Citation: Jielian Yang, Yue Shen, Bing Chen, Qi Wu, Yuemei Liao, Liya Zhou, Jing Luo, Xue Mao, Jin Guo, Binbin Luo, Qi Pang, Chunyan Zhou, Peican Chen, Anxiang Guan. Cu/Ni dual-atom catalysts with charge regulation: Boosting CO₂ electroreduction selectivity via site-specific O/C-terminal asymmetric adsorption[J]. Chinese Chemical Letters, ;2026, 37(9): 112638. doi: 10.1016/j.cclet.2026.112638 shu

Cu/Ni dual-atom catalysts with charge regulation: Boosting CO₂ electroreduction selectivity via site-specific O/C-terminal asymmetric adsorption

Jielian Yang ^a ,
Yue Shen ^a ,
Bing Chen ^a ,
Qi Wu ^a ,
Yuemei Liao ^a ,
Liya Zhou ^{a, *,} ,
Jing Luo ^a ,
Xue Mao ^a ,
Jin Guo ^a ,
Binbin Luo ^a ,
Qi Pang ^a ,
Chunyan Zhou ^b ,
Peican Chen ^{a, *,} ,
Anxiang Guan ^{a, *,}

a.
School of Chemistry and Chemical Engineering, State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, Guangxi Key Laboratory of Electrochemical Energy Materials, Guangxi Colleges and Universities Key Laboratory of Applied Chemistry Technology and Resource Development. Guangxi University, Nanning 530004, China
b.
College of Pharmaceutical Science, Guangxi Medical University, Nanning 530021, China

zhouliya@gxu.edu.cn

peicanchen@gxu.edu.cn

Axguan24@gxu.edu.cn

Received Date: 26 January 2026
Revised Date: 11 March 2026
Accepted Date: 16 March 2026
Available Online: 17 March 2026

Figures(5)

