Direct electrosynthesis of ammonia from nitrate reduction using atomically precise carbonyl-rich metal clusters in neutral media

doi:10.1016/S1872-2067(26)65146-7

Chinese Journal of Catalysis ›› 2026, Vol. 88: 259-268.DOI: 10.1016/S1872-2067(26)65146-7

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Direct electrosynthesis of ammonia from nitrate reduction using atomically precise carbonyl-rich metal clusters in neutral media

Miao Wang^a^,^b^,¹, Tianyu Shen^a^,¹, Heng Zhou^c^,¹, Shuaikang Yang^a, Fengkun Hao^b, Chaohui Wang^b, Mohan Kumar^d, Zuoxiu Tie^a^,^*(), Shuangming Chen^c^,^*(), Zhanxi Fan^b^,^*(), Zhong Jin^a^,^*()

^a State 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 Green Energy Catalysis and Intelligent 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
^b Department of Chemistry, Hong Kong Branch of National Precious Metals Material Engineering Research Center (NPMM), Hong Kong Institute for Clean Energy, City University of Hong Kong, Kowloon, Hong Kong 999077, China
^c National Synchrotron Radiation Laboratory, Chinese Academy of Sciences Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei 230029, Anhui, China
^d Department of Chemistry, PES Institute of Technology and Management, Shivamogga 577204, Karnataka, India

Received:2025-11-12 Accepted:2026-02-05 Online:2026-09-18 Published:2026-09-05
About author:First author contact:1 共同第一作者.
1 Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(U25A20628);The National Natural Science Foundation of China(22561160129);The National Natural Science Foundation of China(22479074);The National Natural Science Foundation of China(22475096);The Equipment Pre-Research and Ministry of Education Joint Fund(8091B02052407);The Fundamental Research Program Key Project of Jiangsu Province(BK20253008);The Science and Technology Major Project of Jiangsu Province(BG2024013);The Scientific and Technological Achievements Transformation Special Fund of Jiangsu Province(BA2023037);The Academic Degree and Postgraduate Education Reforming Project of Jiangsu Province(JGKT24_C001);The Key Core Technology Open Competition Project of Suzhou City(SYG2024122);The Open Research Fund of Suzhou Laboratory(SZLAB-1308-2024-TS005);The Chenzhou National Sustainable Development Agenda Innovation Demonstration Zone Provincial Special Open Competition Project(2023sfq11);The Chenzhou National Sustainable Development Agenda Innovation Demonstration Zone Provincial Special Open Competition Project(2025sfq38);The Fundamental Research Funds for the Central Universities and Nanjing University International Collaboration Initiative(020514380354)

Abstract

Abstract:

Atomically precise metal clusters, as an advantageous platform for investigating the active site architectures and catalytic mechanisms, remain largely underexplored. Here, we demonstrate that carbonyl-rich metal clusters (CRMC) serve as exemplary electrocatalytic platforms, enabling highly efficient and selective electroreduction of nitrate to ammonia under neutral aqueous conditions. To establish a comprehensive structure-performance correlation, we systematically investigated an array of diverse carbonyl-rich metal clusters, including Co₂-CRMC, Co₄-CRMC, Ru₃-CRMC, Fe₂-CRMC, Fe₃-CRMC, Mo-CRMC, W-CRMC and Mn₂-CRMC. Among them, Co₂-CRMC electrode delivered exceptional performance, with a Faradaic efficiency of 97.2% and an ammonia yield rate of 150.5 mmol h⁻¹ g⁻¹_cat., while Co₄-CRMC electrode achieved a Faradaic efficiency of 98.7% and a yield rate of 129.2 mmol h⁻¹ g⁻¹_cat.. Theoretical calculations and mechanism studies reveal that the high catalytic activity stems from enhanced NO₃⁻ adsorption and a reduced energy barrier for the *NO hydrogenation steps. Furthermore, electrostatic potential analyses highlight the critical role of metal-carbonyl ligand interactions in optimizing the electronic environment of metal centers, facilitating stronger NO₃⁻ adsorption. This research offers a profound molecular-level understanding for the design of sophisticated metal-cluster catalysts, opening avenues for efficient nitrogen cycling processes and environmental restoration efforts.

