Highly Stable Layered Coordination Polymer Electrocatalyst Towards Efficient CO 2 -to-CH 4 Conversion.

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 (FE) 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. Our finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO 2 RR. This article is protected by copyright. All rights reserved.