De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities

Farha, Omar K.; Yazaydın, A. Özgür; Eryazici, Ibrahim; Malliakas, Christos D.; Hauser, Bernard A.; Kanatzidis, Mercouri G.; Nguyen, SonBinh T.; Snurr, Randall Q.; Hupp, Joseph T.

doi:10.1038/nchem.834

Cited by 1,616 publications

(1,079 citation statements)

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“…A two-step adsorption was observed in N 2 and Ar isotherms, with Brunauer-Emmett-Teller (BET) and Langmuir surface areas of 3308 and 3845 m 2 g À 1 , respectively, based on the N 2 adsorption data (calculated from the first step of the adsorption isotherm). The stepwise adsorption isotherm can be explained by the existence of both meso-and micro-porous cages in the structure, as observed previously in similar systems 15 . As shown in Fig.…”

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confidence: 78%

“…Recently, remarkable progress has been made in this regard in the development of metal-organic materials (MOMs), such as metal-organic frameworks (MOFs) 5,6 and metal-organic polyhedra (MOPs) 7 , assembled from molecular building units. These materials possess unique properties and vast application potential [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] . The hallmark of these new materials is their modular design, which is far beyond the scope of other porous materials 22,[25][26][27][28][29][30][31][32][33][34][35][36] and allows for facile structure and property tuning.…”

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confidence: 99%

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Porous materials with pre-designed single-molecule traps for CO2 selective adsorption

et al. 2013

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Despite tremendous efforts, precise control in the synthesis of porous materials with pre-designed pore properties for desired applications remains challenging. Newly emerged porous metal-organic materials, such as metal-organic polyhedra and metal-organic frameworks, are amenable to design and property tuning, enabling precise control of functionality by accurate design of structures at the molecular level. Here we propose and validate, both experimentally and computationally, a precisely designed cavity, termed a 'single-molecule trap', with the desired size and properties suitable for trapping target CO 2 molecules. Such a single-molecule trap can strengthen CO 2 -host interactions without evoking chemical bonding, thus showing potential for CO 2 capture. Molecular single-molecule traps in the form of metal-organic polyhedra are designed, synthesised and tested for selective adsorption of CO 2 over N 2 and CH 4 , demonstrating the trapping effect. Building these pre-designed singlemolecule traps into extended frameworks yields metal-organic frameworks with efficient mass transfer, whereas the CO 2 selective adsorption nature of single-molecule traps is preserved.

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confidence: 99%

Porous materials with pre-designed single-molecule traps for CO2 selective adsorption

et al. 2013

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“…However, the crystal density drops dramatically when large organic spacers are employed. Thus, although NU-100 has ultrahigh porosity, it shows a total volumetric H 2 uptake of only 45.7 g L −1 at 70 bar, 77 K, 32,33 lower than the shorter-linked analogues NOTT-115 (49.3 g L −1 , 60 bar, 77 K) 25 and medium-sized NOTT-112 (55.9 g L −1 at 77 bar, 77 K) 24 (Table 2). shorter hexacarboxylate linkers and thus the cuboctahedral cages are more closely-packed in the latter four frameworks, leading to higher H 2 uptakes (all exceeding 2.2 wt%) at 1 bar.…”

Section: Hexacarboxylate Frameworkmentioning

confidence: 98%

Studies on Metal–Organic Frameworks of Cu(II) with Isophthalate Linkers for Hydrogen Storage

et al. 2013

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A note on versions:The version presented here may differ from the published version or from the version of record. If you wish to cite this item you are advised to consult the publisher's version. Please see the repository url above for details on accessing the published version and note that access may require a subscription.For more information, please contact eprints@nottingham.ac.uk ConspectusHydrogen (H 2 ) is a promising alternative energy carrier due to its environmental benefits, high energy density and its abundance. However, development of a practical storage system to enable the "Hydrogen Economy" remains a huge challenge. Metal-organic frameworks (MOFs) are an important class of crystalline coordination polymers constructed by bridging metal centers with organic linkers, and show promise for H 2 storage due to their high surface area and tuneable properties. We summarize our research on novel porous materials with enhanced H 2 storage properties, and describe frameworks derived from 3,5-substituted dicarboxylates (isophthalates) that serve as versatile molecular building blocks for the construction of a range of interesting coordination polymers with Cu(II) ions.A series of materials has been synthesised by connecting linear tetracarboxylate linkers to {Cu(II) 2 } paddlewheel moieties. These (4,4)-connected frameworks adopt the fof-topology in which the Kagomé lattice layers formed by {Cu(II) 2 } paddlewheels and isophthalates are pillared by the bridging ligands. These materials exhibit high structural stability and permanent porosity, and the pore size, geometry and functionality can be modulated by variation of the organic linker to control the overall H 2 adsorption properties. NOTT-103 shows the highest H 2 storage capacity of 77.8 mg g −1 at 77 K, 60 bar among the fof-type frameworks. H 2 adsorption at low, medium and high pressures correlates with the isosteric heat of adsorption, surface area and pore volume, respectively.Tri-branched C 3 -symmetric hexacarboxylate ligands with Cu(II) give highly porous (3,24)-connected frameworks incorporating {Cu(II) 2 } paddlewheels. These ubt-type frameworks comprise three types of polyhedral cage: a cuboctahedron, truncated tetrahedron and a truncated octahedron which are fused in the solid state in the ratio 1:2:1, respectively. Increasing the length of the hexacarboxylate struts directly tunes the porosity of the resultant material from micro-to mesoporosity. These materials show exceptionally high H 2 uptakes owing to their high surface area and pore volume. NOTT-112, the first reported member of this family reported, adsorbs 111 mg g −1 of H 2 at 77 K , 77 bar. More recently, enhanced H 2 adsorption in these ubt-type frameworks has been achieved using combinations of polyphenyl groups linked by alkynes to give an overall gravimetric gas capacity for NU-100 of 164 mg g −1 at 77 K, 70 bar. However, due to its very low density NU-100 shows a lower volumetric capacity of 45.7 g L -1 compared with 55.9 g L -1 for NOTT-112, which adsorbs 2.3 wt% H 2 at 1 ...

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“…Thus, novel and unique crystalline MOF structures have been vigorously pursued in the past decade, leading to widespread efforts by increasing the level of structural complexity to attain more fascinating architectures, such as cage‐in‐cage,11, 12 polyhedron,13, 14 high nuclearity,15, 16 and etc 17, 18. Among them, a rather straightforward way of systematically increasing the structural complexity, that is, to fabricate MOFs in a multiwalled organization has however been less explored.…”

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confidence: 99%

The First Example of Hetero‐Triple‐Walled Metal–Organic Frameworks with High Chemical Stability Constructed via Flexible Integration of Mixed Molecular Building Blocks

Tian

Xie

et al. 2015

Advanced Science

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An unprecedented 3D hetero‐triple‐walled metal‐organic framework is obtained by straightforward elaboration of the mixed molecular building block (MBB) strategy. In this approach, multiple individual flexible and rigid MBBs are integrated into one composite building block as separate layers, which are of the same shape but different sizes. This MOF shows exceptional water stability and the application of Li‐ion battery electrodes.

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De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities

Cited by 1,616 publications

References 36 publications

Porous materials with pre-designed single-molecule traps for CO2 selective adsorption

Porous materials with pre-designed single-molecule traps for CO2 selective adsorption

Studies on Metal–Organic Frameworks of Cu(II) with Isophthalate Linkers for Hydrogen Storage

The First Example of Hetero‐Triple‐Walled Metal–Organic Frameworks with High Chemical Stability Constructed via Flexible Integration of Mixed Molecular Building Blocks

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