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Amorphous K–Co–Mo–Sx Chalcogel: A Synergy of Surface Sorption and Ion-Exchange

Journal Article · · Small
 [1];  [1];  [1];  [2];  [3];  [2];  [1];  [4];  [4];  [1];  [1];  [5];  [1]
  1. Jackson State University, Jackson, MS (United States)
  2. Savannah River National Laboratory (SRNL), Aiken, SC (United States)
  3. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Electrification & Energy Infrastructure Division
  4. University of Saskatchewan, Saskatoon, SK (Canada). Canadian Light Source, Inc.
  5. University of North Carolina, Chapel Hill, NC (United States)
+ Show Author Affiliations

Chalcogel represents a unique class of meso- to macroporous nanomaterials that offer applications in energy and environmental pursuits. We report the synthesis of an ion-exchangeable amorphous chalcogel using a nominal composition of K2CoMo2S10 (KCMS) at room temperature is reported. Synchrotron X-ray pair distribution function (PDF), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) reveal a plausible local structure of KCMS gel consisting of Mo5+2 and Mo4+3 clusters in the vicinity of di/polysulfides which are covalently linked by Co2+ ions. The ionically bound K+ ions remain in the percolating pores of the Co–Mo–S covalent network. XANES of Co K-edge shows multiple electronic transitions, including quadrupole (1s→3d), shakedown (1s→4p + MLCT), and dipole allowed 1s→4p transitions. Remarkably, despite a lack of regular channels as in some crystalline solids, the amorphous KCMS gel shows ion-exchange properties with UO22+ ions. Additionally, it also presents surface sorption via [S∙∙∙∙UO22+] covalent interactions. Overall, this study underscores the synthesis of quaternary chalcogels incorporating alkali metals and their potential to advance separation science for cations and oxo-cationic species by integrating a synergy of surface sorption and ion-exchange.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
2333763
Alternate ID(s):
OSTI ID: 2324703
Journal Information:
Small, Journal Name: Small Journal Issue: 400 Vol. 6; ISSN 1613-6810
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
UO22+ separation
aerogel
chalcogels
ion-exchange
quadrupole and shakedown transitions