Plasmonic O(2) dissociation and spillover expedite selective oxidation of primary C–H bonds

Manipulating O(2) activation via nanosynthetic chemistry is critical in many oxidation reactions central to environmental remediation and chemical synthesis. Based on a carefully designed plasmonic Ru/TiO(2−x) catalyst, we first report a room-temperature O(2) dissociation and spillover mechanism that expedites the “dream reaction” of selective primary C–H bond activation. Under visible light, surface plasmons excited in the negatively charged Ru nanoparticles decay into hot electrons, triggering spontaneous O(2) dissociation to reactive atomic ˙O. Acceptor-like oxygen vacancies confined at the Ru–TiO(2) interface free Ru from oxygen-poisoning by kinetically boosting the spillover of ˙O from Ru to TiO(2). Evidenced by an exclusive isotopic O-transfer from (18)O(2) to oxygenated products, ˙O displays a synergistic action with native ˙O(2)(−) on TiO(2) that oxidizes toluene and related alkyl aromatics to aromatic acids with extremely high selectivity. We believe the intelligent catalyst design for desirable O(2) activation will contribute viable routes for synthesizing industrially important organic compounds.