Solid Base Bi24O31Br10(OH)δ with Active Lattice Oxygen for the Efficient Photo‐Oxidation of Primary Alcohols to Aldehydes

The great oxidizer: Bi₂₄O₃₁Br₁₀(OH)_δ is a very efficient photocatalyst in the selective oxidation of various aliphatic and aromatic alcohols to their corresponding aldehydes and ketones under visible‐light irradiation and ambient conditions. The outstanding performance is associated with basic surface sites and active lattice oxygen, which boost the dehydrogenation step in the photo‐oxidation.

Abstract

The selective oxidation of primary alcohols to aldehydes by O₂ instead of stoichiometric oxidants (for example, Mn^VII, Cr^VI, and Os^IV) 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 Bi₂₄O₃₁Br₁₀(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 Bi₂₄O₃₁Br₁₀(OH)_δ photocatalyst is associated with basic surface sites and active lattice oxygen that boost the dehydrogenation step in the photo‐oxidation of alcohols.

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