Plasmonic O2 dissociation and spillover expedite selective oxidation of primary C-H bonds

Authors：Li, Hao; Shang, Huan; Jiang, Fuze; Zhu, Xingzhong; Ruan, Qifeng; Zhang, Lizhi; Wang, Jing^*

Source：Chemical Science, 2021, 12(46): 15308-15317.

DOI：10.1039/d1sc04632b

• SOLVENT-FREE OXIDATION
• MOLECULAR-OXYGEN
• METAL NANOPARTICLES
• ACTIVATION
• SOLAR
• TIO2
• CONVERSION
• ENERGY
• PHASE
• TRANSFORMATIONS

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/TiO2-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-TiO2 interface free Ru from oxygen-poisoning by kinetically boosting the spillover of O from Ru to TiO2. Evidenced by an exclusive isotopic O-transfer from O-18(2) to oxygenated products, O displays a synergistic action with native O-2(-) on TiO2 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.

• Institution
  南京航空航天大学