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Modeling the Effect of Defects and Disorder in Amorphous Metal-Organic Frameworks.

Published version
Peer-reviewed

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Abstract

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.

Description

Funder: FP7 Ideas: European Research Council; doi: 10.13039/100011199; Grant(s): 758370

Keywords

3403 Macromolecular and Materials Chemistry, 34 Chemical Sciences

Journal Title

Chem Mater

Conference Name

Journal ISSN

0897-4756
1520-5002

Volume Title

34

Publisher

American Chemical Society (ACS)
Sponsorship
Engineering and Physical Sciences Research Council (EP/S015868/1)
Engineering and Physical Sciences Research Council (JM11106)
Royal Society (NA)