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

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.

Keywords

Cu-porphyrin based catalyst / Axial coodinaion / Electrocatalytic carbon dioxide reduction reaction / Chemical Sciences / Physical Chemistry (incl. Structural)

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RIGHTS & PERMISSIONS

Jilin University, The Editorial Department of Chemical Research in Chinese Universities and Springer-Verlag GmbH