pubs.acs.org/JACS Article
Phosphorus-Doped Cu/Fe2O3 Electrocatalysts with Optimized
Synergy between the Different Sites for Efficient Urea
Electrosynthesis
Ting Deng, Shuaiqiang Jia,* Cheng Xue, Hailian Cheng, Jiapeng Jiao, Xiao Chen, Zhanghui Xia,
Mengke Dong, Chunjun Chen, Haihong Wu,* Mingyuan He, and Buxing Han*
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ABSTRACT: Urea electrosynthesis from the coelectrolysis of CO2 and NO3−
(UECN) has emerged as a promising sustainable alternative to traditional energy-
intensive methods; however, the rational design of advanced electrocatalysts capable
of achieving concurrent optimization of Faradaic efficiency (FE) and urea yield rates
continues to pose a fundamental challenge in this field. Herein, we developed a
phosphorus-doped Cu/Fe2O3 electrocatalyst (denoted as P−Cu/Fe2O3), where
phosphorus atoms partially substitute for oxygen atoms within the Cu/Fe2O3
heterostructure. This engineered electrocatalyst achieves exceptional urea electro-
synthesis performance, delivering a very high Faradaic efficiency of 73.81% with a
corresponding yield rate of 62.74 mmol h−1 g−1cat. at −0.68 V vs RHE, which are
superior to most UECN electrocatalysts reported to date. Notably, the urea yield rate
can be further boosted to 97.11 mmol h−1 g−1cat. at −0.88 V vs RHE. Operando
spectroscopic characterization and density functional theory (DFT) simulations indicated that P doping modulates the electronic
structure of the electrocatalyst surface, which promotes the formation of *CO and *NO, lowers the energy barrier for the coupling
of *CO and *NO, and increases *H coverage to facilitate the hydrogenation process during UECN. This multisite cooperative
mechanism establishes a new paradigm for designing high-performance electrocatalysts, demonstrating substantial potential for
industrial-scale urea production.
■ INTRODUCTION
Urea stands as the most extensively utilized nitrogen fertilizer
and promising method.6 However, designing electrocatalysts
with high Faradaic efficiency (FE) and high yield rates for urea
in agriculture, boasting the highest nitrogen content. Currently, electrosynthesis remains a considerable challenge.7
the primary industrial method for nitrogen fixation is the The UECN process is a redox reaction that requires the
Haber-Bosch process (HBP), which involves synthesizing NH3 involvement of multiple reactants and proceeds to the C−N
from N2 and H2 under exceedingly harsh conditions of high coupling step only when the kinetic activation of these
temperature (ranging from 400 to 550 °C) and high pressure reactants is appropriately matched. This process involves
(15−30 MPa).1−3 This process consumes an astonishing 2% of numerous complex Proton-Coupled Electron Transfer
the world’s annual energy, leading to both significant (PCET) steps.8 Recognizing this complexity, researchers
environmental pollution and a waste of resources.4 In light have committed to developing electrocatalysts featuring active
of the rapidly diminishing reserves of fossil fuels and the severe multisites to enhance urea electrosynthesis. For instance, Qin
environmental concerns due to substantial CO2 emissions, et al. reported a Cu-doped MoSe2 electrocatalyst, which boasts
there is an urgent need to develop a sustainable route for urea a Cu−Mo active dual-site that favors urea electrosynthesis by
electrosynthesis, which could significantly reduce greenhouse reducing the energy barrier of the rate-determining step.9
gas emissions and promote environmental sustainability. Urea Wang et al. discovered that Mo sites can facilitate nitrate
electrosynthesis has garnered significant attention due to its reduction to the *NH2 intermediate, while the Co sites can
straightforward operation and relatively mild conditions.
