Molecular Bottom‐Up Design of Single‐Site Copper‐Palladium Catalysts for Selective Glycerol Electro‐Oxidation

ABSTRACT Hybrid water electrolysis is a promising route to generate hydrogen while replacing the challenging and wasteful oxygen evolution reaction (OER) with economically viable alternatives such as the selective glycerol oxidation reaction (GOR). To date, the development of highly active and selective GOR electrocatalysts remains a major challenge because the simultaneous control of reactivity, selectivity, and stability is difficult. Herein, we report a bimetallic Cu‐Pd single‐site catalyst (SSC) for the selective and efficient electrooxidation of glycerol. The catalyst features single‐site copper and palladium atoms in CuN ₄ /PdN ₄ moieties. The catalyst shows high GOR performance with a Faradaic efficiency (FE) for formate of 83% and C3 products (lactate, glycolate, glycerate) of 16% at 1.0 V vs the reversible hydrogen electrode (RHE), as well as long‐term stability (144 h at j = 50 mA cm ⁻² ). Mechanistic studies combining DFT and operando spectroscopy revealed that Pd sites facilitate the adsorption of hydroxyl (C‐OH) species which prevents C‐C bond cleavage and thus the formation of catalyst poisons such as CO or CO ₃ ²⁻ . This work sheds light on the adsorption modulation mechanism of a single‐site catalyst and provides a promising electrocatalytic system for the production of value‐added C1 and C3 products in aqueous solution.