光还原负载Ag优化Cu2O多面体电催化硝酸盐还原合成氨活性

doi:10.3976/j.issn.1002-4026.2025148

Abstract

Abstract: Ammonia is an important chemical feedstock. Its traditional synthesis process, Haber-Bosch process, suffers from issues such as high energy consumption and high emission. Therefore, it is of great significance to develop a green and efficient electrocatalytic ammonia synthesis technology. Aiming at the problems of sluggish reaction kinetics, slow electron transfer rate and easy reconstruction of single Cu2O, 26-faceted Cu2O polyhedral was synthesized by template-free chemical precipitation method, and Ag particles were loaded on the surface of Cu2O by photoreduction method. This approach optimized the electronic structure of the catalyst, promoted interfacial charge transfer, and enhanced the intrinsic catalytic activity for the conversion of key reaction intermediates (such as *NO2and *NH2OH) to NH3. Consequently, it inhibited the hydrogen evolution reaction and by-product formation, thereby improving the electrocatalytic nitrate reduction performance for ammonia synthesis. Electrochemical tests show that Ag-Cu2O exhibits excellent catalytic performance for the nitrate reduction reaction, and achieves a Faradaic efficiency of 88%, which is better than Au-Cu2O and pure Cu2O, while the generation of by-product nitrite and competitive product hydrogen are suppressed. The catalyst demonstrates adaptability to nitrate solutions of varying concentrations, offering potential for treating nitrate wastewater across a wide concentration range. This study provides a new strategy for designing high-performance and high-stability nitrate reduction electrocatalysts, and holds significant reference value for promoting the application of electrocatalytic technology in wastewater treatment and green ammonia synthesis.

Key words: electrocatalysis, nitrate reduction to ammonia, photoreduction, silver, copper oxide

CLC Number:

TQ113.247

CHENG Yahui, GUO Yiran, WEN Chuanjing. Photoreduction of Ag-loaded Cu2O polyhedra for optimizing the electrocatalytic activity of nitrate reduction to ammonia[J].Shandong Science, 0, (): 1-.

References

[1] HUANG H, PERAMAIAH K, HUANG K W. Rethinking nitrate reduction: redirecting electrochemical efforts from ammonia to nitrogen for realistic environmental impacts[J]. Energy & Environmental Science, 2024, 17(8): 2682-2685. DOI:10.1039/D4EE00222A.

[2] JOSEPH SEKHAR S, SAMUEL M S, GLIVIN G, et al. Production and utilization of green ammonia for decarbonizing the energy sector with a discrete focus on Sustainable Development Goals and environmental impact and technical hurdles[J]. Fuel, 2024, 360: 130626. DOI:10.1016/j.fuel.2023.130626.

[3] XIONG J, JIANG L, ZHU B, et al. FeIr alloy optimizes the trade‐off between nitrate reduction and active hydrogen generation for efficient electro‐synthesis of ammonia in neutral media[J]. Advanced Functional Materials, 2025, 35(27): 2423705. DOI:10.1002/adfm.202423705.

[4] JIAO F, XU B. Electrochemical ammonia synthesis and ammonia fuel cells[J]. Advanced Materials, 2019, 31(31): 1805173. DOI:10.1002/adma.201805173.

[5] LI J, XIONG Q, MU X, et al. Recent advances in ammonia synthesis: from Haber‐Bosch process to external field driven strategies[J]. ChemSusChem, 2024, 17(15): e202301775. DOI:10.1002/cssc.202301775.

[6] ERFANI N, BAHARUDIN L, WATSON M. Recent advances and intensifications in Haber-Bosch ammonia synthesis process[J]. Chemical Engineering and Processing - Process Intensification, 2024, 204: 109962. DOI:10.1016/j.cep.2024.109962.

[7] LIU Y, MA J, HUANG S, et al. Highly dispersed copper-iron nanoalloy enhanced electrocatalytic reduction coupled with plasma oxidation for ammonia synthesis from ubiquitous air and water[J]. Nano Energy, 2023, 117: 108840. DOI:10.1016/j.nanoen.2023.108840.

[8] HUANG Y, XU W, LIANG Y, et al. Enrichment of active hydrogen on nanoporous Ru/Co2P for enhanced electrocatalytic nitrate to ammonia[J]. 2025, 516: 164046. DOI:10.2139/ssrn.5177153.

[9] CHEN G F, YUAN Y, JIANG H, et al. Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper-molecular solid catalyst[J]. Nature Energy, 2020, 5(8): 605-613. DOI:10.1038/s41560-020-0654-1.