However, the high dissociation energy of nitrogen (N2, 941
kJ mol−1) and its low solubility (0.02 v/v, 1 atm, 25 °C) Received: June 10, 2025
present considerable challenges, severely limiting its applica- Revised: August 15, 2025
tion in electrocatalysis.5 In comparison, NO3−, with a relatively Accepted: August 18, 2025
low dissociation energy of 204 kJ mol−1, shows promise for Published: August 26, 2025
urea electrosynthesis. The urea electrosynthesis from coelec-
trolysis of CO2 and NO3− (UECN) has proven to be a viable
© 2025 American Chemical Society https://doi.org/10.1021/jacs.5c09805
32924 J. Am. Chem. Soc. 2025, 147, 32924−32931
Journal of the American Chemical Society pubs.acs.org/JACS Article
Figure 1. (a) TEM image and (b) HR-TEM image of P−Cu/Fe2O3. (c) EDS elemental mappings of P−Cu/Fe2O3, with Cu in red, Fe in green, O in blue, and P in yellow. (d) XRD patterns of P−Cu/Fe2O3 and Cu/Fe2O3. (e) P 2p XPS spectra of P−Cu/Fe2O3 and Cu/Fe2O3. (f) Cu K-edge EXAFS spectra and (g) Fe K-edge EXAFS spectra of P−Cu/Fe2O3, Cu/Fe2O3, and the references, respectively. (h) FT-EXAFS spectra of the Cu K-edge and i) FT-EXAFS spectra of the Fe K-edge of P−Cu/Fe2O3, Cu/Fe2O3, and the references, respectively.
enhance CO2 reduction to carbon monoxide (CO), thus contributes to the excellent electrocatalytic performance of synergistically promoting C−N coupling.10 However, despite urea electrosynthesis under ambient conditions. the emphasis placed by previous studies on the significance of CO2 and NO3− activation in the UECN process, these studies neglected the importance of regulating the multiple steps ■ RESULTS AND DISCUSSION The phosphorus-doped Cu/Fe2O3 (denoted as P−Cu/Fe2O3) involved. Notably, H2O plays a crucial role as an indispensable and undoped Cu/Fe2O3 electrocatalysts were synthesized key reactant in UECN. As one of the main side reactions, it is through a composite hydrothermal calcination method. necessary to inhibit the hydrogen evolution reaction (HER), Scanning electron microscopy (SEM) images revealed that but an insufficient H-source supply can directly lead to slow or both P−Cu/Fe2O3 and Cu/Fe2O3 electrocatalysts presented a even halted hydrogenation steps, thereby affecting the entire nanoparticulate morphology, with particles of P−Cu/Fe2O3 reaction process. Therefore, it is particularly significant to being slightly smaller than those of Cu/Fe2O3 (Figure S1). rationally design electrocatalysts, precisely control the *H Further analysis using transmission electron microscopy coverage, and facilitate hydrogenation during the UECN.11 (TEM) confirmed that the diameters of P−Cu/Fe 2 O 3 In this work, we synthesized a P-doped Cu/Fe 2 O 3 nanoparticles were within the range of approximately 20−30 electrocatalyst as an efficient electrocatalyst for urea electro- nm (Figure 1a). High-resolution TEM (HR-TEM) images synthesis. The optimized electrocatalyst showed a max FE of indicated that the lattice fringes of P−Cu/Fe2O3 exhibited 73.81% and a corresponding yield rate of 62.74 mmol h−1 interplanar spacings of 0.210 and 0.269 nm, which are in good agreement with the (111) plane of Cu and the (010) plane of g−1cat. in 0.1 M KNO3 solution. Notably, the maximum yield Fe2O3, respectively12 (Figure 1b). Energy-dispersive X-ray rate reached 97.11 mmol h−1 g−1cat. at −0.88 V vs RHE. The spectroscopy (EDS) revealed the distribution of Cu, Fe, O, experimental results and theoretical calculations further reveal and P elements across the sample, suggesting the formation of that Cu and Fe, as active sites, enable efficient activation of a heterogeneous structure between Cu and Fe2O3 (Figures 1c both CO2 and NO3− reactants, while P doping modulates the and S2). Inductively coupled plasma-atomic emission spec- electronic structure of the electrocatalyst surface, leading to trometer (ICP-AES) analysis indicated an approximate Cu/Fe enhanced *H coverage and facilitating the progress of the molar ratio of 2:1 in P−Cu/Fe2O3 and Cu/Fe2O3 (Table S1), reaction in UECN. The synergistic electrocatalytic effect while EDS mapping and XPS peak area integration further 32925 https://doi.org/10.1021/jacs.5c09805 J. Am. Chem. Soc. 2025, 147, 32924−32931 Journal of the American Chemical Society pubs.acs.org/JACS Article
Figure 2. (a) LSV curves of P−Cu/Fe2O3 and Cu/Fe2O3. FE and yield rate of urea on (b) P−Cu/Fe2O3 and (c) Cu/Fe2O3. (d) Stability test of P−Cu/Fe2O3 at −0.68 V vs RHE.
