Olefin-linked cationic covalent organic frameworks for efficient extraction of ReO4-/99TcO4

Wei-Rong Cui; Wei Xu; Yi-Ru Chen; Kai Liu; Wei-Bin Qiu; Yibao Li; Jian-Ding Qiu

doi:10.1016/j.jhazmat.2022.130603

Olefin-linked cationic covalent organic frameworks for efficient extraction of ReO₄^-/⁹⁹TcO₄

J Hazard Mater. 2023 Mar 15:446:130603. doi: 10.1016/j.jhazmat.2022.130603. Epub 2022 Dec 23.

Authors

Wei-Rong Cui¹, Wei Xu², Yi-Ru Chen², Kai Liu², Wei-Bin Qiu², Yibao Li³, Jian-Ding Qiu⁴

Affiliations

¹ Jiangxi Key Laboratory of Organo-Pharmaceutical Chemistry, Chemistry and Chemical Engineering College, Gannan Normal University, Ganzhou 341000, PR China. Electronic address: wrcui@gnnu.edu.cn.
² Jiangxi Key Laboratory of Organo-Pharmaceutical Chemistry, Chemistry and Chemical Engineering College, Gannan Normal University, Ganzhou 341000, PR China.
³ Jiangxi Key Laboratory of Organo-Pharmaceutical Chemistry, Chemistry and Chemical Engineering College, Gannan Normal University, Ganzhou 341000, PR China. Electronic address: liyibao@gnnu.edu.cn.
⁴ College of Chemistry, Nanchang University, Nanchang 330031, PR China. Electronic address: jdqiu@ncu.edu.cn.

PMID: 36580784
DOI: 10.1016/j.jhazmat.2022.130603

Abstract

Efficient extraction of radioactive ⁹⁹TcO₄^- from strong acid/base solutions by porous adsorbents is extremely desirable but remains a great challenge. To overcome the challenge, here we report the first example of an olefin-linked cationic covalent organic framework (COF) named BDBI-TMT with excellent acid, base and radiation stability is synthesized by integrating robust imidazolium salt-based linkers with triazine building blocks. BDBI-TMT shows an ultra-fast adsorption kinetics (equilibrium is reached within 1 min) and an excellent ReO₄^- (a non-radioactive surrogate of ⁹⁹TcO₄^-) capture capacity of 726 mg g^-1, which can be attributed to the abundance of precisely tailored imidazolium salt-based units on the highly accessible pore walls of the ordered pore channels. Furthermore, the formation of the highly conjugated bulky alkyl skeleton enhances the hydrophobicity of BDBI-TMT, which significantly improves not only the affinity toward ReO₄^-/⁹⁹TcO₄^- but also the chemical stability, allowing selective and reversible extraction of ReO₄^-/⁹⁹TcO₄^- even under extreme conditions. This work demonstrates the great potential of olefin-linked cationic COFs for ReO₄^-/⁹⁹TcO₄^- extraction, providing a new avenue to construct high-performance porous adsorbents for radionuclide remediation.

Keywords: Cationic; Covalent organic frameworks; Extraction; Olefin-linked; ReO(4)(-)/(99)TcO(4)(-).