Engineering d-band structure of Zn-doped CuOxHy for boosting CO2 electroreduction performance

doi:10.1016/S1872-2067(25)64878-9

Abstract

Abstract:

Heterometallic doping can modulate the electron distribution of a catalyst, thereby influencing its intrinsic activity. In this study, we pioneer zinc doping within copper hydroxy oxides (CuO_xH_y) to alter the electronic structure and geometry, unlocking a distinct proton-coupled dynamic catalysis mechanism and significantly improving electrochemical CO₂ reduction reaction (CO₂RR) pathway selectivity toward formate. The Cu_0.4Zn_0.6O_xH_y catalyst, synthesized via a template co-precipitation method, exhibits a 4.1-fold enhancement of Faraday efficiency of formate over pristine CuO_xH_y at ‒1.1 V vs. RHE. In-situ Raman and X-ray photoelectron spectroscopy results confirm that the Cu_0.4Zn_0.6O_xH_y catalyst undergoes surface electron reconfiguration while maintaining bulk structural integrity with sustained Cu redox cycling, preserving the key active sites that sustain performance during CO₂RR. Density functional theory calculations show that Zn doping effectively modulates the d-band center of Cu, enhances interfacial charge transfer with the *HCOO adsorbate, and lowers the energy barrier of the limiting step (CO₂ → *HCOO), thereby boosting CO₂RR performance. This work establishes a design principle for modulating the electronic structure of Cu-based hydroxides by zinc doping, highlighting dopant-induced electronic redistribution as a critical factor for achieving high formate selectivity.

Key words: Electrochemical CO₂ reduction, CuZnO_xH_y nanosheets, In-situ characterization, Faradaic efficiency, Cu/Zn ratio\

Xue Bai, Tianmi Tang, Jingru Sun, Fuquan Bai, Jing Hu, Jingqi Guan. Engineering d-band structure of Zn-doped CuO_xH_y for boosting CO₂ electroreduction performance[J]. Chinese Journal of Catalysis, 2026, 80: 248-257.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64878-9

https://www.cjcatal.com/EN/Y2026/V80/I1/248

Figures/Tables 5

Fig. 1. (a) Synthetic procedure of Cu0.4Zn0.6OxHy. HRTEM images (b,c), FFT images (c1,c2) of the matrix, and EDX mapping (d) of the Cu0.4Zn0.6OxHy. (e) XPS survey spectrum of the Cu0.4Zn0.6OxHy. (f) High resolution Zn 2p XPS spectrum. (g) High-resolution Cu 2p XPS spectrum. (h) High-resolution O 1s XPS spectrum.

Fig. 2. (a) XANES spectra at the Cu K-edge of Cu0.4Zn0.6OxHy, Cu foil, Cu2O and CuO. (b) EXAFS spectra at the Cu K-edge of the Cu0.4Zn0.6OxHy, Cu foil and CuO. (c) FT-EXAFS fitting spectra in R space at the Cu K-edge of Cu0.4Zn0.6OxHy. (d) XANES spectra at the Zn K-edge of Cu0.4Zn0.6OxHy, Zn foil and ZnO. (e) EXAFS spectra at the Zn K-edge of the Cu0.4Zn0.6OxHy, Zn foil and ZnO. (f) FT-EXAFS fitting spectra in R space at the Zn K-edge of Cu0.4Zn0.6OxHy. (g?i) WT-EXAFS plots of Cu foil, CuO and Cu0.4Zn0.6OxHy.

Fig. 3. (a) Faraday efficiencies of HCOOH, CO, H2 and CH3CH2OH on CuOxHy. (b) Partial current density on CuOxHy. (c) High-resolution Cu 2p XPS spectrum after the CO2RR. (d) Faraday efficiencies of HCOOH, CO, H2 and CH3CH2OH on Cu0.4Zn0.6OxHy. (e) Partial current density on Cu0.4Zn0.6OxHy. (f) High resolution O 1s XPS spectrum after the CO2RR.

Fig. 4. (a) Simplified schematic of operando Raman cell setup. (b) 3D color-mapped surface map of Cu0.4Zn0.6OxHy. (c) Operando Raman spectroscopic study on the intermediate adsorption at various potentials.

