Facilitating OH* Generation on Atomic Pd–Cu Dual Sites towards Efficient Glycerol Electrooxidation to Formate

The electrocatalytic glycerol oxidation reaction (GOR) represents a mild and sustainable pathway to produce value‐added chemicals such as formate. However, the rational design and controlled synthesis of efficient catalysts to achieve highly selective C‐C bond cleavage of glycerol towards formate remains a great challenge. Herein, atomic Pd doped Cu3N hollow nanocubes with Pd‐Cu dual sites were prepared via the unique Kirkendall process, exhibiting superior electrocatalytic GOR activity and selectivity towards formate with a maximum Faraday efficiency of 91.6%. In situ spectroscopic characterization and theoretical calculations reveal that Pd atoms located in partial Cu substituent sites could facilitate the generation of active *OH and enhance the adsorption of glycerol molecule on adjacent Cu sites, while Pd atoms located in Cu3N unit center could effectively reduce the energy barrier of C‐C bond cleavage for the rate determining step. Our work provides new insights into the development of well‐defined dual‐site catalysts to boost glycerol electrooxidation to formate.