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Title: Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3)

Abstract

Heavy metal ions (Cd 2+, Hg 2+, As 3+ and Pb 2+) are an important contributor to the contamination of groundwater and other water bodies in and around industrial areas. Herein, we demonstrate the rapid and efficient capacity of a layered metal sulfide material, K2xSn4-xS8-x (x = 0.65-1, KTS-3) for heavy metal ion removal from water. The effect of concentration, pH, kinetics, and competitive ions such as Na +/Ca 2+ on the heavy metal ion removal capacity of KTS-3 was systematically investigated. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder X-ray diffraction studies revealed that the heavy metal ion-exchange of KTS-3 is complete (quantitative replacement of all potassium ions) and topotactic. The heavy metal ion-exchange by using KTS-3 follows the Langmuir-Freundlich model with high exchange capacities, q(m) 205(17) mg g -1 for Cd 2+, 372(21) mg g -1 for Hg 2+ and 391(89) mg g -1 for Pb 2+. KTS-3 retains excellent heavy metal ion-exchange capacity even in very high concentration (1 M) of competing ions (Na +/Ca 2+) and also over a broad pH range (2-12). KTS-3 also exhibits very good ion-exchange capacity for precious Ag + and toxic As 3+ ions. The kinetics of heavy metal ion adsorptionmore » by KTS-3 are rapid (absorbs all ions within a few minutes). These properties and the environmentally friendly character of KTS-3 make it a promising candidate for sequestration of heavy metal ions from water.« less

Authors:
; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); University of Chicago; W.M. Keck Foundation
OSTI Identifier:
1334763
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Materials Chemistry. A; Journal Volume: 4; Journal Issue: 42
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Sarma, Debajit, Islam, Saiful M., Subrahmanyam, K. S., and Kanatzidis, Mercouri G. Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3). United States: N. p., 2016. Web. doi:10.1039/c6ta06404c.
Sarma, Debajit, Islam, Saiful M., Subrahmanyam, K. S., & Kanatzidis, Mercouri G. Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3). United States. doi:10.1039/c6ta06404c.
Sarma, Debajit, Islam, Saiful M., Subrahmanyam, K. S., and Kanatzidis, Mercouri G. 2016. "Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3)". United States. doi:10.1039/c6ta06404c.
@article{osti_1334763,
title = {Efficient and selective heavy metal sequestration from water by using layered sulfide K 2x Sn 4-x S 8-x (x = 0.65–1; KTS-3)},
author = {Sarma, Debajit and Islam, Saiful M. and Subrahmanyam, K. S. and Kanatzidis, Mercouri G.},
abstractNote = {Heavy metal ions (Cd2+, Hg2+, As3+ and Pb2+) are an important contributor to the contamination of groundwater and other water bodies in and around industrial areas. Herein, we demonstrate the rapid and efficient capacity of a layered metal sulfide material, K2xSn4-xS8-x (x = 0.65-1, KTS-3) for heavy metal ion removal from water. The effect of concentration, pH, kinetics, and competitive ions such as Na+/Ca2+ on the heavy metal ion removal capacity of KTS-3 was systematically investigated. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder X-ray diffraction studies revealed that the heavy metal ion-exchange of KTS-3 is complete (quantitative replacement of all potassium ions) and topotactic. The heavy metal ion-exchange by using KTS-3 follows the Langmuir-Freundlich model with high exchange capacities, q(m) 205(17) mg g-1 for Cd2+, 372(21) mg g-1 for Hg2+ and 391(89) mg g-1 for Pb2+. KTS-3 retains excellent heavy metal ion-exchange capacity even in very high concentration (1 M) of competing ions (Na+/Ca2+) and also over a broad pH range (2-12). KTS-3 also exhibits very good ion-exchange capacity for precious Ag+ and toxic As3+ ions. The kinetics of heavy metal ion adsorption by KTS-3 are rapid (absorbs all ions within a few minutes). These properties and the environmentally friendly character of KTS-3 make it a promising candidate for sequestration of heavy metal ions from water.},
doi = {10.1039/c6ta06404c},
journal = {Journal of Materials Chemistry. A},
number = 42,
volume = 4,
place = {United States},
year = 2016,
month = 9
}
  • The fission of uranium produces radionuclides, 137Cs and 90Sr, which are major constituents of spent nuclear fuel. The half-life of 137Cs and 90Sr is nearly 30 years and thus that makes them harmful to human life and the environment. The selective removal of these radionuclides in the presence of high salt concentrations from industrial nuclear waste is necessary for safe storage. We report the synthesis and crystal structure of K 2xSn 4-xS 8-x (x = 0.65–1, KTS-3) a material which exhibits excellent Cs +, Sr 2+ and UO 2 2+ ion exchange properties in varying conditions. Furthermore, the compound adoptsmore » a layered structure which consists of exchangeable potassium ions sandwiched between infinite layers of octahedral and tetrahedral tin centers. K 2xSn 4-xS 8-x (x = 0.65–1, KTS-3) crystallizes in the monoclinic space group P2 1/c with cell parameters a = 13.092(3) Å, b = 16.882(2) Å, c = 7.375(1) Å and β = 98.10(1)°. Refinement of the single crystal diffraction data revealed the presence of Sn vacancies in the tetrahedra that are long range ordered. The interlayer potassium ions of KTS-3 can be exchanged for Cs +, Sr 2+ and UO 2 2+. KTS-3 exhibits rapid and efficient ion exchange behavior in a broad pH range. The distribution coefficients (K d) for KTS-3 are high for Cs + (5.5 × 10 4), Sr 2+ (3.9 × 10 5) and UO 2 2+ (2.7 × 10 4) at neutral pH (7.4, 6.9, 5.7 ppm Cs +, Sr 2+ and UO 2 2+, respectively; V/m ~ 1000 mL g -1). KTS-3 exhibits impressive Cs +, Sr 2+ and UO 2 2+ ion exchange properties in high salt concentration and over a broad pH range, which coupled with the low cost, environmentally friendly nature and facile synthesis underscores its potential in treating nuclear waste.« less
  • A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less
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  • The maximum Cu(II), Ni(II), and Co(II) ion capacities of a silica-poly(ethyleneimine) composite (WP-1) are compared with those of the commercially available iminodiacetic acid chelator resin Amberlite IRC-718. Under batch (static) conditions, IRC-718 exhibits better capacities for these metals than WP-1. Dynamic studies, however, revealed that WP-1 possessed a much higher capacity for all three divalent metals than IRC-718, with relative metal capacities in the order CU(II) {gt} CO(II) {approximately} Ni(II). In the presence of the competing chelator ethylenediaminetetraacetic acid, the Cu(II) capacities of WP-1 and IRC-718 lost 48% and 45%, respectively, of their original adsorption values. Even with this decrease,more » however, WP-1 maintained a higher CU(II) capacity than IRC-718. Repeated cycle testing, using CU(II) solutions at both room temperature and 97 C, was conducted to compare the long-term stability of each material. WP-1 maintained 94% of its original Cu(II) capacity and maintained structural integrity after 3,000 cycles using room temperature copper solutions, while IRC-718 compressed and dropped to 64% of its original capacity. When boiling copper solutions were used, the capacity of WP-1 increased slightly over 1500 cycles, while IRC-718 lost 13% of its original copper capacity and again became compressed, indicating degradation of the polystyrene beads.« less