Enabling Specific Photocatalytic Methane Oxidation by Controlling Free Radical Type

Abstract

Selective CH₄ oxidation to CH₃OH or HCHO with O₂ in H₂O under mild conditions provides a desired sustainable pathway for synthesis of commodity chemicals. However, manipulating reaction selectivity while maintaining high productivity remains a huge challenge due to the difficulty in the kinetic control of the formation of a desired oxygenate against its overoxidation. Here, we propose a highly efficient strategy, based on the precise control of the type of as-formed radicals by rational design on photocatalysts, to achieve both high selectivity and high productivity of CH₃OH and HCHO in CH₄ photooxidation for the first time. Through tuning the band structure and the size of active sites (<i>i.e.</i>, single atoms or nanoparticles) in our Au/In₂O₃ catalyst, we show alternative formation of two important radicals, ^•OOH and ^•OH, which leads to distinctly different reaction paths to the formation of CH₃OH and HCHO, respectively. This approach gives rise to a remarkable HCHO selectivity and yield of 97.62% and 6.09 mmol g^-1 on In₂O₃-supported Au single atoms (Au₁/In₂O₃) and an exceptional CH₃OH selectivity and yield of 89.42% and 5.95 mmol g^-1 on In₂O₃-supported Au nanoparticles (Au_NPs/In₂O₃), respectively, upon photocatalytic CH₄ oxidation for 3 h at room temperature. This work opens a new avenue toward efficient and selective CH₄ oxidation by delicate design of composite photocatalysts.