Multiscale structural control of thiostannate chalcogels with two-dimensional crystalline constituents

Thanh Duy Cam Ha; Heehyeon Lee; Yeo Kyung Kang; Kyunghan Ahn; Hyeong Min Jin; In Chung; Byungman Kang; Youngtak Oh; Myung-Gil Kim

doi:10.1038/s41467-022-35386-z

Multiscale structural control of thiostannate chalcogels with two-dimensional crystalline constituents

Nat Commun. 2022 Dec 23;13(1):7876. doi: 10.1038/s41467-022-35386-z.

Authors

Thanh Duy Cam Ha^#¹, Heehyeon Lee^#^{2

3}, Yeo Kyung Kang¹, Kyunghan Ahn¹, Hyeong Min Jin⁴, In Chung^{5

6}, Byungman Kang⁷, Youngtak Oh⁸, Myung-Gil Kim⁹

Affiliations

¹ School of Advanced Materials Science & Engineering, Sungkyunkwan University, Suwon, 16491, Republic of Korea.
² Department of Materials Science and Engineering, Korea University, Seoul, 02841, Republic of Korea.
³ Center for Sustainable Environment Research, Korea Institute of Science and Technology, Seoul, 02792, Republic of Korea.
⁴ Department of Organic Materials Engineering, Chungnam National University, Daejeon, 34134, Republic of Korea.
⁵ School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea.
⁶ Center for Correlated Electron Systems, Institute for Basic Science (IBS), Seoul, Republic of Korea.
⁷ Nuclear Chemistry Research Division, Korea Atomic Energy Research Institute, Daejeon, 34057, Republic of Korea.
⁸ Center for Sustainable Environment Research, Korea Institute of Science and Technology, Seoul, 02792, Republic of Korea. ytoh@kist.re.kr.
⁹ School of Advanced Materials Science & Engineering, Sungkyunkwan University, Suwon, 16491, Republic of Korea. myunggil@skku.edu.

^# Contributed equally.

Abstract

Chalcogenide aerogels (chalcogels) are amorphous structures widely known for their lack of localized structural control. This study, however, demonstrates a precise multiscale structural control through a thiostannate motif ([Sn₂S₆]^4-)-transformation-induced self-assembly, yielding Na-Mn-Sn-S, Na-Mg-Sn-S, and Na-Sn(II)-Sn(IV)-S aerogels. The aerogels exhibited [Sn₂S₆]^4-:Mn²⁺ stoichiometric-variation-induced-control of average specific surface areas (95-226 m² g^-1), thiostannate coordination networks (octahedral to tetrahedral), phase crystallinity (crystalline to amorphous), and hierarchical porous structures (micropore-intensive to mixed-pore state). In addition, these chalcogels successfully adopted the structural motifs and ion-exchange principles of two-dimensional layered metal sulfides (K_2xMn_xSn_3-xS₆, KMS-1), featuring a layer-by-layer stacking structure and effective radionuclide (Cs⁺, Sr²⁺)-control functionality. The thiostannate cluster-based gelation principle can be extended to afford Na-Mg-Sn-S and Na-Sn(II)-Sn(IV)-S chalcogels with the same structural features as the Na-Mn-Sn-S chalcogels (NMSCs). The study of NMSCs and their chalcogel family proves that the self-assembly principle of two-dimensional chalcogenide clusters can be used to design unique chalcogels with unprecedented structural hierarchy.

Abstract

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