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Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal‐organic frameworks (MOFs, NH2−MIL‐125 and MIL‐125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon‐excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti8O8(OH)4 cluster) of the MOF structure, and the plasmon‐excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4‐benzenedicarboxylate−NH2). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular‐level manipulation of interface charge transfer on plasmonic photocatalysts. [ABSTRACT FROM AUTHOR]

Core-shell TiO2 microspheres possess a unique structure and interesting properties, and therefore, they have received much attention. The high-energy facets of TiO2 also are being widely studied for the high photocatalytic activities they are associated with. However, the synthesis of the core-shell structure is difficult to achieve and requires multiple-steps and/or is expensive. Hydrofluoric acid (HF), which is highly corrosive, is usually used in the controlling high-energy facet production. Therefore, it is still a significant challenge to develop low-temperature, template-free, shapecontrolled, and relative green self-assembly routes for the formation of core-shell-structured TiO2 microspheres with high-energy facets. Here, we report a template- and hydrofluoric acid free solvothermal self-assembly approach to synthesize core-shell TiO2 microspheres covered with high-energy {116}-facet-exposed nanosheets, an approach in which 1,4-butanediamine plays a key role in the formation of nanosheets with exposed {116} facets and the doping of nitrogen in situ. In the structure, nanoparticle aggregates and nanosheets with {116} high-energy facets exposed act as core and shell, respectively. The photocatalytic activity for degradation of 2,4,6-tribromophenol and Rhodamine B under visible irradiation and UV/Vis irradiation has been examined, and improved photocatalytic activity under visible light owing to the hierarchical core-shell structure, {116}-plane-oriented nanosheets, in situ N doping, and large surface areas has been found. [ABSTRACT FROM AUTHOR]

Titanium dioxide with surface-loaded palladium (Pd-TiO2) was able to easily remove all ten bromine atoms from decabromodiphenyl ether (BDE209) within 1 h under the irradiation of sunlight or an artificial light source. By contrast, fewer than three bromine atoms were eliminated on the pristine TiO2 even with prolonged irradiation (5 h). During the photocatalytic debromination, moreover, the formed BDE intermediates exhibited a significant difference between the Pd-TiO2 and pristine TiO2 systems, and much less position selectivity for the debromination on Pd-TiO2 was observed than that on the pristine TiO2 surface. For another polybrominated diphenyl ether (BDE15), pristine TiO2 was incapable of its photocatalytic reduction, whereas the loading of Pd enabled its debromination to diphenyl ether within 20 min. In addition, an evident induction period appeared in the photocatalytic debromination of BDE15 on Pd-TiO2. The experiments imply that the Pd-cocatalyzed effect changes significantly the photocatalytic reductive debromination pathways. [ABSTRACT FROM AUTHOR]

Epoxidation of olefins with H2O2 is one of the most important reactions in organic synthesis. We found that anatase TiO2 can be a good catalyst for the epoxidation of cyclooctene with H2O2 at room temperature. However, the catalyst deactivated quickly in the presence of excess amount of H2O2 because of the formation of inactive side-on Ti-η2-peroxide species on the surface of TiO2, the presence of which was confirmed by isotope-labelled resonance UV Raman spectroscopy and kinetics studies. Interestingly, the epoxidation reaction could be dramatically accelerated under irradiation of UV light with λ≥350 nm. This phenomenon is attributed to the photo-assisted removal of the inactive peroxide species, through which the active sites on the surface of anatase TiO2 are regenerated and the catalytic epoxidation of cyclooctene with H2O2 is resumed. This finding provides an alternative for sustained epoxidation reactions on TiO2 at room temperature. Moreover, it also has significant implications on the deactivation pathway and possible solutions in Ti-based heterogeneous catalysis or photocatalysis. [ABSTRACT FROM AUTHOR]

Epoxidation of olefins with H2O2 is one of the most important reactions in organic synthesis. We found that anatase TiO2 can be a good catalyst for the epoxidation of cyclooctene with H2O2 at room temperature. However, the catalyst deactivated quickly in the presence of excess amount of H2O2 because of the formation of inactive side-on Ti-η2-peroxide species on the surface of TiO2, the presence of which was confirmed by isotope-labelled resonance UV Raman spectroscopy and kinetics studies. Interestingly, the epoxidation reaction could be dramatically accelerated under irradiation of UV light with λ≥350 nm. This phenomenon is attributed to the photo-assisted removal of the inactive peroxide species, through which the active sites on the surface of anatase TiO2 are regenerated and the catalytic epoxidation of cyclooctene with H2O2 is resumed. This finding provides an alternative for sustained epoxidation reactions on TiO2 at room temperature. Moreover, it also has significant implications on the deactivation pathway and possible solutions in Ti-based heterogeneous catalysis or photocatalysis. [ABSTRACT FROM AUTHOR]