Dual‐Metal Sites Drive Tandem Electrocatalytic CO 2 to C 2+ Products

The electrochemical conversion of CO 2 into valuable chemicals is a promising route for renowable energy storage and the mitigation of greenhouse gas emission, and production of multicarbon (C 2+ ) products is highly desired. Here, we report a 1.4 %Pd−Cu@CuPz 2 comprising of dispersive CuO x and PdO dual nanoclusters embedded in the MOF CuPz 2 (Pz=Pyrazole), which achieves a high C 2+ Faradaic efficiency (FE C2+ ) of 81.9 % and C 2+ 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@CuPz 2 compared to Cu@CuPz 2 . Theoretical calculations have revealed that the enhanced interfacial electron transfer facilitates the adsorption of *CO intermediate and *CO−*CO dimerization on the Cu−Pd dual sites bridged by Cu nodes of CuPz 2 . Additionally, the oxophilicity of Pd can stabilize the key intermediate *CH 2 CHO and promote subsequent proton‐coupled electron transfer more efficiently, confirming that the formation pathway is skew towards *C 2 H 5 OH. Consequently, the Cu−Pd dual sites play a synergistic tandem role in cooperatively improving the selectivity of alcohol and accelerating reductive conversion of CO 2 to C 2+ .