Visible-light-driven photocatalysis over nano-TiO2 with different morphologies: From morphology through active site to photocatalytic performance

Enormous efforts have been devoted to exploring the influence of the materials’ morphology on photocatalytic performance, while the role of active site between them attracts less attention. Herein, three types of anatase nano-TiO2 with different morphologies were successfully prepared for visible-light-driven photocatalytic selective oxidation of benzylamine. The material properties of the samples were systematically studied by various characterization techniques such as XRD, SEM, TEM, AFM, XPS, UV–vis DRS, ESR and in situ FTIR. Due to possessing clear advantages especially for having more active sites (coordinatively unsaturated Ti atoms and oxygen vacancies), the TiO2 with porous structure shows more excellent photocatalytic performance than the other samples. Coordinatively unsaturated Ti atoms can chemisorb and activate benzylamine molecules via forming H-N…Ti coordination species, whose absorption property of visible light guarantees that TiO2 samples can achieve the photocatalytic process under visible light. Oxygen vacancies can chemisorb and activate oxygen molecules to form reactive oxygen species (superoxide radical) by the reduction of photogenerated electrons. Finally, a possible synergetic mechanism based on the interaction of reactants and catalyst interfaces was proposed at the molecular level to illustrate the photocatalytic process.