Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water

Gold nanoclusters (phi = 1.3 nm) stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP NCs) readily oxidize benzylic alcohols to the corresponding aldehydes and/or carboxylic acids under ambient temperature in water. Kinetic measurement revealed that smaller Au:PVP NCs exhibit higher catalytic activity than larger (9.5 nm) homologues and, more surprisingly, than Pd:PVP NCs of comparable size (1.5 and 2.2 nm). On the basis of the marked difference in the kinetic isotope effect and activation energy between Au:PVP and Pd:PVP NCs, a reaction mechanism for alcohol oxidation catalyzed by Au:PVP NCs is proposed in which a superoxo-like molecular oxygen species adsorbed on the surface of the small Au NCs abstracts a hydrogen atom from the alkoxide.