均一亚纳米Co簇催化剂用于工业条件下硝酸盐电合成氨

doi:10.1016/S1872-2067(26)65199-6

催化学报 ›› 2027, Vol. 92: 355-364.DOI: 10.1016/S1872-2067(26)65199-6

均一亚纳米Co簇催化剂用于工业条件下硝酸盐电合成氨

李尚纯^a^,¹, 徐贝贝^a^,¹, 逯景宇^a, 赵世杰^c, 张青青^a, 李仁贵^b, 张静^a^,^*()

^a 南京理工大学新能源学院, 江苏江阴 214443
^b 中国科学院大连化学物理研究所, 催化国家重点实验室, 洁净能源国家实验室(大连), 能源材料化学协同创新中心(iChEM), 辽宁大连 116023
^c 双良节能系统股份有限公司, 江苏江阴 214444

收稿日期:2026-02-07 接受日期:2026-04-01 出版日期:2027-01-02 发布日期:2026-10-30
通讯作者: *电子信箱: jingzhang_dicp@njust.edu.cn (张静).
作者简介:第一联系人：
¹共同第一作者.
基金资助:
国家自然科学基金(22402082);国家自然科学基金(22172068);江苏省自然科学基金(BK20241450);江苏省自然科学基金(BK20021485);中央高校基本科研业务费(2025201006);江苏省人才攻关联合体资助(LHT2024018)

Uniform cobalt sub-nanometer clusters catalysts for nitrate-to-ammonia electrosynthesis under industrial conditions

Shangchun Li^a^,¹, Beibei Xu^a^,¹, Jingyu Lu^a, Shijie Zhao^c, Qingqing Zhang^a, Rengui Li^b, Jing Zhang^a^,^*()

^a School of New Energy, Nanjing University of Science & Technology, Jiangyin 214443, Jiangsu, China
^b State Key Laboratory of Catalysis, Dalian National Laboratory for Clean Energy, and The Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^c Shuangliang Eco-Energy Systems Co., Ltd, Jiangyin 214444, Jiangsu, China

Received:2026-02-07 Accepted:2026-04-01 Online:2027-01-02 Published:2026-10-30
Contact: *E-mail: jingzhang_dicp@njust.edu.cn (J. Zhang).
About author:First author contact:
¹ Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22402082);National Natural Science Foundation of China(22172068);Natural Science Foundation of Jiangsu Province(BK20241450);Natural Science Foundation of Jiangsu Province(BK20021485);Fundamental Research Funds for the Central Universities(2025201006);Jiangsu Province Rencai Gongguan Lianheti(LHT2024018)

摘要/Abstract

摘要：

硝酸盐(NO₃^-)作为水体中广泛存在的污染物, 严重威胁饮用水安全与水生态系统健康. 电催化硝酸盐还原反应(NO₃RR)可将硝酸盐直接转化为氨(NH₃), 实现污染治理与资源回收. 然而, 该反应路径复杂、涉及多步质子-电子转移, 且与析氢反应竞争激烈, 导致现有催化剂普遍存在氨选择性低、反应动力学慢和稳定性差的问题. 传统过渡金属纳米颗粒催化剂虽具有一定活性, 但其较大尺寸限制了活性位点密度, 易导致析氢反应(HER)或亚硝酸盐等副产物积累, 并在高电流下发生迁移团聚, 造成性能衰减. 因此, 将金属活性中心缩小至亚纳米尺度, 成为提高原子利用率、调控电子结构以优化反应路径的有效策略. 其中, 氮掺杂碳载体因其表面氮物种对金属的强锚定作用, 是构筑高分散金属位点的理想平台. 然而, 如何构筑亚纳米簇结构并维持长时间稳定, 尤其是在工业级电流密度下抵抗迁移与团聚, 仍是该领域面临的关键挑战.

