Switchable Reaction Pathways of Dynamic Integration for Selective CO2‐to‐Ethanol Conversion

Abstract C‐C coupling is a crucial step for electrocatalytic reduction of CO 2 to valuable multi‐carbon (C 2+ ) products, but the static reactive sites in traditional catalyst design often unfavorable for this process. Herein, a dynamic integration strategy is reported that the derivative Cu electrode with mellitic acid ligand complexes (ED/Cu‐c), which enables selective CO 2 conversion through switchable reaction pathways. The optimized ED/Cu‐c catalyst exhibits an excellent Faradaic efficiency of 58.9% toward ethanol production, with remarkable operational stability over 200 h. Time‐dependent elemental analysis demonstrates the occurrence of the in situ dynamic site dissociative adsorption reaction during the CO 2 reduction reaction, leading to seek the switchable rate‐limiting step with a lower activation energy. Density functional theory calculations demonstrate that the switchable reaction pathways reduce reaction energy barrier of C‐C coupling and facilitates proton‐coupled electron transfer. This work provides a promising approach for developing high‐performance electrocatalysts through dynamic in situ engineering.