Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal-Organic Framework and Examination of Anion Binding Motifs

Riki J. Drout, Kenichi Otake, Ashlee J. Howarth, Timur Islamoglu, Lin Zhu, Chengliang Xiao, Shuao Wang, Omar k Farha

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO4 -) because of the ion's volatility, thereby requiring a different remediation method for this long-lived (t1/2 = 2.1 × 105 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr6-based metal-organic framework (MOF), NU-1000, to capture perrhenate (ReO4 -), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal X-ray diffraction indicates both chelating and nonchelating perrhenate binding motifs are present in both the small pore and the mesopore of NU-1000. Postadsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) further elucidates the uptake mechanism and powder X-ray diffraction (PXRD) and Brunauer-Emmett-Teller (BET) surface area analysis confirm the retention of crystallinity and porosity of NU-1000 throughout adsorption.

Original languageEnglish (US)
Pages (from-to)1277-1284
Number of pages8
JournalChemistry of Materials
Volume30
Issue number4
DOIs
StatePublished - Feb 27 2018

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Sodium Pertechnetate Tc 99m
Vitrification
Borosilicate glass
Chelation
Sorbents
Radioactive wastes
Remediation
X ray powder diffraction
Fourier transform infrared spectroscopy
Anions
Negative ions
Porosity
Metals
Single crystals
Adsorption
X ray diffraction
Kinetics
Ions
Experiments
Radioactive Waste

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Drout, Riki J. ; Otake, Kenichi ; Howarth, Ashlee J. ; Islamoglu, Timur ; Zhu, Lin ; Xiao, Chengliang ; Wang, Shuao ; Farha, Omar k. / Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal-Organic Framework and Examination of Anion Binding Motifs. In: Chemistry of Materials. 2018 ; Vol. 30, No. 4. pp. 1277-1284.
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Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal-Organic Framework and Examination of Anion Binding Motifs. / Drout, Riki J.; Otake, Kenichi; Howarth, Ashlee J.; Islamoglu, Timur; Zhu, Lin; Xiao, Chengliang; Wang, Shuao; Farha, Omar k.

In: Chemistry of Materials, Vol. 30, No. 4, 27.02.2018, p. 1277-1284.

Research output: Contribution to journalArticle

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AU - Drout, Riki J.

AU - Otake, Kenichi

AU - Howarth, Ashlee J.

AU - Islamoglu, Timur

AU - Zhu, Lin

AU - Xiao, Chengliang

AU - Wang, Shuao

AU - Farha, Omar k

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AB - At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO4 -) because of the ion's volatility, thereby requiring a different remediation method for this long-lived (t1/2 = 2.1 × 105 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr6-based metal-organic framework (MOF), NU-1000, to capture perrhenate (ReO4 -), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal X-ray diffraction indicates both chelating and nonchelating perrhenate binding motifs are present in both the small pore and the mesopore of NU-1000. Postadsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) further elucidates the uptake mechanism and powder X-ray diffraction (PXRD) and Brunauer-Emmett-Teller (BET) surface area analysis confirm the retention of crystallinity and porosity of NU-1000 throughout adsorption.

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