Direct Photocatalytic Oxidation of Methane to Formic Acid with High Selectivity via a Concerted Proton–Electron Transfer Process

Light-driven direct conversion of methane to formic acid is a promising approach to convert methane to value-added chemicals and promote sustainability. However, this process remains challenging due to the complex requirements for multiple protons and electrons. Herein, we report the design of WO3-based photocatalysts modified with Pt active sites to address this challenge. We demonstrate that modulating the dimensional effect of Pt on the WO3 support is key to enhancing the catalytic performance of selective CH4-to-HCOOH conversion. The Pt nanoparticles on WO3 exhibit superior conversion rate, selectivity and durability in the production of HCOOH compared to the Pt-free sample and WO3 decorated with Pt single atoms. The optimal PtNPs-WO3 catalyst achieves a HCOOH conversion rate of 17.7 mmol g–1, with 84% selectivity and stability maintained for up to 48 h. Mechanistic studies show that the protonation of O2 to hydroxyl radicals is the limiting step for HCOOH yield. Pt nanoparticles can facilitate electron transfer and promote O2 dissociation, generating hydroxyl radicals via a proton-coupled electron transfer process. This process provides sufficient protons to lower the formation barrier for •OH radicals, thereby promoting the activation of CH4. In addition, Pt nanoparticles regulate the adsorption of oxygenated hydrocarbon intermediates, increasing the selectivity of the reaction. This work advances our understanding of catalyst design for methane conversion and the effective regulation of complex reaction pathways.