Kinetic Understanding of Catalytic Selectivity and Product Distribution of Electrochemical Carbon Dioxide Reduction Reaction

Dai-Jian Su; Shi-Qin Xiang; Shu-Ting Gao; Yimin Jiang; Xiaohong Liu; Wei Zhang; Liu-Bin Zhao; Zhong-Qun Tian

doi:10.1021/jacsau.3c00002

Kinetic Understanding of Catalytic Selectivity and Product Distribution of Electrochemical Carbon Dioxide Reduction Reaction

JACS Au. 2023 Mar 2;3(3):905-918. doi: 10.1021/jacsau.3c00002. eCollection 2023 Mar 27.

Authors

Dai-Jian Su¹, Shi-Qin Xiang¹, Shu-Ting Gao¹, Yimin Jiang¹, Xiaohong Liu², Wei Zhang², Liu-Bin Zhao¹, Zhong-Qun Tian³

Affiliations

¹ Department of Chemistry, School of Chemistry and Chemical Engineering, Southwest University, Chongqing 400715, China.
² Chongqing Institute of Green and Intelligent Technology, Chinese Academy of Sciences, Chongqing 400714, China.
³ State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Collaborative Innovation Center of Chemistry for Energy Materials, Xiamen University, Xiamen 361005, China.

Abstract

CO₂ can be electrochemically reduced to different products depending on the nature of catalysts. In this work, we report comprehensive kinetic studies on catalytic selectivity and product distribution of the CO₂ reduction reaction on various metal surfaces. The influences on reaction kinetics can be clearly analyzed from the variation of reaction driving force (binding energy difference) and reaction resistance (reorganization energy). Moreover, the CO₂RR product distributions are further affected by external factors such as electrode potential and solution pH. A potential-mediated mechanism is found to determine the competing two-electron reduction products of CO₂ that shifts from thermodynamics-controlled product formic acid at less negative electrode potentials to kinetic-controlled product CO at more negative electrode potentials. Based on detailed kinetic simulations, a three-parameter descriptor is applied to identify the catalytic selectivity of CO, formate, hydrocarbons/alcohols, as well as side product H₂. The present kinetic study not only well explains the catalytic selectivity and product distribution of experimental results but also provides a fast way for catalyst screening.