Fast Room‐Temperature Synthesis of an Extremely Alkaline‐Resistant Cationic Metal–Organic Framework for Sequestering TcO₄⁻ with Exceptional Selectivity

Abstract

Leveraging metal–organic framework (MOF) to eliminate radioactive contaminants has invariably received much attention, but low preparation efficiency and poor selectivity have still limited its actual application. Herein, it is found that a fourfold interpenetrated cationic MOF (Ag‐TPPE) can be rapidly synthesized by only mixing, stirring, or sonication at room temperature. More impressively, the preparation process can be completed in <1 min. Up to now, this is the first report that cationic MOFs can be obtained by directly mixing the corresponding raw materials at room temperature. In addition to holding the rare merits of structural stability in extremely strong bases (8 m NaOH), Ag‐TPPE can selectively remove TcO4− in the presence of large excess SO42− or NO3−. Based on its ultra‐high selectivity, Ag‐TPPE exhibits exceptional removal rate for TcO4− from simulated Hanford and Savannah River Site waste streams, which refreshes the record of selective sorption of TcO4− at low solid/liquid ratio, overcoming the drawback of overused sorbent in treatment of radioactive waste solution. Such superior sorption capabilities are thoroughly elucidated by the density functional theory calculations on a molecular level, clearly disclosing that TcO4− can enter into the framework through breathing effect and is trapped in the large cavity through dense hydrogen bonds.

Composite Materials Based on a Zr4+ MOF and Aluminosilicates for the Simultaneous Removal of Cationic and Anionic Dyes from Aqueous Media

“…Thus, in the last decades, special attention has been paid to the research on nanoporous materials, as it has been found that they are good sorbents and play an important role in separation and purification processes. The relatively new class of highly crystalline porous solids, metal–organic frameworks (MOFs), is constantly gaining ground in various research fields, and especially in applications regarding sorption removal and the separation/purification of contaminated wastewater [ 13 , 14 , 15 , 16 ].…”

Anion−π Interaction Powered Perrhenate Recognition and Extraction in Aqueous Media

“…In recent years, due to their facile functionalization, tunable pore size, and high surface areas, different metal–organic framework (MOF) type TcO 4 – /ReO 4 – sorbent materials were developed. MOFs are composed of inorganic nodes in which the transition metal cation can play the role of a soft acid to bind the anions via a metal coordination mechanism, ,− but the ill-defined anion coordination environment is a potential drawback.…”

Twofold Interpenetrated Cationic Metal–Organic Framework with Hydrophobic Channels for Effectively Trapping Toxic Oxo-Anions

“…The crowded distribution of pyridyl and phenyl groups around the metal center could protect the metal nodes from an OH − attack and form hydrophobic 1D channels, resulting that 86% ReO 4 − could be decontaminated when the molar ratio of NO 3 − and ReO 4 − was 1000. 34 In this work, we synthesized a twofold interpenetrated cationic MOF of [Cd(TPPE) (H 2 O) 2 ]•(NO 3 ) 2 (ZJU-X15) with hydrophobic channels to remove ClO − were determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The same method was adopted to investigate the sorption kinetics of ZJU-X15 toward ClO 4 − (50 ppm).…”

“…Another benzene-rich ligand, TPPE was used to synthesize Ag-TPPE with hydrophobic channels. The crowded distribution of pyridyl and phenyl groups around the metal center could protect the metal nodes from an OH – attack and form hydrophobic 1D channels, resulting that 86% ReO 4 – could be decontaminated when the molar ratio of NO 3 – and ReO 4 – was 1000 …”