Anisotropic mechanical properties of polymorphic hybrid inorganic–organic framework materials with different dimensionalities

Tan, Jin‐Chong; Merrill, Crystal A.; Orton, James B.; Cheetham, Anthony K.

doi:10.1016/j.actamat.2009.04.004

Cited by 104 publications

(149 citation statements)

References 31 publications

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“…Moreover, the tetragonal symmetry of the zni topology also gives rise to elastic anisotropy, as indicated by the distinctive moduli measured in the f001g-and f100g-oriented facets (i.e., E f001g ∕E f100g ≃ 1.1). It is noteworthy that the mechanical behavior of ZIF-zni resembles those reported in dense hybrid systems whose stiffnesses are of the order of 10 GPa (20,21). In contrast, our findings show that low-density open frameworks, such as ZIF-8, −20 and −68, can exhibit relatively low stiffnesses with their E values in the range of 3-4 GPa.…”

Section: Resultscontrasting

confidence: 54%

“…It can be seen that the elastic modulus and hardness properties of dense hybrid frameworks [e.g., copper phosphonoacetates (21) and cerium oxalate-formate (20)] are approximately an order of magnitude higher than the ZIF-type materials, but still not comparable with classical ceramic materials such as alumina, zirconia, and tungsten carbide (Fig. 5).…”

Section: Resultsmentioning

confidence: 99%

“…5, where they are plotted alongside the three major categories of conventional materials, i.e., metals, ceramics, and polymers. In addition, we have included the mechanical properties of recently reported dense hybrid systems (20,21) and nanoporous MOF-5 (13) for comparison. It is striking to see that the domain corresponding to ZIFs, to some extent, straddles the border between polymeric (purely organic), ceramic (purely inorganic), and metallic materials.…”

Section: Resultsmentioning

confidence: 99%

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Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

Tan

Bennett

Cheetham

2010

Proc. Natl. Acad. Sci. U.S.A.

493

451

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The mechanical properties of seven zeolitic imidazolate frameworks (ZIFs) based on five unique network topologies have been systematically characterized by single-crystal nanoindentation studies. We demonstrate that the elastic properties of ZIF crystal structures are strongly correlated to the framework density and the underlying porosity. For the systems considered here, the elastic modulus was found to range from 3 to 10 GPa, whereas the hardness property lies between 300 MPa and 1.1 GPa. Notably, these properties are superior to those of other metal-organic frameworks (MOFs), such as MOF-5. In substituted imidazolate frameworks, our results show that their mechanical properties are mainly governed by the rigidity and bulkiness of the substituted organic linkages. The framework topology and the intricate pore morphology can also influence the degree of mechanical anisotropy. Our findings present the previously undescribed structuremechanical property relationships pertaining to hybrid open frameworks that are important for the design and application of new MOF materials.elastic properties | metal-organic frameworks | nanohardness | nanoporosity | zeolitic imidazolate frameworks Z eolitic imidazolate frameworks (ZIFs) represent a unique class of metal-organic frameworks (MOFs) in which the network topology and related properties vary greatly while core chemical connectivity is retained (1, 2). ZIFs currently attract considerable interest by virtue of their exciting potential for hydrogen storage and carbon dioxide capture (3, 4). They adopt porous crystalline structures composed of metal ions and organic linkers, ordered in an analogous fashion to that of silicon and oxygen in zeolites. Specifically, tetrahedral metal centers [typically M ¼ ZnðIIÞ or Co(II)] that are solely coordinated by nitrogen atoms in the 1,3-positions of the imidazolate bridging ligand (Im ¼ C 3 N 2 H − 3 ), subtend an angle of 145°at the M-Im-M center (i.e., analogous to the Si-O-Si angle in silicas and zeolites). Such hybrid architectures can, importantly, give rise to a multitude of extended 3D open frameworks with topologies akin to those found in aluminosilicate zeolites. Over 90 distinct ZIF structures based on 36 of these tetrahedral topologies have been discovered thus far (5). Remarkably, ZIFs combine the classical zeolitic traits of chemical and thermal stability with the rich topological diversity and pore size tunability characteristic of MOFs (6, 7).By and large, research into MOF materials has been motivated by the prospect of discovering new structures with enhanced functional properties for use not only in gas adsorption and separation fields, but also in heterogeneous catalysis and molecular sensing applications (8-11). Indeed, all the aforementioned applications involve subjecting the porous systems to various modes of mechanical stresses and strains, for which their mechanical properties are critical to reach practical implementations. For instance, the open framework needs to exhibit good stiffness, rigidity, and robu...

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Section: Resultscontrasting

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

Tan

Bennett

Cheetham

2010

Proc. Natl. Acad. Sci. U.S.A.

493

451

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“…Assuming that the composite obeys the rule of mixtures relation (in equal strain), 16,39 we estimated the hardness of ZIF-90 to be ∼250 MPa, which is only about half of its sodalite counterpart ZIF-8, whose hardness is ∼530 MPa. 40 The Young modulus of the membrane (subscript m) can be estimated using the following relation, 41 if its Poisson ratio is known and assumed to be isotropic,…”

mentioning

confidence: 99%

Thermo-mechanical properties of mixed-matrix membranes encompassing zeolitic imidazolate framework-90 and polyvinylidine difluoride: ZIF-90/PVDF nanocomposites

et al. 2017

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Mixed-matrix membranes are contemporary nanocomposite materials with many potential applications, from liquid and gas separations to chemical sensors and biomedicine. We report fabrication of a metal-organic framework (MOF)-based nanocomposite, combining polyvinylidene difluoride (PVDF) polymer as the matrix and ZIF-90 nanocrystals of up to 30 wt. % filler content. The focus is to establish the processing—microstructure—mechanical property relationships. We reveal the importance for quantifying salient effects of the filler contents: (i) tensile strength degrades beyond 10 wt. % and (ii) mechanical toughness declines due to membrane embrittlement. These are vital mechanical aspects but widely overlooked in the emergent field of MOF membranes and composites.

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“…While 1, 2, and 4 exhibit negligible creep owing to their 3D Li-O-Li network, they are more compliant than most nonporous inorganic-organic frameworks previously studied. [14] The ionic lithium coordination sphere and torsional degrees of freedom associated with the succinate-based ligands impart more flexibility than, for example, covalent copper-based units [15] and rigid oxalate ligands. [16] The flexibility, both compositional and structural, of this family of compounds suggested that it could be possible to synthesize mixed-ligand phases with continuous variation in properties between two or more pure end members.…”

mentioning

confidence: 99%

Ligand‐Directed Control over Crystal Structures of Inorganic–Organic Frameworks and Formation of Solid Solutions

Yeung

Saines

et al. 2013

Angewandte Chemie

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Anisotropic mechanical properties of polymorphic hybrid inorganic–organic framework materials with different dimensionalities

Cited by 104 publications

References 31 publications

Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

Chemical structure, network topology, and porosity effects on the mechanical properties of Zeolitic Imidazolate Frameworks

Thermo-mechanical properties of mixed-matrix membranes encompassing zeolitic imidazolate framework-90 and polyvinylidine difluoride: ZIF-90/PVDF nanocomposites

Ligand‐Directed Control over Crystal Structures of Inorganic–Organic Frameworks and Formation of Solid Solutions

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