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Title: NDTB-1: A Supertetrahedral Cationic Framework That Removes TcO4- from Solution

Abstract

A cubic thorium borate possesses a porous supertetrahedral cationic framework with extraframework borate anions. These anions are readily exchanged with a variety of environmental contaminants, especially those from the nuclear industry, including chromate and pertechnetate.

Authors:
; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Materials Science of Actinides (MSA)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1064654
DOE Contract Number:
SC0001089
Resource Type:
Journal Article
Resource Relation:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 49; Journal Issue: 1; Related Information: MSA partners with University of Notre Dame (lead); University of California, Davis; Florida State University; George Washington University; University of Michigan; University of Minnesota; Oak Ridge National Laboratory; Oregon state University; Rensselaer Polytechnic Institute; Savannah River National Laboratory
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; 12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; nuclear (including radiation effects), materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Wang, Shuao, Alekseev, Evgeny V., Casey, William H., Phillips, Brian L., Depmeier, Wulf, and Albrecht-Schmitt, Thomas E. NDTB-1: A Supertetrahedral Cationic Framework That Removes TcO4- from Solution. United States: N. p., 2010. Web. doi:10.1002/anie.200906397.
Wang, Shuao, Alekseev, Evgeny V., Casey, William H., Phillips, Brian L., Depmeier, Wulf, & Albrecht-Schmitt, Thomas E. NDTB-1: A Supertetrahedral Cationic Framework That Removes TcO4- from Solution. United States. doi:10.1002/anie.200906397.
Wang, Shuao, Alekseev, Evgeny V., Casey, William H., Phillips, Brian L., Depmeier, Wulf, and Albrecht-Schmitt, Thomas E. Mon . "NDTB-1: A Supertetrahedral Cationic Framework That Removes TcO4- from Solution". United States. doi:10.1002/anie.200906397.
@article{osti_1064654,
title = {NDTB-1: A Supertetrahedral Cationic Framework That Removes TcO4- from Solution},
author = {Wang, Shuao and Alekseev, Evgeny V. and Casey, William H. and Phillips, Brian L. and Depmeier, Wulf and Albrecht-Schmitt, Thomas E.},
abstractNote = {A cubic thorium borate possesses a porous supertetrahedral cationic framework with extraframework borate anions. These anions are readily exchanged with a variety of environmental contaminants, especially those from the nuclear industry, including chromate and pertechnetate.},
doi = {10.1002/anie.200906397},
journal = {Angewandte Chemie (International Edition)},
number = 1,
volume = 49,
place = {United States},
year = {Mon Feb 01 00:00:00 EST 2010},
month = {Mon Feb 01 00:00:00 EST 2010}
}
  • [ThB5O6(OH)6][BO(OH)2]·2.5H2O (Notre Dame Thorium Borate-1, NDTB-1) is an inorganic supertetrahedral cationic framework material that is derived from boric acid flux reactions. NDTB-1 exhibits facile single crystal to single crystal anion exchange with a variety of common anions such as Cl-, Br-, NO3-, IO3-, ClO4-, MnO4-, and CrO42-. More importantly, NDTB-1 is selective for the removal of TcO4- from nuclear waste streams even though there are large excesses of competing anions such as Cl-, NO3-, and NO2-. Competing anion exchange experiments and magic-angle spinning (MAS)-NMR spectroscopy of anion-exchanged NDTB-1 demonstrate that this unprecedented selectivity originates from the ability of NDTB-1 tomore » trap TcO4- within cavities, whereas others remain mobile within channels in the material. The exchange kinetics of TcO4- in NDTB-1 are second-order with the rate constant k2 of 0.059 s-1 M-1. The anion exchange capacity of NDTB-1 for TcO4- is 162.2 mg g-1 (0.5421 mol mol-1) with a maximum distribution coefficient Kd of 1.0534 × 104 mL g-1. Finally, it is demonstrated that the exchange for TcO4- in NDTB-1 is reversible. TcO4- trapped in NDTB-1 can be exchanged out using higher-charged anions with a similar size such as PO43- and SeO42-, and therefore the material can be easily recycled and reused.« less
  • 99Tc magic-angle spinning (MAS) NMR spectra show that TcO 4 - ions, which are generated by nuclear fission and can contaminate the environment, can be trapped within the channels and cavities of a cationic framework material (see picture). These spectra are among the first 99Tc MAS NMR spectra reported to date, and show that the TcO 4 - ions can be efficiently removed from simulated nuclear waste solutions.
  • Realizing the synthesis and crystal structure of microporous materials with pore sizes 10--20 {angstrom} has been a formidable challenge in molecular sieve science. Access to such materials, with uniform pore size, is expected to impact the petrochemical and the life-sciences fields by providing opportunities for the size and shape-selective catalysis/separation of large molecules. In this direction, theoretical approaches to decorating specific 4-connected networks have been proposed, whereby replacing each (T1) tetrahedron, TX{sub 4}, in a given network by a larger tetrahedron (hereafter referred to as a supertetrahedron), signified Tn, yields a porous network due to the increased size of themore » building blocks. With large n, frameworks of unprecedented porosity could be achieved. Recognizing the potential of this approach, the authors have embarked on a program aimed at using inorganic clusters as molecular building blocks in the assembly of extended networks: The copolymerization of Mn(II) with the tetrahedral adamantine Ge{sub 4}S{sub 10}{sup 4{minus}} (T2) cluster, composed of 4 GeX{sub 4/2} tetrahedra, yielded MnGe{sub 4}S{sub 10}{center{underscore}dot}2(CH{sub 3}){sub 4}N having a porous cristobalite network with the organic cations occupying the void space.« less