[10] MAENG J, JANG D, HA J, et al. Oxygen vacancy‐controlled CuOx/N,Se Co‐doped porous carbon via plasma‐treatment for enhanced electro‐reduction of nitrate to green ammonia[J]. Small, 2024, 20(37): 2403253. DOI:10.1002/smll.202403253.

[11] LI P, LI R, LIU Y, et al. Pulsed nitrate-to-ammonia electroreduction facilitated by tandem catalysis of nitrite intermediates[J]. Journal of the American Chemical Society, 2023, 145(11): 6471-6479. DOI:10.1021/jacs.3c00334.

[12] QIU W, CHEN X, LIU Y, et al. Confining intermediates within a catalytic nanoreactor facilitates nitrate-to-ammonia electrosynthesis[J]. Applied Catalysis B: Environment and Energy, 2022, 315: 121548. DOI:10.1016/j.apcatb.2022.121548.

[13] CHAO G, ZONG W, ZHU J, et al. Selective mass accumulation at the metal-polymer bridging interface for efficient nitrate electroreduction to ammonia and Zn-nitrate batteries[J]. Journal of the American Chemical Society, 2025, 147(25): 21432-21442. DOI:10.1021/jacs.5c00400.

[14] ZONG W, GAO H, OUYANG Y, et al. Bio‐inspired aerobic‐hydrophobic janus interface on partially carbonized iron heterostructure promotes bifunctional nitrogen fixation[J]. Angewandte Chemie International Edition, 2023, 62(27): e202218122. DOI:10.1002/anie.202218122.

[15] YANG Y, SUN Y, WANG Y, et al. Self-triggering a locally alkaline microenvironment of Co4Fe6for highly efficient neutral ammonia electrosynthesis[J]. Journal of the American Chemical Society, 2025, 147(10): 8893-8905. DOI:10.1021/jacs.5c00688.

[16] LI Z, ZHENG M, YAN C, et al. Stabilizing Cu0-Cuδ+sites via ohmic contact interface engineering for ampere-level nitrate electroreduction to ammonia[J]. Nature Communications, 2025, 16(1): 8940. DOI:10.1038/s41467-025-63996-w.

[17] ZHANG S, WU J, ZHENG M, et al. Fe/Cu diatomic catalysts for electrochemical nitrate reduction to ammonia[J]. Nature Communications, 2023, 14(1): 3634. DOI:10.1038/s41467-023-39366-9.

[18] ZHANG B, DAI Z, CHEN Y, et al. Defect-induced triple synergistic modulation in copper for superior electrochemical ammonia production across broad nitrate concentrations[J]. Nature Communications, 2024, 15(1): 2816. DOI:10.1038/s41467-024-47025-w.

[19] TANG S, XIE M, YU S, et al. General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate[J]. Nature Communications, 2024, 15(1): 6932. DOI:10.1038/s41467-024-51112-3.

[20] WEI J, WANG J, YU W, et al. Dual-active-site accelerated hydrogenation facilitates efficient electrochemical reduction of nitrate to ammonia[J]. Applied Catalysis B: Environment and Energy, 2025, 378: 125629. DOI:10.1016/j.apcatb.2025.125629.

[21] BOUFELGHA S, AOUDIA K, HAMMACHE H, et al. Synergistic effect between Cu2O electrodeposited thin film and carbon steel substrate on the electrocatalysis of nitrate reduction reaction[J]. Journal of the Indian Chemical Society, 2025, 102(8): 101820. DOI:10.1016/j.jics.2025.101820.

[22] LIU Y, YAO X M, LIU X, et al. Cu2+1O/Ag Heterostructure for boosting the electrocatalytic nitrate reduction to ammonia performance[J]. Inorganic Chemistry, 2023, 62(19): 7525-7532. DOI:10.1021/acs.inorgchem.3c00857.

[23] HAN M, GUO M, YUN Y, et al. Effect of heteroatom and charge reconstruction in atomically precise metal nanoclusters on electrochemical synthesis of ammonia[J]. Advanced Functional Materials, 2022, 32(29): 2202820. DOI:10.1002/adfm.202202820.

[24] YAO Y Q, WANG Z F, SHEN H J, et al. Innovative interfacial hydrogen spillover in Ag-Cu2O for selective electrohydrogenation of furfural[J]. International Journal of Hydrogen Energy, 2025, 158: 150523. DOI:10.1016/j.ijhydene.2025.150523.

[25] FENG A, HU Y, YANG X, et al. ZnO Nanowire arrays decorated with Cu nanoparticles for high-efficiency nitrate to ammonia conversion[J]. ACS Catalysis, 2024, 14(8): 5911-5923. DOI:10.1021/acscatal.3c04398.

