Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO2 Reduction

doi:10.1007/s40242-025-5035-7

高等学校化学研究 ›› 2025, Vol. 41 ›› Issue (3): 525-528.doi: 10.1007/s40242-025-5035-7

Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction

XU Zijun, ZHANG Yifan, SU Yaqiong

School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi'an Jiaotong University, Xi'an 710049, P. R. China

收稿日期:2025-02-28 修回日期:2025-04-15 出版日期:2025-06-01 发布日期:2025-05-27
通讯作者: SU Yaqiong,E-mail:yqsu1989@xjtu.edu.cn E-mail:yqsu1989@xjtu.edu.cn
基金资助:
This work was supported by the Shaanxi Fundamental Science Research Project for Chemistry and Biology, China (No. 23JHQ078).

Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction

XU Zijun, ZHANG Yifan, SU Yaqiong

School of Chemistry, Engineering Research Center of Energy Storage Materials and Devices of Ministry of Education, National Innovation Platform (Center) for Industry-Education Integration of Energy Storage Technology, Xi'an Jiaotong University, Xi'an 710049, P. R. China

Received:2025-02-28 Revised:2025-04-15 Online:2025-06-01 Published:2025-05-27
Contact: SU Yaqiong,E-mail:yqsu1989@xjtu.edu.cn E-mail:yqsu1989@xjtu.edu.cn
Supported by:
This work was supported by the Shaanxi Fundamental Science Research Project for Chemistry and Biology, China (No. 23JHQ078).

摘要/Abstract

摘要： With the increasing global concern over carbon dioxide emissions, the electrocatalytic carbon dioxide reduction reaction (CO₂RR) has gained significant attention. Copper (Cu)-containing materials have shown potential for multielectron transfer reduction products. This study employs density functional theory (DFT) calculations to investigate the effect of axial ligands (O, F, Cl) on the CO₂RR performance of Cu-porphyrin with N-coordinated metal centers. Our study have designed an axial coordinated Cu-porphyrin structure with several ligands. The adsorption energy and Gibbs free energy change were calculated to evaluate the catalytic performance. The results show that the introduction of axial ligands significantly affects the electron density distribution and the catalytic activity. The Cu-porphyrin-O (CuPO) catalyst exhibits stronger adsorption of CO₂ and lower energy barriers for the initial step of CO₂RR process compared to the other catalysts, while the other two catalysts Cu-porphyrin-F (CuPF) and Cu-porphyrin-Cl (CuPCl) greatly promote the potential-determining step (PDS), respectively. The d-band center theory further explains the enhanced adsorption strength of intermediates on these catalysts. Our research provides insights into the design of high-performance CO₂RR single-atom catalysts.

关键词: Cu-porphyrin based catalyst, Axial coodinaion, Electrocatalytic carbon dioxide reduction reaction

Abstract: With the increasing global concern over carbon dioxide emissions, the electrocatalytic carbon dioxide reduction reaction (CO₂RR) has gained significant attention. Copper (Cu)-containing materials have shown potential for multielectron transfer reduction products. This study employs density functional theory (DFT) calculations to investigate the effect of axial ligands (O, F, Cl) on the CO₂RR performance of Cu-porphyrin with N-coordinated metal centers. Our study have designed an axial coordinated Cu-porphyrin structure with several ligands. The adsorption energy and Gibbs free energy change were calculated to evaluate the catalytic performance. The results show that the introduction of axial ligands significantly affects the electron density distribution and the catalytic activity. The Cu-porphyrin-O (CuPO) catalyst exhibits stronger adsorption of CO₂ and lower energy barriers for the initial step of CO₂RR process compared to the other catalysts, while the other two catalysts Cu-porphyrin-F (CuPF) and Cu-porphyrin-Cl (CuPCl) greatly promote the potential-determining step (PDS), respectively. The d-band center theory further explains the enhanced adsorption strength of intermediates on these catalysts. Our research provides insights into the design of high-performance CO₂RR single-atom catalysts.

Key words: Cu-porphyrin based catalyst, Axial coodinaion, Electrocatalytic carbon dioxide reduction reaction

XU Zijun, ZHANG Yifan, SU Yaqiong. Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction[J]. 高等学校化学研究, 2025, 41(3): 525-528.

XU Zijun, ZHANG Yifan, SU Yaqiong. Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction[J]. Chemical Research in Chinese Universities, 2025, 41(3): 525-528.

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Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction

Computational Study of Axial Coordination Cu-porphyrin for Electrochemical CO₂ Reduction

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