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How to cite: Angew. Chem. Int. Ed. 2024, 63, e202407038

Urea Oxidation Hot Paper doi.org/10.1002/anie.202407038

Regulating Reconstruction-Engineered Active Sites for Accelerated

Electrocatalytic Conversion of Urea
Jichao Zhang+, Jianrui Feng+, Jiexin Zhu+, Liqun Kang, Longxiang Liu, Fei Guo, Jing Li,
Kaiqi Li, Jie Chen, Wei Zong, Mingqiang Liu, Ruwei Chen, Ivan P. Parkin,* Liqiang Mai,*
and Guanjie He*

Abstract: Reconstruction-engineered electrocatalysts with enriched high active Ni species for urea oxidation reaction
(UOR) have recently become promising candidates for energy conversion. However, to inhibit the over-oxidation of
urea brought by the high valence state of Ni, tremendous efforts are devoted to obtaining low-value products of nitrogen
gas to avoid toxic nitrite formation, undesirably causing inefficient utilization of the nitrogen cycle. Herein, we proposed
a mediation engineering strategy to significantly boost high-value nitrite formation to help close a loop for the
employment of a nitrogen economy. Specifically, platinum-loaded nickel phosphides (Pt-Ni2P) catalysts exhibit a
promising nitrite production rate (0.82 mol kWh 1 cm 2), high stability over 66 h of Zn-urea-air battery operation, and
135 h of co-production of nitrite and hydrogen under 200 mA cm 2 in a zero-gap membrane electrode assembly (MEA)
system. The in situ spectroscopic characterizations and computational calculations demonstrated that the urea oxidation
kinetics is facilitated by enriched dynamic Ni3 + active sites, thus augmenting the “cyanate” UOR pathway. The C N
cleavage was further verified as the rate-determining step for nitrite generation.

Introduction tween those two pathways and enriched NiOOH species at

high potentials could lead to the dominating role of the
The electrochemical oxidation of small molecules (meth- “cyanate” pathway with toxic nitrite formation.[7] Accord-
anol, ethanol, hydrazine, and urea, etc.), with significantly ingly, complicated and high-cost strategies were imple-
lower thermodynamic potential, exhibits promising routes to mented to improve the selectivity of innocuous nitrogen gas
replace the oxygen evolution reaction (OER) in various (N2) to avoid over-oxidation, pointlessly generating a lot of
energy conversion applications.[1–3] Among those small low economic value of N2.[6,8]
molecule reactants, urea (non-toxicity and non-flammabil- Despite the concern of toxicity for nitrite, it plays a vital
ity), can be easily accessed from domestic wastewater (e.g. role in industrial areas, such as pharmaceuticals, agriculture,
human urine). Nickel-based catalysts have been extensively and food processing.[9,10] Moreover, the bottleneck of NOx
reported due to the highly active dynamic Ni3 + active sites electro-reduction is still limited by the low natural feedstock
for UOR.[4,5] However, the mechanism of the UOR remains for large-scale electrosynthesis of NH3 with high
debated. Two main pathways, involving the “carbonate” concentration.[11] Provided that we produce the high-value
pathway (CO(NH2)2 + 8OH !CO32 + N2 + 6H2O + 6e ) nitrite directly from adequate urea-bearing wastewater (e.g.
and “cyanate” pathway (CO(NH2)2 + 8OH !NCO + NO2 mammalian urine) to offer an oxidized form of N, a closed
+ 6H2O + 6e ), have been extensively investigated.[6] Viktor- loop of environmentally-friendly nitrogen supply chains
iia et al. proposed a potential-dependent relationship be- would be constructed, realizing a sustainable nitrogen