confirmed the successful phosphorus incorporation in P−Cu/ Cu/Fe2O3 closely resemble that of Fe2O3, indicating a similar Fe2O3 with a P mass fraction of 0.35−0.37 wt % (Table S2). state of Fe in both electrocatalysts relative to the reference To further clarify the phase composition of the synthesized Fe2O3 material (Figures 1g,i and S5).20 Collectively, the XPS electrocatalyst, X-ray diffraction (XRD) analysis was per- and XAS analyses have provided insights into the electronic formed. The XRD pattern confirms the presence of metallic properties and valence states of P−Cu/Fe2O3 and Cu/Fe2O3, Cu, evidenced by characteristic peaks at 2θ = 43.30°, 50.43°, offering valuable insights for enhancing their performance in 74.13°, and 89.93° (PDF #04−0836), and the presence of electrocatalytic applications. Fe2O3, indicated by peaks at 2θ = 30.24°, 35.63°, 53.73°, The electrochemical performance of the P−Cu/Fe2O3 and 57.27°, and 62.93° (PDF #33−0664) (Figure 1d).13,14 To Cu/Fe2O3 electrocatalysts was evaluated in an H-type cell further investigate the electronic properties and valence states using a CO2-saturated 0.1 M KNO3 electrolyte with potential of P−Cu/Fe2O3 and Cu/Fe2O3, we performed a detailed control managed by an electrochemical workstation equipped analysis using X-ray photoelectron spectroscopy (XPS) and X- with a three-electrode configuration. Linear scanning voltam- ray absorption spectroscopy (XAS). The XPS analysis revealed metry (LSV) curves of both P−Cu/Fe2O3 and Cu/Fe2O3 in that in both P−Cu/Fe2O3 and Cu/Fe2O3, the Cu element CO2- and Ar-saturated electrolytes are presented in Figure 2a. existed in its zerovalent state, as evidenced by the characteristic Under an Ar-saturated electrolyte, both P−Cu/Fe2O3 and Cu/ Cu 2p3/2 peak positioned at approximately 932.7 eV.15 Fe2O3 showed limited activity, as evidenced by the observed Concurrently, the Fe element was predominantly in the +3 reduction in current density. However, upon the introduction oxidation state, marked by the Fe 2p3/2 peak at around 710.3 of CO2, a significant increase in current density was observed eV.16 It is noteworthy that despite similar valence states of Cu for both P−Cu/Fe2O3 and Cu/Fe2O3, indicating that the and Fe in both P−Cu/Fe2O3 and Cu/Fe2O3, minor variations presence of CO2 significantly enhanced the electrocatalytic in their binding energies were detected. These subtle shifts activity.21,22 Importantly, P−Cu/Fe2O3 displayed superior suggest differences in the local chemical environments or activity compared to Cu/Fe2O3. Further insights were obtained electronic structures (Figure S3). Additionally, the prominent from electrochemical active surface area (ECSA) measure- XPS peak observed at 132.77 eV confirms the successful ments, which revealed that P−Cu/Fe2O3 had a higher density incorporation of phosphorus in P−Cu/Fe2O3, and the peak at of accessible reactive sites compared to Cu/Fe2O3 (Figure 129.76 eV may be ascribed to the formation of the P−Fe bond S6).9 (Figure 1e).17,18 To clarify the states of Cu and Fe in P−Cu/ Ultraviolet-visible spectrum method (UV−vis), high-per- Fe2O3 and Cu/Fe2O3 electrocatalysts, we analyzed the Cu K- formance liquid chromatography method (HPLC), and 1H edge XANES and Fe K-edge XANES spectra (Figure 1f,g). The nuclear magnetic resonance spectra method (1H NMR) were absorption edges of P−Cu/Fe2O3 and Cu/Fe2O3 closely used to determine the content of urea (Figures S7−S10).23,24 match those of the Cu foil, suggesting a comparable electronic The urease decomposition method served as the primary structure (Figure 1f). The Fourier-transformed EXAFS spectra detection approach in this work. Before using the diacetyl- in R space and wavelet transform (WT)-EXAFS at the Cu K- monoxime method, we investigated the influence of NO2− on edge of P−Cu/Fe2O3 and Cu/Fe2O3 reveal a similar local the results (Figure S11). Furthermore, to ensure the accuracy geometric structure surrounding the Cu atoms (Figures 1h and of the data, we used 1H NMR and HPLC to verify the optimal S4).19 The Fe K-edge XANES spectra of P−Cu/Fe2O3 and results (Figure S12). For the quantification of other potential 32926 https://doi.org/10.1021/jacs.5c09805 J. Am. Chem. Soc. 2025, 147, 32924−32931 Journal of the American Chemical Society pubs.acs.org/JACS Article