针对上述挑战, 本文提出精准调控氮掺杂碳载体的N配位环境, 以优化其对钴物种的锚定能力, 成功设计并合成了一种锚定于氮掺杂碳上的Co亚纳米簇催化剂(Co SNC). 系统研究表明, 存在一个最优的N/C比例窗口: 在此窗口内, 载体能够提供充足的吡咯氮锚定位点, 将Co原子稳定限制于亚纳米尺度, 形成高密度、高分散的活性Co簇. 得益于独特的亚纳米分散结构, Co SNC在NO₃RR中展现出卓越的性能, 其氨产率高达6.9 mol h^-1 g_cat^-1, 法拉第效率(FE)达到91.4% (-0.6 V vs. RHE), 显著优于同等条件下Co NPs的性能. 此外, 在模拟工业条件的膜电极组件中, Co SNC在500 mA cm^-2的高电流密度下可稳定运行超过100 h, NH₃法拉第效率保持在80%左右, 展现了优异的实际应用潜力. X-射线光电子能谱证实, 吡咯氮配体向Co中心发生了显著的电子转移, 导致Co 2p结合能负移, 提升了Co位点的电子密度, 从而降低了电荷转移电阻, 增强了反应动力学. 此外, 这种高度分散的Co簇结构创造了独特的反应微环境. 循环伏安电化学测试与原位衰减全反射红外光谱结果表明, Co SNC表面生成的吸附氢物种(H_ads)能被NO₃RR路径高效地消耗, 促进关键中间体NH₂OH生成NH₃, 而非结合生成H₂. 差分电化学质谱法进一步证实, 与Co NPs主要产生H₂的信号不同, Co SNC的质谱信号以NH₃为主导. 这些证据共同揭示了Co SNC能够精准引导反应路径, 加快NH₂OH向NH₃的加氢转化, 同时抑制竞争性HER, 从而实现高选择性合成氨.

综上, 本工作不仅成功开发了一种具有工业级电流密度运行能力的高性能NO₃RR电催化剂, 更重要的是, 通过“N配位环境精准调控-金属亚纳米结构构筑-构效关系微观阐释”的研究链条, 揭示了在氮掺杂碳上实现金属亚纳米级分散与稳定的配位原则, 并阐明了亚纳米分散结构通过优化电子转移与引导氢物种流向以主导高选择性反应路径的微观机制. 该研究为设计面向实际废水处理的高效、稳定电催化剂提供了新的设计思路与理论依据.

关键词: 亚纳米簇, 硝酸根还原, 电催化剂, 工业电流密度, 选择性加氢

Abstract:

The practical application of electrocatalytic nitrate reduction to ammonia (NO₃RR) is limited by insufficient selectivity and stability under industrial current densities, primarily due to competitive side reactions and catalyst structural degradation. A critical challenge lies in the rational design of stable and active sub-nanometer metal clusters, where achieving strong yet precise anchoring of metal atoms to specific nitrogen sites within a carbon matrix is essential to prevent aggregation and tune the electronic structure for optimal performance. In this work, by precisely engineering the local coordination environment of nitrogen dopants, we created tailored anchoring sites that effectively stabilize cobalt atoms, thereby fostering the formation of well-defined cobalt sub-nanometer clusters (Co SNC). Mechanistic investigations reveal that the optimized Co SNC sites facilitate the selective hydrogenation of the key *NH₂OH intermediate to NH₃ via adsorbed hydrogen (*H_ads). Consequently, the engineered catalyst achieves an exceptional ammonia production rate of 6.9 mol h^-1 g_cat^-1 with a Faradaic efficiency of 91.4% at -0.6 V vs. RHE. Moreover, it demonstrates outstanding durability, operating steadily for over 100 h at an industrial-level current density of 500 mA cm^-2@2.09 V in a membrane electrode assembly. This work elucidates the critical role of enhancing the dispersion of metal active sites, providing a viable strategy for designing efficient and stable electrocatalysts toward nitrate-to-ammonia conversion and related processes.

Key words: Sub-nanometer clusters, Nitrate reduction, Electrocatalyst, Industrial-current density, Selective hydrogenation

李尚纯, 徐贝贝, 逯景宇, 赵世杰, 张青青, 李仁贵, 张静. 均一亚纳米Co簇催化剂用于工业条件下硝酸盐电合成氨[J]. 催化学报, 2027, 92: 355-364.

