Modeling the Effect of Defects and Disorder in Amorphous Metal-Organic Frameworks.
Modeling the Effect of Defects and Disorder in Amorphous Metal-Organic Frameworks.
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DOI：
10.1021/acs.chemmater.2c01528
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发表时间：
2022-10-25
影响因子：
8.6
通讯作者：
Jelfs, Kim E.
中科院分区：
文献类型：
--
作者：
Bechis, Irene;Sapnik, Adam F.;Tarzia, Andrew;Wolpert, Emma H.;Addicoat, Matthew A.;Keen, David A.;Bennett, Thomas D.;Jelfs, Kim E.
非晶态金属有机骨架（aMOF）是一类无序骨架材料，具有由无机节点和有机连接体之间的连接给出的确定的局部有序性，但缺乏长程有序。由于缺乏长程有序，我们对这些系统中底层结构-性能关系的了解有限，这阻碍了 aMOF 功能的合理开发，这使得实验表征特别具有挑战性。在这里，我们使用一种通用的建模方法来生成基于 Fe 三聚体和 1,3,5-苯三甲酸 (BTC) 连接体 Fe-BTC 的 aMOF 的计算机结构模型。我们为这种材料构建了一个相空间，其中包括具有不同程度的缺陷和局部有序的九个非晶相。这些模型通过结构分析、孔隙分析和对分布函数的组合进行分析。因此，我们能够系统地探索这些特征的变化对无序 MOF 系统的影响，无论是单独的还是组合的，这是仅通过实验不可能实现的。我们发现局部有序程度对结构和性能的影响比缺陷程度更大。这里提出的方法是通用的，可以研究不同的结构特征和 MOF 化学性质，从而能够推导合理开发 aMOF 的设计规则。
Amorphous metal–organic frameworks (aMOFs) are a class of disordered framework materials with a defined local order given by the connectivity between inorganic nodes and organic linkers, but absent long-range order. The rational development of function for aMOFs is hindered by our limited understanding of the underlying structure–property relationships in these systems, a consequence of the absence of long-range order, which makes experimental characterization particularly challenging. Here, we use a versatile modeling approach to generate in silico structural models for an aMOF based on Fe trimers and 1,3,5-benzenetricarboxylate (BTC) linkers, Fe-BTC. We build a phase space for this material that includes nine amorphous phases with different degrees of defects and local order. These models are analyzed through a combination of structural analysis, pore analysis, and pair distribution functions. Therefore, we are able to systematically explore the effects of the variation of each of these features, both in isolation and combined, for a disordered MOF system, something that would not be possible through experiment alone. We find that the degree of local order has a greater impact on structure and properties than the degree of defects. The approach presented here is versatile and allows for the study of different structural features and MOF chemistries, enabling the derivation of design rules for the rational development of aMOFs.
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影响因子：
4.3
作者：
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影响因子：
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