Electrocatalytic Nitrate Reduction for Selective Ammonia Production: Mechanisms and Prospects
DOI:
https://doi.org/10.62051/Keywords:
Nitrate reduction; Electrocatalysis; Ammonia synthesis; Reaction mechanism.Abstract
Electrocatalytic nitrate reduction to ammonia driven by renewable energy offers the dual benefits of environmental remediation and sustainable ammonia synthesis. However, this process is a complex multi-electron, multi-proton reaction involving a variety of reaction pathways, making it crucial to understand its mechanism at the molecular level. This review first outlines the necessity and advantages of electrocatalytic nitrate reduction to ammonia, as well as its electrochemical principles and fundamentals. It then focuses on the reaction mechanisms and pathways, along with in situ characterization techniques used to monitor reaction intermediates and identify active sites. Finally, future research directions are proposed, and the applications and economic value in sustainable ammonia synthesis and energy conversion are systematically discussed. This review aims to decode the principles of nitrate reduction to ammonia and provide guidance for the rational design and development of electrocatalysts to achieve a sustainable and efficient nitrogen cycle.
References
[1] N. Gruber, J.N. Galloway, An Earth-system perspective of the global nitrogen cycle, Nature 451(7176) (2008) 293–296.
[2] V. Rosca, M. Duca, M.T. de Groot, M.T.M. Koper, Nitrogen Cycle Electrocatalysis, Chemical Reviews 109(6) (2009) 2209–2244.
[3] J. Penuelas, J. Sardans, Human-driven global nutrient imbalances increase risks to health, Eco-Environment & Health 2(4) (2023) 246–251.
[4] H.-j. Chen, Z.-q. Xu, S. Sun, Y. Luo, Q. Liu, M.S. Hamdy, Z.-s. Feng, X. Sun, Y. Wang, H.-j. Chen, Plasma-etched Ti2O3 with oxygen vacancies for enhanced NH3 electrosynthesis and Zn–NO3− batteries Plasma-etched Ti2O3with oxygen vacancies for enhanced NH3 electrosynthesis and Zn–NO3− batteries, Inorganic Chemistry Frontiers 9(18) (2022) 4608–4613.
[5] C. Zhang, Y. Zhang, R. Deng, L. Yuan, Y. Zou, T. Bao, X. Zhang, G. Wei, C. Yu, C. Liu, Enabling Logistics Automation in Nanofactory: Cobalt Phosphide Embedded Metal–Organic Frameworks for Efficient Electrocatalytic Nitrate Reduction to Ammonia, Advanced Materials 36(26) (2024).
[6] Y. Chen, S. Ji, C. Chen, Q. Peng, D. Wang, Y. Li, Single-Atom Catalysts: Synthetic Strategies and Electrochemical Applications, Joule 2(7) (2018) 1242–1264.
[7] S. Ye, Z. Chen, G. Zhang, W. Chen, C. Peng, X. Yang, L. Zheng, Y. Li, X. Ren, H. Cao, D. Xue, J. Qiu, Q. Zhang, J. Liu, S. Ye, Elucidating the activity, mechanism and application of selective electrosynthesis of ammonia from nitrate on cobalt phosphide, Energy & Environmental Science 15(2) (2022) 760–770.
[8] P. Xu, S. Agarwal, L. Lefferts, Mechanism of nitrite hydrogenation over Pd/γ-Al2O3 according a rigorous kinetic study, Journal of Catalysis 383 (2020) 124–134.
[9] W.-J. Sun, H.-Q. Ji, L.-X. Li, H.-Y. Zhang, Z.-K. Wang, J.-H. He, J.-M. Lu, Built-in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra-Low Concentration and Electroreduction to Ammonia Built‐in Electric Field Triggered Interfacial Accumulation Effect for Efficient Nitrate Removal at Ultra‐Low Concentration and Electroreduction to Ammonia, Angewandte Chemie International Edition 60(42) (2021) 22933–22939.
[10] J. Yuan, H. Yin, X. Jin, D. Zhao, Y. Liu, A. Du, X. Liu, A.P. O’Mullane, A practical FeP nanoarrays electrocatalyst for efficient catalytic reduction of nitrite ions in wastewater to ammonia, Applied Catalysis B: Environmental 325 (2023) 122353.