Figure 3. In situ ATR-SEIRAS spectra of 1100−2200 cm−1 on (a) P−Cu/Fe2O3 and (b) Cu/Fe2O3 electrodes under various potentials, respectively (the attached figure is an enlarged analysis diagram for the range from 2000 to 2200 cm−1). (c) Online DEMS of gaseous intermediates/products over P−Cu/Fe2O3 during UECN. (d) In situ Raman spectra on P−Cu/Fe2O3 electrodes under various potentials. (e,f) In situ ATR-SEIRAS spectra of 3000−3800 cm−1 on P−Cu/Fe2O3 and Cu/Fe2O3. The OH stretching bands attributed to ice-like water, liquid-like water, and isolated water, as determined by Gaussian fitting, are shown in blue, yellow, and red, respectively. (g) Plot of the population of different types of interfacial water vs potential on P−Cu/Fe2O3 and Cu/Fe2O3 (the one filled with diagonal lines in the pattern is Cu/Fe2O3).
products, NH3/NH4+ was quantified by the indophenol blue incorporation of P promotes the formation of *H, which can method, while NO2− was quantified by the naphthylenedi- promote hydrogenation steps and facilitate the progress of the amine hydrochloride method (Figure S13). The detailed reaction during UECN.25,26 Subsequently, we conducted a P discussion of the analysis methods is provided in the concentration gradient electrochemical test. The experimental Supporting Information. The accuracy of these experimental results showed that the performance was the best when the measurements was further validated by nuclear magnetic amount of sodium pyrophosphate added was 15 mmol (Figure resonance and the isotope tracer method. Gas chromatography S14). These results indicate that incorporating an appropriate was employed for the detection of gaseous products. As shown amount of P into the electrocatalyst significantly improves the in Figure 2b, we applied these conditions across a potential Faradaic efficiency and yield of urea. range and found high selectivity and activity between −0.48 to Subsequently, we explored the impact of varying concen- −0.98 V vs RHE. The optimal urea selectivity was achieved at trations of NO3− in the electrolyte on urea electrosynthesis. a potential of −0.68 V vs RHE on P−Cu/Fe2O3, and the The results indicated that optimal electrocatalytic performance maximum FE was 73.81% and the corresponding yield rate of was attained at an NO3− concentration of 0.1 M (Figure S15). 62.74 mmol h−1 g−1cat. at a current density of 6.63 mA cm−2. To investigate the effect of electrolyte composition on UECN Notably, the maximum yield rate reached 97.11 mmol h−1 performance, we also introduced 0.05 M KHCO3 or 0.05 M g−1cat. at −0.88 V vs RHE. In comparison, the electrolysis K2SO4 with a 0.1 M KNO3 solution as the electrolyte, results for Cu/Fe2O3 showed a maximum FE of 51.4% and the respectively. The results demonstrated that the pure 0.1 M corresponding yield rate of 13.48 mmol h−1 g−1cat. at −0.58 V KNO3 electrolyte exhibited optimal performance (Figure S16). vs RHE and the current density of 2.02 mA cm−2 (Figure 2c). To identify the nitrogen sources in urea electrosynthesis, With increasing negativity of potential, the byproduct NH4+ isotope-labeling experiments were conducted using CO2- decreased, while NO2− increased. For P−Cu/Fe2O3, a slight saturated solutions of K14NO3 or K15NO3. This experiment increase in the FE of hydrogen suggested that the confirmed the formation of both 14NH2CO14NH2 and 32927 https://doi.org/10.1021/jacs.5c09805 J. Am. Chem. Soc. 2025, 147, 32924−32931 Journal of the American Chemical Society pubs.acs.org/JACS Article
