用杂原子调控Ni单原子催化剂的局部环境以实现高效CO2电还原

doi:10.1016/S1872-2067(25)64679-1

催化学报 ›› 2025, Vol. 74: 120-129.DOI: 10.1016/S1872-2067(25)64679-1

用杂原子调控Ni单原子催化剂的局部环境以实现高效CO₂电还原

王刚^a, Imran Muhammad^a, 阎慧敏^a, 李隽^a^,^b^,^*(), 王阳刚^a^,^*()

^a南方科技大学化学系, 广东省催化化学重点实验室, 广东深圳 518055
^b清华大学化学系, 稀土新材料教育部工程研究中心, 北京 100084

收稿日期:2025-01-07 接受日期:2025-03-04 出版日期:2025-07-18 发布日期:2025-07-20
通讯作者: *电子信箱: junli@tsinghua.edu.cn (李隽),wangyg@sustech.edu.cn (王阳刚).
基金资助:
国家自然科学基金(22373045);国家重点研发计划(2023YFA1509004);广东省“珠江”人才计划(2019QN01L353);国家自然科学基金单原子催化研究中心(22388102);深圳市科技委(JCYJ20210324103608023);深圳市科技委(KCXST20221021111207017);深圳市科技委(JCYJ20220818100410023)

Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO₂ electroreduction

Gang Wang^a, Imran Muhammad^a, Hui-Min Yan^a, Jun Li^a^,^b^,^*(), Yang-Gang Wang^a^,^*()

^aDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China
^bDepartment of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing 100084, China

Received:2025-01-07 Accepted:2025-03-04 Online:2025-07-18 Published:2025-07-20
Contact: *E-mail: junli@tsinghua.edu.cn (J. Li), wangyg@sustech.edu.cn (Y.-G. Wang).
Supported by:
National Natural Science Foundation of China(22373045);National Key Research and Development Program of China(2023YFA1509004);Guangdong “Pearl River” Talent Plan(2019QN01L353);NSFC Center for Single-Atom Catalysis(22388102);Science, Technology and Innovation Commission of Shenzhen Municipality(JCYJ20210324103608023);Science, Technology and Innovation Commission of Shenzhen Municipality(KCXST20221021111207017);Science, Technology and Innovation Commission of Shenzhen Municipality(JCYJ20220818100410023)

摘要/Abstract

摘要：

电化学CO₂还原反应(CO₂RR)作为一种有效缓解环境问题和能源危机的技术路径, 其核心在于高效电催化剂的开发. 近年来, 分散在氮掺杂石墨烯载体上的Ni单原子催化剂(SAC)因其在CO₂还原为CO过程中表现出的高选择性而受到广泛关注. 然而, Ni活性中心的化学吸附惰性导致其仅在较高过电位下才表现出电化学活性, 这严重制约了其实际应用. 因此, 探索如何提高Ni SAC的电催化CO₂RR性能具有重要的研究意义.

本文提出了一种基于杂原子掺杂调控Ni SAC活性中心电子结构以提升CO₂电还原性能的策略. 首先, 分别考察P和S杂原子在Ni₁/N₄C结构中的掺杂方式, 通过形成能计算筛选出两种相对稳定的掺杂构型: Ni₁/PN₄和Ni_1/SN₃C, 并利用热力学循环构建Pourbaix图, 证实了其在电化学反应条件下的结构稳定性. 其次, 通过电子结构分析发现, 在未掺杂的Ni₁/N₄C催化剂上, 由于Ni原子d_z₂轨道与COOH中间体π*轨道相互作用形成的反键轨道(d_z₂-π*)*位于费米能级以下, 导致COOH中间体的吸附稳定性较差; 而杂原子掺杂可以诱导Ni原子的d_z₂轨道显著上移, 使得反键轨道(d_z₂-π*)*移至费米能级以上, 从而削弱了反键轨道的电子占据, 增强了关键中间体COOH的吸附稳定性. 进一步在全显式溶剂模型, 采用限制性从头算分子动力学的方法, 对Ni₁/SN₃C催化剂上的CO₂电还原反应机理进行了深入研究, 揭示了质子转移过程是该反应的决速步骤, 其动力学能垒随电势负移而降低. 最后通过微观动力学模型评估了电势依赖的CO₂电还原反应速率, 并预测了S原子掺杂将使Ni SAC上的CO₂还原起始电位从−0.88 V优化至−0.80 V vs. RHE, 催化活性显著提升.

