ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Figure 1Loading Img

Porous Semiconducting K–Sn–Mo–S Aerogel: Synthesis, Local Structure, and Ion-Exchange Properties

  • Alicia Blanton
    Alicia Blanton
    CSET/Environmental Science PhD Program, Jackson State University, Jackson, Mississippi 39217, United States
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
  • Taohedul Islam
    Taohedul Islam
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
  • Subrata Chandra Roy
    Subrata Chandra Roy
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
  • Ahmet Celik
    Ahmet Celik
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
    More by Ahmet Celik
  • Jing Nie
    Jing Nie
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
    More by Jing Nie
  • David R. Baker
    David R. Baker
    Army Research Directorate, U.S. Army Research Laboratory, Adelphi, Maryland 20783, United States
  • Dien Li
    Dien Li
    Savannah River National Laboratory, Aiken, South Carolina 29808, United States
    More by Dien Li
  • Kathryn Taylor-Pashow
    Kathryn Taylor-Pashow
    Savannah River National Laboratory, Aiken, South Carolina 29808, United States
  • Xianchun Zhu
    Xianchun Zhu
    Department of Civil Engineering, Jackson State University, Jackson, Mississippi 39217, United States
    More by Xianchun Zhu
  • Avijit Pramanik
    Avijit Pramanik
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
  • Ruhul Amin
    Ruhul Amin
    Electrification & Energy Infrastructure Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee TN-37830, United States
    More by Ruhul Amin
  • Renfei Feng
    Renfei Feng
    Canadian Light Source, Saskatoon, Saskatchewan S7N 2 V3, Canada
    More by Renfei Feng
  • Roman Chernikov
    Roman Chernikov
    Canadian Light Source, Saskatoon, Saskatchewan S7N 2 V3, Canada
  • , and 
  • Saiful M. Islam*
    Saiful M. Islam
    Department of Chemistry, Physics, and Atmospheric Sciences, Jackson State University, Jackson, Mississippi 39217, United States
    *Email: [email protected]
Cite this: Chem. Mater. 2023, 35, 24, 10446–10456
Publication Date (Web):November 28, 2023
https://doi.org/10.1021/acs.chemmater.3c01675
Copyright © 2023 American Chemical Society

    Article Views

    568

    Altmetric

    -

    Citations

    -
    LEARN ABOUT THESE METRICS
    Other access options
    Supporting Info (1)»

    Abstract

    Abstract Image

    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.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.chemmater.3c01675.

    • Experimental details; TEM, HAADF-STEM, EXAFS analysis; PXRD, and FT-IR analysis of postinteracted KTMS aerogel; time-dependent and concentration-dependent sorption analysis of UO22+, Sr2+, and Cs+ (PDF)

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    This article has not yet been cited by other publications.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    MENDELEY PAIRING EXPIRED
    Your Mendeley pairing has expired. Please reconnect