Figure 4. Gibbs free energy of (a) CO2RR to *CO, (b) NO3RR to *NO, (c) H2O dissociation to *H, and (d) C−N coupling process to urea over P−Cu/Fe2O3 and Cu/Fe2O3. (e) Schematic diagram of the mechanism. 15 NH2CO15NH2 products, providing clear evidence of nitrogen To explore the reaction mechanism of coelectroreduction of incorporation into the urea molecules (Figure S17). To further CO2 and NO3− to urea in this system, we conducted a series of determine the carbon source during the urea electrosynthesis in situ spectroscopic measurements on P−Cu/Fe2O3 and Cu/ process, we also introduced 13CO2 into a 0.1 M KNO3 solution Fe2O3. In situ attenuated total reflection surface-enhanced for an isotope-labeling experiment. This experiment confirmed infrared absorption spectroscopy (ATR-SEIRAS) was em- the formation of the NH213CONH2 product, which verified ployed to capture reaction intermediates and elucidate the that the carbon source in the urea product was from CO2 reaction mechanism (Figure S24). The results reveal that with (Figure S18). The key parameters to evaluate the electrosyn- the more negative test potential, C−N and C�O character- thesis of urea include FE and yield rate. When compared with istic peaks of urea emerged at 1496 cm−1 and 1669 cm−1 for others, P−Cu/Fe2O3 demonstrated a higher FE and higher P−Cu/Fe2O3, respectively.27 The characteristic peaks of Cu/ yield rate than most reported (Table S3). The durability of P− Fe2O3 were found at 1491 cm−1 and 1663 cm−1 (Figure 3a,b). Cu/Fe2O3 was assessed by a cycling test conducted in a CO2- Most importantly, a weak peak of *OCNO species was saturated 0.1 M KNO3 electrolyte in an H-type cell. As shown observed at ∼2104 cm−1 for P−Cu/Fe2O3, which was derived in Figure 2d, the results showed that the FE and yield rate of from the C−N coupling of oxygen-containing species urea did not change considerably after 15 cycles (data were according to previous reports (*CO + *NO → *OCNO) collected once an hour). In addition, to further evaluate the (Figure 3a).28 Notably, no significant *ONCO peak was structural stability of P−Cu/Fe2O3, we conducted compre- detected in Cu/Fe2O3 (Figure 3b), indicating that the high hensive characterizations after electrochemical testing. XAS production of the *ONCO intermediate may be the key factor analysis indicated that the chemical valence states of both Cu for the high performance of urea electrosynthesis on P−Cu/ and Fe remained virtually unchanged (Figures S19−S22). Fe2O3. Furthermore, online differential electrochemical mass Furthermore, XPS results revealed no significant shifts in the P spectrometry (DEMS) successfully detected signals emanating 2p binding energy (Figure S23). Collectively, these results from NO2, NO, and CO-related intermediates, reinforcing the demonstrate the outstanding stability of the P−Cu/Fe2O3 plausibility of our proposed reaction pathways (Figure 3c).29 catalyst during the electrochemical process. Complementary to this, in situ Raman spectroscopy of P−Cu/ 32928 https://doi.org/10.1021/jacs.5c09805 J. Am. Chem. Soc. 2025, 147, 32924−32931 Journal of the American Chemical Society pubs.acs.org/JACS Article
Fe2O3 unveiled C−N stretching vibration signals near 1000 investigated through computational simulations, and there cm−1 (Figure 3d).3 In situ ATR-SEIRAS and Raman results are three critical steps: (1) *NO + *CO (aq) → *NO−CO were cross-validated with online DEMS data, ensuring the (First C−N Coupling): The energy barrier for this initial C−N accuracy of the intermediate species identified and the reaction coupling step was 0.32 eV on P−Cu/Fe2O3, which was lower pathways proposed. Based on the aforementioned in situ test than that of Cu/Fe2O3 (0.75 eV). The reduced barrier aligns results, we further verified the validity of *CO and *NO as key with experimental observations, confirming that P-doping intermediates through control experiments (Table S4). In promotes coupling kinetics despite remaining a nonsponta- order to investigate the effect of P incorporation on the neous process; (2) *NO−CO + *NO → *NO−CO−NO interfacial water structure, we analyzed the wide peak (Second C−N Coupling): A stark contrast in energy barriers representing the tensile vibration mode of the O−H bond at was observed between Cu/Fe2O3 (0.75 eV) and P−Cu/Fe2O3 3000−3800 cm−1, which