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Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties
Abstract
Chalcogenide-based aerogels are emerging porous semiconducting nanomaterials that appeal to applications in clean energy and the environment. Here, we report a novel gel, potassium–tin–molybdenum–sulfides (KTMS), that integrates the electrostatically bound K+ ions in the covalent network of Sn–Mo–S. Its gelation requires a concurrent reduction of Mo6+ → Mo4+/5+ and the oxidation of S2– → Sn– (n ≈ 1) and Sn2+ → Sn4+. KTMS is an amorphous semiconductor showing quantum confinement effects on band gap energies, 2.1 → 1.4 → 0.9 eV for its wet- → aero- → xerogels. Synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS) revealed a complex local structure of KTMS consisting of molecular Mo2(S2)6 and Mo3S(S2)6 clusters. In addition, the Sn–S coordination is related to crystalline Na4Sn3S8 and SnS2. KTMS also demonstrated the removal of the radionuclides of Cs+, Sr2+, and UO22+ from ppm to ppb levels with distribution constants (Kd) up to ≥104 mL/g. Notably, despite the lack of atomic periodicity in the amorphous KTMS, the K+ ion is ion-exchangeable with chemically diverse Sr2+, Cs+, and UO22+ in aqueous solutions; especially the ion-exchange properties of Sr2+ and UO22+≡(O=U=O)2+ is not known to any chalcogels known to date. The sequestration of Cs+more »
- Authors:
-
[2];
[3];
[1];
[4];
[5];
[1]
- Jackson State Univ., Jackson, MS (United States)
- Army Research Lab., Adelphi, MD (United States)
- Savannah River National Laboratory (SRNL), Aiken, SC (United States)
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Canadian Light Source, Saskatoon, SK (Canada)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF); National Institutes of Health (NIH)
- OSTI Identifier:
- 2305794
- Grant/Contract Number:
- AC05-00OR22725; NSF-2100797; 1U54MD015929; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 35; Journal Issue: 24; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; aerogels; extended x-ray absorption fine structure; ions; nanoparticles; sorption
Citation Formats
Blanton, Alicia, Islam, Taohedul, Roy, Subrata Chandra, Celik, Ahmet, Nie, Jing, Baker, David R., Li, Dien, Taylor-Pashow, Kathryn, Zhu, Xianchun, Pramanik, Avijit, Amin, Ruhul, Feng, Renfei, Chernikov, Roman, and Islam, Saiful M. Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties. United States: N. p., 2023.
Web. doi:10.1021/acs.chemmater.3c01675.
Blanton, Alicia, Islam, Taohedul, Roy, Subrata Chandra, Celik, Ahmet, Nie, Jing, Baker, David R., Li, Dien, Taylor-Pashow, Kathryn, Zhu, Xianchun, Pramanik, Avijit, Amin, Ruhul, Feng, Renfei, Chernikov, Roman, & Islam, Saiful M. Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties. United States. https://doi.org/10.1021/acs.chemmater.3c01675
Blanton, Alicia, Islam, Taohedul, Roy, Subrata Chandra, Celik, Ahmet, Nie, Jing, Baker, David R., Li, Dien, Taylor-Pashow, Kathryn, Zhu, Xianchun, Pramanik, Avijit, Amin, Ruhul, Feng, Renfei, Chernikov, Roman, and Islam, Saiful M. Tue .
"Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties". United States. https://doi.org/10.1021/acs.chemmater.3c01675.
@article{osti_2305794,
title = {Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties},
author = {Blanton, Alicia and Islam, Taohedul and Roy, Subrata Chandra and Celik, Ahmet and Nie, Jing and Baker, David R. and Li, Dien and Taylor-Pashow, Kathryn and Zhu, Xianchun and Pramanik, Avijit and Amin, Ruhul and Feng, Renfei and Chernikov, Roman and Islam, Saiful M.},
abstractNote = {Chalcogenide-based aerogels are emerging porous semiconducting nanomaterials that appeal to applications in clean energy and the environment. Here, we report a novel gel, potassium–tin–molybdenum–sulfides (KTMS), that integrates the electrostatically bound K+ ions in the covalent network of Sn–Mo–S. Its gelation requires a concurrent reduction of Mo6+ → Mo4+/5+ and the oxidation of S2– → Sn– (n ≈ 1) and Sn2+ → Sn4+. KTMS is an amorphous semiconductor showing quantum confinement effects on band gap energies, 2.1 → 1.4 → 0.9 eV for its wet- → aero- → xerogels. Synchrotron X-ray pair distribution function (PDF) and extended X-ray absorption fine structure (EXAFS) revealed a complex local structure of KTMS consisting of molecular Mo2(S2)6 and Mo3S(S2)6 clusters. In addition, the Sn–S coordination is related to crystalline Na4Sn3S8 and SnS2. KTMS also demonstrated the removal of the radionuclides of Cs+, Sr2+, and UO22+ from ppm to ppb levels with distribution constants (Kd) up to ≥104 mL/g. Notably, despite the lack of atomic periodicity in the amorphous KTMS, the K+ ion is ion-exchangeable with chemically diverse Sr2+, Cs+, and UO22+ in aqueous solutions; especially the ion-exchange properties of Sr2+ and UO22+≡(O=U=O)2+ is not known to any chalcogels known to date. The sequestration of Cs+ and Sr2+ was achieved by the exchange of K+ in the amorphous KTMS, and the removal of [O=U6+=O]2+ synergistically involves surface sorption via -S····U6+=O22+ covalent interactions and ion-exchange via the hard–soft Lewis acid–base paradigm. Overall, cooperative roles played by the diverse bonding motifs, surface-exposed Lewis basic frameworks, and polarizability of the (poly)sulfides make it an exceptional adsorbent for chemically diverse radioactive species. This finding will guide the design of superior sorbents for chemically distinct metal ion separation.},
doi = {10.1021/acs.chemmater.3c01675},
journal = {Chemistry of Materials},
number = 24,
volume = 35,
place = {United States},
year = {Tue Nov 28 00:00:00 EST 2023},
month = {Tue Nov 28 00:00:00 EST 2023}
}
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