综上所述, 本文通过原子尺度揭示了杂原子掺杂对金属中心电子结构及界面反应动力学的调控机制, 不仅为深入理解催化剂的构效关系提供了理论见解, 同时为高性能电催化剂的设计与优化提供了新的思路和方向.

关键词: Ni单原子催化剂, 杂原子掺杂, CO₂电还原, 从头算分子动力学

Abstract:

The Ni single-atom catalyst dispersed on nitrogen doped graphene support has attracted much interest due to the high selectivity in electro-catalyzing CO₂ reduction to CO, yet the chemical inertness of the metal center renders it to exhibit electrochemical activity only under high overpotentials. Herein, we report P- and S- doped Ni single-atom catalysts, i.e. symmetric Ni₁/PN₄ and asymmetric Ni₁/SN₃C can exhibit high catalytic activity of CO₂ reduction with stable potential windows. It is revealed that the key intermediate *COOH in CO₂ electroreduction is stabilized by heteroatom doping, which stems from the upward shift of the axial d_z₂ orbital of the active metal Ni atom. Furthermore, we investigate the potential-dependent free energetics and dynamic properties at the electrochemical interface on the Ni₁/SN₃C catalyst using ab initio molecular dynamics simulations with a full explicit solvent model. Based on the potential-dependent microkinetic model, we predict that S-atom doped Ni SAC shifts the onset potential of CO₂ electroreduction from -0.88 to -0.80 V vs. RHE, exhibiting better activity. Overall, this work provides an in-depth understanding of structure-activity relationships and atomic-level electrochemical interfaces of catalytic systems, and offers insights into the rational design of heteroatom-doped catalysts for targeted catalysis.

Key words: Ni single-atom catalyst, Heteroatom doping, CO₂ electroreduction, Ab initio molecular dynamics

王刚, Imran Muhammad, 阎慧敏, 李隽, 王阳刚. 用杂原子调控Ni单原子催化剂的局部环境以实现高效CO₂电还原[J]. 催化学报, 2025, 74: 120-129.

Gang Wang, Imran Muhammad, Hui-Min Yan, Jun Li, Yang-Gang Wang. Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO₂ electroreduction[J]. Chinese Journal of Catalysis, 2025, 74: 120-129.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(25)64679-1

https://www.cjcatal.com/CN/Y2025/V74/I7/120

图/表 5

Fig. 1. (a) Schematic diagram of possible sites for heteroatom-doped Ni1/N4C catalyst. Formation energies and corresponding geometric configurations of P (b) and S (c) atom doping at different sites. Pourbaix diagrams of Ni1/PN4 (d) and Ni1/SN3C (e) catalysts.

Fig. 2. (a) DOS of Ni/N4C, COOH adsorbed on Ni/N4C SAC and COOH molecular fragment. (b) Energy levels of the interaction between Ni dz2 orbitals and COOH π* orbitals with corresponding wave functions. (c) DOS of COOH adsorbed on different Ni SACs. (d) COHP of the Ni-C pair and its Ni(dz2)-C component. The labeled numbers denote the integral COHP values below the Fermi level. (e) Free energy diagrams for CO2RR to CO on different Ni SACs based on CHE method.

Fig. 3. (a) Free energy profiles with error bars of *CO2 adsorption on the Ni1/SN3C catalyst at different applied potentials (vs. RHE). (b) Bader charge variation of adsorbed *CO2 and Ni atom. The statistical bond angles of adsorbed *CO2 (c) and the statistical number of hydrogen bonds between aqueous solvent and adsorbed *CO2 (d) at different applied potentials. The analysis was based on the final 2 ps AIMD trajectory.

