Molecular Scale Interfacial Water Management Switching Reaction Pathway of Carbon Dioxide Electroreduction
Zongying Li, Rongzhen Chen, Wangxin Ge, Kunchi Xie, Yating Wang, Ling Zhang, Zhen Song, Fengwang Li, Yuhang Li, Chunzhong Li
Abstract
Abstract The electrochemical carbon dioxide reduction reaction (eCO 2 RR) involves numerous intermediates and simultaneous interactions between these intermediates and water (H 2 O) molecules. Although extensive research has focused on stabilizing the carbon‐related intermediates, limited attention has been paid to investigating the local regulations of H 2 O molecules at molecular level. Considering the electrocatalytic interface, H 2 O is critical during CO 2 RR process, as H 2 O molecules are directly involved in CO 2 reduction process or indirectly modify the solid–liquid interfacial structure, thereby impacting the reaction process. In this study, we use a model copper‐based catalyst containing palladium and indium dopants that have different hydrogen and oxygen adsorption capabilities to investigate the influence of H 2 O molecules on CO 2 electroreduction selectivity. We find, by enhancing the participation of isolated H 2 O molecules, instead of asymmetric H‐bonded H 2 O or ice‐like H 2 O, in the local electrocatalytic microenvironment during CO 2 reduction process, that the cathodic products remarkably change from 95% C 1 FE to 70% C 2 FE. We unveil, via in situ ATR‐SEIRAS measurement, that the H 2 O microenvironment regulation can promote the formation of key intermediates, thus tuning the CO 2 reduction pathways.