Covalent organic framework modified carbon nanotubes for removal of uranium (VI) from mining wastewater

Abstract

The wastewater containing uranium produced in the mining process is harmful to the environment and life safety due to the inherent biotoxicity and radioactivity of uranium. In this paper, 4,4′-diamino-[1,1′-biphenyl]-3,3′-diol and 2,4,6-triformylphloroglucinol were in situ synthesized β-ketoenamine covalent organic frameworks (COFs) on the surface of carbon nanotubes (CNTs) to obtain a composite of CNT/COF-OH for removal uranium in the rare earth tailings wastewater. Grafting COFs with a large number of specific uranium-binding groups and redox-active sites on the surface of CNTs, CNT/COF-OH can effectively enhance the uranium ion selectivity and adsorption capacity. Furthermore, CNTs have good electron transport capacity and π-conjugation properties, electrons can be effectively transferred from CNTs to COFs, which increases the electron density of the adsorption functional groups, resulting in an increase of the adsorption energy and reductive activity for U (VI), thus improving the removal efficiency. In addition, the skeleton of COFs can be supported by CNTs, thus reducing collapse. Through the synergistic effect of composite, CNT/COF-OH had a good uranium adsorption capacity of 518.2 mg g−1. The adsorption capacity of CNT/COF-OH was increased by 390.7 %, 54.6 %, and 84.5 % compared with those of single CNTs, COF-OH, and mixed CNT + COF-OH, respectively. The selective separation coefficient of CNT/COF-OH was 1.6 times higher than that of COF-OH. The experiment of uranium removal was carried out in the rare earth tailings wastewater using CNT/COF-OH, the removal rate reached 96.7 %. The COFs modified CNTs with synergistic effect have important theoretical and practical significance for the safety problems caused by harmful ions in wastewater.