Selective Photocatalytic Oxidation of Thioanisole on DUT-67(Zr) Mediated by Surface Coordination.

DUT-67(Zr) was obtained by a solvothermal route and applied to photocatalytic selective synthesis of thioanisole under light illuminating. The conversion of thioanisole is up to 95%, and the selectivity of methyl phenyl sulfoxide is 98%. The activity of DUT-67(Zr) is over 10 times higher than that of UiO-66. This great increased activity is attributed to the high percentages of oxygen vacancies on DUT-67(Zr). The ESR result shows there are more oxygen vacancies that can expose high density unsaturated Zr sites on DUT-67(Zr). The in situ FTIR reveals that unsaturated Zr sites on DUT-67(Zr) possess Lewis acidity which facilitate the adsorption of the substrates to form the coordination species, promoting the activation of thioanisole. The absorption edge of DUT-67(Zr) with coordination species red-shifts to 360 nm, which can be presented by DRS. Furthermore, the oxygen molecules can be activated by excited electrons to form •O2-. Finally, a possible photocatalytic process of oxidating thioanisole to methyl phenyl sulfoxide based on the coordination effect between DUT-67(Zr) and thioanisole is proposed at a molecular level.

Flowerlike BiOCl nanospheres fabricated by an in situ self-assembly strategy for efficiently enhancing photocatalysis.

For semiconductor-based photocatalytic reactions, defect engineering has been proven as an efficient approach to enhance the photocatalytic performance. In this work, a synergistically PVP/EG-assisted in situ self-assembly strategy has been successfully developed for preparing flowerlike BiOCl nanospheres (NSP) assembled by ultrathin nanosheets (thickness of 3.8 nm) with abundant oxygen vacancies (OVs). During the hydrothermal process, PVP plays a template role in controlling the orientation of the crystallite growth, leading to the forming of nanosheets. Meanwhlie, ethylene glycol would induce the self-assembly of nanosheets into a loose hierarchical architecture duo to its stereo-hindrance effect. NSP achieves a twice higher photocatalytic conversion of benzylamine than BiOCl nanosheets (NST) under visible light. XPS, ESR, NH3-TPD results manifest that NSP possesses more active sites including OVs and unsaturated Bi atoms than NST, because of avoiding the accumulation of ultrathin nanosheets. In situ FTIR reveals that benzylamine molecules can be chemisorbed and activated on BiOCl interfaces via forming -N…Bi- species. The OVs can facilitate the forming of superoxide radicals (•O2-), achieving the selective photooxidation. Finally, a possible synergetic mechanism based on the interaction of reactants and catalyst interfaces was proposed to illustrate the photocatalytic process at the molecular level.