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

Journal Article · · Chemistry of Materials
 [1];  [2];  [2];  [2];  [3];  [3];  [3];  [4]
  1. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Northwestern University
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  3. 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)
  4. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry

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.

Research Organization:
Northwestern Univ., Evanston, IL (United States). Actinide Center of Excellence
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); National Natural Science Foundation of China (NNSFC)
Grant/Contract Number:
NA0003763
OSTI ID:
1420780
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 30; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Successful Decontamination of 99 TcO 4 in Groundwater at Legacy Nuclear Sites by a Cationic Metal‐Organic Framework with Hydrophobic Pockets journal March 2019
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Successful Decontamination of 99 TcO 4 in Groundwater at Legacy Nuclear Sites by a Cationic Metal-Organic Framework with Hydrophobic Pockets journal March 2019
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
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Optimizing radionuclide sequestration in anion nanotraps with record pertechnetate sorption journal April 2019
Finding a receptor design for selective recognition of perrhenate and pertechnetate: hydrogen vs. halogen bonding journal January 2018
Revisiting the structural homogeneity of NU-1000, a Zr-based metal–organic framework journal January 2018
Efficient extraction of inorganic selenium from water by a Zr metal–organic framework: investigation of volumetric uptake capacity and binding motifs journal January 2018
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Exceptional TcO 4 sorption capacity and highly efficient ReO 4 luminescence sensing by Zr 4+ MOFs journal January 2018
Single crystal structure and photocatalytic behavior of grafted uranyl on the Zr-node of a pyrene-based metal–organic framework journal January 2020
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A Ca 2+ MOF combining highly efficient sorption and capability for voltammetric determination of heavy metal ions in aqueous media journal January 2019
Selective and efficient removal of perrhenate by an imidazolium based hexapodal receptor in water medium journal January 2020