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

作者：Junjun Li, Yizhen Zhang, Liya Zhang, Qi Zhou, Jiangrong Yang, Yu Fu, Le Yu, Yuanmiao Sun, Zhenhua Li, Yuchen Qin, Yi Ding, Hui Zhang, Hui Zhang, Dingsheng Wang, Zhicheng Zhang · 发表于：Angewandte Chemie International Edition · 年份：2025 · DOI：10.1002/anie.202425006 · 被引用次数：37 · 研究领域：Electrocatalysts for Energy Conversion、Catalytic Processes in Materials Science、CO2 Reduction Techniques and Catalysts

Abstract 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.