New Reaction Pathway Induced by Plasmon for Selective Benzyl Alcohol Oxidation on BiOCl Possessing Oxygen Vacancies.

Selective organic transformation under mild conditions constitutes a challenge in green chemistry, especially for alcohol oxidation, which typically requires environmentally unfriendly oxidants. Here, we report a new plasmonic catalyst of Au supported on BiOCl containing oxygen vacancies. It photocatalyzes selective benzyl alcohol oxidation with O2 under visible light through synergistic action of plasmonic hot electrons and holes. Oxygen vacancies on BiOCl facilitate the trapping and transfer of plasmonic hot electrons to adsorbed O2, producing •O2- radicals, while plasmonic hot holes remaining on the Au surface mildly oxidize benzyl alcohol to corresponding carbon-centered radicals. The hypothesized concerted ring addition between these two radical species on the BiOCl surface highly favors the production of benzaldehyde along with an unexpected oxygen atom transfer from O2 to the product. The results and understanding acquired in this study, based on the full utilization of hot charge carriers in a plasmonic metal deposited on a rationally designed support, will contribute to the development of more active and/or selective plasmonic catalysts for a wide variety of organic transformations.