Selective Aerobic Oxidation of C−H Bond over C−C Bond by Single-Atom Catalysts

Aerobic oxidation of C − H bonds is a fundamental transformation in industry catalysis with broad applications. A primary challenge for C − H bond selective activation is that the desired products often exhibit greater reactivity than the starting hydrocarbons, complicating the achievement of both high conversion and selectivity. Here, we demonstrate that oxide-supported single-atom catalysts (SACs) are effective for the selective aerobic oxidation of C − H bonds with higher bond energy over C − C bond with lower bond energy, facilitating the formation of ketone products without generating any C − C breaking over-oxidation products. Comprehensive studies have revealed that SACs exhibit a unique inactivity for further oxidation of ketones due to their inability to activate the ketone via its enol form, effectively circumventing over-oxidation through C − C bond cleavage and disrupting the conventional activity-selectivity tradeoff. This finding is general and applies for a variety of SACs across variety hydrocarbon substrates, heralding a promising pathway for heterogeneous catalysis of selective C − H activation.