Decorating titania with ultrasmall UiO-66-H crystallites enables quantitative photocatalytic oxidation of methane to oxygenates
- Geqian Fang
- Nour Alhajjar
- Wenjun Yu
- Maya Marinova
- Karima Ben Tayeb
- Jian Lin
- Thomas Roland
- Pardis Simon
- Vincent De Waele
- Vitaly V. Ordomsky
- Andrei Y. Khodakov
2026-04-29
Selective photocatalytic oxidation of methane to liquid oxygenates under ambient conditions remains challenging due to the inert C–H bond and propensity for over-oxidation. Controlling carrier transfer and reactive oxygen species is therefore essential to the selective methane photooxidation. Ultrasmall zirconium metal–organic framework (UiO-66-H) nanocrystals in situ grown on titania form a heterojunction that promotes efficient charge separation and tunes the interfacial band alignment. Comprehensive experiments and characterization reveal that this heterojunction precisely regulates • OH and • OOH generation, enabling controlled, radical-mediated oxidation of methane with a competitive oxygenate yield and nearly 100% selectivity at room temperature using air as an oxidant. In this work, ultrasmall metal–organic framework–semiconductor heterojunctions with a built-in electric field provide an effective route for developing efficient, low-cost photocatalysts for methane chemical valorization under mild, solar-driven conditions.