Fig. 5. (a) Introduction of transition metal heteroatom to modulate the coordination structure of CuOxHy. (b) Density of states plot for Cu0.4Zn0.6OxHy and CuOxHy. Charge density differences for *HCOO adsorption configurations on (c) CuOOH and (d) Cu0.4Zn0.6OxHy. (e) Free-energy diagrams for the electroreduction of CO2 to HCOOH on Cu0.4Zn0.6OxHy and CuOxHy. (f) Free-energy diagrams for HER on Cu0.4Zn0.6OxHy and CuOxHy.

References

[1]	W. Xie, B. Li, L. Liu, H. Li, M. Yue, Q. Niu, S. Liang, X. Shao, H. Lee, J.-Y. Lee, M. Shao, Q. Wang, D. O’Hare, H. He, Chem. Soc. Rev., 2025, 54, 898-959.
[2]	B. Li, L. Liu, M. Yue, Q. Niu, M. Li, T. Zhang, W. Xie, Q. Wang, Green Chem., 2024, 26, 103-121.
[3]	H. Zhang, C. Gu, M. Fan, Z. Zhao, X. Kong, Z. Geng, Sci. China Chem., 2024, 67, 3925-3933.
[4]	C. Yue, X. Yang, X. Zhang, S. Wang, W. Xu, R. Chen, J. Wang, J. Yin, Y. Huang, X. Li, Adv. Energy Mater., 2024, 14, 2470166.
[5]	Y. Qiao, S. Shen, C. Mao, Y. Xiao, W. Lai, Y. Wang, X. Zhong, Y. Lu, J. Li, J. Ge, H.-Y. Hsu, Y. Su, M. Shao, Z. Hu, H. Huang, Angew. Chem. Int. Ed., 2025, 64, e202424248.
[6]	A. Husile, Z. Wang, J. Guan, Chem. Sci., 2025, 16, 5413-5446.
[7]	T. Zhao, J. Li, J. Liu, F. Liu, K. Xu, M. Yu, W. Xu, F. Cheng, ACS Catal., 2023, 13, 4444-4453.
[8]	X. Xu, J. Guan, Adv. Funct. Mater., 2025, DOI:10.1002/adfm.202505823.
[9]	C. Peng, J. Ma, G. Luo, S. Yan, J. Zhang, Y. Chen, N. Chen, Z. Wang, W. Wei, T.-K. Sham, Y. Zheng, M. Kuang, G. Zheng, Angew. Chem. Int. Ed., 2024, 63, e202316907.
[10]	M. Wang, H. Chen, M. Wang, J. Wang, Y. Tuo, W. Li, S. Zhou, L. Kong, G. Liu, L. Jiang, G. Wang, Angew. Chem. Int. Ed., 2023, 62, e202306456.
[11]	J. H. Lee, W. Jang, H. Lee, D. Oh, W. Y. Noh, K. Y. Kim, J. Kim, H. Kim, K. An, M. G. Kim, Y. Kwon, J. S. Lee, S. Cho, Nano Lett., 2024, 24, 9322-9330.
[12]	T. Zhao, T. Yan, Y. Sun, Z. Wang, Q. Cai, J. Zhao, Z. Chen, J. Mater. Chem. A, 2023, 11, 19444-19454.
[13]	S. Chen, J. Guan, Chin. J. Catal., 2024, 66, 20-52.
[14]	Z. Li, B. Sun, D. Xiao, H. Liu, Z. Wang, Y. Liu, Z. Zheng, P. Wang, Y. Dai, B. Huang, H. Cheng, Angew. Chem. Int. Ed., 2025, 64, e202413832.
[15]	W. Chen, X. Du, S. Tao, B. Lin, I. Tranca, F. Tielens, M. Ma, Z. Liu, Chem. Phys. Rev., 2025, 6, 011302.
[16]	Z. Li, P. Wang, X. Lyu, V. K. R. Kondapalli, S. Xiang, J. D. Jimenez, L. Ma, T. Ito, T. Zhang, J. Raj, Y. Fang, Y. Bai, J. Li, A. Serov, V. Shanov, A. I. Frenkel, S. D. Senanayake, S. Yang, T. P. Senftle, J. Wu, Nat. Chem. Eng., 2024, 1, 159-169.
[17]	S. Yang, Z. Liu, H. An, S. Arnouts, J. de Ruiter, F. Rollier, S. Bals, T. Altantzis, M. C. Figueiredo, I. A. W. Filot, E. J. M. Hensen, B. M. Weckhuysen, W. van der Stam, ACS Catal., 2022, 12, 15146-15156.
[18]	Y. Hu, D. Lu, W. Zhou, X. Wang, Y. Li, J. Mater. Chem. A, 2023, 11, 1937-1943.
[19]	Z. Liu, R. D. E. Krösschell, I. A. W. Filot, E. J. M. Hensen, Electrochim. Acta, 2024, 493, 144409.