[*] J. Zhang,+ J. Feng,+ F. Guo, K. Li, J. Chen, W. Zong, M. Liu, R. Chen, L. Liu
I. P. Parkin, G. He Department of Materials, University of Oxford, Parks Road, Oxford
Christopher Ingold Laboratory, Department of Chemistry, University OX1 3PH
College London (UCL), 20 Gordon Street, London WC1H 0AJ, UK J. Li
E-mail: [email protected] Materials Research Institute, School of Engineering and Materials
[email protected] Science, Faculty of Science and Engineering, Queen Mary University
J. Zhu,+ L. Mai of London, Mile End Road, London E1 4NS, UK
State Key Laboratory of Advanced Technology for Materials Syn- [+] J. C. Z, J. R. F, and J. X. Z contributed equally to this work.
thesis and Processing, Wuhan University of Technology, Wuhan
© 2024 The Authors. Angewandte Chemie International Edition
Hubei 430070, China
published by Wiley-VCH GmbH. This is an open access article under
E-mail: [email protected]
the terms of the Creative Commons Attribution License, which
L. Kang permits use, distribution and reproduction in any medium, provided
Department of Inorganic Spectroscopy, Max-Planck-Institute for the original work is properly cited.
Chemical Energy Conversion, Stiftstr. 34–36, 45470 Mülheim an der
Ruhr, Germany

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economy, and simultaneously reducing the risk to the disclosed that the notable enriched Ni3 + active species would
ecological environment. accelerate urea conversion mainly according to the
As revealed by numerous studies, over 50 % conversion “cyanate” pathway for high-value nitrite formation (Fig-
from urea to nitrite (NO2 ) could be achieved by nickel ure 1b). More CNO species were detected, demonstrating
oxide/hydroxide, particularly at high potentials.[12] However, rapid C N bond cleavage during the UOR process. Besides,
the strong dependence on the applied potential to generate Incorporating Pt sites could significantly lower the energy
abundant high-active NiOOH species is not desirable for barrier for C N bond cleavage, which was found as the rate-
energy-saving vision. As compared to widely-used nickel determining step to generate high-value nitrite products.
oxide/hydroxide catalysts, nickel phosphides, sulfides, and This facile and feasible mediation strategy opens a unique
nitrides exhibit good metallic electrical conductivity to avenue to fix issues during UOR and is anticipated to be
facilitate electron transfer.[13–15] Notably, the stronger nucle- extended to other energy conversion scenarios.
ophilicity of the in situ formed phosphate species (HPO4
pKa = 12.7, HSO4 pKa = 1.99, HNO3 pKa = 1.3) during the
surface reconstruction makes it possible to facilitate the Results
adsorption and dehydrogenation of urea molecules.[16] None-
theless, the surface reconstruction of nickel phosphides to in Catalyst Synthesis and Electrochemical Performance Analysis
situ generate more NiOOH species has been hindered by
the electro-repulsion between phosphate and hydroxide The Pt was first incorporated on nickel phosphide catalysts
anion, which has been recently ascertained by Qiao’s based on nickel foams via solution reduction synthesis. A
group.[13] Furthermore, as revealed by our previous single phase of Ni2P (PDF No. 89-4864) was revealed by the
studies,[17,18] due to the insufficient Ni3 + active sites, the X-ray diffraction (XRD) patterns (Supplementary Fig-
competition issue between UOR and OER is another ure S1a). The high-resolution transmission electron micro-
enormous challenge to overcome (Figure 1a).[17,19,20] scopy (HRTEM) image presents Pt nanoparticles with (111)
Metal mediation engineering strategies have been con- lattice, indicating successful construction of Pt sites on Ni2P
sidered an effective route to modulate the proton-coupled- catalysts (Supplementary Figure S1b). The corresponding
electron-transfer (PCET) process.[21] Despite the enormous energy dispersive spectroscopy (EDS) line scanning and
efforts to develop the non-noble metal mediation method, mapping images further indicate the uniform distribution of
Platinum (Pt) still possesses a higher activity and ultra-stable Pt on the Ni2P catalyst. The different feed amounts of Pt
durability in numerous energy conversion systems.[22] Pt with precursors were also investigated by microwave plasma
partially filled 5d orbitals creates the possibility of interact- atomic emission spectrometers (MP-AES), with the loading
ing with various molecules, enabling fast electron transfer mass of 20, 80, and 131 μg cm 2 when utilizing 20, 50, and
around the reaction microenvironments.[23] Motivated by the 150 μL Pt precursors (Sary Figure 2a). According to the
tuning ability of adsorption/desorption for reactants and results of XRD patterns and scanning electron microscope
intermediates from Pt sites, we herein proposed a Pt- (SEM) images, the Pt was incorporated into Ni2P catalysts
mediated strategy to facilitate the OH adsorption and with a notable change in the roughness of morphologies
optimize the electron distribution around Pt Ni sites, thus (Supplementary Figure S2b and S3), offering a strong
generating abundant dynamic Ni3 + active sites during sur- possibility of optimizing the interaction between reactants/
face reconstruction of nickel phosphides. Combined with in intermediates with electrode surface.
situ spectroscopic investigation and DFT calculations, it is

