Metal-Organic Framework Crystal-Glass Composites

Hou, Jingwei; Ashling, Christopher W.; Collins, Sean M.; Krajnc, Andraž; Zhou, Chao; Longley, Louis; Johnstone, Duncan N.; Chater, Philip A.; Li, Shichun; Coudert, François‐Xavier; Keen, David A.; Midgley, Paul A.; Mali, Gregor; Chen, Vicki; Bennett, Thomas D.

doi:10.26434/chemrxiv.7093862

Cited by 17 publications

(33 citation statements)

References 28 publications

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“…MIL--53--np and MIL--53--as), the composite has the greatest CO 2 capacity under ambient conditions. We also note that, as observed by Hou et al, 21 mesopores are expected in all of the composites, which will enhance CO 2 uptake capacity.…”

supporting

confidence: 81%

“…A sample of (MIL--53) 0.25 (a g ZIF--62) 0.75 was previously observed to possess a CO 2 gas uptake of 66% that of a pure sample of MIL--53--np. 21 Given that (i) MIL--53--lp is the main contributor to the adsorption capacity, and (ii) the phase of MIL--53 remains unaltered to loadings of ⩽ 60 wt.%, the adsorption capacities are expected to increase across those composites displaying only the MIL--53--lp phase. Changes in adsorption trends are however expected on moving to compositions above 60 wt.%, i.e.…”

Section: Bulk Structure and Propertiesmentioning

confidence: 99%

“…The glassy state of MOFs has been used to create MOF crystal--glass composites (MOF--CGCs), in which a crystalline phase is incorporated into a MOF--glass matrix. 21 The first example of such a material was synthesized by forming a physical mixture of crystalline MIL-- 53 This mixture was heated above the melting temperature of ZIF--62, and cooled to room temperature to form the MOF--CGC (MIL--53) 0.25 (a g ZIF--62) 0.75 , (i.e. a MOF--CGC composed of 25 wt.% MIL--53 in a g ZIF--62, where a g denotes the glassy form).…”

mentioning

confidence: 99%

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

Ashling¹,

Johnstone²,

Widmer³

et al. 2019

Preprint

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Metal-organic framework crystal-glass composites (MOF-CGCs) are materials in which a crystalline MOF is dispersed within a MOF glass. In this work, we explore the room temperature stabilisation of the open-pore form of MIL-53(Al), usually observed at high-temperature, which occurs upon encapsulation within a ZIF-62(Zn) MOF glass matrix. A series of MOF-CGCs containing different loadings of MIL-53 were synthesised and characterised using X-ray diffraction and nuclear magnetic resonance spectroscopy. An upper limit of MIL-53 that can be stabilised in the composite was determined. The nanostructure of the composites was probed using pair distribution function analysis and scanning transmission electron microscopy. The distribution and integrity of the crystalline component was determined, and these findings related to the MOF-CGC gas adsorption capacity in order to identify the optimal loading necessary for maximum CO<sub>2</sub> sorption capacity.

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supporting

confidence: 81%

Section: Bulk Structure and Propertiesmentioning

confidence: 99%

mentioning

confidence: 99%

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

Ashling¹,

Johnstone²,

Widmer³

et al. 2019

Preprint

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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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“…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>

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Metal-Organic Framework Crystal-Glass Composites

Cited by 17 publications

References 28 publications

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

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

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

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

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