Interfacial polarized Ptδ- sites drive efficient and direct photocatalytic conversion of methane to formaldehyde by regulating radical species via d–p orbital interactions

The direct photocatalytic oxidation of inert methane (CH 4 ) to high-value-added oxygenates remains a significant challenge. This study precisely controls generated reactive oxygen species (ROS) types by modulating interfacial electronic interactions in Zn-Pt δ− -PS photocatalysts, promoting CH 4 conversion into formaldehyde (HCHO). Under ambient conditions, a HCHO production rate reached 3308 μmol·g −1 with a high selectivity of 77%. In situ spectroscopy and theoretical studies demonstrated that the elevated Pt d-band center in Pt-*OOH (* represents the adsorption state) lowered the occupancy of antibonding orbitals, thereby enhancing the interaction between Pt and *OOH, markedly polarizing the O O bond, facilitating its cleavage, and enabling the preferential in situ generation of •OH rather than •OOH. Furthermore, adequate •OH radical accelerated activation of the C H bond in CH 4 and induced the cleavage of its O H bond in methanol (CH 3 OH), promoting HCHO formation. This strategy may guide the rational design of the catalyst's electronic structure to enhance CH 4 photocatalytic oxidation. Download: Download high-res image (175KB) Download: Download full-size image