Optimized kinetic pathways of active hydrogen generation at Cu2O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia

doi:10.1016/S1872-2067(25)64848-0

Chinese Journal of Catalysis ›› 2025, Vol. 79: 78-90.DOI: 10.1016/S1872-2067(25)64848-0

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Optimized kinetic pathways of active hydrogen generation at Cu₂O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia

Xi Chen^a^,¹, Wei Jin^a^,¹, Xinyu Zhong^c, Hongqiao Lin^b, Junjie Ding^d, Xinyu Liu^a, Hui Wang^a, Fasheng Chen^a, Yan Xiong^b^,^*(), Changchun Ding^a^,^*(), Zhong Jin^b^,^*(), Minghang Jiang^a^,^b^,^*()

^aDepartment of Chemistry, School of Science, Xihua University, Chengdu 610039, Sichuan, China
^bState Key Laboratory of Coordination Chemistry, MOE Key Laboratory of Mesoscopic Chemistry, MOE Key Laboratory of High Performance Polymer Materials and Technology, Jiangsu Key Laboratory of Clean Energy Catalysis and Intelligent Green Chemical Engineering, Suzhou Key Laboratory of Green Intelligent Manufacturing of New Energy Materials and Devices, Tianchang New Materials and Energy Technologies Research Center, Institute of Green Chemistry and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, Jiangsu, China
^c Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China
^dCollege of Physics and Center of Quantum Materials and Devices, Chongqing University, Chongqing 401331, China

Received:2025-07-04 Accepted:2025-08-23 Online:2025-12-18 Published:2025-10-27
Contact: Yan Xiong, Changchun Ding, Zhong Jin, Minghang Jiang
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22561160129);National Natural Science Foundation of China(22479074);National Natural Science Foundation of China(22475096);Natural Science Foundation of Sichuan Prov-ince(2023NSFSC1074);Natural Science Foundation of Sichuan Prov-ince(2023NSFSC0909);Talent Introduction Plan of Xihua University(Z222051);General Project of the Joint Fund of Equipment Pre-research and the Ministry of Education(8091B02052407);Fundamental Reaearch Program Key Project of Jiangsu Province(BK20253008);Natural Science Foundation of Jiangsu Province(BK20240400);Natural Science Foundation of Jiangsu Province(BK20241236);Science and Technology Major Project of Jiangsu Province(BG2024013);Scientific and Technological Achievements Transformation Special Fund of Jiangsu Province(BA2023037);Academic Degree and Postgraduate Education Reform Project of Jiangsu Province(JGKT24_C001);Key Core Technology Open Competition Project of Suzhou City(SYG2024122);Open research fund of Suzhou Laboratory(SZLAB-1308-2024-TS005);Chenzhou National Sustainable Development Agenda Innovation Demonstration Zone Provincial Special Project(2023sfq11)

Abstract

Abstract:

In this paper we report the preparation of nano-dendritic Cu₂O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient, energy-consumption-free, and environmentally friendly chemical replacement method. The analysis results reveal that the incorporation of cobalt in its atomic form enhances the adsorption of nitrate species onto the catalyst surface, whereas doping with metallic cobalt promotes the production of active hydrogen (*H). By adjusting the doping concentration of cobalt, we effectively control its doping form (atomic and metallic states) on the surface of dendritic copper, thereby enabling controllable modulation of the active hydrogen concentration on the catalyst surface. By ensuring sufficient consumption of *H during the NITRR process while avoiding excessively high concentrations that could trigger detrimental hydrogen evolution reaction side reactions, this approach remarkably enhances the selectivity of ammonia synthesis in NITRR. This study offers an effective approach to regulate the *H concentration on the surface of the catalyst through adjusting the metal doping form, thereby improving the performance of ammonia synthesis from NITRR.

Key words: Modulation of the active hydrogen concentration, Adjusting the Co doping form, Electrocatalytic nitrate reduction reaction, Electrocatalytic ammonia synthesis

Xi Chen, Wei Jin, Xinyu Zhong, Hongqiao Lin, Junjie Ding, Xinyu Liu, Hui Wang, Fasheng Chen, Yan Xiong, Changchun Ding, Zhong Jin, Minghang Jiang. Optimized kinetic pathways of active hydrogen generation at Cu₂O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia[J]. Chinese Journal of Catalysis, 2025, 79: 78-90.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64848-0

https://www.cjcatal.com/EN/Y2025/V79/I12/78

Figures/Tables 5

Fig. 1. Schematic diagram of the synthesis process, morphological and structural analysis of samples. (a) Schematic illustration of the preparation of Cox-Cu2O/Cu (x = 0, 0.05, 0.10, or 0.34) samples. SEM (b), element mapping images (c-f), TEM (g) and HR-TEM (h) images of Cox-Cu2O/Cu sample.