[20]	Z. Liu, X. Zong, D. G. Vlachos, I. A. W. Filot, E. J. M. Hensen, Chin. J. Catal., 2023, 50, 249-259.
[21]	S. B. Varandili, D. Stoian, J. Vavra, K. Rossi, J. R. Pankhurst, Y. T. Guntern, N. López, R. Buonsanti, Chem. Sci., 2021, 12, 14484-14493.
[22]	S. Zhang, W. Ruan, J. Guan, Adv. Energy Mater., 2025, 15, 2404057.
[23]	X. Bai, Z. Duan, B. Nan, L. Wang, T. Tang, J. Guan, Chin. J. Catal., 2022, 43, 2240-2248.
[24]	Y. Le, H. Zhong, Y. Yang, R. He, G. Yao, F. Jin, J. Energy Chem., 2017, 26, 936-941.
[25]	X. Li, Q. Chen, W. Sun, C. He, Z. Wen, Angew. Chem. Int. Ed., 2024, 63, e202412410.
[26]	Y. Li, M. Lu, Y. Wu, Q. Ji, H. Xu, J. Gao, G. Qian, Q. Zhang, J. Mater. Chem. A, 2020, 8, 18215-18219.
[27]	J. Jiao, X. Kang, J. Yang, S. Jia, Y. Peng, S. Liu, C. Chen, X. Xing, M. He, H. Wu, B. Han, J. Am. Chem. Soc., 2024, 146, 15917-15925.
[28]	X. Chen, D. A. Henckel, U. O. Nwabara, Y. Li, A. I. Frenkel, T. T. Fister, P. J. A. Kenis, A. A. Gewirth, ACS Catal., 2020, 10, 672-682.
[29]	S.-F. Hung, A. Xu, X. Wang, F. Li, S.-H. Hsu, Y. Li, J. Wicks, E. G. Cervantes, A. S. Rasouli, Y. C. Li, M. Luo, D.-H. Nam, N. Wang, T. Peng, Y. Yan, G. Lee, E. H. Sargent, Nat. Commun., 2022, 13, 819.
[30]	M. Long, X. Liu, M. Wang, M. Shu, W. Shan, H. Wang, J. Mater. Chem. A, 2025, 13, 7295-7301.
[31]	B. Zhang, Y. Chang, Y. Wu, Z. Fan, P. Zhai, C. Wang, J. Gao, L. Sun, J. Hou, Adv. Energy Mater., 2022, 12, 2200321.
[32]	H. Li, P. Wei, D. Gao, G. Wang, Curr. Opin. Green Sustain. Chem., 2022, 34, 100589.
[33]	M. He, C. Li, H. Zhang, X. Chang, J. G. Chen, W. A. Goddard III, M.-J. Cheng, B. Xu, Q. Lu, Nat. Commun., 2020, 11, 3844.
[34]	W. Shan, R. Liu, H. Zhao, Z. He, Y. Lai, S. Li, G. He, J. Liu, ACS Nano, 2020, 14, 11363-11372.
[35]	N. J. Firet, W. A. Smith, ACS Catal., 2017, 7, 606-612.
[36]	B. Peng, H. She, Z. Wei, Z. Sun, Z. Deng, Z. Sun, W. Chen, Nat. Commun., 2025, 16, 2217.
[37]	N. Sun, Z. Zheng, Z. Lai, J. Wang, P. Du, T. Ying, H. Wang, J. Xu, R. Yu, Z. Hu, C.-W. Pao, W.-H. Huang, K. Bi, M. Lei, K. Huang, Adv. Mater., 2024, 2404772.
[38]	H. Wang, H. Yuan, W. Wang, L. Shen, J. Sun, X. Liu, J. Yang, X. Wang, T. Wang, N. Wen, Y. Gao, K. Song, D. Chen, S. Wang, Y.-W. Zhang, J. Wang, ACS Nano, 2024, 18, 33405-33417.
[39]	T. Tang, X. Bai, X. Xu, Z. Wang, J. Guan, J. Colloid Interface Sci., 2025, 680, 676-683.
[40]	L. Xiao, X. Bai, J. Han, Z. Wang, J. Guan, Chin. J. Catal., 2025, 71, 340-352.
[41]	Q. Li, J. Wu, L. Lv, L. Zheng, Q. Zheng, S. Li, C. Yang, C. Long, S. Chen, Z. Tang, Adv. Mater., 2024, 36, 2305508.
[42]	W. Lyu, Y. Liu, J. Zhou, D. Chen, X. Zhao, R. Fang, F. Wang, Y. Li, Angew. Chem. Int. Ed., 2023, 62, e202310733.
[43]	S. Chen, C. Ye, Z. Wang, P. Li, W. Jiang, Z. Zhuang, J. Zhu, X. Zheng, S. Zaman, H. Ou, L. Lv, L. Tan, Y. Su, J. Ouyang, D. Wang, Angew. Chem. Int. Ed., 2023, 62, e202315621.
[44]	Y. Zhao, Y. Ding, W. Li, C. Liu, Y. Li, Z. Zhao, Y. Shan, F. Li, L. Sun, F. Li, Nat. Commun., 2023, 14, 4491.