can reflect the unique hydrogen (0.37 eV); (3) *NO−CO−NO + H2O (l) + e− → *NO− bonding of water (Figure 3e,f). According to Gaussian fitting, CO−NOH + OH− (aq): This is a hydrogenation step. The the three peaks represent ice-like water, liquid-like water, and energy barrier decreased from 0.13 eV (on Cu/Fe2O3) to isolated water.30 It can be seen from the fitting results that after −0.23 eV (on P−Cu/Fe2O3), rendering the hydrogenation of adding P, the peak strength at 3000−3800 cm−1 increases, and adsorbed species thermodynamically spontaneous in the P- we conclude that the change in electronic structure may doped system (Tables S7 and S8). In summary, the modify the behavior of water molecules on the electrocatalyst introduction of P promotes the formation of *CO and *NO, surface. The introduction of P increases the isolated water which provides a basis for the subsequent coupling reactions.35 content (Figure 3g).31 The variation in isolated water content Additionally, by reducing the energy barrier for H2O is consistent with the variation trend of the FE of urea, which is dissociation, an ample supply of *H is ensured, thereby found in both P−Cu/Fe2O3 and Cu/Fe2O3. It has been lowering the energy barrier for the hydrogenation step in reported that isolated water is more likely to produce active UECN (Figure 4e). This mechanism provides a theoretical hydrogen species, improving *H coverage and promoting basis for subsequent electrocatalyst design. hydrogenation steps to facilitate the reaction.32 In order to eliminate the interference of the N−H bond, we performed a set of control experiments without adding NO3− and the ■ CONCLUSIONS In conclusion, this study establishes that the multisite synergy conclusions are consistent (Figure S25). in P−Cu/Fe2O3 electrocatalysts creates a tandem mechanism Based on the above in situ ATR-SEIRAS, Raman, and DEMS for urea electrosynthesis from CO2 and NO3−. In situ studies, a tandem process of the CO2RR and NO3RR is spectroscopic measurements and theoretical calculations revealed during the urea electrosynthesis on P−Cu/Fe2O3. indicate that Cu, Fe, and P incorporation exhibits excellent Density functional theory (DFT) calculations were conducted synergistic effects within the electrocatalyst. P doping to illustrate the mechanism through a free energy diagram modulates the electronic structure of the electrocatalyst representing the lowest energy pathway. The optimized surface, not only promoting the formation of *CO and *NO adsorption configurations of reaction intermediates on the and lowering the energy barrier for the coupling of *CO and simulated interface structures are shown in Tables S5 and S6. *NO, but also increasing *H coverage and facilitating the First of all, we prepared P−Cu and P−Fe2O3 electrocatalysts hydrogenation process during UECN. All these factors are for the CO2RR and NO3RR, respectively. The results showed favorable to UECN, leading to very high efficiency. This work that CO2 tended to be activated at the Cu sites, while NO3− underscores the significance of multisite electrocatalysts for tended to be activated at the Fe sites. Based on reasonable UECN and provides a profound understanding of the inferences drawn from experimental results, we utilized the Cu synergistic tandem effects for designing efficient urea electro- site as the adsorption site for activating CO2 and the Fe site as synthesis catalysts. We believe that many efficient electro- the adsorption site for activating NO3− in our simulation catalysts can be designed on the basis of synergy among calculations (Figures S26 and S27). In Figure 4a, we analyze different components. the interfacial systems before and after doping. The rate- determining step (RDS) for both systems is identified as: ∗ + CO2 (aq) + H2O (l) + e− → ∗COOH + OH− (aq). For P− ■ * ASSOCIATED CONTENT sı Supporting Information Cu/Fe2O3, the energy barrier for the formation of *COOH is The Supporting Information is available free of charge via the 0.96 eV. This is lower than the energy barrier