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 Cu 3 N 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 Cu 3 N 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.