Task-Specific Tailored Cationic Polymeric Network with High Base-Resistance for Unprecedented (99)TcO(4)(–) Cleanup from Alkaline Nuclear Waste

[Image: see text] Direct removal of (99)TcO(4)(–) from alkaline nuclear waste is desirable because of the nuclear waste management and environmental protection relevant to nuclear energy but is yet to be achieved given that combined features of decent base-resistance and high uptake selectivity toward anions with low charge density have not been integrated into a single anion-exchange material. Herein, we proposed a strategy overcoming these challenges by rationally modifying the imidazolium unit of a cationic polymeric network (SCU-CPN-4) with bulky alkyl groups avoiding its ring-opening reaction induced by OH(–) because of the steric hindrance effect. This significantly improves not only the base-resistance but also the affinity toward TcO(4)(–) as a result of enhanced hydrophobicity, compared to other existing anion-exchange materials. More importantly, SCU-CPN-4 exhibits record high uptake selectivity, fast sorption kinetics, sufficient robustness, and promising reusability for removing (99)TcO(4)(–) from the simulated high-level waste stream at the U.S. Savannah River Site, a typical alkaline nuclear waste, in both batch experiment and dynamic column separation test for the first time.