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

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

Abstract

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

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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64679-1

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

Figures/Tables 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.

References

[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.

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

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 15

Recommended Articles

Metrics

[1]	Xiao-Han Li, Bo-Wen Zhang, Wan-Feng Xiong, Ze Li, Xiao-Yu Xiang, Si-Ying Zhang, Duan-Hui Si, Hong-Fang Li, Rong Cao. Highly selective CO₂ electroreduction to ethylene on long alkyl chains-functionalized copper nanowires [J]. Chinese Journal of Catalysis, 2025, 73(6): 196-204.
[2]	Shuhao Wei, Guojun Lan, Yiyang Qiu, Di Lin, Wei Kong, Ying Li. Advances in metal-free carbon catalysts for acetylene hydrochlorination: From heteroatom doping to intrinsic defects over the past decade [J]. Chinese Journal of Catalysis, 2025, 70(3): 8-43.
[3]	Xingxing Jiang, Yuxin Zhao, Yan Kong, Jianju Sun, Shangzhao Feng, Qi Hu, Hengpan Yang, Chuanxin He. Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity [J]. Chinese Journal of Catalysis, 2024, 58(3): 216-225.
[4]	Huanhuan Yang, Shiying Li, Qun Xu. Efficient strategies for promoting the electrochemical reduction of CO₂ to C₂₊ products over Cu-based catalysts [J]. Chinese Journal of Catalysis, 2023, 48(5): 32-65.
[5]	Wenqian Yang, Ziqian Xue, Jun Yang, Jiahui Xian, Qinglin Liu, Yanan Fan, Kai Zheng, Peiqin Liao, Hui Su, Qinghua Liu, Guangqin Li, Cheng-Yong Su. Fe nanoparticles embedded in N-doped porous carbon for enhanced electrocatalytic CO₂ reduction and Zn-CO₂ battery [J]. Chinese Journal of Catalysis, 2023, 48(5): 185-194.
[6]	Han Zheng, Zhengwu Yang, Xiangdong Kong, Zhigang Geng, Jie Zeng. Progresses on carbon dioxide electroreduction into methane [J]. Chinese Journal of Catalysis, 2022, 43(7): 1634-1641.
[7]	Ernest Pahuyo Delmo, Yian Wang, Jing Wang, Shangqian Zhu, Tiehuai Li, Xueping Qin, Yibo Tian, Qinglan Zhao, Juhee Jang, Yinuo Wang, Meng Gu, Lili Zhang, Minhua Shao. Metal organic framework-ionic liquid hybrid catalysts for the selective electrochemical reduction of CO₂ to CH₄ [J]. Chinese Journal of Catalysis, 2022, 43(7): 1687-1696.
[8]	Qian Sun, Chen Jia, Yong Zhao, Chuan Zhao. Single atom-based catalysts for electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2022, 43(7): 1547-1597.
[9]	Ming He, Bingjun Xu, Qi Lu. Probing the role of surface speciation of tin oxide and tin catalysts on CO₂ electroreduction combining in situ Raman spectroscopy and reactivity investigations [J]. Chinese Journal of Catalysis, 2022, 43(6): 1473-1477.
[10]	HuangJingWei Li, Huimin Zhou, Yajiao Zhou, Junhua Hu, Masahiro Miyauchi, Junwei Fu, Min Liu. Electric-field promoted C-C coupling over Cu nanoneedles for CO₂ electroreduction to C₂ products [J]. Chinese Journal of Catalysis, 2022, 43(2): 519-525.
[11]	Jun Gong, Jinmeng Li, Chang Liu, Fengyuan Wei, Jinlong Yin, Wenzheng Li, Li Xiao, Gongwei Wang, Juntao Lu, Lin Zhuang. Guanine-regulated proton transfer enhances CO₂-to-CH₄ selectivity over copper electrode [J]. Chinese Journal of Catalysis, 2022, 43(12): 3101-3106.
[12]	Tongbao Wang, Guangtai Han, Ziyun Wang, Yuhang Wang. Overcoming coke formation in high-temperature CO₂ electrolysis [J]. Chinese Journal of Catalysis, 2022, 43(12): 2938-2945.
[13]	Hong Liu, Jian Liu, Bo Yang. Tunable activity of electrocatalytic CO dimerization on strained Cu surfaces: Insights from ab initio molecular dynamics simulations [J]. Chinese Journal of Catalysis, 2022, 43(11): 2898-2905.
[14]	Yu Ding, Bo-Qiang Miao, Yue Zhao, Fu-Min Li, Yu-Cheng Jiang, Shu-Ni Li, Yu Chen. Direct growth of holey Fe₃O₄-coupled Ni(OH)₂ sheets on nickel foam for the oxygen evolution reaction [J]. Chinese Journal of Catalysis, 2021, 42(2): 271-278.
[15]	Jiaqi Shao, Yi Wang, Dunfeng Gao, Ke Ye, Qi Wang, Guoxiong Wang. Copper-indium bimetallic catalysts for the selective electrochemical reduction of carbon dioxide [J]. Chinese Journal of Catalysis, 2020, 41(9): 1393-1400.