Solid Base Bi24 O31 Br10 (OH)δ with Active Lattice Oxygen for the Efficient Photo-Oxidation of Primary Alcohols to Aldehydes

Angew Chem Int Ed Engl. 2019 May 6;58(19):6265-6270. doi: 10.1002/anie.201900773. Epub 2019 Feb 27.

Abstract

The selective oxidation of primary alcohols to aldehydes by O2 instead of stoichiometric oxidants (for example, MnVII , CrVI , and OsIV ) is an important but challenging process. Most heterogeneous catalytic systems (thermal and photocatalysis) require noble metals or harsh reaction conditions. Here we show that the Bi24 O31 Br10 (OH)δ photocatalyst is very efficient in the selective oxidation of a series of aliphatic (carbon chain from C1 to C10 ) and aromatic alcohols to their corresponding aldehydes/ketones under visible-light irradiation in air at room temperature, which would be challenging for conventional thermal and light-driven processes. High quantum efficiencies (71 % and 55 % under 410 and 450 nm irradiation) are reached in a representative reaction, the oxidation of isopropanol. We propose that the outstanding performance of the Bi24 O31 Br10 (OH)δ photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo-oxidation of alcohols.

Keywords: active lattice oxygen; photo-oxidation; primary alcohols; solid base; visible-light photocatalysis.