[26] X. Chen, W. Jin, X. Zhong, H. Lin, J. Ding, X. Liu, H. Wang, F. Chen, Y. Xiong, C. Ding, Z. Jin, M. Jiang, Optimized kinetic pathways of active hydrogen generation at Cu2O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia, Chinese J. Catal, 79 (2025) 78-90.https://doi.org/10.1016/S1872-2067(25)64848-0.

[27] K. Wu, C. Sun, Z. Wang, Q. Song, X. Bai, X. Yu, Q. Li, Z. Wang, H. Zhang, J. Zhang, X. Tong, Y. Liang, A. Khosla, Z. Zhao, Surface reconstruction on uniform Cu nanodisks boosted electrochemical nitrate reduction to ammonia, ACS Materials Lett. 4 (2022) 650-656.https://doi.org/10.1021/acsmaterialslett.2c00149.

[28] Y. Hai, X. Li, Y. Cao, X. Wang, L. Meng, Y. Yang, M. Luo, Ammonia synthesis via electrocatalytic nitrate reduction using NiCoO2nanoarrays on a copper foam, ACS Appl. Mater. Interfaces 16 (2024) 11431-11439.https://doi.org/10.1021/acsami.3c16456.

[29] Y. Li, J. Guo, Y. Yang, B. Wang, H. Wen, T.S. Bui, S.L.Y. Chang, N.M. Bedford, E. Lovell, R. Daiyan, R. Amal, Y. Hou, R. Tilley, Z. Xia, L. Dai, Atomically dispersed copper electrocatalysts with proton‐feeding centers for efficient ammonia synthesis by nitrate electroreduction, Adv Funct Materials (2025) e08619.https://doi.org/10.1002/adfm.202508619.

[30] Y. Dong, C. Zhao, Y. Li, Y. Guo, X. Liu, W. Liu, R. Souiki, S. Ding, B. Guo, Ammonia synthesis by nitrate reduction catalyzed by copper porphyrin metal-organic framework in tandem with cuprous oxide, ACS Appl. Energy Mater. 8 (2025) 9038-9048.https://doi.org/10.1021/acsaem.5c00651.

[31] D. Jang, J. Maeng, J. Kim, H. Han, G.H. Park, J. Ha, D. Shin, Y.J. Hwang, W.B. Kim, Boosting electrocatalytic nitrate reduction reaction for ammonia synthesis by plasma-induced oxygen vacancies over MnCuOx, Appl. Surf. Sci. 610 (2023) 155521.https://doi.org/10.1016/j.apsusc.2022.155521.

[32] H. Liu, S. Zhang, T. Premy, C. Zhang, F. Liu, Pulsed electrocatalysis on iron-decorated copper foam enables efficient and selective ammonia synthesis from low-concentration nitrate, Journal of Environmental Chemical Engineering 13 (2025) 118539. https://doi.org/10.1016/j.jece.2025.118539.

[33] C. Guo, S. Yang, L. Wei, Z. Wang, J. Su, L. Guo, Modulation of the lattice structure of CuFe/copper foam catalysts by doping with Bi to improve the efficiency of electrocatalytic ammonia synthesis, ACS Sustainable Chem. Eng. 13 (2025) 1604-1616.https://doi.org/10.1021/acssuschemeng.4c08210.

[34] F. Chen, X. Zhong, J. Ding, X. Chen, X. Liao, Z. Jiang, Y. Xiong, Z. Jin, M. Jiang, Trimesic acid modified copper‑cobalt layered double hydroxide nanosheets boost electrocatalytic reduction of nitrate to ammonia, J. Colloid Interf. Sci. 701 (2026) 138664.https://doi.org/10.1016/j.jcis.2025.138664.

[35] Q. Wang, Y. Shen, Electrocatalytic reduction of nitrate into ammonia by bimetallic copper-nickel catalysts, 987 (2025) 119110.https://doi.org/10.2139/ssrn.5143338.

[36] X. Guo, R.-T. Gao, Z. Gao, L. Wang, Grain boundary engineering on Cu-based electrocatalysts promotes nitrate reduction to ammonia production, J. Energy Chem. 106 (2025) 351-359.https://doi.org/10.1016/j.jechem.2025.01.036.

[37] Y. Wang, T. Bao, L. Chen, C. Zhang, J. Wang, Y. Zou, Y. Xi, Z. Li, C. Yu, C. Liu, Boosting nitrate‐to‐ammonia conversion over copper‐based electrocatalysts by facilitating hydrogenation and product desorption, Angew Chem Int Ed 64 (2025) e202509090.https://doi.org/10.1002/anie.202509090.

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Photoreduction of Ag-loaded Cu2O polyhedra for optimizing the electrocatalytic activity of nitrate reduction to ammonia

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