Calix[4]pyrrole-based Crosslinked Polymer Networks for Highly Effective Iodine Adsorption from Water

Abstract

A series of calix[4]pyrrole-based crosslinked polymer networks designed for iodine capture is reported. These materials were prepared by Sonogashira coupling of α,α,α,α-tetra(4-alkynylphenyl)calix[4]pyrrole with bishalide building blocks with different electronic properties and molecular sizes. Despite their low Brunauer-Emmett-Teller surface areas, iodine vapor adsorption capacities of up to 3.38 g g^-1 were seen, a finding ascribed to the presence of a large number of effective sorption sites including macrocyclic π-rich cavities, aryl units, and alkyne groups within the material. One particular system, C[4]P-BTP, was found to be highly effective at iodine capture from water (uptake capacity of 3.24 g g^-1 from a concentrated aqueous KI/I₂ solution at ambient temperature). Fast capture kinetics (k_obs =7.814 g g^-1 min^-1 ) were seen. Flow-through adsorption experiments revealed that C[4]P-BTP is able to remove 93.2 % of iodine from an aqueous source phase at a flow rate of 1 mL min^-1 .

Keywords: adsorption; calix[4]pyrrole; iodine; porous organic polymers.