Integrating wide bandgap semiconductor photocatalysts with visible-light-active inorganic nanoparticles (such as Au and CdS) as sensitizers is one of the most efficient methods to improve their photocatalytic activity in the visible light region. However, as for all such composite photocatalysts, a rational design and precise control over their architecture is often required to achieve optimal performance. Herein, a new TiO2-based ternary composite photocatalyst with superior visible light activity was designed and synthesized. In this composite photocatalyst, the location of the visible light sensitizers was engineered according to the intrinsic facet-induced effect of well-faceted TiO2 nanocrystals on the spatial separation of photogenerated carriers. Experimentally, core-shell structured Au@CdS nanoparticles acting as visible light sensitizers were selectively deposited onto photoreductive {101} facets of well-faceted anatase TiO2 nanocrystals through a two-step in situ photodeposition route. Because the combination of Au@CdS and specific {101} facets of TiO2 nanocrystals facilitates the transport of charges photogenerated under visible light irradiation, this well-designed ternary composite photocatalyst exhibited superior activity in visible-light-driven photocatalytic H2 evolution, as expected.

The photocatalytic activity of faceted TiO2nanocrystals was efficiently enhanced by selectively loading α-Fe2O3and Pt co-catalysts onto specific facets.

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Polymeric nanoreactors in water fabricated by the self-assembly of amphiphilic copolymers have attracted much attention due to their good catalytic performance without using organic solvents. However, the disassembly and instability of relevant nanostructures often compromise their potential applicability. Herein, the preparation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-containing nanoreactors by the self-assembly of amphiphilic bottlebrush copolymers has been demonstrated. First, a macromonomer having a norbornenyl polymerizable group was prepared by RAFT polymerization of hydrophobic and hydrophilic monomers. The macromonomer was further subjected to ring-opening metathesis polymerization to produce an amphiphilic bottlebrush copolymer. Further, TEMPO, as a catalyst, was introduced into the hydrophobic block through the activated ester strategy. Finally, TEMPO-functionalized polymeric nanoreactors were successfully obtained by self-assembly in water. The nanoreactors exhibited excellent catalytic activities in selective oxidation of alcohols in water. More importantly, the reaction kinetics showed that the turnover frequency is greatly increased compared to that of the similar nanoreactor prepared from liner copolymers under the same conditions. The outstanding catalytic activities of the nanoreactors from bottlebrush copolymers could be attributed to the more stable micellar structure using the substrate concentration effect. This work presents a new strategy to fabricate stable nanoreactors, paving the way for highly efficient organic reactions in aqueous solutions.

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