[11] H. Xu, Y. Ma, J. Chen, W.-x. Zhang, J. Yang, H. Xu, Electrocatalytic reduction of nitrate – a step towards a sustainable nitrogen cycle, Chemical Society Reviews 51(7) (2022) 2710–2758.
[12] G.-F. Chen, Y. Yuan, H. Jiang, S.-Y. Ren, L.-X. Ding, L. Ma, T. Wu, J. Lu, H. Wang, Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst, Nature Energy 5(8) (2020) 605–613.
[13] Y. Wang, C. Wang, M. Li, Y. Yu, B. Zhang, Y. Wang, Nitrate electroreduction: mechanism insight, in situ characterization, performance evaluation, and challenges Nitrate electroreduction: mechanism insight, in-situ characterization, performance evaluation, and challenges, Chemical Society Reviews 50(12) (2021) 6720–6733.
[14] J. Theerthagiri, J. Park, H.T. Das, N. Rahamathulla, E.S.F. Cardoso, A.P. Murthy, G. Maia, D.V.N. Vo, M.Y. Choi, Electrocatalytic conversion of nitrate waste into ammonia: a review, Environmental Chemistry Letters 20(5) (2022) 2929–2949.
[15] S. Garcia-Segura, M. Lanzarini-Lopes, K. Hristovski, P. Westerhoff, Electrocatalytic reduction of nitrate: Fundamentals to full-scale water treatment applications, Applied Catalysis B: Environmental 236 (2018) 546–568.
[16] M. Jiang, Q. Zhu, X. Song, Y. Gu, P. Zhang, C. Li, J. Cui, J. Ma, Z. Tie, Z. Jin, Batch-Scale Synthesis of Nanoparticle-Agminated Three-Dimensional Porous Cu@Cu2O Microspheres for Highly Selective Electrocatalysis of Nitrate to Ammonia, Environmental Science & Technology 56(14) (2022) 10299–10307.
[17] X. Zhao, Y. Jiang, M. Wang, Y. Huan, Q. Cheng, Y. He, T. Qian, C. Yan, Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions, Journal of Energy Chemistry 92 (2024) 459–483.
[18] M.C.P.M. da Cunha, M. Weber, F.C. Nart, On the adsorption and reduction of NO3− ions at Au and Pt electrodes studied by in situ FTIR spectroscopy, Journal of Electroanalytical Chemistry 414(2) (1996) 163–170.
[19] I. Katsounaros, G. Kyriacou, Influence of nitrate concentration on its electrochemical reduction on tin cathode: Identification of reaction intermediates, Electrochimica Acta 53(17) (2008) 5477–5484.
[20] J. Zheng, T. Lu, T.M. Cotton, G. Chumanov, Photoinduced Electrochemical Reduction of Nitrite at an Electrochemically Roughened Silver Surface, The Journal of Physical Chemistry B 103(31) (1999) 6567–6572.
[21] J. Yang, M. Duca, K.J.P. Schouten, M.T.M. Koper, Formation of volatile products during nitrate reduction on a Sn-modified Pt electrode in acid solution, Journal of Electroanalytical Chemistry 662(1) (2011) 87–92.
[22] M. Duca, M.O. Cucarella, P. Rodriguez, M.T.M. Koper, Direct Reduction of Nitrite to N2 on a Pt(100) Electrode in Alkaline Media, Journal of the American Chemical Society 132(51) (2010) 18042–18044.
[23] D.A. Nguyen, M.A. Iwaniw, H.S. Fogler, Kinetics and mechanism of the reaction between ammonium and nitrite ions: experimental and theoretical studies, Chemical Engineering Science 58(19) (2003) 4351–4362.
[24] M.D. Bartberger, W. Liu, E. Ford, K.M. Miranda, C. Switzer, J.M. Fukuto, P.J. Farmer, D.A. Wink, K.N. Houk, The reduction potential of nitric oxide (NO) and its importance to NO biochemistry, Proceedings of the National Academy of Sciences 99(17) (2002) 10958–10963.
[25] H. Niu, Z. Zhang, X. Wang, X. Wan, C. Shao, Y. Guo, Theoretical Insights into the Mechanism of Selective Nitrate‐to‐Ammonia Electroreduction on Single‐Atom Catalysts, Advanced Functional Materials 31(11) (2020).
