Mechanism unravelling for ultrafast and selective 99TcO4β uptake by a radiation-resistant cationic covalent organic framework: a combined radiological experiment and molecular dynamics simulation study†
Abstract
99Tc is one of the most problematic fission products in the nuclear fuel cycle owing to its large inventory in used nuclear fuel, long half-life, potential radiation hazard, high environmental mobility of its major species 99TcO4β, and its redox-active nature. Ideally, 99TcO4β should be removed at the first stage, when the used fuel rods are dissolved in highly concentrated nitric acid solution, which can substantially reduce its interference with the solvent extraction process through catalytic redox reactions with the key actinides and diminish the chance of discharge into the environment as the volatile species during the waste vitrification process. However, this task cannot be achieved by any of the reported anion-scavenging materials including traditional polymeric anion-exchange resins, inorganic cationic framework materials, and recently developed cationic metalβorganic framework materials, because they either are not stable under the extreme conditions of the combined high acidity and strong radiation field or do not possess the required uptake selectivity towards 99TcO4β in the presence of a huge excess of competing anions such as NO3β and SO42β. Herein, we present the first study of 99TcO4β removal under extreme conditions by a two-dimensional conjugated cationic covalent organic framework material, SCU-COF-1. This material exhibits ultrahigh acid stability, great resistance towards both large-dose Ξ² and Ξ³ irradiation and unprecedented 99TcO4β uptake capabilities including extremely fast sorption kinetics (sorption equilibrium can be reached within 1 min), ultrahigh uptake capacity (702.4 mg gβ1 for the surrogate ReO4β at a slightly elevated temperature), and good anion-exchange selectivity towards 99TcO4β. These excellent features endow SCU-COF-1 with the practical capabilities of separating 99TcO4β from both simulant highly acidic fuel reprocessing solutions (3 M nitric acid) and low-activity waste streams at the US legacy nuclear site. The anion-exchange mechanism and the 99TcO4β uptake selectivity are further demonstrated and clearly visualized by the molecular dynamics simulation investigations.
- This article is part of the themed collection: SU 120: Celebrating 120 Years of Soochow University