Key words: Carbonyl-enriched metal clusters, Atomically precise architectures, Electrochemical nitrate reduction, Ammonia electrosynthesis, Density functional theory calculations

Miao Wang, Tianyu Shen, Heng Zhou, Shuaikang Yang, Fengkun Hao, Chaohui Wang, Mohan Kumar, Zuoxiu Tie, Shuangming Chen, Zhanxi Fan, Zhong Jin. Direct electrosynthesis of ammonia from nitrate reduction using atomically precise carbonyl-rich metal clusters in neutral media[J]. Chinese Journal of Catalysis, 2026, 88: 259-268.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65146-7

https://www.cjcatal.com/EN/Y2026/V88/I9/259

Figures/Tables 5

Fig. 1. Structural and compositional characterizations. Crystal structures of carbonyl-enriched Co2-CRMC (a) and Co4-CRMC clusters (b). PXRD patterns (c) and FTIR spectra (d) of two carbonyl-rich cobalt clusters. Survey XPS spectra (e) and high-resolution XPS spectra (f) at O 1s level of two cobalt clusters. High-resolution XPS spectra at C 1s level for Co2-CRMC (g) and Co4-CRMC clusters (h).

Fig. 2. Fine structure characterizations. (a) XPS spectra at Co 2p level for carbonyl-enriched Co2-CRMC and Co4-CRMC clusters. Co K-edge XANES (b) and EXAFS (c) spectra of two cobalt clusters along with other reference samples. (d-f) Co K-edge EXAFS fitting curves of two cobalt cluster samples. (g-j) Co K-edge wavelet transformations of two cobalt clusters along with other reference samples.

Fig. 3. Electrocatalytic NITRR activities of two carbonyl-rich cobalt cluster electrodes. (a) LSV curves of the two samples tested in 0.1 mol L-1 Na2SO4-0.1 mol L-1 KNO3 mixed electrolyte. FE values and NH3 yield rates of Co2-CRMC (b) and Co4-CRMC (c) electrodes for the NITRR. (d) LSV curves of the two samples tested in 0.5 mol L-1 KNO3 electrolyte. FE values and NH3 yield rates of Co2-CRMC (e) and Co4-CRMC (f) electrodes for the NITRR. XPS spectra at Co 2p level (g), C 1s (h), and O 1s (i) levels of Co2-CRMC electrode before and after the NITRR process. (j) Typical SEM image and elemental mappings of Co2-CRMC clusters supported on carbon paper (CP) after the NITRR process.

Fig. 4. Theoretical calculations and mechanism studies. (a) The PDOS analysis of Co-3d and NO3−-2p adsorbed on the carbonyl-rich Co2-CRMC model. (b) The ESP surface analysis of the Co2-CRMC model. (c) The charge density difference of the NO3− adsorbed on the Co2-CRMC model. The cyan and yellow regions corroborate charge depletion and charge accumulation, respectively. The isosurface value is 0.03 eV Å−3. (d) Calculated free-energy diagrams of the possible electrocatalytic NITRR pathways on the Co2-CRMC model. The inserts illustrate the optimized adsorption configurations of various reaction intermediates along the N-end pathway. (e) In-situ DEMS patterns of NITRR on Co2-CRMC electrode. (f) In-situ ATR-FTIR spectra of Co2-CRMC electrode under various applied potentials.

Fig. 5. The NITRR tests in flow cell. (a) Schematic illustration of the flow-cell system. (b) LSV curves of Co2-CRMC and Co4-CRMC electrodes tested in 0.1 mol L-1 Na2SO4−0.1 mol L-1 KNO3 mixed electrolyte. (c) Time-dependent industrially relevant current density curve of Co4-CRMC electrode at an applied potential of −0.6 V (vs. RHE).

