Interplay between noble gases and MOFs: Insights from 129Xe and 83Kr NMR spectroscopy

IF 12.5 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES

Science Advances Pub Date : 2025-10-08 DOI:10.1126/sciadv.aea1857

Wanli Zhang, Vinicius Martins, Jeffrey Collins, Reza Moshrefi, Samantha Michelle Gateman, Victor V. Terskikh, Yining Huang

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Abstract

Efficient separation and storage of radioactive noble gas isotopes [krypton-85 (⁸⁵Kr) and xenon-131m/133/135 (^131m/133/135Xe)] from off-gas during spent nuclear fuel reprocessing are vital for environmental protection and noble gas recovery. Metal-organic frameworks (MOFs) are promising adsorbents, yet atomic-level insights into Xe and Kr adsorption remain limited. Here, we report the first application of high-field solid-state ⁸³Kr nuclear magnetic resonance (NMR), alongside extensive ¹²⁹Xe NMR, to investigate gas adsorption in eight MOFs representing three design strategies: ultramicroporous one-dimensional–channel MOFs with pore sizes matching noble gas diameters, functionalized MOFs, and MOFs with open metal sites. Single-gas and coadsorption studies reveal distinct adsorption sites, guest-host interactions, and gas dynamics in each MOF. Most MOFs retain crystallinity after exposure to 60-kilogray γ radiation. Several radiation-sensitive MOFs exhibit enhanced stability in the presence of Xe, suggesting that Xe adsorption enhances framework stability and may broaden the range of MOFs usable under γ radiation in nuclear off-gas separation. These findings offer valuable molecular-level design insights.

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稀有气体和mof之间的相互作用：来自129 Xe和83 Kr核磁共振光谱的见解

乏核燃料后处理废气中放射性惰性气体同位素[氪-85 （85 Kr）和氙-131m/133/135 (131m/133/135 Xe)]的有效分离和储存对于环境保护和惰性气体回收至关重要。金属有机框架（mof）是很有前途的吸附剂，但对Xe和Kr吸附的原子水平的了解仍然有限。在这里，我们报告了高场固态83氪核磁共振（NMR）和广泛的129氙核磁共振（NMR）的首次应用，以研究八种mof中的气体吸附，这些mof代表了三种设计策略：孔径与稀有气体直径匹配的超微孔一维通道mof，功能化mof和开放金属位点的mof。单气体和共吸附研究揭示了每个MOF中不同的吸附位点、主客相互作用和气体动力学。大多数mof在暴露于60千克γ辐射后仍保持结晶度。一些辐射敏感mof在Xe的存在下表现出更强的稳定性，这表明Xe的吸附增强了骨架的稳定性，并可能扩大在核废气分离中γ辐射下可用的mof的范围。这些发现提供了有价值的分子水平的设计见解。

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来源期刊

Science Advances 综合性期刊-综合性期刊

CiteScore

21.40

自引率

1.50%

发文量

1937

审稿时长

29 weeks

期刊介绍： Science Advances, an open-access journal by AAAS, publishes impactful research in diverse scientific areas. It aims for fair, fast, and expert peer review, providing freely accessible research to readers. Led by distinguished scientists, the journal supports AAAS's mission by extending Science magazine's capacity to identify and promote significant advances. Evolving digital publishing technologies play a crucial role in advancing AAAS's global mission for science communication and benefitting humankind.