Fig. 4. Free energy profiles with error bars of *COOH (a) and *CO (c) formation. Bader charge variation of adsorbed *COOH (b) and *CO (d) and Ni atom on the Ni1/SN3C catalyst at different applied potentials (vs. RHE).

Fig. 5. Reaction free energy diagrams of CO2RR on Ni1/N4C [46] (a) and Ni1/SN3C (b) catalysts at different applied potentials (vs. RHE). (c) COHP of Ni-C pairs in the adsorbed intermediates *CO2 and *COOH at about -0.72 V vs. RHE. The labeled numbers denote the integral COHP values below the Fermi level. (d) Calculated partial current densities for CO evolution during CO2 reduction on Ni1/N4C and Ni1/SN3C catalysts.

参考文献

[1]	S. Nitopi, E. Bertheussen, S. B. Scott, X. Y. Liu, A. K. Engstfeld, S. Horch, B. Seger, I. E. L. Stephens, K. R. Chan, C. Hahn, J. K. Nørskov, T. F. Jaramillo, I. Chorkendorff, Chem. Rev., 2019, 119, 7610-7672.
[2]	M. H. Jiang, H. Z. Wang, M. F. Zhu, X. J. Luo, Y. He, M. J. Wang, C. K. Wu, L. Y. Zhang, X. Li, X. M. Liao, Z. J. Jiang, Z. Jin, Chem. Soc. Rev., 2024, 53, 5149-5189.
[3]	S. Jin, Z. M. Hao, K. Zhang, Z. H. Yan, J. Chen, Angew. Chem. Int. Ed., 2021, 60, 20627-20648.
[4]	Y. L. Gao, X. Y. Tu, X. J. Liu, Y. Zhang, M. H. Huang, J. W. Zhu, H. Q. Jiang, ChemCatChem, 2024, 16, e202400361.
[5]	H. Guo, D. H. Si, H. J. Zhu, Z. A. Chen, R. Cao, Y. B. Huang, Angew. Chem. Int. Ed., 2024, 63, e202319472.
[6]	B. T. Qiao, A. Q. Wang, X. F. Yang, L. F. Allard, Z. Jiang, Y. T. Cui, J. Y. Liu, J. Li, T. Zhang, Nat. Chem., 2011, 3, 634-641.
[7]	X. F. Yang, A. Q. Wang, B. T. Qiao, J. Li, J. Y. Liu, T. Zhang, Acc. Chem. Res., 2013, 46, 1740-1748.
[8]	H. Y. Zhuo, X. Zhang, J. X. Liang, Q. Yu, H. Xiao, J. Li, Chem. Rev., 2020, 120, 12315-12341.
[9]	H. Y. Wu, B. Q. Tian, W. H. Xu, K. K. Abdalla, Y. Kuang, J. Z. Li, X. M. Sun, J. Am. Chem. Soc., 2024, 146, 32, 22266-22275.
[10]	Z. Y. Jin, D. X. Jiao, Y. L. Dong, L. Liu, J. C. Fan, M. Gong, X. C. Ma, Y. Wang, W. Zhang, L. Zhang, Z. G. Yu, M. Voiry, W. T. Zheng, X.Q. Cui, Angew. Chem. Int. Ed., 2024, 63, e202318246.
[11]	J. Wang, M. Y. Zheng, X. Zhao, W. L. Fan, ACS Catal., 2022, 12, 5441-5454.
[12]	Y. Z. Dai, H. Li, C. H. Wang, W. Q. Xue, M. L. Zhang, D. H. Zhao, J. Xue, J. W. Li, L. H. Luo, C. X. Liu, X. Li, P. X. Cui, Q. Jiang, T. T. Zheng, S. Q. Gu, Y. Zhang, J. P. Xiao, C. Xia, J. Zeng, Nat. Commun., 2023, 14, 3382.
[13]	J. Gu, C. S. Hsu, L. C. Bai, H. M. Chen, X. L. Hu, Science, 2019, 364, 1091-1094.
