Discrete Supertetrahedral T5 Selenide Clusters and Their Se/S Solid Solutions: Ionic‐Liquid‐Assisted Precursor Route Syntheses and Photocatalytic Properties
Yanqi Wang, Zhipeng Zhu, Zhaofeng Sun, Qianqian Hu, Jian‐Rong Li, Jiang Jiang, Xiao‐Ying Huang
Abstract
Abstract Although supertetrahedral T n sulfide clusters ( n= 2–6) have been extensively explored, the synthesis of T n 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] 12 Cu 5 In 30 Q 52 Cl 3 (Im) (Q=Se ( T5‐1 ), Se 48.5 S 3.5 ( T5‐2 ); Bmmim=1‐butyl‐2,3‐dimethylimidazolium, Im=imidazole), [Bmmim] 11 Cd 6 In 28 Q 52 Cl 3 (MIm) (Q=Se ( T5‐3 ), Se 28.5 S 23.5 ( T5‐4 ), Se 16 S 36 ( T5‐5 ); MIm=1‐methylimidazole), and [Bmmim] 9 Cd 6 In 28 Se 8 S 44 Cl(MIm) 3 ( T5‐6 ). The cluster compounds T5‐1 and T5‐3 represent the largest molecular supertetrahedral T n 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 H 2 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 H 2 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.