Figure 1. Schematic illustration of current issues and our solutions. a Issues correlated to the competition and low-value products due to
insufficient active sites for reconstruction-engineered catalysts. b The highlight of Pt-Ni2P catalysts.

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Figure 2. 2 Electrochemical performance. a Polarization curves of Ni2P and Pt-Ni2P catalysts. b–c In situ EIS for OER at different potentials. d
Polarization curves of Pt/C and Pt-Ni2P catalysts. e Intermittent UOR test. f RRDE system (1600 rpm) for oxygen reduction detection with the
applied potential bias of 0.2 V vs RHE on the ring electrode. g Stability test at 100 mA cm 2 over 90 hours (adding fresh electrolyte every 30 hours).

The electrochemical UOR performance was subse- Bode plot can be observed at high frequency, corresponding
quently evaluated in a three-electrode system. The Pt-Ni2P to the surface oxidation to form Ni3 + species (Supplemen-
catalysts required only 1.38 V vs. RHE to reach the current tary Figure S5).[24–26] It is notable that the phase angle
density of 100 mA cm 2 (Figure 2a) and yield a remarkably remarkably decreases when the potential reaches 1.37 V vs.
smaller Tafel slope (28.3 mV dec 1), implying accelerated RHE and disappears after 1.42 V vs. RHE, signifying the
UOR kinetics and outperform most recently reported rapid formation of Ni3 + species on the surface. To probe the
electrocatalysts (Supplementary Figure S4a and Table S1). role of Pt sites in the generation of Ni3 + species, the
The potential was negatively shifted by 203 mV as compared Faradaic charge transfer for Ni2 + to Ni3 + was calculated
to the OER under the current density of 100 mA cm 2 (Supplementary Figure S6a and b). Introducing Pt sites
(Supplementary Figure S4b). The feed amounts of the Pt remarkably boosted the Ni3 + active species formation with a
precursor (50 μL) were confirmed as the optimized ratio higher Faradaic charge of 854 mC. Additionally, the reduc-
with good commercial feasibility (Supplementary Fig- tion peak of cyclic voltammetry (CV) curves during UOR
ure S4c). features an enhanced and negative trend than Ni2P catalysts.
The in situ electrochemical impedance spectroscopy This reduction peak correlated to Ni3 + to Ni2 + elucidated a
(EIS) investigation was thereafter performed to unearth the higher concentration of Ni3 + species when incorporating Pt
potential-dependent interfacial charge transfer in different sites (Supplementary Figure S6c). The electrochemical dou-
phases. To obviate the effect of urea dehydrogenation on ble-layer capacitance (Cdl) can reflect the electrochemically
the Ni3 + species formation, in situ EIS studies were active surface area (ECSA). The Cdl of Pt Ni2P is
conducted in 1 M KOH (Figure 2b and c). The peak in the

