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 (CO2 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 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 CO2 RR 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 CO2 RR. The finding of this work provides a new perspective on designing molecularly stable, highly active catalysts for CO2 RR.

Multivalent Cu sites synergistically adjust carbonaceous intermediates adsorption for electrocatalytic ethanol production.

Copper (Cu)-based catalysts show promise for electrocatalytic CO2 reduction (CO2RR) to multi-carbon alcohols, but thermodynamic constraints lead to competitive hydrocarbon (e.g., ethylene) production. Achieving selective ethanol production with high Faradaic efficiency (FE) and current density is still challenging. Here we show a multivalent Cu-based catalyst, Cu-2,3,7,8-tetraaminophenazine-1,4,6,9-tetraone (Cu-TAPT) with Cu2+ and Cu+ atomic ratio of about 1:2 for CO2RR. Cu-TAPT exhibits an ethanol FE of 54.3 ± 3% at an industrial-scale current density of 429 mA cm-2, with the ethanol-to-ethylene ratio reaching 3.14:1. Experimental and theoretical calculations collectively unveil that the catalyst is stable during CO2RR, resulting from suitable coordination of the Cu2+ and Cu+ with the functional groups in TAPT. Additionally, mechanism studies show that the increased ethanol selectivity originates from synergy of multivalent Cu sites, which can promote asymmetric C-C coupling and adjust the adsorption strength of different carbonaceous intermediates, favoring hydroxy-containing C2 intermediate (*HCCHOH) formation and formation of ethanol.