节点-连接体连通性对对苯二甲酸钍配位聚合物辐射稳定性的影响

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-04-24 DOI:10.1021/acs.inorgchem.5c00764

Zoë C. Emory, Heather J. Culbertson, Cale B. Gaster, Jay A. LaVerne, Peter C. Burns

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引用次数: 0

摘要

金属有机框架（MOFs）具有高孔隙率和可调整的特性，是核燃料循环应用的理想候选材料。然而，要在这种情况下有效使用，这些材料必须在电离辐射条件下保持稳定。以往的研究探讨了金属节点身份、拓扑结构和连接体类型的变化，而本研究则侧重于保持金属和连接体成分的一致性，以确定可增强辐射稳定性的结构特征。我们研究了三种钍-对苯二甲酸盐杂化材料--Th(BDC)2(DMF)2（1,4-苯二甲酸，二甲基甲酰胺）、Th(BDC)2 和 Th-UiO-66--在氦离子高达 227 MGy 的剂量下的抗辐射性。通过粉末 X 射线衍射 (PXRD)、漫反射红外傅立叶变换光谱 (DRIFTS) 和密度泛函理论 (DFT) 计算对结构稳定性进行了评估。确定了 Th(BDC)2(DMF)2 和 Th-UiO-66 的辐射稳定性阈值，其中 Th(BDC)2 即使在最高辐射剂量下也表现出超常的稳定性。观察到的稳定性趋势是 Th(BDC)2 > Th(BDC)2(DMF)2 > Th-UiO-66。值得注意的是，Th(BDC)2(DMF)2 中加入 DMF 增强了其辐射耐受性，这可能是由于 DMF 起到了牺牲配体的作用，在较高剂量下保持了连接体的完整性。此外，更独特的节点连接和更短的配体间距也有助于提高这些材料的辐射稳定性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Influence of Node–Linker Connectivity on Radiolytic Stability of Thorium-Terephthalate Coordination Polymers

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Influence of Node–Linker Connectivity on Radiolytic Stability of Thorium-Terephthalate Coordination Polymers

Metal–organic frameworks (MOFs) are promising candidates for applications in the nuclear fuel cycle due to their high porosity and tunable properties. However, for effective use in this context, these materials must be stable under ionizing radiation conditions. While previous studies have explored variations in metal node identities, topologies, and linker types, this study focuses on maintaining consistent metal and linker components to identify structural features that enhance radiation stability. We investigated the radiation resistance of three thorium-terephthalate hybrid materials─Th(BDC)₂(DMF)₂ (1,4-benzenedicarboxylic acid, dimethylformamide), Th(BDC)₂, and Th-UiO-66─irradiated with He-ions up to a dose of 227 MGy. Structural stability was assessed through powder X-ray diffraction (PXRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and density functional theory (DFT) calculations. The radiation stability thresholds were identified for Th(BDC)₂(DMF)₂ and Th-UiO-66, with Th(BDC)₂ demonstrating exceptional stability even at the highest radiation dose. The observed stability trend is Th(BDC)₂ > Th(BDC)₂(DMF)₂ > Th-UiO-66. Notably, the inclusion of DMF in Th(BDC)₂(DMF)₂ enhanced its radiation tolerance, likely due to DMF acting as a sacrificial ligand, preserving linker integrity at higher doses. Additionally, more unique node–linker connections and shorter interligand distances contributed to the improved radiolytic stability of these materials.

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.