Electron-donating N--Ti3+-Ov interfacial sites with high selectivity for the oxidation of primary C-H bonds

Element doping can fabricate different types of oxygen vacancies (O-v) on TiO2, but the effects of O-v coordination and configuration on the oxidation reaction remain unclear. Here, we modify the local geometric ligand environment of Ov by doping N and B into anatase TiO2 (N-TiO2 and B-TiO2). N--Ti3+-Ov is induced in N-TiO2 by substituting O with N, which has similar ionic size and electronega-tivity, and Ti3+-Ov is found in TiO2 and B-TiO2. Density functional theory calculations indicate that N--Ti3+-Ov is more reactive than Ti3+-Ov toward O-2 activation. The resultant N-TiO2-0.25 enriched in N--Ti3+-Ov contributes to a rapid formation of superoxygen spe-cies (dO(2)(-)), which increase the oxidation rate of primary C-H bonds in toluene, and thus exhibits much higher selectivity and yield. The fabrication of N--Ti3+-Ov develops doped catalysts with improved Ov reactivity and enhanced primary C-H bond oxidation selectivity.