxide, but also help to control water pollution, and finally real- ior of urea synthesis by carbon dioxide and nitrate-ion coupling
ize the efficient green synthesis of urea. over metallophthalocyanine catalysts.[30] The carbon monoxide for-
The electrochemical reduction of carbon dioxide and nitrite mation rate from carbon dioxide reduction at Ni–phthalocyanine
for urea synthesis was first reported by Shibata et al. using catalyst is significantly improved than that at metal catalyst.
Cu-loaded gas-diffusion electrode. With 1 bar carbon dioxide However, these catalysts have poor abilities to reduce nitrate ions
and 0.02 M nitrite ions as feedstocks, the Faradic efficiency of to nitrite ions and ammonium ions, hindering the electrochemical
37% has been achieved at the applied potential of 0.75 V (vs. urea synthesis. Thus, it was confirmed that simultaneous reduc-
standard hydrogen electrode (SHE)).[26] Then, the reactivity of urea tion of carbon dioxide and nitrate ions is necessary in this coupling
synthesis on zinc electrode was investigated, and the nitrite ion reaction.[30]
concentration, pressure of carbon dioxide, and the reaction tem- Recently, new progress has been made in the production of
perature for urea production have been optimized.[27] The authors urea by the coupling of carbon dioxide and nitrite ions. Feng
found that cadmium electrode, zirconium boride, and Ni–phtha- et al. demonstrated Te-doped Pd nanocrystals (NCs) for efficient
locyanine are beneficial for catalyzing urea synthesis from carbon electrochemical urea production.[31] The 3d3/2 and 3d5/2 peaks of
dioxide and nitrite ions coreduction, and the Faradic efficiency for Pd0 exhibit a small negative shift for Te–Pd NCs, suggesting the
this reaction can reach the highest values of 55%, 33%, and 40%, electron transfer from Te to Pd (Figure 7a). Due to the tailoring of
respectively.[28] With nitrate ions as the nitrogen source, the electronic structure, the carbon dioxide adsorption and the
Figure 7. Recent progress of electrocatalytic urea production by coupling carbon dioxide and nitrite ions. a) Pd 3d XPS spectra of Te–Pd NCs and Pd NCs.
Faradic efficiency versus the applied potentials for urea electrosynthesis on b) Te–Pd NCs and c) Pd NCs. a–c) Reproduced with permission.[31] Copyright
2020, American Chemical Society. d) Schematic illustration of synthesis of ZnO–V porous nanosheets. e) EPR spectra of ZnO and ZnO–V porous
nanosheets. Faradic efficiencies and urea yield rates under the given potentials over f ) ZnO and g) ZnO–V. d–g) Reproduced with permission.[32]
Copyright 2021, Elsevier Ltd. h) XRD results for undoped TiO2 and Cu–TiO2–Vo. i) Faradic efficiencies of the major reduction products for
Cu–TiO2–Vo catalyst. h,i) Reproduced with permission.[33] Copyright 2020, Elsevier Ltd.
Table 1. The performances of electrocatalytic coupling of carbon source and nitrogen source for urea synthesis.
Catalyst[ref.] Carbon source Nitrogen source Electrolyte Applied potential Urea yield rate Faradic
efficiency
Polypyrrole film[15] 30 bar CO2 30 bar N2 0.1 M Li2SO4 þ 0.03 M Hþ 0.325 V versus NHE 31.8 μg h1 cm2 6.9%
PdCu/TiO2-400[12] 1 bar CO2 1 bar N2 1 M KHCO3 0.4 V versus RHE 3.36 mmol h1 g1 8.92%
Bi/BiVO4[18] 1 bar CO2 1 bar N2 0.1 M KHCO3 0.4 V versus RHE 5.91 mmol h1 g1 12.55%
BiFeO3/BiVO4[19] 1 bar CO2 1 bar N2 0.1 M KHCO3 0.4 V versus RHE 4.94 mmol h1 g1 17.18%
Te–Pd NCs[31] 1 bar CO2 0.01 M NO2 0.1 M KHCO3 þ 0.01 M KNO2 1.1 V versus RHE 12.2%
ZnO–V[32] 1 bar CO2 0.1 M NO2 0.2 M NaHCO3 þ 0.1 M NaNO2 0.79 V versus RHE 5.52 mmol h1 cm2 23.26%
Cu–TiO2–Vo[33] 1 bar CO2 0.02 M NO2 0.2 M KHCO3 þ 0.02 M KNO2 0.4 V versus RHE 20.8 μmol h1 43.1%

Cu [26]
1 bar CO2 0.02 M NO2 0.2 M KHCO3 þ 0.02 M KNO2 0.75 V versus SHE 37%
Cd[28a] 1 bar CO2 0.02 M NO2 0.2 M KHCO3 þ 0.02 M KNO2 1.0 V versus SHE 55%
ZrB2[28b] 1 bar CO2 0.02 M NO2 0.2 KHCO3 þ 0.02 M KNO2 1.3 V vs SHE 33%

