Ag+‐Doped InSe Nanosheets for Membrane Electrode Assembly Electrolyzer toward Large‐Current Electroreduction of CO2 to Ethanol

It is an appealing approach to CO2 utilization through CO2 electroreduction (CO2 ER) to ethanol at high current density; however, the commonly used Cu-based catalysts cannot sustain large current during CO2 ER despite their capability for ethanol production. Herein, we report that Ag+ -doped InSe nanosheets with Se vacancies can address this grand challenge in a membrane electrode assembly (MEA) electrolyzer. As revealed by our experimental characterization and theoretical calculation, the Ag+ doping, which can tailor the electronic structure of InSe while diversifying catalytically active sites, enables the formation of key reaction intermediates and their sequential evolution into ethanol. More importantly, such a material can well work for large-current conditions in MEA electrolyzers with In2+ species stabilized via electron transfer from Ag to Se. Remarkably, in an MEA electrolyzer by coupling cathodic CO2 ER with anodic oxygen evolution reaction (OER), the optimal catalyst exhibits an ethanol Faradaic efficiency of 68.7 % and a partial current density of 186.6 mA cm-2 on the cathode with a full-cell ethanol energy efficiency of 26.1 % at 3.0 V. This work opens an avenue for large-current production of ethanol from CO2 with high selectivity and energy efficiency by rationally designing electrocatalysts.