Identifying the Recognition Site for Selective Trapping of ⁹⁹TcO₄– in a Hydrolytically Stable and Radiation Resistant Cationic Metal–Organic Framework

Effective and selective removal of ⁹⁹TcO₄⁻ from aqueous solution is highly desirable for both waste partitioning and contamination remediation purposes in the modern nuclear fuel cycle, but is of significant challenge. We report here a hydrolytically stable and radiation-resistant cationic metal-organic framework (MOF), SCU-101, exhibiting extremely fast removal kinetics, exceptional distribution coefficient, and high sorption capacity toward TcO₄⁻. More importantly, this material can selectively remove TcO₄⁻ in the presence of large excesses of NO₃⁻ and SO₄²⁻, as even 6000 times of SO₄²⁻ in excess does not significantly affect the sorption of TcO₄⁻. These superior features endow that SCU-101 is capable of effectively separating TcO₄⁻ from Hanford low-level waste melter off-gas scrubber simulant stream. The sorption mechanism is directly unraveled by the single crystal structure of TcO₄⁻-incorporated SCU-101, as the first reported crystal structure to display TcO₄⁻ trapped in a sorbent material. A recognition site for the accommodation of TcO₄⁻ is visualized and is consistent with the DFT analysis results, while no such site can be resolved for other anions.