Ni–phthalocyanine [28c]
1 bar CO2 0.02 M NO2 0.2 M KHCO3 þ 0.02 M KNO2 1.5 V versus SHE 40%
Zn[29] 1 bar CO2 0.02 M NO3 0.2 M KHCO3 þ 0.02 M KNO3 1.75 V versus SHE 35%
ammonia production were promoted by Te doping, inducing electroreduction of pristine ZnO precursor,[32] as shown in
urea production with high efficiency. Figure 7d. The electron spin resonance (EPR) signal at g ¼ 1.95
The introduction of oxygen vacancy into the electrocatalyst is corresponding to oxygen vacancies is observed in ZnO
an efficient strategy to boost the electrochemical performance, (Figure 7e). Compared with the ZnO nanosheets counterpart,
resulting from the increase of active sites and the improved the electrocatalytic performances of urea synthesis on ZnO–V
adsorption of feedstock and the enhanced stabilization of nanosheets were obviously improved; among them, the
intermediate species.[12,32,33] Meng et al. successfully prepared Faradic efficiency of urea production can reach 23.26% at
the oxygen vacancy-rich ZnO porous nanosheets via the 0.79 V (vs. RHE). Heteroatom doping can also introduce
Figure 8. Reaction mechanism studies for electrocatalytic urea synthesis from carbon dioxide and nitrite ion coupling. a) Scheme of the urea synthesis on
Te–Pd NCs. Reproduced with permission.[31] Copyright 2020, American Chemical Society. b) In situ diffuse reflectance infrared Fourier transform spec-
troscopy spectra of ZnO–V under carbon dioxide, nitrite ions, and both. c) Schematic illustration of urea formation over ZnO–V. Reproduced with
permission.[32] Copyright 2021, Elsevier Ltd.
abundant oxygen vacancies into the oxide electrocatalyst. Cao site of coupling reaction, the intermediate interaction mecha-
et al. demonstrated that the low-valence Cu doped into TiO2 nism, and the driving force. 3) It is necessary to study and ana-
nanotubes could yield an oxygen vacancy-rich catalyst.[33] The lyze the reaction pathways of the subreactions (carbon dioxide
X-ray diffraction (XRD) peaks of Cu–TiO2–Vo gradually shift reduction, nitrogen reduction, and nitrite/nitrate reduction),
toward higher diffraction angles, suggesting the decrease in the product selectivity, and efficiency on the electrocatalytic per-
the TiO2 lattice constant, as shown in Figure 7h. The obviously formance of urea synthesis, so as to guide the rational design of
increasing ratio of Ti3þ/Ti4þ confirms the introduction of abun- urea electrocatalysts. Meanwhile, the performance of urea syn-
dant oxygen vacancies, inducing efficient nitrite adsorption and thesis should be improved from the perspective of catalytic sys-
activation on TiO2; meanwhile, the low-valence Cu dopants tem optimization, such as the application of ionic liquids as
served as effective catalytic sites to reduce carbon dioxide into electrolyte with high gas solubility and the design of the reactor.
active species. This oxygen vacancy-rich Cu–TiO2 electrocatalyst 4) The demonstrated approaches in this review have realized the
enables high urea production rate (20.8 μmol h1) and corre- electrocatalytic coupling of C─N bond for urea synthesis, and
sponding Faradic efficiency (43.1%) at a low potential of other carbon sources such as some organic matter can also be
0.4 V (vs. RHE). The performances of electrocatalytic coupling used in the C–N coupling reaction to expand the application
of carbon source (carbon dioxide) and nitrogen source (nitrogen, of electrocatalytic amine synthesis. It is necessary to regulate
nitrite, nitrate) for direct urea synthesis are shown in Table 1. and balance the adsorption behavior of carbon species and nitro-
The mechanism of electrochemical urea synthesis from cou- gen on the catalyst surface, and both the driving force for cou-
pling of carbon dioxide and nitrite/nitrate ions has been studied. pling and the identification of active sites are required to be
Most of the reports demonstrated that urea formation is derived investigated.
from the reaction between CO* and NH2* intermediate species
based on the comparative experimental results (Figure 8a).[31,34]
Replacing the feedstock from nitrite/nitrate to ammonia or car- Acknowledgements
bon dioxide to carbon monoxide would not yield urea products.
The authors acknowledge the financial support from the National Natural
Feng et al. proved the feasibility of this mechanism by theoretical Science Foundation of China (grant nos. 21825201 and U19A2017) and
calculations.[31] However, according to Meng’s report, the urea the Natural Science Foundation of Hunan Province (grant no.
formation pathway of COOH* and NH2* coupling has been pro- 2020JJ5039).
posed by means of online differential electrochemical mass spec-
trometry and in situ diffuse reflectance infrared Fourier
transform spectroscopy (Figure 8b,c).[32] The mechanism of urea Conflict of Interest
synthesis is still controversial, and further research is needed to
clarify the reaction pathways. The authors declare no conflict of interest.
4. Conclusion and Outlook Keywords

The electrocatalytic coupling of C─N bond for urea synthesis is C─N bonds, coupling reactions, electrocatalysis, molecule fixations, urea
an energy-saving and environment-friendly alternative for the syntheses
industrial urea synthetic process. With rational design of
Received: June 14, 2021
the electrocatalysts and optimization of the catalytic system, Revised: July 27, 2021
the effective utilization of resources and the expansion applica- Published online: October 15, 2021
tion range of electrocatalysis have been realized. However, the
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Chen Chen received his Ph.D. in 2020 from the Department of Chemistry and Chemical Engineering,
Hunan University. He is currently a postdoctoral fellow cooperating with Professor Shuangyin Wang in
Hunan University. His current interests include the catalytic fixation and conversion of small molecules
and electrocatalytic urea synthesis.
Shuangyin Wang received his B.S. degree in 2006 from Zhejiang University and his Ph.D. in 2010 from
Nanyang Technological University, Singapore. He is currently a professor of the Key Laboratory for
Graphene Materials and Devices and College of Chemistry and Chemical Engineering, Hunan University.
His research interests are in plasma technology, defects in various crystals, and their application for
electrochemical energy storage and conversion.

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26884046, 2021, 11, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/smsc.202100070 by EBMG ACCESS - ETHIOPIA, Wiley Online Library on [04/01/2023].

Electrocatalytic C–N Coupling for Urea Synthesis

or carbon monoxide only yields products

4. Conclusion and Outlook Keywords

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