Competitive photooxidation of small colorless organics controlled by oxygen vacancies under visible light

Visible-light photooxidation sensitized by surface attachment of small colorless organics on semiconductor photocatalysts has emerged as an economical method for photocatalytic synthesis or degradation. In particular, heteroatom (X = N and Cl)-containing substrates could undergo either C-N coupling or dechlorination degradation via sensitizing TiO2, but the mechanism in conducting the competitive visible-light sensitized photooxidations is still vague. Herein, the visible-light photooxidation of colorless 4-chlorobenzene-1,2-diamine (o-CAN) on TiO2 was revealed, contributing to selective C-N coupling rather than dechlorination. Oxygen vacancies (OVs) were in situ generated on the TiO2 surface, which could be dominant in weakening the Cl-Ti adsorption of o-CAN and regulating the activation of O2 for selective C-N coupling. The C-N coupling product, functionalized as the sensitizer, further promoted the visible-light photooxidation upon N-Ti and Cl-Ti coordination. This process was then confirmed by on-line mass spectrometric analysis, and the intermediates as well as their kinetics were determined. Thereby, theoretical calculations were employed to verify the roles of OVs in competitive photooxidation and lowering the energy barriers as well. Based on the comprehensive characterizations of both the catalysts and intermediates, this work has provided insights into competitive photooxidations under visible light. Competitive photooxidation of colorless 4-chlorobenzene-1,2-diamine (o-CAN) on TiO2 was controlled by in situ generated oxygen vacancies (OVs) via regulating substrate adsorption and O2 activation, which was monitored via on-line mass spectrometry.