Strategies for high-temperature methyl iodide capture in azolate-based metal-organic frameworks.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 38521857.
- Also identified by DOI 10.1038/s41467-024-47035-8 and PMC identifier 10960856.
- Licence recorded as CC BY.
- The licence permits redistribution, so the abstract is shown in full and the full text is available from the publisher.
Abstract
Efficiently capturing radioactive methyl iodide (CH<sub>3</sub>I), present at low concentrations in the high-temperature off-gas of nuclear facilities, poses a significant challenge. Here we present two strategies for CH<sub>3</sub>I adsorption at elevated temperatures using a unified azolate-based metal-organic framework, MFU-4l. The primary strategy leverages counter anions in MFU-4l as nucleophiles, engaging in metathesis reactions with CH<sub>3</sub>I. The results uncover a direct positive correlation between CH<sub>3</sub>I breakthrough uptakes and the nucleophilicity of the counter anions. Notably, the optimal variant featuring SCN<sup>-</sup> as the counter anion achieves a CH<sub>3</sub>I capacity of 0.41 g g<sup>-1</sup> at 150 °C under 0.01 bar, surpassing all previously reported adsorbents evaluated under identical conditions. Moreover, this capacity can be easily restored through ion exchange. The secondary strategy incorporates coordinatively unsaturated Cu(I) sites into MFU-4l, enabling non-dissociative chemisorption for CH<sub>3</sub>I at 150 °C. This modified adsorbent outperforms traditional materials and can be regenerated with polar organic solvents. Beyond achieving a high CH<sub>3</sub>I adsorption capacity, our study offers profound insights into CH<sub>3</sub>I capture strategies viable for practically relevant high-temperature scenarios.