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11.5 mF cm 2, higher than Ni2P (Supplementary Figure S6 d– spectra, two peaks situated at 474 and 553 cm 1, correspond-
f), substantiating increased ECSA via introducing Pt sites. ing to Ni3 + O in NiOOH species (Figure 3a),[30] emerged at
The Pt/C catalyst was further utilized as the control 1.42 V vs. RHE, which is notably lower than that of pure
sample to verify the activity of Pt during UOR (Figure 2d). Ni2P catalysts (1.57 V vs. RHE) (Supplementary Fig-
It was discovered that the onset potential of the Pt/C catalyst ure S10). When the applied potential came back to OCP,
was around 1.6 V vs. RHE, corroborating an undesirable the peaks of Ni3 + O could not be discernible. As for OER
activity for urea conversion with only Pt sites. To further process, the paired peaks of Ni3 + O occurred after 1.37 V
comprehend the electrochemical process of the UOR, the vs. RHE and could be maintained at OCP (Supplementary
intermittent UOR test was carried out by separating the Figure S11a). Impressively, as revealed by Raman spectra,
process of the urea dehydrogenation and proton deintercala- the Ni oxyhydroxides species accumulated during OER at
tion from the catalyst (Figure 2e). An oxidation current 1.47 V vs. RHE over 600 s would be rapidly reduced when
related to forming NiOOH species was first observed in 1 M adding urea into the electrolyte at OCP (Supplementary
KOH at 1.47 V vs. RHE and lasted for 2 mins. The 0.33 M Figure S11b), which is in line with the results of intermittent
urea was then injected at the open circuit potential (OCP) UOR test (Figure 2e).
and lasted for 1 min. Intriguingly, no reduction current was To capture the intermediates and disclose the reaction
observed at a cathodic applied potential of 1.2 V vs. RHE. pathway, in situ attenuated total reflection surface-enhanced
Contrastingly, a significant reduction occurred without add- IR absorption spectroscopy (ATR-SEIRAS) studies were
ing urea. According to the above results, it can be speculated performed during UOR. The peaks related to the adsorption
that the electro-generation of oxyhydroxide species would vibration of the OH species at 3730, 3700, 3630, and
proceed during surface reconstruction and accept protons 3600 cm 1 showcase notable adsorption of OH species to
from urea to be reduced to hydroxide spontaneously, and facilitate the surface reconstruction when loading Pt sites on
thus without reduction current being detected. Ni2P (Figure 3b and Supplementary Figure S12).[31] The
The OER competing effect is another enormous chal- peak centered at 2168 cm 1, corresponding to the CNO
lenge to obviate during UOR. The rotating ring-disk species in the solution could be found and was much more
electrode (RRDE) system with the elimination of the mass pronounced as the potential increases.[32] As compared to
transfer could be an effective method to measure the O2 pure Ni2P catalysts, the enhanced C N bond cleavage in
generation for evaluation of the selectivity. It was perceived urea demonstrated rapid urea conversion with Pt mediation.
that negligible oxygen reduction current could be observed The above findings in terms of surface chemistry, morphol-
before 1.65 V vs. RHE for both Pt-Ni2P and Ni2P catalysts. ogies, and spectroscopic observations, validate that introduc-
