K–Co–Mo–Sx chalcogel: high-capacity removal of Pb2+ and Ag+ and the underlying mechanisms

Nie, Jing; Chandra Roy, Subrata; Dhami, Sital; Islam, Taohedul; Amin, Ruhul; Zhu, Xianchun; Taylor-Pashow, Kathryn; Han, Fengxiang X.; Islam, Saiful M.

doi:10.1039/d4ta05158k

K–Co–Mo–S_x chalcogel: high-capacity removal of Pb²⁺ and Ag⁺ and the underlying mechanisms

Journal Article · Tue Oct 08 00:00:00 EDT 2024 · Journal of Materials Chemistry. A

DOI:https://doi.org/10.1039/d4ta05158k· OSTI ID:2474723

Nie, Jing ^[1]; Chandra Roy, Subrata ^[1]; Dhami, Sital ^[1]; ^[1]; ^[2]; Zhu, Xianchun ^[1]; ^[3]; Han, Fengxiang X. ^[1]; ^[1]

Jackson State University, Jackson, MS (United States)
Oak Ridge National Laboratory, Knoxville, TN (United States)
Savannah River National Laboratory (SRNL), Aiken, SC (United States)

Chalcogenide-based aerogels, known as chalcogels, represent a novel class of nanoparticle-based porous amorphous materials characterized by high surface polarizability and Lewis base properties, exhibiting promising applications in clean energy and separation science. This work presents a K–Co–Mo–S_x (KCMS) chalcogel as a highly efficient sorbent for heavy metal ions and details its sorption mechanisms. Its incoherent structure comprises Mo₂^V(S₂)₆ and Mo₃^IVS(S₆)₂ anion-like clusters with four- and six-coordinated Co–S polyhedra, forming a Co–Mo–S covalent network that hosts K⁺ ions through electrostatic attraction. The interactions of KCMS with heavy metal ions, particularly Pb²⁺ and Ag⁺, reveal that KCMS is exceptionally effective in removing these ions from ppm concentrations down to trace levels (≤5 ppb). KCMS rapidly removes Ag⁺ (≈81.7%) and Pb²⁺ (≈99.5%) within five minutes, achieving >99.9% removal within an hour, with a distribution constant K_d ≥10⁸ mL g^-1. KCMS exhibits an impressive removal capacity of 1378 mg g^-1 for Ag⁺ and 1146 mg g^-1 for Pb²⁺, establishing it as one of the most effective materials known to date for heavy metal removal. This material is also effective for the removal of Ag⁺ and Pb²⁺ along with Hg²⁺, Ni²⁺, Cu²⁺, and Cd²⁺ from various water sources even in the presence of highly concentrated and chemically diverse cations, anions, and organic species. Analysis of the post-interacted KCMS by synchrotron X-ray pair distribution function (PDF), X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDS) revealed that the sorption of Pb²⁺, Ag⁺, and Hg²⁺ mainly occurs by the exchange of K⁺ and Co²⁺. Despite being amorphous, this material exhibits unprecedented ion-exchange mechanisms both for the ionically and covalently bound K⁺ and Co²⁺, respectively. In conclusion, this discovery advances our knowledge of amorphous gels and guides material synthesis principles for the highly selective and efficient removal of heavy metal ions from water.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Jackson State University, MS (United States); Savannah River National Laboratory (SRNL), Aiken, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Minority Serving Institution Partnership Program (MSIPP); NSF Division of Chemistry; USDOE Building EPSCoR-State/National Laboratory Partnerships

Grant/Contract Number:: SC0023485; AC02-06CH11357; AC05-00OR22725

OSTI ID:: 2474723

Alternate ID(s):: OSTI ID: 2472648
OSTI ID: 2574582

Journal Information:: Journal of Materials Chemistry. A, Journal Name: Journal of Materials Chemistry. A Journal Issue: 43 Vol. 12; ISSN 2050-7488

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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chalcogels
heavy metal remediation
ion-exchange
wastewater

K–Co–Mo–Sx chalcogel: high-capacity removal of Pb2+ and Ag+ and the underlying mechanisms

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K–Co–Mo–S_x chalcogel: high-capacity removal of Pb²⁺ and Ag⁺ and the underlying mechanisms