Dual-atom catalysts (DACs) show great potential for boosting reaction kinetics and diversifying active sites via the synergistic effects of two metal atoms. However, the influence of intermetallic interactions on catalytic performance remains underexplored. Herein, we report a Cu/Ni dual-atom catalyst anchored on N-doped carbon (Cu/Ni-N-C) for the electrochemical CO₂ reduction reaction (CO₂RR). Advanced experimental and theoretical approaches, including X-ray absorption fine structure (XAFS) analysis and density functional theory (DFT) calculations, were employed to systematically investigate the mechanism of intermetallic interactions. Experimental results demonstrate that the monometallic Cu-N-C catalyst achieves a maximum CO Faradaic efficiency (FE) of 38.35% at -1 V vs. RHE, with a non-negligible CH₄ FE of 21.89% at -1.4 V vs. RHE. In contrast, the Cu_0.5Ni_0.5–N-C catalyst exhibits significantly enhanced performance for CO formation, reaching a high CO FE of 96.78% with partial current density of 24.80 mA/cm² and a negligible CH₄ formation. The reason for this selectivity shift is that Ni atoms within the Cu-Ni diatomic pairs in the Cu/Ni-N-C catalyst attract the electron cloud of Cu atoms. This reduces the electron cloud density near Cu atoms, and thus weakens the adsorption of CO₂RR intermediates on Cu sites. DFT calculations further reveal that charge regulation between Cu and Ni is the key to the improved CO selectivity: electron-deficient Cu atoms act as O-terminal adsorption sites to bind the oxygen atoms of CO₂, while electron-enriched Ni atoms serve as C-terminal adsorption sites to anchor the carbon atoms. This asymmetric adsorption mode promotes CO₂ polarization and activation, narrows the HOMO-LUMO band gap for efficient electron transfer, and reduces the thermodynamic barrier for ^*COOH intermediate formation (ΔG = 1.78 eV vs. 2.52 eV for Cu-N-C). Additionally, the shortened Ni-C bond (1.921 Å vs. 2.207 Å for Cu-N-C) and elongated C–OH bond (1.388 Å vs. 1.376 Å for Cu-N-C) in ^*COOH on Cu_0.5Ni_0.5–N-C further favor CO generation. This work provides new insights into the precise design of DACs by regulating intermetallic interactions, advancing their industrial applications in CO₂RR.
- Cu/Ni dual-atom catalysts,
- Intermetallic interactions,
- CO₂ reduction,
- O-terminal adsorption,
- C-terminal adsorption
1. [1]
  I. Song, Y. Eom, M. P, et al., Small 19 (2023) 2300049. doi: 10.1002/smll.202300049
2. [2]
  F.M. Mota, D.H. Kim, Chem. Soc. Rev. 48 (2019) 205–259. doi: 10.1039/C8CS00527C
3. [3]
  Y. Birdja, E. Pérez-Gallent, M. Figueiredo, et al., Nat. Energy 4 (2019) 732–745. doi: 10.1038/s41560-019-0450-y
4. [4]
  Y. Chen, X. Pan, L. Li, et al., Small 21 (2025) 2411249. doi: 10.1002/smll.202411249
5. [5]
  G. Jeong, Y. Tan, J. Song, et al., Chem. Eng. J. 426 (2021) 131063. doi: 10.1016/j.cej.2021.131063
6. [6]
  B. Chen, D. Shi, R. Deng, et al., ACS Catal. 14 (2024) 16224–16233. doi: 10.1021/acscatal.4c05169
7. [7]
  X. Zhang, X. Zhu, S. Bo, et al., Nat. Commun. 13 (2022) 5337. doi: 10.1038/s41467-022-33066-6
8. [8]
  M. Hulsey, V. Fung, X. Hou, et al., Angew. Chem. Int. Ed. 61 (2022) e202208237. doi: 10.1002/anie.202208237
9. [9]
  H. Fei, J. Dong, Y. Feng, et al., Nat. Catal. 1 (2018) 63–72. doi: 10.1038/s41929-017-0008-y
10. [10]
  C. Xia, Y. Qiu, Y. Xia, et al., Nat. Chem. 13 (2021) 887–894. doi: 10.1038/s41557-021-00734-x
11. [11]
  X. Liu, F. He, Y. Lu, et al., Chem. Eng. J. 453 (2023) 139833. doi: 10.1016/j.cej.2022.139833
12. [12]
  J. Pei, H. Shang, J. Mao, et al., Nat. Commun. 15 (2024) 416.
13. [13]
  X. Niu, J. Wei, D. Xu, et al., Nano Res. 17 (2024) 4702–4710. doi: 10.1007/s12274-023-6317-3
14. [14]
  J. Leverett, T. Tran-Phu, J. Yuwono, et al., Adv. Energy Mater. 12 (2022) 2201500. doi: 10.1002/aenm.202201500
15. [15]
  A. Guan, Y. Fan, S. Xi, et al., ACS Mater. Lett. 5 (2023) 19–26. doi: 10.1021/acsmaterialslett.2c01023