Engineering d-band structure of Zn-doped CuO_xH_y for boosting CO₂ electroreduction performance

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 12

Recommended Articles

Metrics

[1]	Lei Xiong, Xianbiao Fu. Recent advances and challenges in electrochemical CO₂ reduction to CH₄ [J]. Chinese Journal of Catalysis, 2025, 73(6): 39-61.
[2]	Chenghong Hu, Yue Zhang, Yi Zhang, Qintong Huang, Kui Shen, Liyu Chen, Yingwei Li. Single-atomic Fe sites modulated by Sn regulator for enhanced electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 72(5): 222-229.
[3]	Fanrong Chen, Jiaju Fu, Liang Ding, Xiaoying Lu, Zhe Jiang, Xiaoling Zhang, Jin-Song Hu. Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate [J]. Chinese Journal of Catalysis, 2025, 71(4): 138-145.
[4]	Mingzhi Wang, Wensheng Fang, Deyu Zhu, Chenfeng Xia, Wei Guo, BaoYu Xia. Tandem design on electrocatalysts and reactors for electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 69(2): 1-16.
[5]	Yuxing Xu, Leilei Wang, Qin Liu, Botao Teng, Chuanqiang Wu, Binghui Ge, Wentuan Bi, Minghui Gu, Mengkai Zhang, Huan Yan, Junling Lu. Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 79(12): 68-77.
[6]	Jialin Wang, Kaini Zhang, Ta Thi Thuy Nga, Yiqing Wang, Yuchuan Shi, Daixing Wei, Chung-Li Dong, Shaohua Shen. Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO₂ reduction [J]. Chinese Journal of Catalysis, 2024, 64(9): 54-65.
[7]	Mengna Wang, Qi Wang, Tianfu Liu, Guoxiong Wang. Unexpected effect of second-shell defect in iron-nitrogen-carbon catalyst for electrochemical CO₂ reduction reaction: A DFT study [J]. Chinese Journal of Catalysis, 2024, 66(11): 247-256.
[8]	Lei Bian, Zi-Yang Zhang, Hao Tian, Na-Na Tian, Zhi Ma, Zhong-Li Wang. Grain boundary-abundant copper nanoribbons on balanced gas-liquid diffusion electrodes for efficient CO₂ electroreduction to C₂H₄ [J]. Chinese Journal of Catalysis, 2023, 54(11): 199-211.
[9]	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.
[10]	Chunpeng Wang, Zhe Wang, Shanjun Mao, Zhirong Chen, Yong Wang. Coordination environment of active sites and their effect on catalytic performance of heterogeneous catalysts [J]. Chinese Journal of Catalysis, 2022, 43(4): 928-955.
[11]	Renyang Zheng, Zaiku Xie. Full life cycle characterization strategies for spatiotemporal evolution of heterogeneous catalysts [J]. Chinese Journal of Catalysis, 2021, 42(12): 2141-2148.
[12]	Yishu Fu, Yanan Li, Xia Zhang, Yuyu liu, Xiaodong Zhou, Jinli Qiao. Electrochemical CO₂ reduction to formic acid on crystalline SnO₂ nanosphere catalyst with high selectivity and stability [J]. Chinese Journal of Catalysis, 2016, 37(7): 1081-1088.