Engineering a Cu‐Pd Paddle‐Wheel Metal−Organic Framework for Selective CO 2 Electroreduction

Optimizing the binding energy between the intermediate and the active site is a key factor for tuning catalytic product selectivity and activity in the electrochemical carbon dioxide reduction reaction. Copper active sites are known to reduce CO2 to hydrocarbons and oxygenates, but suffer from poor product selectivity due to the moderate binding energies of several of the reaction intermediates. Here, we report an ion exchange strategy to construct Cu‐Pd paddle wheel dimers within Cu‐based metal‐organic frameworks (MOFs), [Cu3‐xPdx(BTC)2] (BTC = benzentricarboxylate), without altering the overall MOF structural properties. Compared to the pristine Cu MOF ([Cu3(BTC)2], HKUST‐1), the Cu‐Pd MOF shifts CO2 electroreduction products from diverse chemical species to selective CO generation. In situ X‐ray absorption fine structure analysis of the catalyst oxidation state and local geometry, combined with theoretical calculations, reveal that the incorporation of Pd within the Cu‐Pd paddle wheel node structure of the MOF promotes adsorption of the key intermediate COOH* at the Cu site. This permits CO‐selective catalytic mechanisms and thus advances our understanding of the interplay between structure and activity toward electrochemical CO2 reduction using molecular catalysts.