Impressively, the intensified OER competition on Ni2P ing Pt sites can remarkably enhance the OH species
would be detected at 1.67 V vs. RHE. There is a ~100 mV adsorption to form active Ni3 + species during surface
positive shift for Pt-Ni2P catalysts to be affected by the OER reconstruction, thus improving the UOR kinetics.
competition, demonstrating a relatively promising selectivity Density functional theory (DFT) calculation was then
as compared to pure Ni2P catalysts. Moreover, over 90 hours carried out to certify the consistency with the experimental
of chronopotentiometry test was operated at a constant observations. It showed that more negative adsorption
current density of 100 mA cm 2, verifying good stability for energy of OH species on Pt-Ni2P surface than that of pure
practical applications under industrial currents (Figure 2g). Ni2P (Supplementary Figure S13), including adsorption con-
To decipher the effect of Pt mediation on Ni2P catalysts figuration of Ni OH (-0.99 eV) and P OH (-0.93 eV). The
and establish the structure-performance relationship, mech- charge density distribution plots of (001) surface demon-
anism studies were accordingly performed. The XRD strated an intensification of nonuniform charge distributions
patterns after the stability test over 90 h exhibit negligible with Pt mediation (Figure 3c and d). The charge gradient
variation with only one single phase of Ni2P (Supplementary formation would significantly affect the d-band center (Ed).
Figure S7). Significant P leaching was revealed by XPS The density of states (DOS) of Pt Ni2P and Ni2P were
spectra before and after UOR, signifying surface reconstruc- subsequently calculated. It was evidenced that both Pt Ni2P
tion proceeding during UOR (Supplementary Figure S8a). and Ni2P exhibit metallic character with zero band gaps,
The peaks from XPS spectra of Pt 4f located at 71.3 and indicating an easy electron transfer for the electrochemical
74.5 eV correspond to metallic Pt,[27,28] elucidating the stable process. The DOS near the Fermi level (Ef) mainly
existence of Pt sites during long-term stability test (Supple- originates from Ni 3d states. With Pt mediation, the
mentary Figure S8b). The morphology changes were then enhancement of d-states near the Ef would result in Ni site
unearthed by SEM and HRTEM (Supplementary Fig- upshifts from 1.74 eV to 1.64 eV (Supplementary Fig-
ure S9). Nanosheet-like structures were observed on the ure S14b). It is well-known that the Ed model is a good
edge of the catalysts, which might be the formation of Ni descriptor for adsorbate-metal interaction.[33] Introducing Pt
(oxy)hydroxide species as revealed by previous studies.[29] sites on Ni2P can strengthen the interaction with the OH
Specifically, the amorphous layer was discovered, close to species, thus boosting the generation of active Ni3 + species
the Ni2P phase, affirming the electro-generation of amor- during surface reconstruction.
phous Ni (oxy)hydroxides on the edge of Ni2P catalysts Based on the above experimental studies and theoretical
during surface reconstruction. calculations, it could be deduced that the surface reconstruc-
The surface reconstruction was further dissected by in tion process of Ni2P is fast and self-terminates to form stable
situ spectroscopic investigation. As revealed by Raman high valence Ni active sites. The reconstituted Ni oxy-