of the rate- Internet at .The Supporting Information is available free of determining step for Cu/Fe2O3. The reduced energy barrier charge at https://pubs.acs.org/doi/10.1021/jacs.5c09805. facilitates the formation of the *CO intermediate.33 In Figure Additional information about experimental details, 4b, the Fe site in P−Cu/Fe2O3 is more conducive to activating materials, methods, characterization methods, and NO3− to produce *NO intermediates.8 Free energy analysis of DFT calculation details (PDF) H2O dissociation energetics on P−Cu/Fe2O3 and Cu/Fe2O3 revealed that P incorporation significantly lowers the activation barrier for *H formation (Figure 4c), which aligns with the result detected by in situ ATR-SEIRAS. This *H-mediated ■ AUTHOR INFORMATION Corresponding Authors pathway is postulated to accelerate the hydrogenation step, Shuaiqiang Jia − Shanghai Key Laboratory of Green thereby driving the overall reaction kinetics. It is concluded Chemistry and Chemical Processes, State Key Laboratory of that P−Cu/Fe2O3 provides an advantageous condition for the Petroleum Molecular & Process Engineering, School of occurrence of C−N coupling.34 Additionally, DFT calculations Chemistry and Molecular Engineering, East China Normal were further carried out to theoretically understand the University, Shanghai 200062, China; Institute of Eco- influence of the introduction of P on the UECN process. As Chongming, Shanghai 202162, China; Email: sqjia@ shown in Figure 4d, the mechanism was systematically chem.ecnu.edu.cn 32929 https://doi.org/10.1021/jacs.5c09805 J. Am. Chem. Soc. 2025, 147, 32924−32931 Journal of the American Chemical Society pubs.acs.org/JACS Article
Haihong Wu − Shanghai Key Laboratory of Green Chemistry Chunjun Chen − Shanghai Key Laboratory of Green and Chemical Processes, State Key Laboratory of Petroleum Chemistry and Chemical Processes, State Key Laboratory of Molecular & Process Engineering, School of Chemistry and Petroleum Molecular & Process Engineering, School of Molecular Engineering, East China Normal University, Chemistry and Molecular Engineering, East China Normal Shanghai 200062, China; Institute of Eco-Chongming, University, Shanghai 200062, China; Institute of Eco- Shanghai 202162, China; orcid.org/0000-0001-6266- Chongming, Shanghai 202162, China 8290; Email: hhwu@chem.ecnu.edu.cn Mingyuan He − Shanghai Key Laboratory of Green Chemistry Buxing Han − Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum and Chemical Processes, State Key Laboratory of Petroleum Molecular & Process Engineering, School of Chemistry and Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Molecular Engineering, East China Normal University, Shanghai 200062, China; Institute of Eco-Chongming, Shanghai 200062, China; Institute of Eco-Chongming, Shanghai 202162, China Shanghai 202162, China; Beijing National Laboratory for Complete contact information is available at: Molecular Sciences, CAS Key Laboratory of Colloid and https://pubs.acs.org/10.1021/jacs.5c09805 Interface and Thermodynamics, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Notes Chemistry, Chinese Academy of Sciences, Beijing 100049, The authors declare no competing financial interest. China; orcid.org/0000-0003-0440-809X; Email: hanbx@iccas.ac.cn
Authors ■ ACKNOWLEDGMENTS The work was supported by the National Key R&D Program of China (2023YFA1507901), the National Natural Science Ting Deng − Shanghai Key Laboratory of Green Chemistry Foundation of China (22403030, 22238011, 22121002), and and Chemical Processes, State Key Laboratory of Petroleum the Fundamental Research Funds for the Central Universities. Molecular & Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062, China; Institute of Eco-Chongming, Shanghai 202162, China ■ REFERENCES (1) Yuan, J.; Hu, L.; Huang, J.; Chen, Y.; Qiao, S.; Xie, H. Photo/ electrochemical urea synthesis via CO2 coupling with nitrogenous Cheng Xue − Shanghai Key Laboratory of Green Chemistry small molecules: Status and challenges for the development of and Chemical Processes, State