Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts

TLDR: It is considered more feasible that the rate-deter-mining step is the cleavage of the C-H bond at the R-carbon atom, and the active site consists of an ensemble of metallic Auatoms and a cationic Au.

Abstract: ion from a primary OH group of glyc-erol. 223,231 A similar mechanism was proposed manyyears ago for alcohol oxidation on Pt/C, involving asecond step, the transfer of a hydride ion to the Ptsurface (Scheme 11). 8,87,237 We consider it more feasible that the rate-deter-mining step is the cleavage of the C-H bond at theR-carbon atom. A similar mechanism is now generallyaccepted for Au electrodes (Scheme 12). 238 Despite thestructural differences between Au nanoparticles andan extended Au electrode surface, there are alsosimilarities, such as the critical role of aqueousalkaline medium and the absence of deactivation dueto decomposition products (CO and C x H y frag-ments). 239,240 An important question is the nature of active siteson Au nanoparticles. Electrooxidation of ethanol onAu nanoparticles supported on glassy carbon re-quired the partial coverage of Au surface by oxides. 241 Another analogy might be the model proposed for COoxidation. 219,242,243 According to this suggestion, theactive site consists of an ensemble of metallic Auatoms and a cationic Au