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Figure 3. Mechanism investigation during UOR. a. Raman spectra at different applied potentials during UOR. b ATR-SEIRAS results at different
applied potentials during UOR. c–d Charge density distribution plots of (001) surface for Ni2P and Pt-Ni2P catalysts. e Charge density difference of
Pt-NiOOH (The blue/yellow region represents the electron accumulation and depletion). f Schematic illustrations of the reaction process for Ni2P
and Pt-Ni2P catalysts. g Faradaic efficiency of NO2 . h. Free energy of the reaction pathway during UOR.

hydroxide surface layer is the real active species during 74 � 1 % (Figure 3g). The FE of N2 and O2 was also obtained
UOR. Thereafter, the NiOOH (001) model was utilized to (Supplementary Figure S15). The FE of N2 and O2 are less
investigate the electrochemical conversion of urea. Differ- than 50 %, demonstrating the main products of nitrite. The
ential charge density exhibited an electron depletion region FENO2 at different times, including 0.5, 2.4, 10.0, and 23.0 h,
around the Pt sites. The ‘electron-donating’ groups ( NH2) respectively, were evaluated. With the increase in operating
in urea would be preferentially adsorbed on the positive time, the FENO2 exhibits a relatively stable selectivity
region to accelerate the urea splitting process (Figure 3e). (Supplementary Figure S16). The free energy of the reaction
As evidenced by in situ spectroscopic observations pathway during UOR was subsequently calculated (Fig-
(Figure 3b), a stronger vibration peak of CNO species ure 3h and Supplementary Figure S17). It was found that the
would signify that the C N bond can be more readily rate-determining step was the C N cleavage to form the
cleaved on Pt-NiOOH (Figure 3f). It was suggested by intermediates of *NH2 and CNO species and relatively
previous studies that the “cyanate” pathway with over 50 % lower free energy of 0.64 eV than that of NiOOH (1.48 eV)
selectivity of NO2 was probably contributed by enriched was found after incorporating Pt sites. This result strongly
NiOOH sites.[8] To verify the formation of NO2 during validates that the Pt sites could remarkably reduce the
UOR, the electrolyte was collected and quantitatively energy barrier to promote the the C N cleavage during urea
determined by a Griess test.[34] The Faradaic efficiencies conversion.
(FE) of NO2 for both Ni2P and Pt Ni2P catalysts were all Although some studies have been working on obviating
above 50 % and gradually enhanced as the applied potential the over-oxidation of N-products, complicated strategies
increased. With Pt mediation, the highest FENO2 could reach with high costs are implemented to generate low-economic

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N2. In terms of the high value of nitrite in the areas of Another proof of concept for substituting OER with
pharmaceuticals, agriculture, and food processing industries, UOR in energy conversion systems is the zinc (Zn)-air
direct utilization of urea-bearing wastewater to synthesize battery. The cycling measurements over 66 hours were
nitrite chemicals would be of great importance for the carried out with and without adding urea, labeled as Zn-air
sustainable nitrogen economy, specifically when coupled battery and Zn-urea-air battery. The charging process
with an anodic reaction like hydrogen production, NOx involving OER would proceed with UOR instead. The
electro-reduction, etc (Figure 4a). charging curves of the Zn-air battery and Zn-urea-air
To achieve this promising vision, the hydrogen evolution battery demonstrated a remarkable reduction of the charg-
reaction (HER) performance of as-prepared Pt Ni2P cata- ing voltage after adding urea to the electrolyte (Supplemen-
lysts was evaluated, which exhibits superior activities than tary Figure S20). The cycling stability test during 66 h
commercial Pt/C catalysts and high stability at 100 mA cm 2 further exhibits about ~162 mV decrease in the charging
over 100 h (Supplementary Figure S18). As for the two- voltage than that of the Zn-air battery (Figure 4d).
electrode system, the Pt Ni2P catalyst also shows outstand- To realize urea-assisted hydrogen production for large-
ing activities compared to pure Ni2P and has potential to scale applications by direct usage of urea-bearing waste-
replace OER in practical scenarios (Supplementary Fig- water, the membrane electrode assembly (MEA) test was
ure S19). During 12 hours chronopotentiometry tests at conducted (Figure 4e). Impressively, as-prepared Pt Ni2P
100 mA cm 2, the cell voltage was stable without conspic- catalysts possessed superior activity (Supplementary Fig-
uous increases. Moreover, the nitrite production rate could ure S21) and stability at industrial-level current densities of
reach 0.82 mol kWh 1 cm 2 after introducing Pt sites (Fig- 200 mA cm 2 during chronopotentiometry measurement
ure 4c). over 135 h. No conspicuous voltage depletion could be

Figure 4. Applicability verification. a Schematic illustrations of nitrite direct production from urea-bearing wastewater. b stability test during
12 hours for nitrite production. c. Yield rate of nitrite. d Electrochemical measurement for Zn-air battery and Zn-urea-air battery (current density of
5 mA cm 2); e Urea-assisted hydrogen production at current density of 200 mA cm 2 during MEA tests.

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observed, implying the possibility for extensive practical Data Availability Statement
applications.
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
Conclusion
Keywords: Mediation engineering strategy · Urea oxidation
In conclusion, the high activity, selectivity, and stability of reaction · Dynamic active sites · High-value products
nitrite production are achieved on Pt-mediated Ni2P cata-
lysts. By incorporating the low loading mass of Pt
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