[26] H.-J. Chun, V. Apaja, A. Clayborne, K. Honkala, J. Greeley, Atomistic Insights into Nitrogen-Cycle Electrochemistry: A Combined DFT and Kinetic Monte Carlo Analysis of NO Electrochemical Reduction on Pt(100), ACS Catalysis 7(6) (2017) 3869–3882.
[27] Y. Zeng, C. Priest, G. Wang, G. Wu, Restoring the Nitrogen Cycle by Electrochemical Reduction of Nitrate: Progress and Prospects, Small Methods 4(12) (2020).
[28] A.C.A. de Vooys, G.L. Beltramo, B. van Riet, J.A.R. van Veen, M.T.M. Koper, Mechanisms of electrochemical reduction and oxidation of nitric oxide, Electrochimica Acta 49(8) (2004) 1307–1314.
[29] X. Zhang, X. Liu, Z.-F. Huang, L. Guo, L. Gan, S. Zhang, M. Ajmal, L. Pan, C. Shi, X. Zhang, G. Yang, J.-J. Zou, Tandem Nitrate Electroreduction to Ammonia with Industrial-Level Current Density on Hierarchical Cu Nanowires Shelled with NiCo-Layered Double Hydroxide, ACS Catalysis 13(22) (2023) 14670–14679.
[30] D. Liu, L. Qiao, S. Peng, H. Bai, C. Liu, W.F. Ip, K.H. Lo, H. Liu, K.W. Ng, S. Wang, X. Yang, H. Pan, Recent Advances in Electrocatalysts for Efficient Nitrate Reduction to Ammonia, Advanced Functional Materials 33(43) (2023).
[31] M.R. Gennero de Chialvo, A.C. Chialvo, Kinetics of hydrogen evolution reaction with Frumkin adsorption: re-examination of the Volmer–Heyrovsky and Volmer–Tafel routes, Electrochimica Acta 44(5) (1998) 841–851.
[32] X. Wang, H. Yao, C. Zhang, C. Li, K. Tong, M. Gu, Z. Cao, M. Huang, H. Jiang, Double‐Tuned RuCo Dual Metal Single Atoms and Nanoalloy with Synchronously Expedited Volmer/Tafel Kinetics for Effective and Ultrastable Ampere‐Level Current Density Hydrogen Production, Advanced Functional Materials 33(40) (2023).
[33] J. Wang, W. Zang, X. Liu, J. Sun, S. Xi, W. Liu, Z. Kou, L. Shen, J. Wang, Switch Volmer-Heyrovsky to Volmer-Tafel Pathway for Efficient Acidic Electrocatalytic Hydrogen Evolution by Correlating Pt Single Atoms with Clusters Switch Volmer‐Heyrovsky to Volmer‐Tafel Pathway for Efficient Acidic Electrocatalytic Hydrogen Evolution by Correlating Pt Single Atoms with Clusters, Small 20(25) (2024) 2309427.
[34] M. Jiang, A. Tao, Y. Hu, L. Wang, K. Zhang, X. Song, W. Yan, Z. Tie, Z. Jin, Crystalline Modulation Engineering of Ru Nanoclusters for Boosting Ammonia Electrosynthesis from Dinitrogen or Nitrate, ACS Applied Materials & Interfaces 14(15) (2022) 17470–17478.
[35] D. Xu, Y. Li, L. Yin, Y. Ji, J. Niu, Y. Yu, Electrochemical removal of nitrate in industrial wastewater, Frontiers of Environmental Science & Engineering 12(1) (2018) 9.
[36] Z. Gong, W. Zhong, Z. He, Q. Liu, H. Chen, D. Zhou, N. Zhang, X. Kang, Y. Chen, Regulating surface oxygen species on copper (I) oxides via plasma treatment for effective reduction of nitrate to ammonia, Applied Catalysis B: Environmental 305 (2022) 121021.
[37] F. Lv, M. Sun, Y. Hu, J. Xu, W. Huang, N. Han, B. Huang, Y. Li, F. Lv, Near-unity electrochemical conversion of nitrate to ammonia on crystalline nickel porphyrin-based covalent organic frameworks, Energy & Environmental Science 16(1) (2023) 201–209.
[38] Y. Lv, S.W. Ke, Y. Gu, B. Tian, L. Tang, P. Ran, Y. Zhao, J. Ma, J.L. Zuo, M. Ding, Highly Efficient Electrochemical Nitrate Reduction to Ammonia in Strong Acid Conditions with Fe2M-Trinuclear-Cluster Metal–Organic Frameworks, Angewandte Chemie International Edition 62(27) (2023).
