Direct observation of enhanced iodine binding within a series of functionalised metal-organic frameworks with exceptional irradia-tion stability

Jiangnan Li, Xinran Zhang, Mengtian Fan, Yinlin Chen, Yujie Ma, Gemma Smith, Inigo Vitorica-Yrezabal, Daniel Lee, Shaojun Xu, Martin Schroder, Sihai Yang

Research output: Contribution to journalArticlepeer-review

Abstract

Optimisation of active sites and stability under irradiation are important targets for sorbent materials that might be used for iodine (I2) storage. Herein, we report the direct observation of I2 binding in a series of Cu(II)-based isostructural metal-organic frameworks, MFM-170, MFM-172, MFM-174, NJU-Bai20 and NJU-Bai21, incorporating various functional groups (-H, -CH3, –NH2, -C≡C- and -CONH-, respectively). MFM-170 shows a reversible uptake of 3.37 g g-1 and high packing density of 4.41 g cm-3 for physiosorbed I2. The incorporation of –NH2 and -C≡C- moieties in MFM-174 and NJU-Bai20, respectively, enhance the binding of I2, affording uptakes of up to 3.91 g g-1. In addition, an exceptional I2 packing density of 4.83 g cm-3 is achieved in MFM-174, comparable to that of solid iodine (4.93 g cm-3). In situ crystallographic studies shows the formation of supramo-lecular and chemical interactions [I···N, I···H2N] and [I···C≡C, I-C=C-I] between –NH2, -C≡C- sites and adsorbed I2 molecules. These observations have been confirmed via a combination of solid-state nuclear resonance, X-ray photoelectron, and Raman spectroscopies. Importantly, γ-irradiation confirmed the ultra-resistance of MFM-170, MFM-174 and NJU-Bai20 suggesting their potential as efficient sorbents for clean-up of radioactive waste.
Original languageEnglish
JournalJournal of the American Chemical Society
Publication statusAccepted/In press - 4 Apr 2024

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