Promoting CO(2) Electroreduction to Acetate by an Amine-Terminal, Dendrimer-Functionalized Cu Catalyst

[Image: see text] Acetate derived from electrocatalytic CO(2) reduction represents a potential low-carbon synthesis approach. However, the CO(2)-to-acetate activity and selectivity are largely inhibited by the low surface coverage of in situ generated *CO, as well as the inefficient ethenone intermediate formation due to the side reaction between CO(2) and alkaline electrolytes. Tuning catalyst microenvironments by chemical modification of the catalyst surface is a potential strategy to enhance CO(2) capture and increase local *CO concentrations, while it also increases the selectivity of side reduction products, such as methane or ethylene. To solve this challenge, herein, we developed a hydrophilic amine-tailed, dendrimer network with enhanced *CO intermediate coverage on Cu catalytic sites while at the same time retaining the in situ generated OH(–) as a high local pH environment that favors the ethenone intermediate toward acetate. The optimized amine-network coordinated Cu catalyst (G(3)-NH(2)/Cu) exhibits one of the highest CO(2)-to-acetate Faradaic efficiencies of 47.0% with a partial current density of 202 mA cm(–2) at −0.97 V versus the reversible hydrogen electrode.