Key Laboratory of Petroleum mechanism and catalysts. Appl. Catal., B 2023, 339, 123146. Molecular & Process Engineering, School of Chemistry and (2) Zhang, X.; Zhu, X.; Bo, S.; Chen, C.; Cheng, K.; Zheng, J.; Li, S.; Molecular Engineering, East China Normal University, Tu, X.; Chen, W.; Xie, C.; et al. Electrocatalytic Urea Synthesis with Shanghai 200062, China; Institute of Eco-Chongming, 63.5% Faradaic Efficiency and 100% N-Selectivity via One-step C−N Shanghai 202162, China coupling. Angew. Chem., Int. Ed. 2023, 135 (33), No. e202305447. Hailian Cheng − Shanghai Key Laboratory of Green (3) Luo, Y.; Xie, K.; Ou, P.; Lavallais, C.; Peng, T.; Chen, Z.; Zhang, Chemistry and Chemical Processes, State Key Laboratory of Z.; Wang, N.; Li, X.-Y.; Grigioni, I.; et al. Selective electrochemical Petroleum Molecular & Process Engineering, School of synthesis of urea from nitrate and CO2 via relay catalysis on hybrid Chemistry and Molecular Engineering, East China Normal catalysts. Nat. Catal. 2023, 6 (10), 939−948. (4) Jiang, M.; Zhu, M.; Wang, M.; He, Y.; Luo, X.; Wu, C.; Zhang, University, Shanghai 200062, China; Institute of Eco- L.; Jin, Z. Review on Electrocatalytic Coreduction of Carbon Dioxide Chongming, Shanghai 202162, China and Nitrogenous Species for Urea Synthesis. ACS Nano 2023, 17 (4), Jiapeng Jiao − Shanghai Key Laboratory of Green Chemistry 3209−3224. and Chemical Processes, State Key Laboratory of Petroleum (5) Li, P.; Zhu, Q.; Liu, J.; Wu, T.; Song, X.; Meng, Q.; Kang, X.; Molecular & Process Engineering, School of Chemistry and Sun, X.; Han, B. Efficient C−N coupling for urea electrosynthesis on Molecular Engineering, East China Normal University, defective Co3O4 with dual-functional sites. Chem. Sci. 2024, 15 (9), Shanghai 200062, China; Institute of Eco-Chongming, 3233−3239. Shanghai 202162, China (6) Liu, X.; Jiao, Y.; Zheng, Y.; Jaroniec, M.; Qiao, S.-Z. Mechanism Xiao Chen − Shanghai Key Laboratory of Green Chemistry of C-N bonds formation in electrocatalytic urea production revealed and Chemical Processes, State Key Laboratory of Petroleum by ab initio molecular dynamics simulation. Nat. Commun. 2022, 13 (1), 5471. Molecular & Process Engineering, School of Chemistry and (7) Zhang, Z.; Li, D.; Tu, Y.; Deng, J.; Bi, H.; Yao, Y.; Wang, Y.; Li, Molecular Engineering, East China Normal University, T.; Luo, Y.; Sun, S.; et al. Electrocatalytic synthesis of C−N coupling Shanghai 200062, China; Institute of Eco-Chongming, compounds from CO2 and nitrogenous species. Sus. Mater. 2024, 4 Shanghai 202162, China (2), No. e193. Zhanghui Xia − Shanghai Key Laboratory of Green Chemistry (8) Song, X.; Ma, X.; Chen, T.; Xu, L.; Feng, J.; Wu, L.; Jia, S.; and Chemical Processes, State Key Laboratory of Petroleum Zhang, L.; Tan, X.; Wang, R.; et al. Urea Synthesis via Co-electrolysis Molecular & Process Engineering, School of Chemistry and of CO2 and Nitrate over Heterostructured Cu-Bi Catalysts. J. Am. Molecular Engineering, East China Normal University, Chem. Soc. 2024, 146 (37), 25813−25823. Shanghai 200062, China; Institute of Eco-Chongming, (9) Jiang, J.; Wu, G.; Sun, M.; Liu, Y.; Yang, Y.; Du, A.; Dai, L.; Mao, Shanghai 202162, China X.; Qin, Q. Cu−Mo Dual Sites in Cu-Doped MoSe2 for Enhanced Electrosynthesis of Urea. ACS Nano 2024, 18 (21), 13745−13754. Mengke Dong − Shanghai Key Laboratory of Green (10) Gao, Y.; Wang, J.; Sun, M.; Jing, Y.; Chen, L.; Liang, Z.; Yang, Chemistry and Chemical Processes, State Key Laboratory of Y.; Zhang, C.; Yao, J.; Wang, X. Tandem Catalysts Enabling Efficient Petroleum Molecular & Process Engineering, School of C−N Coupling toward the Electrosynthesis of Urea. Angew. Chem., Chemistry and Molecular Engineering, East China Normal Int. Ed. 2024, 63 (23), No. e202402215. University, Shanghai 200062, China; Institute of Eco- (11) Cheng, M.; Wang, S.; Dai, Z.; Xia, J.; Zhang, B.; Feng, P.; Zhu, Chongming, Shanghai 202162, China Y.; Zhang, Y.; Zhang, G. Rectifying Heterointerface Facilitated C-N
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