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[Cs6Cl][Ga5GeQ12] (Q = S, Se): two novel porous layered chalcohalides exhibiting two-band emission and ion exchange properties

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Abstract

The salt-inclusion materials have drawn significant attention for their manifold structural chemistry and novel physical/chemical properties. Herein, two new salt-inclusion chalcohalides, [Cs6Cl][Ga5GeQ12] (Q = S, Se), have been discovered via high-temperature flux methods. The two isostructural compounds are constructed by porous [Ga5GeQ12]5− layers with [ClCs6]5+ octahedra filled in the holes. The [Ga5GeQ12]5− layer is composed of the honeycomb-like (Ga/Ge)18Q42 rings containing (Ga/Ge)3Q9 trimer as basic unit. The band gaps of the two compounds are 3.90 and 2.89 eV, respectively. [Cs6Cl][Ga5GeS12] exhibits interesting two-band emission properties which are related to the intermediate-band electronic structure revealed by density functional theory (DFT) calculations. Owing to the porous layered structure, [Cs6Cl][Ga5GeS12] exhibits topological ion exchange ability towards Cd2+ ions with the maximum sorption capacity of 250 mg/g and high distribution coefficient (Kd) near 106 mL/g. This work further enriches the structural diversity of salt-inclusion materials and extends their potential application range to ion exchange adsorption.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22005006, 21871008, 22001263) and the China Postdoctoral Science Foundation (2019M660298, 2020T130009).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing, 100871, China

    Ruiqi Wang & Fuqiang Huang

  2. Qian Xuesen Laboratory of Space Technology, China Academy of Space Technology, Beijing, 100094, China

    Xian Zhang

  3. State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 200050, China

    Fuqiang Huang

Authors
  1. Ruiqi Wang
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  2. Xian Zhang
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  3. Fuqiang Huang
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Correspondence to Xian Zhang or Fuqiang Huang.

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Supporting information The supporting information is available online at http://chem.scichina.com and http://link.springer.com/journal/11426. The supporting materials are published as submitted, without typesetting or editing. The responsibility for scientific accuracy and content remains entirely with the authors.

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Wang, R., Zhang, X. & Huang, F. [Cs6Cl][Ga5GeQ12] (Q = S, Se): two novel porous layered chalcohalides exhibiting two-band emission and ion exchange properties. Sci. China Chem. 65, 1903–1910 (2022). https://doi.org/10.1007/s11426-022-1277-x

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