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- Boström, Hanna L. B., et al.
(författare)
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How Reproducible is the Synthesis of Zr-Porphyrin Metal-Organic Frameworks? An Interlaboratory Study
- 2024
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Ingår i: Advanced Materials. - 0935-9648 .- 1521-4095. ; 36:15
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Tidskriftsartikel (refereegranskat)abstract
- Metal-organic frameworks (MOFs) are a rapidly growing class of materials that offer great promise in various applications. However, the synthesis remains challenging: for example, a range of crystal structures can often be accessed from the same building blocks, which complicates the phase selectivity. Likewise, the high sensitivity to slight changes in synthesis conditions may cause reproducibility issues. This is crucial, as it hampers the research and commercialization of affected MOFs. Here, it presents the first-ever interlaboratory study of the synthetic reproducibility of two Zr-porphyrin MOFs, PCN-222 and PCN-224, to investigate the scope of this problem. For PCN-222, only one sample out of ten was phase pure and of the correct symmetry, while for PCN-224, three are phase pure, although none of these show the spatial linker order characteristic of PCN-224. Instead, these samples resemble dPCN-224 (disordered PCN-224), which has recently been reported. The variability in thermal behavior, defect content, and surface area of the synthesised samples are also studied. The results have important ramifications for field of metal-organic frameworks and their crystallization, by highlighting the synthetic challenges associated with a multi-variable synthesis space and flat energy landscapes characteristic of MOFs. It performed an interlaboratory study of the synthesis of the metal-organic frameworks (MOFs) PCN-222 and PCN-224. Ten participants independently synthesized the two MOFs and the products are analyzed, primarily by X-ray diffraction. The success rates are low (one-three samples corresponding to a pure sample of the correct phase), thus highlighting the problems with irreproducibility in MOF synthesis. image
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- Cliffe, Matthew J., et al.
(författare)
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Correlated defect nanoregions in a metal-organic framework
- 2014
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723. ; 5, s. 4176-
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Tidskriftsartikel (refereegranskat)abstract
- Throughout much of condensed matter science, correlated disorder is a key to material function. While structural and compositional defects are known to exist within a variety of metal-organic frameworks (MOFs), the prevailing understanding is that these defects are only ever included in a random manner. Here we show-using a combination of diffuse scattering, electron microscopy, anomalous X-ray scattering and pair distribution function measurements-that correlations between defects can in fact be introduced and controlled within a hafnium terephthalate MOF. The nanoscale defect structures that emerge are an analogue of correlated Schottky vacancies in rocksalt-structured transition metal monoxides and have implications for storage, transport, optical and mechanical responses. Our results suggest how the diffraction behaviour of some MOFs might be reinterpreted, and establish a strategy of exploiting correlated nanoscale disorder as a targetable and desirable motif in MOF design.
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