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Discrete Supertetrahedral T5 Selenide Clusters and Their Se/S Solid Solutions: Ionic-Liquid-Assisted Precursor Route Syntheses and Photocatalytic Properties
Although supertetrahedral Tn sulfide clusters (n=2?6) have been extensively explored, the synthesis of Tn selenide clusters with n>4 has not been achieved thus far. Reported here are ionic-liquid (IL)-assisted precursor route syntheses, characterizations, and the photocatalytic properties of six new M-In-Q (M=Cu or Cd; Q=Se or Se/S) chalcogenide compounds, namely [Bmmim]12Cu5In30Q52Cl3(Im) (Q=Se (T5-1), Se48.5S3.5 (T5-2); Bmmim=1-butyl-2,3-dimethylimidazolium, Im=imidazole), [Bmmim]11Cd6In28Q52Cl3(MIm) (Q=Se (T5-3), Se28.5S23.5 (T5-4), Se16S36 (T5-5); MIm=1-methylimidazole), and [Bmmim]9Cd6In28Se8S44Cl(MIm)3 (T5-6). The cluster compounds T5-1 and T5-3 represent the largest molecular supertetrahedral Tn selenide clusters to date. Under visible-light illumination, the Cu-In-Q compounds showed photocatalytic activity towards the decomposition of crystal violet, whereas the Cd-In-Q compounds exhibited good photocatalytic H2 evolution activity. Interestingly, the experimental results show that the photocatalytic performances of the selenide/sulfide solid solutions were significantly better than those of their selenide analogues, for example, the degradation time of the organic dye with T5-2 was much shorter than that with T5-1, whereas the photocatalytic H2 evolution efficiencies with T5-3?T5-6 improved significantly with increasing sulfur content. This work highlights the significance of IL-assisted precursor route synthesis and the tuning of photocatalytic properties through the formation of solid solutions.
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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”