Shangchun Li, Beibei Xu, Jingyu Lu, Shijie Zhao, Qingqing Zhang, Rengui Li, Jing Zhang. Uniform cobalt sub-nanometer clusters catalysts for nitrate-to-ammonia electrosynthesis under industrial conditions[J]. Chinese Journal of Catalysis, 2027, 92: 355-364.

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图/表 4

Fig. 1. (a) Schematic synthesis of Co SNC and Co NPs. (b) XRD patterns of Co NPs, Co SNC and NC. (c) HRTEM image of Co NPs. (d) HAADF-STEM image of Co SNC. (e) N 1s XPS spectra of Co SNC-N0.8, Co SNC-N0.9 and Co SNC. (f) Co 2p XPS spectra of Co SNC-N0.8, Co SNC-N0.9 and Co SNC.

Fig. 2. (a) LSV curves comparing the electrochemical performance of different catalysts in the presence and absence of 1 mol L-1 NO3-. (b) FENH3 and NH3 yield of Co SNC and Co NPs. (c) FENH3 and NH3 yield rates of Co SNC under different potentials in UV-vis and ion chromatography tests. (d) FENH3 and NH3 yield rates of Co SNC with different potentials and different concentrations of KNO3. (e) TOF of Co SNC and Co NPs in 1 mol L-1 NO3-. (f) ECSA of NC, Co SNC and Co NPs. (g) Cycling tests of Co SNC in 1 mol L-1 KOH and 1 mol L-1 KNO3 electrolyte at -0.8 V vs. RHE. (h) Comparison with recently reported NO3RR electrocatalysts.

Fig. 3. (a) Schematic illustration of AEM configuration. (b) Activation curves of the AEM. (c) Stability of the Co SNC electrode in the AEM device at 500 mA cm-2.

Fig. 4. (a) CV curves of Co SNC in 1 mol L-1 KOH with and without NO3-. (b) CV curves of Co NPs in 1 mol L-1 KOH with and without NO3-. (c) Potential-dependent in-situ FTIR spectra of Co SNC catalyst. (d) Potential-dependent in-situ FTIR spectra of Co NPs catalyst. (e) In-situ DEMS results of Co SNC catalyst. (f) In-situ DEMS results of Co NPs catalyst. (g) Proposed reaction mechanisms on Co SNC and Co NPs catalysts.

