Highly Stable Layered Coordination Polymer Electrocatalyst toward Efficient CO2‐to‐CH4 Conversion

Abstract Cu 2+ ‐based materials, a class of promising catalysts for the electrocatalytic carbon dioxide reduction reaction (CO 2 RR) to value‐added chemicals, usually undergo inevitable and uncontrollable reorganization processes during the reaction, resulting in catalyst deactivation or the new active sites formation and bringing great challenges to exploring their structure–performance relationships. Herein, a facile strategy is reported for constructing Cu 2+ and 3, 4‐ethylenedioxythiophene (EDOT) coordination to stabilize Cu 2+ ions to prepare a novel layered coordination polymer (CuPEDOT). CuPEDOT enables selective reduction of CO 2 to CH 4 with 62.7% Faradaic efficiency at the current density of 354 mA cm −2 in a flow cell, and the catalyst is stable for at least 15 h. In situ spectroscopic characterization and theoretical calculations reveal that CuPEDOT catalyst can maintain the Cu 2+ ‐EDOT coordination structurally stable in CO 2 RR and significantly promote the further hydrogenation of *CO intermediates, favoring the formation of CH 4 instead of dimerization to C 2 products. The strong coordination between EDOT and Cu 2+ prevents the reduction of Cu 2+ ions during CO 2 RR. The finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO 2 RR.