Further design of quaternary diammonium reagents hosted on polymer nanofibers for hexachloridoiridate(IV) specificity, P. Moleko-Boyce, M. Ngayeka, and Z. Tshentu

This paper is focused on the development of iridium(IV)-specific quaternary diammonium cations containing electron-donating substituents in the benzyl group of methyl and electron-withdrawing substituents such as triflouromethyl and nitro groups. Quaternary diammonium cations used were tetra- 4-methylbenzyl-1,10-diammonium decane chloride (QuatDMDAMeBnz), tetrabenzyl-1,10- diammoniumdecane chloride (QuatDMDABnz), tetra-3-trifluoromethylbenzyl-1,10- diammoniumdecane chloride (QuatDMDACF3Bnz) and tetra-4-nitrobenzyl-1,10-diammoniumdecane chloride (QuatDMDANO2Bnz). Polyvinylbenzylchloride (PVBC) nanofibres were used as support material, and the functionalised nanofibres were used for separation of Ir(IV) from Rh(III). The sorbent materials were characterised by FTIR and elemental analysis. The efficiency of the quaternary diammonium cations was investigated in a column study under dynamic flow adsorption conditions. Column sorption of [IrCl6]2- and [RhCl5(H2O)]2- on nanofibres functionalised with diammonium cations showed [RhCl5(H2O)]2- was not adsorbed by the sorbent materials while [IrCl6]2- was loaded onto the column. The loading capacities of [IrCl6]2- on the quaternary diammonium sorbent materials increased in the order of F-QuatDMDAMeBnz (3.08 mg/g) < F-QuatDMDABnz (3.39 mg/g) < FQuatDMDACF3Bnz (5.46 mg/g) < F-QuatDMDANO2Bnz (7.10 mg/g). The loading capacity for Ir(IV) with quaternary diammonium cationic nanofibres increased with an increase in the electron-withdrawing nature of the substituent on the quaternising group. The charge delocalising ability of the 4-nitrobenzyl group resulted in the best interaction of the decamethylene diammonium cation with [IrCl6]2-. Keywords: Iridium(IV), rhodium(III), quaternary diammonium, polymer nanofibres, separation