[14]	X. Q. Wang, Z. Chen, X. Y, Zhao, T. Yao, W. X. Chen, R. You, C. M. Zhao, G. Wu, J. Wang, W. X. Huang, J. L. Yang, X. Hong, S. Q. Wei, Y. E. Wu, Y. D. Li, Angew. Chem. Int. Ed., 2018, 57, 1944-1948.
[15]	W. Ju, A. Bagger, G. P. Hao, A. S. Varela, I. Sinev, V. Bon, B. R. Cuenya, S. Kaskel, J. Rossmeisl, P. Strasser, Nat. Commun., 2017, 8, 944.
[16]	X. M. Hu, H. H. Hval, E. T. Bjerglund, K. J. Dalgaard, M. R. Madsen, M. M. Pohl, E. Welter, P. Lamagni, K. B. Buhl, M. Bremholm, M. Beller, S. U. Pedersen, T. Skrydstrup, K. Daasbjerg, ACS Catal., 2018, 8, 6255-6264.
[17]	X. G. Li, W. T. Bi, M. L. Chen, Y. X. Sun, H. X. Ju, W. S. Yan, J. F. Zhu, X. J. Wu, W. S. Chu, C. Z. Wu, Y. Xie, J. Am. Chem. Soc., 2017, 139, 14889-14892.
[18]	Q. Sun, C. Jia, Y. Zhao, C. Zhao, Chin. J. Catal., 2022, 43, 1547-1597.
[19]	Y. Q. Li, Z. H. Wei, Z. Y. Sun, H. Z. Zhai, S. H. Li, W. X. Chen, Small, 2024, 20, 2401900.
[20]	W. R. Chen, X. X. Jin, L. X. Zhang, L. Z. Wang, J. L. Shi, Adv. Sci., 2024, 11, 2304424.
[21]	X. H. Sun, L. Sun, G. N. Li, Y. X. Tuo, C. L. Ye, J. R. Yang, J. X. Low, X. Yu, J. H. Bitter, Y. P. Lei, D. S. Wang, Y. D. Li, Angew. Chem. Int. Ed., 2022, 61, e202207677.
[22]	S. Y. Chen, X. Q. Li, C. W. Kao, T. Luo, K. J. Chen, J. W. Fu, C. Ma, H. M. Li, M. Li, T. S. Chan, M. Liu, Angew. Chem. Int. Ed., 2022, 61, e202206233.
[23]	J. J. Pei, H. S. Shang, J. J. Mao, Z. Chen, R. Sui, X. J. Zhang, D. N. Zhou, Y. Wang, F. Zhang, W. Zhu, T. Wang, W. X. Chen, Z. B. Zhuang, Nat. Commun., 2024, 15, 416.
[24]	H. B. Yang, S. F. Hung, S. Liu, K. D. Yuan, S. Miao, L. P. Zhang, X. Huang, H. Y. Wang, W. Z. Cai, R. Chen, J. J. Gao, X. F. Yang, W. Chen, Y. Q. Huang, H. M. Chen, C. M. Li, T. Zhang, B. Liu, Nat. Energy, 2018, 3, 140-147.
[25]	X. H. Zhao, Y. Y. Liu, J. Am. Chem. Soc., 2020, 142, 5773-5777.
[26]	J. K. Nørskov, J. Rossmeisl, A. Logadottir, L. Lindqvist, J. R. Kitchin, T. Bligaard, H. Jónsson, J. Phys. Chem. B, 2004, 108, 17886-17892.
[27]	H. J. Jing, J. Long, H. Li, X. Y. Fu, J. P. Xiao, Chin. J. Catal., 2023, 48, 205-213.
[28]	J. Y. Liu, S. A. Wang, Y. Y. Tian, H. Q. Guo, X. Chen, W. W. Lei, Y. F. Yu, C. H. Wang, Angew. Chem. Int. Ed., 2025, 64, e202414314.
[29]	W. Xun, X. Yang, Q. S. Jiang, M. J. Wang, Y. Z. Wu, P. Li, ACS Appl. Energy Mater., 2023, 6, 3236-3243.
[30]	G. Kresse, J.Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[31]	G. Kresse, J.Furthmüller, Phys. Rev. B, 1996, 54, 11169-11186.
[32]	J. P. Perdew, K. Burke, Phys. Rev. Lett., 1996, 77, 3865-3868.
