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

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.

Authors:
 [1];  [1];  [1];  [1];  [2];  [2];  [2];  [3]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  2. Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences (RAD-X); Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions, Suzhou (China)
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States). Actinide Center of Excellence
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1420780
Grant/Contract Number:  
NA0003763
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 4; Related Information: The Supporting Information is available on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b04619.Adsorption capacity data, PXRD patterns, nitrogen adsorption isotherms, and DRIFTS spectra (PDF)Crystallographic data (TXT); Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; 38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; metal-organic framework; capture; perrhenate; pertechnetate

Citation Formats

Drout, Riki J., Otake, Kenichi, Howarth, Ashlee J., Islamoglu, Timur, Zhu, Lin, Xiao, Chengliang, Wang, Shuao, and Farha, Omar K. Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b04619.
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. United States. doi:10.1021/acs.chemmater.7b04619.
Drout, Riki J., Otake, Kenichi, Howarth, Ashlee J., Islamoglu, Timur, Zhu, Lin, Xiao, Chengliang, Wang, Shuao, and Farha, Omar K. Wed . "Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs". United States. doi:10.1021/acs.chemmater.7b04619. https://www.osti.gov/servlets/purl/1420780.
@article{osti_1420780,
title = {Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs},
author = {Drout, Riki J. and Otake, Kenichi and Howarth, Ashlee J. and Islamoglu, Timur and Zhu, Lin and Xiao, Chengliang and Wang, Shuao and Farha, Omar K.},
abstractNote = {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.},
doi = {10.1021/acs.chemmater.7b04619},
journal = {Chemistry of Materials},
number = 4,
volume = 30,
place = {United States},
year = {2018},
month = {1}
}

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Works referencing / citing this record:

Successful Decontamination of 99 TcO 4 in Groundwater at Legacy Nuclear Sites by a Cationic Metal-Organic Framework with Hydrophobic Pockets
journal, March 2019

  • Sheng, Daopeng; Zhu, Lin; Dai, Xing
  • Angewandte Chemie International Edition, Vol. 58, Issue 15
  • DOI: 10.1002/anie.201814640

High Uptake of ReO 4 and CO 2 Conversion by a Radiation-Resistant Thorium-Nickle [Th 48 Ni 6 ] Nanocage-Based Metal-Organic Framework
journal, March 2019

  • Xu, Hang; Cao, Chun-Shuai; Hu, Han-Shi
  • Angewandte Chemie International Edition, Vol. 58, Issue 18
  • DOI: 10.1002/anie.201901786

Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework
journal, January 2018

  • Islamoglu, Timur; Otake, Ken-ichi; Li, Peng
  • CrystEngComm, Vol. 20, Issue 39
  • DOI: 10.1039/c8ce00455b

Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs
journal, January 2018

  • Drout, Riki J.; Howarth, Ashlee J.; Otake, Ken-ichi
  • CrystEngComm, Vol. 20, Issue 40
  • DOI: 10.1039/c8ce00992a

A Ca 2+ MOF combining highly efficient sorption and capability for voltammetric determination of heavy metal ions in aqueous media
journal, January 2019

  • Pournara, Anastasia D.; Margariti, Antigoni; Tarlas, Georgios D.
  • Journal of Materials Chemistry A, Vol. 7, Issue 25
  • DOI: 10.1039/c9ta03337h

Successful Decontamination of 99 TcO 4 in Groundwater at Legacy Nuclear Sites by a Cationic Metal-Organic Framework with Hydrophobic Pockets
journal, March 2019

  • Sheng, Daopeng; Zhu, Lin; Dai, Xing
  • Angewandte Chemie International Edition, Vol. 58, Issue 15
  • DOI: 10.1002/anie.201814640

High Uptake of ReO 4 and CO 2 Conversion by a Radiation-Resistant Thorium-Nickle [Th 48 Ni 6 ] Nanocage-Based Metal-Organic Framework
journal, March 2019

  • Xu, Hang; Cao, Chun-Shuai; Hu, Han-Shi
  • Angewandte Chemie International Edition, Vol. 58, Issue 18
  • DOI: 10.1002/anie.201901786

Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework
journal, January 2018

  • Islamoglu, Timur; Otake, Ken-ichi; Li, Peng
  • CrystEngComm, Vol. 20, Issue 39
  • DOI: 10.1039/c8ce00455b

Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs
journal, January 2018

  • Drout, Riki J.; Howarth, Ashlee J.; Otake, Ken-ichi
  • CrystEngComm, Vol. 20, Issue 40
  • DOI: 10.1039/c8ce00992a

A Ca 2+ MOF combining highly efficient sorption and capability for voltammetric determination of heavy metal ions in aqueous media
journal, January 2019

  • Pournara, Anastasia D.; Margariti, Antigoni; Tarlas, Georgios D.
  • Journal of Materials Chemistry A, Vol. 7, Issue 25
  • DOI: 10.1039/c9ta03337h