Thiostannate coordination transformation-induced self-crosslinking chalcogenide aerogel with local coordination control and effective Cs+ remediation functionality. Issue 6 (29th January 2020)

• Record Type: Journal Article
• Authors: Kang, Yeo Kyung; Lee, Heehyeon; Ha, Thanh Duy Cam; Won, Jong Kook; Jo, Hongil; Ok, Kang Min; Ahn, Sangdoo; Kang, Byungman; Ahn, Kyunghan; Oh, Youngtak; Kim, Myung-Gil
• Is Part Of: Journal of materials chemistry. Volume 8:Issue 6(2020)
• Page Start: 3468
• Page End: 3480
• Publication Date: 2020-01-29
• Subjects: Materials -- Research -- Periodicals; Chemistry, Analytic -- Periodicals; Environmental sciences -- Research -- Periodicals; 543.0284
• DOI: 10.1039/c9ta11282k
• Languages: English
• ISSNs: 2050-7488

Abstract

Abstract : Self-crosslinking polymerization between Sn2 S6 4− clusters resulted transition metal free chalcogel with local coordination control and effective Cs + remediation functionality. Abstract : Thiostannate ammonium chalcogenide aerogel (TAC) is synthesized through a unique self-crosslinking polymerization reaction between tetrahedral thiostannate dimer clusters ([Sn2 S6 ] 4− ) and various ammonium ligands (NR4 + ). TAC is a unique and rare chalcogenide aerogel (so called "chalcogel") stabilized without using a cationic transition metal center. In-depth and synergistic structural analyses reveal that after the self-condensation reaction, the thiostannate clusters are stabilized into a three-dimensional solid network with the support of an ammonium spacer. Consequently, thiostannate coordination is successfully transformed from tetrahedral to a distorted trigonal bipyramidal geometry, yielding a [Sn3 S7 ] 2− cluster-based porous chalcogenide network. This organic/inorganic heterostructure has a large specific surface area (158–363 m 2 g −1 ), macroscopically random orientation of pores, soft basicity, controllable hosting ammonium ligand, and rapid mass transport through multiscale channels. These characteristics enable remarkable radionuclide control functionality such as large Cs + adsorption capacity (141–220 mg g −1 ), high selectivity towards cations with intermediate chemical hardness ( e.g., Cs + ), structural integrity over a wide pH range (2–8), and rapid ion uptake (50% in 30 min and complete equilibrium within 3 h). This study demonstrates that the self-crosslinking mechanism of chalcometallate clusters can be utilized as a diverse platform to synthesize a broad range of chalcogenide heterostructures with desirable functionalities.