Chelation and Stabilization of Dynamic Single- Atom Cu in Metal–Organic Frameworks for Selective Hydrogenation Reactions
Yushan Wu, Yawen Tong, Yao Luo, Junchen Xu, Xiang‐Kui Gu, Mingyue Ding
Abstract
Selective hydrogenation of unsaturated carbonyl compounds into alcohols is of great importance in the fine chemical industry. Herein, we reported a robust and reusable single-atom Cu catalyst, Cu 1 @MOF-303, fabricated by a covalent attachment of Cu atoms to the adjacent pair of unsaturated N atoms from two neighboring organic ligands in a metal–organic framework for the selective hydrogenation of aldehydes/ketones, exhibiting high activity with complete conversion and 95% selectivity accompanied by a high product formation rate of 23.6 h –1 . A combination of experimental and theoretical studies revealed that the distinctive electronic and structural attributes rendered Cu 1 @MOF-303 capable of adsorbing targeted functional groups in reactants and desorbing desired products preferentially due to the atomically dispersed Cu species chelated and stabilized by N atoms as well as the dynamic changes by breaking the interfacial Cu–N bonds on reactant adsorption and making these bonds on product desorption, thereby enhancing the catalytic activity and stability.