参考文献

[1]	S. Yin, Z. Guan, Y. Zhu, D. Guo, X.-A. Chen, S. Wang, ACS Nano, 2024, 18, 27833-27852.
[2]	F.-Y. Chen, A. Elgazzar, S. Pecaut, C. Qiu, Y. Feng, S. Ashokkumar, Z. Yu, C. Sellers, S. Hao, P. Zhu, H. Wang, Nat. Catal., 2024, 7, 1032-1043.
[3]	S. Luo, H. Guo, T. Li, H. Wu, F. Zhang, C. Tang, G. Chen, G. Yang, Y. Zhou, Appl. Catal. B, 2024, 351, 123967.
[4]	K. Veerathangam, A. Nancy Anna Anasthasiya, Y. Liu, J. Yin, P. Phiri, Y. Li, J. Yu, Y. Cheng, N. Liu, L. Xu, H. Li, J. Environ. Chem. Eng., 2025, 13, 117055.
[5]	X. Fu, J. B. Pedersen, Y. Zhou, M. Saccoccio, S. Li, R. Sažinas, K. Li, S. Z. Andersen, A. Xu, N. H. Deissler, J. B. V. Mygind, C. Wei, J. Kibsgaard, P. C. K. Vesborg, J. K. Nørskov, I. Chorkendorff, Science, 2023, 379, 707-712.
[6]	M. Wei, Y. Huang, Y. Wei, S. Chen, Z. Zhang, Z. Ge, J. Chen, F. Saleem, W. Liu, ACS Appl. Mater. Interfaces, 2025, 17, 27671-27696.
[7]	J. Bai, Z. Dong, X. Jiang, Q. Zhou, J. Zhao, J. Mei, Z. Tan, T. Liao, Z. Sun, Adv. Sci., 2025, 12, e08614.
[8]	X. Tang, W. Liu, C. Lei, Y. Ling, S. Kang, Nano Energy, 2025, 135, 110708.
[9]	H. Zhang, H. Wang, X. Cao, M. Chen, Y. Liu, Y. Zhou, M. Huang, L. Xia, Y. Wang, T. Li, D. Zheng, Y. Luo, S. Sun, X. Zhao, X. Sun, Adv. Mater., 2024, 36, 2312746.
[10]	Y. Zhao, J. Shen, J. Yuan, H. Mao, X. Cheng, Z. Xu, Z. Bian, Nano Energy, 2024, 124, 109499.
[11]	Y. Zhang, H. Liang, Chem. Synth., 2024, 4, 39.
[12]	L. Bai, F. Franco, J. Timoshenko, C. Rettenmaier, F. Scholten, H. S. Jeon, A. Yoon, M. Rüscher, A. Herzog, F. T. Haase, S. Kühl, S. W. Chee, A. Bergmann, R. C. Beatriz, J. Am. Chem. Soc., 2024, 146, 9665-9678.
[13]	T. Zhang, K. Shi, B. Wang, X. Hou, ACS Catal., 2025, 15, 9814-9844.
[14]	J. Xu, S. Zhang, H. Liu, S. Liu, Y. Yuan, Y. Meng, M. Wang, C. Shen, Q. Peng, J. Chen, X. Wang, L. Song, K. Li, W. Chen, Angew. Chem. Int. Ed., 2023, 62, e202308044.
[15]	Z. J. Cui, P. W. Zhao, H. H. Wang, C. L. Li, W. C. Peng, J. P. Liu, Adv. Funct. Mater., 2024, 34, 2410941.
[16]	J. Li, M. Li, N. An, S. Zhang, Q. Song, Y. Yang, J. Li, X. Liu, Proc. Natl. Acad. Sci. USA, 2022, 119, e2123450119.
[17]	Y. Wang, J. Liu, Q. Wang, Y. Xu, Q. Zhang, Chem. Eng. J., 2026, 527, 171580.
[18]	W. He, J. Zhang, S. Dieckhöfer, S. Varhade, A. C. Brix, A. Lielpetere, S. Seisel, J. R. C. Junqueira, W. Schuhmann, Nat. Commun., 2022, 13, 1129.
[19]	X. Zhou, W. Xu, Y. Liang, H. Jiang, Z. Li, S. Wu, Z. Gao, Z. Cui, S. Zhu, ACS Catal., 2024, 14, 12251-12259.
[20]	R. Li, T. Gao, W. Qiu, M. Xie, Z. Jin, P. Li, Nano Res., 2024, 17, 2438-2443.
[21]	C.-L. Yu, H.-Y. Chen, N.-C. Lo, C.-L. Lee, P.-Y. Chen, J. Electroanal. Chem., 2022, 914, 116325.
[22]	L. Liu, T. Chen, Z. Chen, Adv. Sci., 2024, 11, 2308046.
[23]	L. Gong, J. Zhu, F. Xia, Y. Zhang, W. Shi, L. Chen, J. Yu, J. Wu, S. Mu, ACS Catal., 2023, 13, 4012-4020.