[33]	J. Vandevondele, M. Krack, F. Mohamed, M. Parrinello, T. Chassaing, J. Hutter, Comput. Phys. Commun., 2005, 167, 103-128.
[34]	J. VandeVondele, J. Hutter, J. Chem. Phys., 2007, 127, 114105.
[35]	C. Hartwigsen, S. Goedecker, J. Hutter, Phys. Rev. B, 1998, 58, 3641-3662.
[36]	S. Grimme, J. Antony, S. Ehrlich, H. Krieg, J. Chem. Phys., 2010, 132, 154104.
[37]	G. J. Martyna, M. L. Klein, M. Tuckerman, J. Chem. Phys., 1992, 97, 2635-2643.
[38]	W. G. Hoover, Phys. Rev. A, 1985, 31, 1695-1697.
[39]	G. D. Liberto, L. Giordano, G. Pacchioni, ACS Catal., 2024, 14, 45-55.
[40]	F. Wu, X. K. Liu, S. Q. Wang, L. F. Hu, S. Kunze, Z. G. Xue, Z. H. Shen, Y. X. Yang, X. Q. Wang, M. H. Fan, H. G. Pan, X. P. Gao, T. Yao, Y. E. Wu, Nat. Commun., 2024, 15, 6972.
[41]	S. Liu, H. B. Yang, S. F. Hung, J. Ding, W. Z. Cai, L. H. Liu, J. J. Gao, X. N. Li, X. Y. Ren, Z. C. Kuang, Y. Q. Huang, T. Zhang, B. Liu, Angew. Chem. Int. Ed., 2020, 59, 798-803.
[42]	S. Vijay, W. Ju, S. Bruckner, S. C. Tsang, P. Strasser, K. R. Chan, Nat. Catal., 2021, 4, 1024-1031.
[43]	R. Dronskowski, P. E. Blochl, J. Phys. Chem., 1993, 97, 8617-8624.
[44]	V. L. Deringer, A. L. Tchougréeff, R. Dronskowski, J. Phys. Chem. A, 2011, 115, 5461-5466.
[45]	H. Cao, Z. S. Zhang, J. W. Chen, Y. G. Wang, ACS Catal., 2022, 12, 6606-6617.
[46]	H. Y. Zhao, H. Cao, Z. S. Zhang, Y. G. Wang, ACS Catal., 2022, 12, 11380-11390.
[47]	W. Y. Deng, P. Zhang, B. Seger, J. L. Gong, Nat. Commun., 2022, 13, 803.
[48]	Q. Zhang, H. J. Tsai, F. H. Li, Z. M. Wei, Q. Y. He, J. Ding, Y. H. Liu, Z. Y. Lin, X. J. Yang, Z. Y. Chen, F. X. Hu, X. Yang, Q. Tang, H. B. Yang, S. F. Hung, Y. M. Zhai, Angew. Chem. Int. Ed., 2023, 62, e202311550.
[49]	J. C. Zhang, W. Z. Cai, F. X. Hu, H. B. Yang, B. Liu, Chem. Sci., 2021, 12, 6800-6819.
[50]	Y. Li, N. M. Adli, W. T. Shan, M. Y. Wang, M. J. Zachman, S. Hwang, H. Tabassum, S. Karakalos, Z. X. Feng, G. F. Wang, Y. C. Li, G. Wu, Energy Environ. Sci., 2022, 15, 2108-2119.
[51]	Z. D. Li, D. He, X. X. Yan, S. Dai, S. Younan, Z. J. Ke, X. Q. Pan, X. H. Xiao, H. J. Wu, J. Gu, Angew. Chem. Int. Ed., 2020, 59, 18572-18577.
[52]	Y. Z. Zhou, Q. Zhou, H. J. Liu, W. J. Xu, Z. X. Wang, S. C. Qiao, H. H. Ding, D. L. Chen, J. F. Zhu, Z. M. Qi, X. J. Wu, Q. He, L. Song, Nat. Commun., 2023, 14, 3776.
[53]	Y. J. He, Z. Abedi, C. Y. Ni, S. Milliken, K. M. O’Connor, D. G. Ivey, J. G. C. Veinot, ACS Appl. Nano Mater., 2022, 5, 12496-12505.