References

[1]	C. Tang, S.-Z. Qiao, Chem. Soc. Rev., 2019, 48, 3166-3180.
[2]	A. Good, Science, 2018, 359, 869-870.
[3]	R. Shi, X. Zhang, G. Waterhouse, X. Zhao, R. Zhang, Adv. Energy Mater., 2020, 10, 2000659.
[4]	J. Zhang, X. Tian, M. Liu, H. Guo, J. Zhou, Q. Fang, Z. Liu, Q. Wu, J. Lou, J. Am. Chem. Soc., 2019, 141, 19269-19275.
[5]	L. Hui, Y. Xue, H. Yu, Y. Liu, Y. Fang, C. Xing, B. Huang, Y. Li, J. Am. Chem. Soc., 2019, 141, 10677-10683.
[6]	L. Zhang, L.-X. Ding, G.-F. Chen, X. Yang, H. Wang, Angew. Chem. Int. Ed., 2019, 58, 2638-2642.
[7]	S.-J. Li, D. Bao, M.-M. Shi, B.-R. Wulan, J.-M. Yan, Q. Jiang, Adv. Mater., 2017, 29, 1700001.
[8]	B. Yu, H. Li, J. White, S. Donne, J. Yi, S. Xi, Y. Fu, G. Henkelman, H. Yu, Z. Chen, T. Ma, Adv. Funct. Mater., 2020, 30, 1905665.
[9]	M. Jiang, L. Han, P. Peng, Y. Hu, Y. Xiong, C. Mi, Z. Tie, Z. Xiang, Z. Jin, Nano Lett., 2022, 22, 372-379.
[10]	Q. Gao, H. S. Pillai, Y. Huang, S. Liu, Q. Mu, X. Han, Z. Yan, H. Zhou, Q. He, H. Xin, H. Zhu, Nat. Commun., 2022, 13, 2338.
[11]	C. Liu, G. Zhang, W. Zhang, Z. Gu, G. Zhu, Proc. Natl. Acad. Sci. USA, 2023, 120, e2209979120.
[12]	K. C. Majhi, H. Chen, A. Batool, Q. Zhu, Y. Jin, S. Liu, P. H.-L. Sit, J. C.-H. Lam, Angew. Chem. Int. Ed., 2025, 64, e202500167.
[13]	P. H. van Langevelde, I. Katsounaros, M. T. M. Koper, Joule, 2021, 5, 290-294.
[14]	Z. Zhang, Y. Lv, Y. Gu, X. Zhou, B. Tian, A. Zhang, Z. Yang, S. Chen, J. Ma, M. Ding, J.-L. Zuo, Angew. Chem. Int. Ed., 2025, 64, e202418272.
[15]	Y. Wang, M. Sun, J. Zhou, Y. Xiong, Q. Zhang, C. Ye, X. Wang, P. Lu, T. Feng, F. Hao, F. Liu, J. Wang, Y. Ma, J. Yin, S. Chu, L. Gu, B. Huang, Z. Fan, Proc. Natl. Acad. Sci. U. S. A., 2023, 120, e2306461120.
[16]	Z. Song, Y. Liu, Y. Zhong, Q. Guo, J. Zeng, Z. Geng, Adv. Mater., 2022, 34, 2204306.
[17]	S.-E. Bae, K. L. Stewart, A. A. Gewirth, J. Am. Chem. Soc., 2007, 129, 10171-10180.
[18]	S.-J. Zheng, X.-Y. Dong, H. Chen, R.-W. Huang, J. Cai, S.-Q. Zang, Angew. Chem. Int. Ed., 2025, 64, e202413033.
[19]	P. Li, R. Li, Y. Liu, M. Xie, Z. Jin, G. Yu, J. Am. Chem. Soc., 2023, 145, 6471-6479.
[20]	S. Liang, X. Teng, H. Xu, L. Chen, J. Shi, Angew. Chem. Int. Ed., 2024, 63, e202400206.
