Dual-metal sites drive tandem electrocatalytic CO2 to C2+ products.

Abstract

The electrochemical conversion of CO2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C2+) products is highly desired. Here, we report a 1.4%Pd-Cu@CuPz2 comprising of dispersive CuOx and PdO dual nanoclusters embedded in the MOF CuPz2(Pz= Pyrazole), which achieves a high C2+ Faradaic efficiency (FEC2+) of 81.9% and C2+ alcohol FE of 47.5% with remarkable stability when using 0.1 M KCl aqueous solution as electrolyte in a typical H-cell. Particularly, the FE of alcohol is obviously improved on 1.4%Pd-Cu@CuPz2 compared to Cu@CuPz2. Theoretical calculations have revealed thatrevealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO-*CO dimerizationon the Cu-Pd dual sites bridged by Cu nodes of CuPz2. Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH2CHO and promote subsequent proton-coupled electron transfermore efficiently, confirming that the formation pathway is skew towards *C2H5OH. Consequently, the Cu-Pd dual sitesplay a synergistic tandemrole in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO2 to C2+.