Construction of Ketoenamine-Based Covalent Organic Frameworks with Electron-Rich Sites for Efficient and Rapid Removal of Iodine from Solution.

Porous covalent organic frameworks (COFs) have been widely used for the efficient removal of iodine from solution due to their abundance of electron-rich sites. In this study, two kinds of ketoenamine-based COFs, TpBD-(OMe) 2 and TpBD-Me 2 , are successfully synthesized via Schiff base reaction under solvothermal conditions using 1, 3, 5-triformylphoroglucinol as aldehyde monomer, o-tolidine and o-dianisidine as amino monomers. The ability of TpBD-(OMe) 2 and TpBD-Me 2 to adsorb iodine in cyclohexane or aqueous solutions has been quantitatively analyzed and interpreted in terms of adsorption sites. TpBD-Me 2 possesses two adsorption sites, -NH- and -C=O, and exhibits an adsorption capacity of 681.67 mg/g in cyclohexane, with an initial adsorption rate of 0.6 g/mol/min with respect to COF unit cell. The adsorption capacity of TpBD-(OMe) 2 can be as high as 728.77 mg/g, and the initial adsorption rate of TpBD-(OMe) 2 can reach 1.2 g/mol/min in the presence of oxygen atoms between the methyl group and the benzene ring. Compared with TpBD-Me 2 , the higher adsorption capacity and adsorption rate of TpBD-(OMe) 2 towards iodine are not only reflected in organic solvents, but also in aqueous solutions. It is proven through X-ray photoelectron spectroscopy and Raman spectroscopy that iodine exists in the form of I 2 , I 3 - , and I 5 - within TpBD-(OMe) 2 and TpBD-Me 2 after adsorption. This work not only expands the application of COFs in the field of iodine adsorption, but also provides research ideas and important an experimental basis for the optimization of iodine adsorption sites.