[21]	L. Liu, S.-J. Zheng, H. Chen, J. Cai, S.-Q. Zang, Angew. Chem. Int. Ed., 2024, 63, e202316910.
[22]	G. Ma, F. Sun, L. Qiao, Q. Shen, L. Wang, Q. Tang, Z. Tang, Nano Res., 2023, 16, 10867-10872.
[23]	R. Zhang, H. Hong, X. Liu, S. Zhang, C. Li, H. Cui, Y. Wang, J. Liu, Y. Hou, P. Li, Z. Huang, Y. Guo, C. Zhi, Angew. Chem. Int. Ed., 2023, 62, e202309930.
[24]	Q. Yang, Q. Xu, H.-L. Jiang, Chem. Soc. Rev., 2017, 46, 4774-4808.
[25]	L. Jiao, Y. Wang, H.-L. Jiang, Q. Xu, Adv. Mater., 2018, 30, 1703663.
[26]	M. Wang, Y.-R. Meng, W. Xu, T. Shen, Y. Wang, Q. Yu, C. Liu, Y. Gu, Z. Tie, Z. Fan, J.-L. Zuo, J. Su, Z. Jin, J. Am. Chem. Soc., 2025, 147, 18327-18337.
[27]	Y. Xiong, B. Li, Y. Gu, T. Yan, Z. Ni, S. Li, J.-L. Zuo, J. Ma, Z. Jin, Nat. Chem., 2023, 15, 286-293.
[28]	Z. Jiang, Y. Wang, Z. Lin, Y. Yuan, X. Zhang, Y. Tang, H. Wang, H. Li, C. Jin, Y. Liang, Energy Environ. Sci., 2023, 16, 2239-2246.
[29]	J. Su, S. Yuan, H.-Y. Wang, L. Huang, J.-Y. Ge, E. Joseph, J. Qin, T. Cagin, J.-L. Zuo, H.-C. Zhou, Nat. Commun., 2017, 8, 2008.
[30]	Y. Tang, Y. Liu, Y. Xia, F. Zhao, B. Zeng, Anal. Chem., 2023, 95, 4795-4802.
[31]	B. Lan, X. Zhang, Y. Wang, C. Wei, G. Wen, Carbon, 2022, 192, 384-394.
[32]	L. Li, D. Li, Q. Bai, Y. Wang, C. Li, Y. Shen, H. Uyama, Energy Fuels, 2023, 37, 16942-16950.
[33]	Y.-B. Liu, Y.-N. Wang, H.-M. Lu, S. Liang, B.-L. Xu, Y.-N. Fan, Chem. Eur. J., 2016, 11, 3159-3164.
[34]	M. Wang, S. Li, Y. Gu, W. Xu, H. Wang, J. Sun, S. Chen, Z. Tie, J.-L. Zuo, J. Ma, J. Su, Z. Jin, J. Am. Chem. Soc., 2024, 146, 20439-20448.
[35]	L. Sun, V. Reddu, S. Xi, C. Dai, Y. Sheng, T. Su, A. C. Fisher, X. Wang, Adv. Energy Mater., 2022, 12, 2202108.
[36]	L. Liu, T. Xiao, H. Fu, Z. Chen, X. Qu, S. Zheng, Appl. Catal. B, 2023, 323, 122181.
[37]	X. Dai, L. Tian, Z. Liu, W. Xu, Y.-P. Liu, Y. Liu, ACS Nano, 2022, 16, 18398-18407.
[38]	J. Wang, C. Cai, Y. Wang, X. Yang, D. Wu, Y. Zhu, M. Li, M. Gu, M. Shao, ACS Catal., 2021, 11, 15135-15140.
[39]	M. Xie, S. Tang, Z. Li, M. Wang, Z. Jin, P. Li, X. Zhan, H. Zhou, G. Yu, J. Am. Chem. Soc., 2023, 145, 13957-13967.
[40]	Y. Yu, C. Wang, Y. Yu, Y. Wang, B. Zhang, Sci. China Chem., 2020, 63, 1469-1476.
[41]	N. Zhang, J. Shang, X. Deng, L. Cai, R. Long, Y. Xiong, Y. Chai, ACS Nano, 2022, 16, 4795-4804.
