Organic frameworks confined Cu single atoms and nanoclusters for tandem electrocatalytic CO2 reduction to methane

Abstract The electrochemical reduction reaction of carbon dioxide (CO 2 RR) is considered to be an effective way to realize carbon neutrality. As a type of intensively studied materials, covalent organic frameworks (COFs) with a tunable pore structure and various functional groups are promising catalysts for CO 2 RR. Herein, COF synthesized by 2,6‐diaminoanthraquinone and 2,4,6‐triformylphloroglucinol is employed to assist the synthesis of electrocatalysts from Cu single atoms (SAs) to nanoclusters by controlling the electrodeposition. A tandem catalyst for CO 2 ‐to‐CH 4 conversion is thus achieved by the Cu nanoclusters dispersed among the isolated Cu SAs in the COF network. It is proposed that CO 2 is first reduced to CO over the atomically isolated Cu SAs, followed by diffusion onto the neighboring Cu nanoclusters for further reduction into CH 4 . In addition, mechanistic analysis suggests that the coordinated K + ions on the COF network promote the activation of CO 2 and the adsorption of reaction intermediates, thus realizing the suppressed hydrogen evolution reaction and selective production of CH 4 . This study presents a new insight of COFs for the confined synthesis of a tunable SA to nanocluster electrocatalysts, disclosing the great potential of COFs in electrocatalysis.