Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites

Ashling, Christopher W.; Johnstone, Duncan N.; Widmer, Remo N.; Hou, Jingwei; Collins, Seán; Sapnik, Adam; Bumstead, Alice; Midgley, Paul A.; Chater, Philip A.; Keen, David A.; Bennett, Thomas D.

doi:10.26434/chemrxiv.8921765

Cited by 10 publications

(11 citation statements)

References 27 publications

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“… 35 Further, SED has been applied to beam sensitive materials revealing crystallinity in organic molecular crystals, 36 polymers, 37 halide perovskites, 38 and MOFs. 39 , 40 Here, we apply SED to directly visualize nanoscale defect domains in UiO-66(Hf).…”

Section: Introductionmentioning

confidence: 99%

Direct Imaging of Correlated Defect Nanodomains in a Metal–Organic Framework

et al. 2020

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Defect engineering can enhance key properties of metal–organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the subnanometer imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap uniquely enabling both nanoscale crystallographic analysis and the low-dose formation of multiple diffraction contrast images for defect analysis in MOFs. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or “microstructure”, in functional MOF design.

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Section: Introductionmentioning

confidence: 99%

Direct Imaging of Correlated Defect Nanodomains in a Metal–Organic Framework

et al. 2020

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“…Research into a subfamily of metal-organic frameworks (MOFs) called zeolitic imidazolate frameworks (ZIFs) has enabled access to high-temperature ZIF liquids and microporous glasses after quenching (7). ZIF glasses have distinct physicochemical properties in terms of their porosity, reactivity, mechanical rigidity/ductility and optical response (8)(9)(10), and have been used as host matrices for crystalline MOFs (11,12). Together, these properties make ZIF glasses prime candidates for addressing the multiple challenges for LHP composite formation.…”

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confidence: 99%

Liquid-phase sintering of lead halide perovskites and metal-organic framework glasses

Hou

Chen

Shukla

et al. 2021

Science

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Stable emission in glass Lead halide perovskites can exhibit bright, narrow band photoluminescence but have stability issues related to formation of inactive phases and the loss of lead ions. Hou et al . show that the black, photoactive phase of cesium lead iodide can be stabilized by forming a composite with a glassy phase of a metal-organic framework through liquid-phase sintering. The photoluminescence is at least two orders of magnitude greater than that of the pure perovskite. The glass stabilizes the perovskite under high laser excitation, and about 80% of the photoluminescence was maintained after 10,000 hours of water immersion. —PDS

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“…32 Further, SED has been applied to beam sensitive materials revealing crystallinity in organic molecular crystals 33 , polymers 34 and MOFs. 35,36 Here, we apply SED to directly visualize nanoscale defect domains in UiO-66(Hf).…”

Section: Sed Is a Four-dimensional Scanning Transmission Electron Micmentioning

confidence: 99%

Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework

Johnstone

Firth²,

Grey³

et al. 2020

Preprint

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<p>Defect engineering can enhance key properties of metal-organic frameworks (MOFs). Tailoring the distribution of defects, for example in correlated nanodomains, requires characterization across length scales. However, a critical nanoscale characterization gap has emerged between the bulk diffraction techniques used to detect defect nanodomains and the sub-nanometre imaging used to observe individual defects. Here, we demonstrate that the emerging technique of scanning electron diffraction (SED) can bridge this gap. We directly image defect nanodomains in the MOF UiO-66(Hf) over an area of ca. 1 000 nm and with a spatial resolution ca. 5 nm to reveal domain morphology and distribution. Based on these observations, we suggest possible crystal growth processes underpinning synthetic control of defect nanodomains. We also identify likely dislocations and small angle grain boundaries, illustrating that SED could be a key technique in developing the potential for engineering the distribution of defects, or “microstructure”, in functional MOF design.</p>

show abstract

Synthesis and Properties of a Compositional Series of MIL-53(Al) Metal-Organic Framework Crystal-Glass Composites

Cited by 10 publications

References 27 publications

Direct Imaging of Correlated Defect Nanodomains in a Metal–Organic Framework

Direct Imaging of Correlated Defect Nanodomains in a Metal–Organic Framework

Liquid-phase sintering of lead halide perovskites and metal-organic framework glasses

Direct Imaging of Correlated Defect Nanodomains in a Metal-Organic Framework

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