16. [16]
  D. Koshy, D. Chen, D. Lee, et al., Angew. Chem. Int. Ed. 59 (2020) 4043–4050. doi: 10.1002/anie.201912857
17. [17]
  M. Fang, X. Wang, X. Li, et al., ChemCatChem 13 (2021) 603–609. doi: 10.1002/cctc.202001667
18. [18]
  S. Liang, J. Xiao, T. Zhang, et al., Angew. Chem. Int. Ed. 62 (2023) 202310740. doi: 10.1002/anie.202310740
19. [19]
  X. Li, M. Qin, X. Wu, et al., Small 19 (2023) 2302530. doi: 10.1002/smll.202302530
20. [20]
  S. Lu, M. Mazur, K. Guo, et al., Small 20 (2024) 2309251. doi: 10.1002/smll.202309251
21. [21]
  X. Wang, N. Zhang, S. Guo, et al., J. Am. Chem. Soc. 146 (2024) 21357–21366. doi: 10.1021/jacs.4c03576
22. [22]
  L. Zhang, N. Zhang, H. Shang, et al., Nat. Commun. 15 (2024) 9440. doi: 10.1038/s41467-024-53871-5
23. [23]
  D. Yao, C. Tang, X. Zhi, et al., Adv. Mater. 35 (2023) 2209386. doi: 10.1002/adma.202209386
24. [24]
  Y. Chen, J. Zhao, X. Pan, et al., Angew. Chem. Int. Ed. 63 (2024) e202411543. doi: 10.1002/anie.202411543
25. [25]
  B. Hu, Y. Cao, Front. Energy. 19 (2025) 757–766. doi: 10.1007/s11708-025-1021-5
26. [26]
  H. Xu, S. Fan, H. Liu, et al., Energy Storage Mater. 82 (2025) 104604. doi: 10.1016/j.ensm.2025.104604
27. [27]
  A. Guan, Z. Chen, Y. Quan, et al., ACS Energy Lett. 5 (2020) 1044–1053. doi: 10.1021/acsenergylett.0c00018
28. [28]
  L. Zhou, C. Yang, J. Wen, et al., J. Mater. Chem. A 5 (2017) 19343–19350. doi: 10.1039/C7TA05522F
29. [29]
  Y. Qian, P. Du, P. Wu, et al., J. Phys. Chem. C 120 (2016) 9884–9896. doi: 10.1021/acs.jpcc.6b02670
30. [30]
  Z. Gu, N. Yang, P. Han, et al., Small Methods. 3 (2019) 1800449. doi: 10.1002/smtd.201800449
31. [31]
  H. Wang, H. Zou, Y. Liu, et al., Sci. Rep. 11 (2021) 21414. doi: 10.1038/s41598-021-00776-8
1. [1]
  Min Zhang , Weimin Wang , Jun Li , Xun Zhu , Qian Fu . Efficient large-current conversion of CO₂ to C₂H₅OH via a ^*CO-^*OCH₂ coupling pathway on alkanethiol-modified Cu₂O array electrode. Chinese Chemical Letters, 2026, 37(1): 111926-. doi: 10.1016/j.cclet.2025.111926
2. [2]
  Xiaofan ZHANG , Yu DUAN , Meijie SHI , Nan LU , Renhong LI , Xiaoqing YAN . Z-scheme Co₃O₄/BiOBr heterojunction for efficient photoreduction CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(9): 1878-1888. doi: 10.11862/CJIC.20250079
3. [3]
  Zekun Zhang , Shiji Li , Qian Zhang , Shanshan Li , Liu Yang , Wei Yan , Hao Xu . Further study of CO₂ electrochemical reduction to gas products on Cu: Influence of the electrolyte. Chinese Chemical Letters, 2025, 36(9): 110742-. doi: 10.1016/j.cclet.2024.110742
4. [4]
  Zhou Li , Mengxue Yu , Shixin Chang , Zhibin Huang , Zhenmin Cheng , Weibin Zhang , Sónia A. C. Carabineiro , Zhigao Xu , Kangle Lv . Enhancing the photocatalytic activity of crystalline g-C3N4 towards NO oxidation and CO2 reduction through K+-doping and cyano defect engineering. Chinese Journal of Structural Chemistry, 2026, 45(1): 100698-100698. doi: 10.1016/j.cjsc.2025.100698
5. [5]
  Zhilei Chen , Zhaoxia Li , Yunjiang Yu , Mingdeng Xiang , Cheng Ding , Entian Cui , Jizhou Jiang . Unveiling the enhanced activity origin of BiO_1-xCl/C₃N₅ photocatalyst in CO₂-to-CO directional conversion. Chinese Chemical Letters, 2026, 37(9): 112313-. doi: 10.1016/j.cclet.2025.112313
6. [6]
  Ziruo Zhou , Wenyu Guo , Tingyu Yang , Dandan Zheng , Yuanxing Fang , Xiahui Lin , Yidong Hou , Guigang Zhang , Sibo Wang . Defect and nanostructure engineering of polymeric carbon nitride for visible-light-driven CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100245-100245. doi: 10.1016/j.cjsc.2024.100245
7. [7]
  Na Lu , Tingting Pang , Xuedong Jing , Yongan Zhu , Linqun Yu , Sining Ben , Yuchan Song , Shiwen Du , Wei Lu , Zhenyi Zhang . Optimizing the Schottky Barrier in AuAg Alloy Decorated TiO2 Nanofibers to Enhance Hot-Electron-Induced CO2 Reduction. Chinese Journal of Structural Chemistry, 2025, 44(8): 100633-100633. doi: 10.1016/j.cjsc.2025.100633
