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A rational design of anion-exchange materials for the selective elimination of radioactive anionic contaminants poses a great challenge. Rather than relying on a size-compatible effect, the combination of a nano-sieve pore, hydrophobic cationic cavity, and soft-acidic open metal sites within one sorbent is an emerging strategy for meeting the requirement. Here, we designed a porous cationic Ag(I) metal-organic framework (MOF), TNU-132, which combined multiple features and showed superior perrhenate/pertechnetate capture selectivity in the presence of a large excess of 300-fold NO and 2000-fold SO. The mechanism of this high selectivity can be well elucidated by the anion exchange experiments of TNU-132 in the CrO/ReO mixture. That is, the separation process underwent two sequential steps, the nano-sieving procedure and then a reconstruction process in the crystalline sorbent. These results were further confirmed by scanning transmission electron microscopy (STEM), energy-dispersive X-ray spectroscopy (EDS), and/or single-crystal X-ray diffraction (SC-XRD) of oxoanion-loaded materials.
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http://dx.doi.org/10.1039/d1dt04175d | DOI Listing |
Dalton Trans
August 2025
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310058, China.
Recent studies have extensively reported the use of cationic metal-organic frameworks (MOFs) for capturing perrhenate/pertechnetate (ReO/TcO) from waste water. Despite the high sorption efficiency of some materials, their stability in strongly acidic and alkaline environments remains inadequate, which hinders their further application in nuclear waste post-processing. Herein, we constructed two different copper-based cationic metal-organic frameworks (ZJU-X16 and ZJU-X17) with excellent resistance to strong acids and alkalis.
View Article and Find Full Text PDFChemistry
September 2024
School of Chemical Science, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Kolkata, 700032, India.
Efficient recognition and extraction of hazardous anionic pollutants from water medium is of great significance for environmental concerns, representing a challenging area of research in supramolecular chemistry. In this study, we present, for the first time, a comprehensive demonstration of the ability of chalcogen bonding (ChB) to recognize and remove the ReO from 100 % water medium. The anion recognition ability is well elucidated through solution phase NMR and ITC studies, which clearly reveal the selective binding of ReO over other oxo-anions.
View Article and Find Full Text PDFACS Appl Mater Interfaces
May 2023
School of Chemical Science, Indian Association for the Cultivation of Science, 2A & 2B Raja S. C. Mullick Road, Kolkata700032, India.
A halogen bond-based water-soluble tetrapodal iodoimidazolium receptor, , exhibited a high degree of efficiency (∼96%) in extracting ReO from 100% aqueous medium within a wide range of concentrations and of pH values along with excellent reusability. The solid-state X-ray diffraction study showed the trapping of ReO by via the Re-O····I halogen bonding interaction. XPS studies also suggested the interaction between I and ReO through polarization of the electron density of I atoms by ReO.
View Article and Find Full Text PDFInorg Chem
July 2022
College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China.
Albeit reported substantial sorbents for elimination of TcO, the issue of secondary contamination caused by released counterions (such as NO) from the cationic metal-organic framework (MOF) has not come into the sufficient limelight for researchers. Herein, our efforts are dedicated to settle the matter through synthesis of NiCl based on the cationic MOF (ZJU-X4). Less harmful chlorides are used as exchangeable anions for replacing hazardous anions.
View Article and Find Full Text PDFDalton Trans
March 2022
Tianjin Key Laboratory of Structure and Performance for Functional Molecules, College of Chemistry, Tianjin Normal University, Tianjin 300387, P. R. China.
A rational design of anion-exchange materials for the selective elimination of radioactive anionic contaminants poses a great challenge. Rather than relying on a size-compatible effect, the combination of a nano-sieve pore, hydrophobic cationic cavity, and soft-acidic open metal sites within one sorbent is an emerging strategy for meeting the requirement. Here, we designed a porous cationic Ag(I) metal-organic framework (MOF), TNU-132, which combined multiple features and showed superior perrhenate/pertechnetate capture selectivity in the presence of a large excess of 300-fold NO and 2000-fold SO.
View Article and Find Full Text PDF