Modulating Anion Nanotraps via Halogenation for High-Efficiency 99TcO4-/ReO4- Removal under Wide-Ranging pH Conditions.

Abstract

Efficient and sustainable methods for 99TcO4- removal from acidic nuclear waste streams, contaminated water, and highly alkaline tank wastes are highly sought after. Herein, we demonstrate that ionic covalent organic polymers (iCOPs) possessing imidazolium-N+ nanotraps allow the selective adsorption of 99TcO4- under wide-ranging pH conditions. In particular, we show that the binding affinity of the cationic nanotraps toward 99TcO4- can be modulated by tuning the local environment around the nanotraps through a halogenation strategy, thereby enabling universal pH 99TcO4- removal. A parent iCOP-1 possessing imidazolium-N+ nanotraps showed fast kinetics (reaching adsorption equilibrium in 1 min), a high adsorption capacity (up to 1434.1 ± 24.6 mg/g), and exceptional selectivity for 99TcO4- and ReO4- (nonradioactive analogue of 99TcO4-) removal in contaminated water. By introducing F groups near the imidazolium-N+ nanotrap sites (iCOP-2), a ReO4- removal efficiency over 58% was achieved in 60 min in 3 M HNO3 solution. Further, introduction of larger Br groups near the imidazolium-N+ binding sites (iCOP-3) imparted a pronounced steric effect, resulting in exceptional adsorption performance for 99TcO4- under super alkaline conditions and from low-activity waste streams at US legacy Hanford nuclear sites. The halogenation strategy reported herein guides the task-specific design of functional adsorbents for 99TcO4- removal and other applications.