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We focused on identifying a catalytic active site structure at the atomic level and elucidating the mechanism at the elementary reaction level of liquid-phase organic reactions with a heterogeneous catalyst. In this study, we experimentally and computationally investigated efficient C-H bond activation for the selective aerobic α,β-dehydrogenation of saturated ketones by using a Pd-Au bimetallic nanoparticle catalyst supported on CeO 2 (Pd/Au/CeO 2 ) as a case study. Detailed characterization of the catalyst with various observation methods revealed that bimetallic nanoparticles formed on the CeO 2 support with an average size of about 2.5 nm and comprised a Au nanoparticle core and PdO nanospecies dispersed on the core. The formation mechanism of the nanoparticles was clarified through using several CeO 2 -supported controlled catalysts. Activity tests and detailed characterizations demonstrated that the dehydrogenation activity increased with the coordination numbers of Pd-O species in the presence of Au(0) species. Such experimental evidence suggests that a Pd(II)-(μ-O)-Au(0) structure is the true active site for this reaction. Based on density functional theory calculations using a suitable Pd 1 O 2 Au 12 cluster model with the Pd(II)-(μ-O)-Au(0) structure, we propose a C-H bond activation mechanism via concerted catalysis in which the Pd atom acts as a Lewis acid and the adjacent μ-oxo species acts as a Brønsted base simultaneously. The calculated results reproduced the experimental results for the selective formation of 2-cyclohexen-1-one from cyclohexanone without forming phenol, the regioselectivity of the reaction, the turnover-limiting step, and the activation energy.

C–H Bond Activation Mechanism by a Pd(II)–(μ-O)–Au(0) Structure Unique to Heterogeneous Catalysts