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

Cu2+‐based materials, a class of promising catalysts for the electrocatalytic carbon dioxide reduction reaction (CO2RR) 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 Cu2+ and 3, 4‐ethylenedioxythiophene (EDOT) coordination to stabilize Cu2+ ions to prepare a novel layered coordination polymer (CuPEDOT). CuPEDOT enables selective reduction of CO2 to CH4 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 Cu2+‐EDOT coordination structurally stable in CO2RR and significantly promote the further hydrogenation of *CO intermediates, favoring the formation of CH4 instead of dimerization to C2 products. The strong coordination between EDOT and Cu2+ prevents the reduction of Cu2+ ions during CO2RR. The finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO2RR. A novel layered coordination polymer (CuPEDOT) is developed to stabilize Cu2+ through Cu2+ and ethylenedioxythiophene coordination, which has high electrochemical and structural stability in electrocatalytic carbon dioxide reduction reaction.