Experimental and theoretical insights into copper phthalocyanine-based covalent organic frameworks for highly efficien radioactive iodine capture

摘要

Exploring efficient materials for capturing radioactive iodine in nuclear waste is of great significance for the progress of nuclear energy as well as the protection of ecological environment.Covalent organic frameworks(COFs)have emerged as promising adsorbents because of their predesignable and functionalizable skeleton structures.However,it remains a grand challenge to achieve large scale preparation of COFs.In this work,we developed a mild and efficient microwave irradiation method instead of the traditional solvothermal method to prepare copper phthalocyanine-based covalent organic frameworks(Cu_(x)Pc-COFs)within only 15 min.The nitrogen-rich 1,2,4,5-tetracarbonitrilebenzene(TCNB)was selected as the solely organic ligand to construct copper phthalocyanine-based 2D conjugated COFs.The resultant Cu_(x)Pc-COFs exhibited excellent iodine enrichment with 2.99 g/g for volatile iodine and 492.27 mg/g for iodine-cyclohexane solution,respectively,outperforming that of many porous materials.As indicated by spectroscopic analysis and DFT calculations,this impressive adsorption performance can be attributed to the charge transfer arising from nitrogen-rich phthalocyanine structures and electron-richπ-conjugated systems with iodine molecules.Moreover,the strong electrostatic interaction between Cu(Ⅱ)on chelate centers and polyiodide anions(I_(x)^(-))also play an important role in the firmly trapping radioactive iodine.Therefore,this study provides a facile and intelligent approach to implement metal-based COFs for the remediation of toxic radioactive iodine.