Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of...Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.展开更多
基金the National Natural Science Foundation of China(Nos.22025206,21991094)supported by the Ministry of ScienceTechnology of the People’s Republic of China(No.2018YFE0118100)+1 种基金the CAS-NSTDA Joint Research Project(No.GJHZ2075)Dalian Science and Technology Innovation Fund(No.2019J11CY009).
文摘Selective oxidation of saturated C(sp^(3))-H bonds in hydrocarbon to target chemicals under mild conditions remains a signifi-cant but challenging task because of the chemical inertness and high dissociation energy of C(sp^(3))-H bonds.Semiconductor photocatalysis can induce the generation of holes and oxidative radicals,off ering an alternative way toward selective oxidation of hydrocarbons under ambient conditions.Herein,we constructed N-doped TiO_(2) nanotubes(N-TNTs)that exhibited remark-able activity and selectivity for toluene oxidation under visible light,delivering the conversion of toluene and selectivity of benzaldehyde of 32% and>99%,respectively.Further mechanistic studies demonstrated that the incorporation of nitrogen induced the generation of N-doping level above the O 2p valance band,directly contributing to the visible-light response of TiO_(2).Furthermore,hydroxyl radicals generated by photogenerated holes at the orbit of O 2p were found to be unselective for the oxidation of toluene,aff ording both benzaldehyde and benzoic acid.The incorporation of nitrogen was able to inhibit the generation of hydroxyl radicals,terminating the formation of benzoic acid.
