Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy
Elucidating correlated defects in metal organic frameworks using theory-guided inelastic neutron scattering spectroscopy
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DOI：
10.1039/d2mh00914e
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发表时间：
2022-10-31
影响因子：
13.3
通讯作者：
Moule, Adam J.
中科院分区：
文献类型：
--
作者：
Cavalcante, Lucas S. R.;Dettmann, Makena A.;Moule, Adam J.
结合金属氧化物簇节点的金属有机框架（MOFs），例如UiO-66，已经被广泛研究，特别是在它们与理想的无缺陷晶体结构的偏差方面。虽然已经提出了缺陷，如缺失的接头，缺失的节点，和存在的外来合成衍生的节点配体（如乙酸酯和甲酸酯），其确切的结构仍然未知。先前，已经证明缺陷是相关的并且跨越多个单位单元。这些研究中使用的高度专业化的技术不容易适用于其他MOFs。因此，有必要开发新的实验和计算方法，以了解更广泛的各种MOFs中的缺陷的结构和性质。在这里，我们展示了如何通过非弹性中子散射（INS）光谱测量的低频声子模式可以与密度泛函理论（DFT）模拟相结合，为UiO-66的缺陷结构提供前所未有的见解。我们能够识别和分配指纹区域中的峰（
Metal organic frameworks (MOFs) that incorporate metal oxide cluster nodes, exemplified by UiO-66, have been widely studied, especially in terms of their deviations from the ideal, defect-free crystalline structures. Although defects such as missing linkers, missing nodes, and the presence of adventitious synthesis-derived node ligands (such as acetates and formates) have been proposed, their exact structures remain unknown. Previously, it was demonstrated that defects are correlated and span multiple unit cells. The highly specialized techniques used in these studies are not easily applicable to other MOFs. Thus, there is a need to develop new experimental and computational approaches to understand the structure and properties of defects in a wider variety of MOFs. Here, we show how low-frequency phonon modes measured by inelastic neutron scattering (INS) spectroscopy can be combined with density functional theory (DFT) simulations to provide unprecedented insights into the defect structure of UiO-66. We are able to identify and assign peaks in the fingerprint region (