Fig. 2. Spectroscopic analysis of the samples. (a) XRD patterns of Cox-Cu2O/Cu (x = 0, 0.05, 0.10, or 0.34) samples. High-resolution XPS spectra at the Cu 2p (b) and Co 2p (c) edge. (d) Co K-edge XANES spectra. (e) Fourier transformations of the k3-weighted χ(k)-function of the EXAFS spectra at Co K-edge. (f) Fitting results of the EXAFS spectra of Co0.10-Cu2O/Cu at K space and R-space, respectively. Wavelet transforms of the Cu K-edge and Co K-edge FT-EXAFS spectra of Co0.10-Cu2O/Cu (g), Co foil (h), and CoO (i).

Fig. 3. Electrocatalytic NITRR performance of the synthesized samples. (a) LSV curves of Co0.10-Cu2O/Cu sample. (b) Time-dependent current density curves of Co0.10-Cu2O/Cu in 0.1 mol·L-1 Na2SO4 that contained 500 ppm NO3- for the NITRR. (c) UV-vis absorption spectra of the electrolyte after the NITRR test of Co0.10-Cu2O/Cu. The NH3 yield (d) and corresponding FENH3 values (e) of Cu2O/Cu, Co0.05-Cu2O/Cu, Co0.10-Cu2O/Cu, and Co0.34-Cu2O/Cu samples. (f) Nyquist plots of Cu2O/Cu, Co0.05-Cu2O/Cu, Co0.10-Cu2O/Cu, and Co0.34-Cu2O/Cu. (g) UV-vis absorption spectra of Co0.10-Cu2O/Cu after NITRR test for 10 min at various applied potentials and then coloured by the Griess indicator. (h) The NO2- yields and corresponding FENO2- values for Co0.10-Cu2O/Cu sample. (i) UV-vis absorption spectra of product solution after the NITRR test of Co0.10-Cu2O/Cu for 10 min at various applied potentials and then coloured by the para-dimethylamino-benzaldehyde indicator.

Fig. 4. (a) UV-vis absorption spectra of the product solution under various test conditions and then coloured by the indophenol indicator. (b) 1H NMR spectra of product solution after NITRR test of Co0.10-Cu2O/Cu using 15NO3- and 14NO3- as the N-sources, respectively. (c) Cycling stability test of Co0.10-Cu2O/Cu at -0.8 V vs. RHE. (d) Time-dependent NH3 concentration and corresponding FENH3 after different reaction durations of Co0.10-Cu2O/Cu at a potential of -0.8 V vs. RHE. The inset in (d) shows the corresponding time-dependent current density curves of stability tests. (e) Schematic diagram of proton exchange membrane flow cell and flow field structure. (f) I-t curves of Co0.10-Cu2O/Cu conducted in a flow-type electrolytic cell, with the apparatus configuration depicted in the inset of Fig. 4(f).

Fig. 5. (a) In-situ infrared spectra of Co0.10-Cu2O/Cu sample at different negative applied potentials in the 0.1 mol·L-1 Na2SO4 electrolytes containing 500 ppm NO3-. (b) Adsorption energies of NO3- on Cu2O/Cu and cobalt-doped Cu2O/Cu (Co-Cu2O/Cu). (c) Free energy diagrams of possible NITRR pathways on Cu2O/Cu and Co-Cu2O/Cu surfaces, respectively. (d) PDOS of Co 3d in Co-Cu2O/Cu and that of Cu 3d in Cu2O/Cu. (e) Comparison of adsorption energy of H2O on the surfaces of Cu2O/Cu, Co-Cu2O/Cu and Co/Cu, respectively. (f) Free energy diagram for HER on Cu2O/Cu, Co-Cu2O/Cu and Co/Cu surfaces. (g) LSV curves of Co0.10-Cu2O/Cu in 0.1 mol·L-1 Na2SO4 and 500 ppm NO3- with or without 0.5 mol·L-1 TBA. (h) NH3 yield of Co0.10-Cu2O/Cu at given potentials for the NITRR with or without 0.5 mol·L-1 TBA.

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Optimized kinetic pathways of active hydrogen generation at Cu₂O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia

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