[24]	X. Cheng, Z. Shen, L. Jiao, L. Yang, X. Wang, Q. Wu, Z. Hu, EnergyChem, 2021, 3, 100066.
[25]	S. Zhang, J. Yi, M. Liu, L. Shi, M. Chen, L. Wu, ACS Nano, 2024, 18, 26722-26732.
[26]	R. Li, T. Gao, P. Wang, W. Qiu, K. Liu, Y. Liu, Z. Jin, P. Li, Appl. Catal. B, 2023, 331, 122677.
[27]	Y. Xue, Q. Yu, Q. Ma, Y. Chen, C. Zhang, W. Teng, J. Fan, W.-X. Zhang, Environ. Sci. Technol., 2022, 56, 14797-14807.
[28]	S. Zhang, P. Gao, Q. Liu, Z. Zhang, B. Leng, J. Chen, X. Li, Nat. Commun., 2024, 15, 10877.
[29]	J. Sun, M. Shen, A.-J. Chang, C. Liang, C. Xiong, C. Hou, J. Li, P. Wang, J. Li, J. Huang, Chem. Eng. J., 2025, 503, 158551.
[30]	M. Salverda, A. R. Thiruppathi, F. Pakravan, P. C. Wood, A. Chen, Molecules, 2022, 27, 8643.
[31]	Y. Zhuang, J.-L. Ma, W.-J. Feng, Catalysts, 2022, 12, 951.
[32]	X. Cheng, C. Tang, C. Yan, J. Du, A. Chen, X. Liu, L. Jewell, Q. Zhang, Mater. Today Nano, 2023, 22, 100321.
[33]	M. Huang, X. Zhu, W. Shi, Q. Qin, J. Yang, S. Liu, L. Chen, R. Ding, L. Gan, X. Yin, Sci. Adv., 2025, 11, eads6658.
[34]	W. Zheng, F. Chen, Q. Zeng, Z. Li, B. Yang, L. Lei, Q. Zhang, F. He, X. Wu, Y. Hou, Nano-Micro Lett., 2020, 12, 108.
[35]	W. Zhang, A. Mehmood, G. Ali, H. Liu, L. Chai, J. Wu, M. Liu, Angew. Chem. Int. Ed., 2025, 64, e202424552.
[36]	Y. Yang, W. Zhang, G. Wu, Q. Huang, J. Wen, D. Wang, M. Liu, Angew. Chem. Int. Ed., 2025, 64, e202504423.
[37]	K. Li, J. Zhang, R. Wu, Y. Yu, B. Zhang, Adv. Sci., 2016, 3, 1500426.
[38]	B. Zhang, Z. Dai, Y. Chen, M. Cheng, H. Zhang, P. Feng, B. Ke, Y. Zhang, G. Zhang, Nat. Commun., 2024, 15, 2816.
[39]	C. Yang, Y. Tang, Q. Yang, B. Wang, X. Liu, Y. Li, W. Yang, K. Zhao, G. Wang, Z. Wang, F. Yu, J. Hazard. Mater., 2024, 480, 136036.
[40]	G. Chang, X. Chen, J.-J. Lv, Z. Kong, Z.-J. Wang, Nano-Micro Lett., 2026, 18, 73.
[41]	K. Fan, W. Xie, J. Li, Y. Sun, P. Xu, Y. Tang, Z. Li, M. Shao, Nat. Commun., 2022, 13, 7958.
[42]	M. Zheng, Y. Wan, Z.-H. Huang, F. Kang, R. Lv, Adv. Mater., 2026, 38, e14834.
[43]	Z. Xiang, Y.-R. Lu, L. Meng, J. Lan, F. Xie, S. Gao, J. Li, M. Luo, M. Peng, Y. Tan, Adv. Mater., 2025, 37, 2501886.
[44]	K. Wu, W. Wu, S. Liu, R. Zhang, Y. Chen, J. Li, X. Wei, K. Pang, K. Wan, W. Dai, C. Tang, J. Li, C. Long, F. Dong, Angew. Chem. Int. Ed., 2026, 65, e24218.
[45]	J. Zhong, H. Duan, M. Cai, Y. Zhu, Z. Wang, X. Li, Z. Zhang, W. Qu, K. Zhang, D. Han, D. Cheng, Y. Shen, M. Xie, E. Cortes, D. Zhang, Angew. Chem. Int. Ed., 2025, 64, e202507956.
[46]	J. Fang, Q. Zheng, Y. Lou, K. Zhao, S. Hu, G. Li, O. Akdim, X. Huang, S. Sun, Nat. Commun., 2022, 13, 7899.

均一亚纳米Co簇催化剂用于工业条件下硝酸盐电合成氨

Uniform cobalt sub-nanometer clusters catalysts for nitrate-to-ammonia electrosynthesis under industrial conditions

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