Highly efficient and rapid Cs + uptake by the layered metal sulfide K 2xMn xSn 3-xS 6 (KMS-1)

Manolis J. Manos, Mercouri G Kanatzidis

Research output: Contribution to journalArticle

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Abstract

The details of the ion-exchange properties of the layered sulfide material K 2xMn xSn 3-xS 6 (x = 0.5-0.95) (KMS-1) with Cs + and Rb + cations are reported. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder and single-crystal diffraction studies revealed that the Cs + and Rb + ion exchange of KMS-1 is complete (quantitative replacement of K + ions) and topotactic. These data also revealed that the Cs + exchange is accompanied with a rare topotactic oxidation of Mn 2+ to Mn 3+ caused by atmospheric oxygen, while the Rb + ion exchange only slightly alters the oxidation state of the layer manganese atoms. The absorption of Cs + by KMS-1 follows the Langmuir model with a high exchange capacity of 226(4) mg/g (pH *ap; 7) and distribution coefficients as high as 2 × 10 4 mL/g. KMS-1 displays significant cesium uptake both under strongly acidic (pH 0.7-2.6) or basic conditions (pH 10-12). The kinetics of Cs+ capture by KMS-1 is fast (>90% removal of ̃1 ppm of Cs + within only 5 min). KMS-1 was also found capable to efficiently absorb Cs + from complex solutions containing various competitive cations in large excess. KMS-1 (containing Mn 3+ ions) can be regenerated and reused for Cs + exchange with an exchange capacity very similar to that of the pristine KMS-1. The results indicate that layered metal sulfides with ion-exchange properties may be considered as highly selective and cost-effective sorbents for remediation of water contaminated with the radioactive 137Cs isotope. The selectivity over other alkali ions for Cs originates not from a size effect but from the more favorable Cs⋯S soft Lewis acid/Lewis base interactions.

Original languageEnglish
Pages (from-to)6599-6607
Number of pages9
JournalJournal of the American Chemical Society
Volume131
Issue number18
DOIs
Publication statusPublished - May 13 2009

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Ion Exchange
Sulfides
Ion exchange
Metals
Ions
Cations
Lewis Bases
Photoelectron Spectroscopy
Lewis Acids
Cesium
Positive ions
Alkalies
Manganese
Oxidation
Radioisotopes
Powders
Sorbents
Remediation
Oxygen
Costs and Cost Analysis

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Highly efficient and rapid Cs + uptake by the layered metal sulfide K 2xMn xSn 3-xS 6 (KMS-1). / Manos, Manolis J.; Kanatzidis, Mercouri G.

In: Journal of the American Chemical Society, Vol. 131, No. 18, 13.05.2009, p. 6599-6607.

Research output: Contribution to journalArticle

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abstract = "The details of the ion-exchange properties of the layered sulfide material K 2xMn xSn 3-xS 6 (x = 0.5-0.95) (KMS-1) with Cs + and Rb + cations are reported. X-ray photoelectron spectroscopy (XPS), elemental analyses, and powder and single-crystal diffraction studies revealed that the Cs + and Rb + ion exchange of KMS-1 is complete (quantitative replacement of K + ions) and topotactic. These data also revealed that the Cs + exchange is accompanied with a rare topotactic oxidation of Mn 2+ to Mn 3+ caused by atmospheric oxygen, while the Rb + ion exchange only slightly alters the oxidation state of the layer manganese atoms. The absorption of Cs + by KMS-1 follows the Langmuir model with a high exchange capacity of 226(4) mg/g (pH *ap; 7) and distribution coefficients as high as 2 × 10 4 mL/g. KMS-1 displays significant cesium uptake both under strongly acidic (pH 0.7-2.6) or basic conditions (pH 10-12). The kinetics of Cs+ capture by KMS-1 is fast (>90{\%} removal of ̃1 ppm of Cs + within only 5 min). KMS-1 was also found capable to efficiently absorb Cs + from complex solutions containing various competitive cations in large excess. KMS-1 (containing Mn 3+ ions) can be regenerated and reused for Cs + exchange with an exchange capacity very similar to that of the pristine KMS-1. The results indicate that layered metal sulfides with ion-exchange properties may be considered as highly selective and cost-effective sorbents for remediation of water contaminated with the radioactive 137Cs isotope. The selectivity over other alkali ions for Cs originates not from a size effect but from the more favorable Cs⋯S soft Lewis acid/Lewis base interactions.",
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