[42]	L. Li, C. Tang, X. Cui, Y. Zheng, X. Wang, H. Xu, S. Zhang, T. Shao, K. Davey, S.-Z. Qiao, Angew. Chem. Int. Ed., 2021, 60, 14131-14137.
[43]	Y. Lv, S.-W. Ke, Y. Gu, B. Tian, L. Tang, P. Ran, Y. Zhao, J. Ma, J.-L. Zuo, M. Ding, Angew. Chem. Int. Ed., 2023, 62, e202305246.
[44]	M. Jiang, Q. Zhu, X. Song, Y. Gu, P. Zhang, C. Li, J. Cui, J. Ma, Z. Tie, Z. Jin, Environ. Sci. Technol., 2022, 56, 10299-10307.
[45]	H. Hu, R. Miao, F. Yang, F. Duan, H. Zhu, Y. Hu, M. Du, S. Lu, Adv. Energy Mater., 2024, 14, 2302608.
[46]	G.-F. Chen, Y. Yuan, H. Jiang, S.-Y. Ren, L.-X. Ding, L. Ma, T. Wu, J. Lu, H. Wang, Nat. Energy, 2020, 5, 605-613.
[47]	B. P. Chaplin, J. R. Shapley, C. J. Werth, Catal. Lett., 2009, 130, 56-62.
[48]	Z.-Y. Wu, M. Karamad, X. Yong, Q. Huang, D. A. Cullen, P. Zhu, C. Xia, Q. Xiao, M. Shakouri, F.-Y. Chen, J. Y. Kim, Y. Xia, K. Heck, Y. Hu, M. S. Wong, Q. Li, I. Gates, S. Siahrostami, H. Wang, Nat. Commun., 2021, 12, 2870.
[49]	Z. Gao, Y. Lai, Y. Tao, L. Xiao, L. Zhang, F. Luo, ACS Cent. Sci., 2021, 7, 1066-1072.
[50]	Y. Wang, W. Zhou, R. Jia, Y. Yu, B. Zhang, Angew. Chem. Int. Ed., 2020, 59, 5350-5354.
[51]	R. Zhang, X. Ma, S. Zhang, H. Cui, C. Li, Y. Wang, Q. Li, C. Peng, Y. Guo, C. Zhi, Angew. Chem. Int. Ed., 2025, 64, e202507724.
[52]	A. Aminu, B. M. Pirzada, S. H. Talib, J. Shaya, I. Yildiz, S. Mohamed, A. Qurashi, Nano Res. Energy, 2025, 4, e9120161.
[53]	S. Tang, M. Xie, S. Yu, X. Zhan, R. Wei, M. Wang, W. Guan, B. Zhang, Y. Wang, H. Zhou, G. Zheng, Y. Liu, J. H. Warner, G. Yu, Nat. Commun., 2024, 15, 6932.
[54]	Y. Ma, L. Guo, L. Chang, W. Guo, T. Zhou, F. Hao, W. Su, J. Zhou, G. Wang, M. Shao, J. Yu, J. Yin, Y. Wang, F. Liu, A. Zhang, K. Qian, J. Wang, X. Zhang, W. Zhou, S. Chu, C. Ling, L. Gan, Z. Guo, Z. Fan, Nat. Commun., 2025, 16, 7632.
[55]	S. Han, H. Li, T. Li, F. Chen, R. Yang, Y. Yu, B. Zhang, Nat. Catal., 2023, 6, 402-414.
[56]	Y. Huang, C. He, C. Cheng, S. Han, M. He, Y. Wang, N. Meng, B. Zhang, Q. Lu, Y. Yu, Nat. Commun., 2023, 14, 7368.

Direct electrosynthesis of ammonia from nitrate reduction using atomically precise carbonyl-rich metal clusters in neutral media

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