Theoretical Insights into Enhancing Catalytic Performance of Al-Cu Alloy for CO2 Electroreduction toward Ethene Production

Han Lei; Wenhua Zhang; Jinlong Yang

doi:10.1021/acs.jpclett.4c00943

Theoretical Insights into Enhancing Catalytic Performance of Al-Cu Alloy for CO₂ Electroreduction toward Ethene Production

J Phys Chem Lett. 2024 May 30;15(21):5643-5653. doi: 10.1021/acs.jpclett.4c00943. Epub 2024 May 20.

Authors

Han Lei¹, Wenhua Zhang², Jinlong Yang¹

Affiliations

¹ Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
² Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, China.

PMID: 38767198
DOI: 10.1021/acs.jpclett.4c00943

Abstract

The understanding of the reaction mechanism of CO₂ electroreduction (CO₂RR) is essential for the precise design of catalysts for specific products with high selectivity. In this work, combined with the computational hydrogen electrode model and kinetic energy barrier calculations, CO₂RR pathways on Cu(100) and Al₁Cu₃(100) are intensively investigated. The free energy barrier of the rate-determining step of ethylene formation is reduced from 1.08 eV for *CCOH formation on Cu(100) to 0.51 eV for *CH₂OCHOH formation on Al₁Cu₃(100) and enhances the catalytic activity. The reaction free energy of *CO-*CO coupling is remarkably reduced from 0.86 eV on Cu(100) to -0.43 eV on Al₁Cu₃(100) and the coupling barrier is reduced from 0.97 to 0.37 eV, suppressing the production of gas phase CO and enhancing the production of C₂ products. Furthermore, the selectivity toward C-O breaking of *CH₂CHOH on Cu(100) and *CH₂CH₂OH on Al₁Cu₃(100) ensures high selectivity toward ethene rather than ethanol.