[39] R. Zhang, C. Li, H. Cui, Y. Wang, S. Zhang, P. Li, Y. Hou, Y. Guo, G. Liang, Z. Huang, C. Peng, C. Zhi, Electrochemical nitrate reduction in acid enables high-efficiency ammonia synthesis and high-voltage pollutes-based fuel cells, Nature Communications 14(1) (2023).
[40] H. Shin, S. Jung, S. Bae, W. Lee, H. Kim, Nitrite Reduction Mechanism on a Pd Surface, Environmental Science & Technology 48(21) (2014) 12768–12774.
[41] K. Fan, W. Xie, J. Li, Y. Sun, P. Xu, Y. Tang, Z. Li, M. Shao, Active hydrogen boosts electrochemical nitrate reduction to ammonia, Nature Communications 13(1) (2022).
[42] W. Yang, Z. Chang, X. Yu, R. Shen, L. Wang, X. Cui, J. Shi, Triple Regulations via Fe Redox Boosting Nitrate Reduction to Ammonia at Industrial Current Densities, Angewandte Chemie International Edition 64(3) (2025) e202415300.
[43] J. Li, G. Zhan, J. Yang, F. Quan, C. Mao, Y. Liu, B. Wang, F. Lei, L. Li, A.W.M. Chan, L. Xu, Y. Shi, Y. Du, W. Hao, P.K. Wong, J. Wang, S.-X. Dou, L. Zhang, J.C. Yu, Efficient Ammonia Electrosynthesis from Nitrate on Strained Ruthenium Nanoclusters, Journal of the American Chemical Society 142(15) (2020) 7036–7046.
[44] M.T. de Groot, M.T.M. Koper, The influence of nitrate concentration and acidity on the electrocatalytic reduction of nitrate on platinum, Journal of Electroanalytical Chemistry 562(1) (2004) 81–94.
[45] R. Lange, E. Maisonhaute, R. Robin, V. Vivier, On the kinetics of the nitrate reduction in concentrated nitric acid, Electrochemistry Communications 29 (2013) 25–28.
[46] M. Dortsiou, G. Kyriacou, Electrochemical reduction of nitrate on bismuth cathodes, Journal of Electroanalytical Chemistry 630(1-2) (2009) 69–74.
[47] Y. Chen, C. Chen, W.-H. Huang, C.-W. Pao, C.-C. Chang, T. Mao, J. Wang, H. Fu, F. Lai, N. Zhang, T. Liu, Charge Redistribution in High-Entropy Perovskite Oxide Porous Nanotubes Boosts Nitrate Electroreduction to Ammonia, ACS Nano 18(31) (2024) 20530–20540.
[48] J. Lv, X. Sun, F. Wang, R. Yang, T. Zhang, T. Liang, W. Rong, Q. Yang, W. Xue, L. Wang, X. Xu, Y. Liu, Engineering Nickel Dopants in Atomically Thin Molybdenum Disulfide for Highly Efficient Nitrate Reduction to Ammonia, Advanced Functional Materials 34(49) (2024).
[49] S. Lu, G. Lin, H. Yan, Y. Li, T. Qi, Y. Li, S. Liang, L. Jiang, In Situ Facet Transformation Engineering over Co3O4 for Highly Efficient Electroreduction of Nitrate to Ammonia, ACS Catalysis 14(19) (2024) 14887–14894.
[50] Y. Liu, X. Zhao, C. Long, X. Wang, B. Deng, K. Li, Y. Sun, F. Dong, In situ constructed dynamic Cu/Ce(OH) interface for nitrate reduction to ammonia with high activity, selectivity and stability, Chinese Journal of Catalysis 52 (2023) 196–206.
[51] Z. Zhang, X. Feng, Z. Zhang, L. Chen, W. Liu, L. Tong, X. Gao, J. Zhang, Graphdiyne Enabled Nitrogen Vacancy Formation in Copper Nitride for Efficient Ammonia Synthesis, Journal of the American Chemical Society 146(21) (2024) 14898–14904.
Downloads
Published
Issue
Section
License
Copyright (c) 2026 Menghuai Tang

This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.







