Large-scale screening of hypothetical metal–organic frameworks

Wilmer, Christopher E.; Leaf, Michael; Lee, Chang Yeon; Farha, Omar K.; Hauser, Bernard A.; Hupp, Joseph T.; Snurr, Randall Q.

doi:10.1038/nchem.1192

Cited by 1,176 publications

(1,454 citation statements)

References 51 publications

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“…CH 4 and CH 4 -framework interactions. 21 This is supported by the calculations which showed that with the loading augmentation, an additional increase of ~2 kJ mol -1 to the average adsorption strength is observed, apparently due to favorable CH 4 …. CH 4 interactions.…”

Section: Resultsmentioning

confidence: 56%

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage

Spanopoulos¹,

Tsangarakis²,

Klontzas³

et al. 2016

J. Am. Chem. Soc.

195

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Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH 4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH 4 uptake among the tbo family, comparable to the best performing MOFs for CH 4 storage. The corresponding gravimetric (BET) and volumetric surface area of 3971 m 2 g -1 and 2363 m 2 cm -3 represent an increase of respectively 115 % and 47 % in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and 42 % and 20 % higher than tbo-MOF-2. High pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH 4 uptakes, reaching 372 cm 3 (STP) g -1 and 221 cm 3 (STP) cm -3 respectively at 85 bar and 298 K. The corresponding working capacities between 5-80 bar were found to be 294 cm 3 (STP) g -1 and 175 cm 3 (STP) cm -3 and are placed among the best performing MOFs for CH 4 storage particularly at relatively low temperature. To gain insight on the mechanism accounting for the resultant enhanced CH 4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH 4 adsorption sites near the organic linker with similar adsorption energetics as the open metal sites. The present findings supports the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH 4 storage capacity via expansion and functionalization of the quadrangular pillars. INTRODUCTIONThe utilization of fossil fuels in the energy production and the mobile transportation sector results in the emission of massive amounts of CO 2 in the atmosphere, instigating numerous health and environmental issues. 1 Thus, prompt deployment of environmental friendly fuels is of utmost importance. Natural gas, consisting of nearly 95% CH 4 , is a good candidate for replacing gasoline in mobile transportation and coal in stationary power plants, since it can sustain the same energy demand with amply lessened release of CO, CO 2 , NO x , SO 2 pollutants. 2 Nevertheless, the deployment of methane as a typical fuel in the automotive industry has been hindered by practicalities associated to cost-effective and efficient storage of methane at concrete temperatures and pressures. 3

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Section: Resultsmentioning

confidence: 56%

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage

Spanopoulos¹,

Tsangarakis²,

Klontzas³

et al. 2016

J. Am. Chem. Soc.

195

View full text Add to dashboard Cite

show abstract

“…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. This therefore enables precise control of functions by accurate design of structures at the molecular level.…”

mentioning

confidence: 99%

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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“…The first of said algorithms was published in 2012 along with a database of 138,000 hypothetically generated materials 51 . Here chemical building blocks were extracted from x-ray resolved experimental MOF structures based on a logical partition of the chemical units, such that each building block represented simple geometric shapes (squares, triangles, tetrahedra, octahedra, etc.).…”

Section: H1 Database Development and The Quest For Diversitymentioning

confidence: 99%

Computational development of the nanoporous materials genome

2017

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H1 Abstract.There is currently a large push towards big data and data mining in materials research to accelerate discovery. Zeolites, metal-organic frameworks (MOFs) and other related crystalline porous materials are not immune to this recent phenomenon, as evidenced by the proliferation of porous structure databases and computational gas adsorption screening studies over the past decade. The strive to identify the best materials for a variety of gas separation and storage applications has not only led to collections of thousands of synthesised structures, but the development of hypothetical material building algorithms.The materials databases assembled with these algorithms expand greatly on the range of complex pore structures that have been synthesised, with the rationale that we have discovered only a small fraction of realisable structures and expanding upon these will accelerate rational design. In this review, we highlight some of the methods developed to build these databases, and some of the important outcomes resulting from large-scale computational screening efforts. SummaryIn the field of nanoporous materials discovery, we are witnessing the emergence of big data analytics combined with traditional computational thermodynamics calculations. This review turns a critical eye on the current state of the art, with a focus on computational database generation and results from large-scale screening for gas separations. H1 Introduction.The discovery, in the late 19 th century, that zeolites could trap interesting and valuable particles in their pores opened up an entire field of research 1,2 . This seemingly simple phenomenon was an enormous boon to the oil and gas industry, seeing as how cheap, but effective porous materials could serve as a catalyst for hydrocarbon cracking. From their humble beginnings (being carved out of rock faces), zeolites, and their ability to selectively trap guests in their pores, have become integral in not only the oil and gas industry, but in detergents (as ion exchangers) and natural gas purification to name a few 1 .Zeolites have since enjoyed an almost exclusive dominance in porous materials research until the late 20 th century, when we began to observe the creation of more diverse materials in terms of chemistry, network connectivity, and physical properties.At present, there are a little over 200 known zeolite structures, which is only a small fraction of the total number of structures that have been predicted 3 . In addition, if we were also able to expand the chemical diversity of these materials beyond the conventional Si 4+ , O 2-, and Al 3+ ions found in zeolites, one could envision designing materials for virtually any gas separation application. Thus when the first articles arose in the 1990's characterising Metal-Organic Frameworks (MOFs) [4][5][6][7][8] , and later Covalent Organic Frameworks (COFs) 9,10 , Zeolitic Imidazolate Frameworks (ZIFs) 11 , and Porous Polymer Networks (PPNs) 12 the excitement was palpable. It was recognised early-on by Yaghi, O'Keeffe, ...

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Large-scale screening of hypothetical metal–organic frameworks

Cited by 1,176 publications

References 51 publications

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage

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

Computational development of the nanoporous materials genome

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Large-scale screening of hypothetical metal–organic frameworks

Cited by 1,176 publications

References 51 publications

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH4 Storage

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH4 Storage

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

Computational development of the nanoporous materials genome

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Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage

Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH₄ Storage