用杂原子调控Ni单原子催化剂的局部环境以实现高效CO₂电还原

Regulating the local environment of Ni single-atom catalysts with heteroatoms for efficient CO₂ electroreduction

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 5

参考文献

相关文章 13

编辑推荐

Metrics

[1]	李晓寒, 张博雯, 熊晚枫, 李泽, 向小宇, 张思颖, 司端惠, 李红芳, 曹荣. 长烷基链功能化修饰铜纳米线电还原CO₂高选择性制乙烯[J]. 催化学报, 2025, 73(6): 196-204.
[2]	陈繁荣, 傅佳驹, 丁亮, 卢晓英, 蒋哲, 张小玲, 胡劲松. 硫锚定策略提升亚3纳米In₂S₃纳米颗粒电还原CO₂至甲酸盐的稳定性[J]. 催化学报, 2025, 71(4): 138-145.
[3]	魏抒豪, 蓝国钧, 邱一洋, 林迪, 孔薇, 李瑛. 乙炔氢氯化非金属碳催化剂的研究进展: 从杂原子掺杂到本征缺陷[J]. 催化学报, 2025, 70(3): 8-43.
[4]	王金鑫, 张嘉奇, 陈晨. 电催化二氧化碳还原转化到多碳产物: 铜基催化剂动态表面的视角[J]. 催化学报, 2025, 68(1): 83-102.
[5]	郑汉, 杨正午, 孔祥栋, 耿志刚, 曾杰. 二氧化碳电还原为甲烷的研究进展[J]. 催化学报, 2022, 43(7): 1634-1641.
[6]	刘储浩, 吴悦, 方锦杰, 余坷, 李慧, 贺文君, 张永臻, 柳守杰, 陈郑, 董京, 陈晨. 氮掺杂碳催化剂在高效电化学CO₂还原中的协同效应[J]. 催化学报, 2022, 43(7): 1697-1702.
[7]	孙倩, 贾忱, 赵勇, 赵川. 单原子基催化剂用于电化学CO₂还原[J]. 催化学报, 2022, 43(7): 1547-1597.
[8]	王同宝, 韩光泰, 王子运, 王昱沆. 克服高温二氧化碳电解产生的碳沉积问题[J]. 催化学报, 2022, 43(12): 2938-2945.
[9]	刘宏, 刘健, 杨波. Cu表面应变效应调控电催化CO二聚反应活性的第一性原理分子动力学模拟[J]. 催化学报, 2022, 43(11): 2898-2905.
[10]	Behnaz Rahmani Didar, Axel Groß. 利用第一性原理模拟研究Li和LiO₂的溶剂化结构和动力学及其在非水有机电解质溶剂中的转化[J]. 催化学报, 2022, 43(11): 2850-2857.
[11]	王敏, 解琦, 陈会敏, 刘光波, 崔学晶, 姜鲁华. N,O共修饰的Ni纳米颗粒/氮掺杂介孔碳CO₂高效电还原催化剂[J]. 催化学报, 2021, 42(12): 2306-2312.
[12]	邵加奇, 王毅, 高敦峰, 叶克, 王琪, 汪国雄. Cu-In二元金属催化剂上CO₂电化学还原[J]. 催化学报, 2020, 41(9): 1393-1400.
[13]	李国栋, 覃永杰, 吴玉, 裴蕾, 胡琪, 杨恒攀, 张黔玲, 刘剑洪, 何传新. 氮硫共掺杂高比表面中空碳球的制备及其在电催化二氧化碳还原中的应用[J]. 催化学报, 2020, 41(5): 830-838.