8. [8]
  Chuncheng Xu , Suqin Han , Kaiyang Zhang , Qiuling Feng , Lan Bao , Mingming Gao , Wen-Yan Gao , Yen Leng Pak , Hongyu Mou , Liwei Chen , Xing Gao , Yuchen Hao . Structure–function correlation and design principles of two-dimensional bismuth nanosheets for efficient electrochemical CO₂ reduction. Chinese Chemical Letters, 2026, 37(3): 112179-. doi: 10.1016/j.cclet.2025.112179
9. [9]
  Huarui Han , Yangrui Xu , Yu Cheng , Liguang Tang , Jie Jin , Xinlin Liu , Changchang Ma , Ziyang Lu . Frustrated Lewis pairs in CO2 photoreduction: A review on synergistic activation and charge separation. Chinese Journal of Structural Chemistry, 2025, 44(10): 100728-100728. doi: 10.1016/j.cjsc.2025.100728
10. [10]
  Sihong Li , Weiping Deng , Qijie Mo , Haili Song , Chunying Chen , Li Zhang . Engineering S-coordinated Ru single-atoms in a porphyrinic metal-organic framework for CO2 photoreduction. Chinese Journal of Structural Chemistry, 2026, 45(3): 100841-100841. doi: 10.1016/j.cjsc.2025.100841
11. [11]
  Yaoyin Lou , Xiaoyang Jerry Huang , Kuang-Min Zhao , Mark J. Douthwaite , Tingting Fan , Fa Lu , Ouardia Akdim , Na Tian , Shigang Sun , Graham J. Hutchings . Stable core-shell Janus BiAg bimetallic catalyst for CO₂ electrolysis into formate. Chinese Chemical Letters, 2025, 36(3): 110300-. doi: 10.1016/j.cclet.2024.110300
12. [12]
  Cheng-Cheng Jiao , Guang-Xing Dong , Ke Su , You-Xiang Feng , Min Zhang , Tong-Bu Lu . The construction of InVO₄/BiVO₄ heterojunction via cation-exchange for efficient and highly selective CO₂ photoreduction to methanol. Chinese Chemical Letters, 2026, 37(1): 110752-. doi: 10.1016/j.cclet.2024.110752
13. [13]
  Xinyu Wu , Jianfeng Lu , Zihao Zhu , Suijun Liu , Herui Wen . Recent advances of metal-organic frameworks and MOF-derived materials based on p-block metal for the electrochemical reduction of carbon dioxide. Chinese Chemical Letters, 2025, 36(7): 110151-. doi: 10.1016/j.cclet.2024.110151
14. [14]
  Xuejiao Wang , Suiying Dong , Kezhen Qi , Vadim Popkov , Xianglin Xiang . Photocatalytic CO₂ Reduction by Modified g-C₃N₄. Acta Physico-Chimica Sinica, 2024, 40(12): 2408005-0. doi: 10.3866/PKU.WHXB202408005
15. [15]
  Fangfang WANG , Jiaqi CHEN , Weiyin SUN . CuBi@Cu-MOF composite catalysts for electrocatalytic CO₂ reduction to HCOOH. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 97-104. doi: 10.11862/CJIC.20240350
16. [16]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 100024-0. doi: 10.3866/PKU.WHXB202404012
17. [17]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
18. [18]
  Yilin Cui , Zhongfu Li , Weikun Zhang , Yu Gao , Zhichao Dong , Conghua Liu . Sulfur vacancies boosting C₂H₄ selectivity of 2D/2D In_2.77S₄/CuInS₂ S-scheme heterojunction for CO₂ photoreduction. Acta Physico-Chimica Sinica, 2026, 42(7): 100274-. doi: 10.1016/j.actphy.2026.100274
19. [19]
  Irshad Ahmad , Yifei Zhang , Ayman Al-Qattan , S. AlFaify , Gao Li . Unlocking the engineering of solar-driven ZnO composites: From fundaments to sustainable and eco-friendly chemical energy. Chinese Journal of Structural Chemistry, 2025, 44(11): 100700-100700. doi: 10.1016/j.cjsc.2025.100700
20. [20]
  Yahui Li , Quanchen Feng , Krisztina László , Ying Wang . High-throughput screening of high C/N-ratio homonuclear dual-atom catalysts for electrochemical reduction of nitrate to ammonia. Chinese Chemical Letters, 2026, 37(3): 111536-. doi: 10.1016/j.cclet.2025.111536

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(10)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Cu/Ni dual-atom catalysts with charge regulation: Boosting CO2 electroreduction selectivity via site-specific O/C-terminal asymmetric adsorption

Metrics

通讯作者: 陈斌, bchen63@163.com

Cu/Ni dual-atom catalysts with charge regulation: Boosting CO₂ electroreduction selectivity via site-specific O/C-terminal asymmetric adsorption