Few-Atom Copper Catalyst for the Electrochemical Reduction of CO to Acetate:Synergetic Catalysis between Neighboring Cu Atoms

Single-atom catalysts(SACs)are gaining increasing recognition because of their superior catalytic properties for various reactions.However,the performance of SACs is often limited by the lack of neighboring metal centers to cooperate in catalysis.Herein,a synergetic interaction between neighboring Cu atoms of a few-atom catalyst(FAC)on graphdiyne(GDY)is found to greatly enhance the production of acetate in the CO electroreduction reaction relative to Cu SACs.In a 1.0 M KOH electrolyte,this Cu FAC exhibits an acetate Faradaic efficiency of 53.8±1.5%,an ultrahigh relative purity of up to 97 wt%for liquid products,and excellent stability over 23 h continuous electrolysis at–0.8 V versus reversible hydrogen electrode.Theoretical studies suggest that the intersite catalytic communication between two neighboring metal atoms confined in each pore of GDY facilitates the formation of acetic acid through either stepwise hydrogenation of CH_(2)CO^(*)or the direct reaction of H_(2)Owith CH_(2)CO^(*).Our study demonstrates the unprecedented synergetic catalysis of Cu FAC in promoting the selective CO electroreduction toward acetate production.