Microporous Organic Polymers for Methane Storage

Wood, Colin D.; Tan, Bien; Trewin, Abbie; Su, Fabing; Rosseinsky, Matthew J.; Bradshaw, Darren; Sun, Yan; Zhou, Li; Cooper, Andrew I.

doi:10.1002/adma.200702397

Cited by 367 publications

(248 citation statements)

References 31 publications

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“…Hypercross-linked polymers represent a new class of porous materials that are prepared mainly by a Friedel-Crafts alkylation reaction [28][29][30] . The permanent porosity in hypercross-linked polymers is a result of extensive cross-linking reactions, which prevent the polymer chains from collapsing into a dense, non-porous state [31][32][33] .…”

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confidence: 99%

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates

et al. 2014

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High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energyand environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

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confidence: 99%

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates

et al. 2014

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“…Microporous organic polymers (MOPs), which are composed of light, non-metallic elements and have large specic surface area, narrow pore size distribution and high chemical and thermal stability, present a small energy penalty and cost for state-of-the-art gas uptake applications. Versatile microporous organic polymers such as covalent organic frameworks (COFs), 6 polymers of intrinsic microporosity (PIMs), 7,8 porous aromatic frameworks (PAFs), 9 hypercrosslinked polymers (HCPs), 10,11 crystalline triazine-based organic frameworks (CTFs), 12,13 and conjugated microporous polymers (CMPs), 14,15 have been shown to exhibit high gas storage and separation capacities.…”

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confidence: 99%

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Qiao

Yang

2014

J. Mater. Chem. A

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Two novel conjugated microporous networks, P-1 and P-2, with carbazole-spacer-carbazole topological model structures, were designed and prepared by FeCl 3 oxidative coupling polymerization. Monomer m-1 (fluorenone spacer) was modified with a thiophene Grignard to form the fluorenyl tertiary alcohol monomer m-2, and this step can increase the polymerization branches from four to five and incorporate the polar -OH group into the building block. N 2 adsorption isotherms show that, after modification, the Brunauer-Emmett-Teller (BET) surface area of P-2 (1222 m 2 g À1) is two times that of P-1 (611 m 2 gand the total pore volume increases 1.63 times from 0.95 to 1.55 at P/P 0 ¼ 0.99. However, the domain pore size (centred at 1.19 nm) and the pore distribution of both networks are not changed. It demonstrates that the domain pore width may be determined by the size of the rigid carbazole-spacercarbazole backbone, not the degree of crosslinking when the networks were prepared under same polymerization conditions in this system. Hydrogen physisorption isotherms of P-1 and P-2 show that the H 2 storage can be up to 1.05 wt% and 1.66 wt% at 77 K and 1.1 bar, and the isosteric heat is 9.89 kJ mol À1 and 10.86 kJ mol À1 , respectively. At 273 K and 1.1 bar, the CO 2 uptake capacity of P-2 can be up to 14.5 wt% which is 1.63 times that of P-1 under the same conditions. The H 2 and CO 2 uptake capacities of P-2 are among the highest reported for conjugated microporous networks under similar conditions. The CO 2 /CH 4 and CO 2 /N 2 selectivity results indicate that P-1 exhibits a slightly higher separation ability than P-2. There is often a trade-off between absolute uptake and selectivity in other microporous organic polymers. Fine design and tailoring the topological structure of the monomer can change the adsorption isosteric enthalpy and optimize the gas uptake performance. The obtained networks with the carbazole-spacer-carbazole rigid backbone show promise for potential use in clean energy applications and the environmental field.

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“…N 2 sorption isotherms for PRP 1-5 and PCoP were collected and are shown in could potentially indicate the presence of a mixed microporous/mesoporous pore system or alternatively can be attributed to gas condensation within the voids between sub micrometer agglomerates. 37 This behavior could be ascribed to structural defects resulting from less than complete crosscoupling of the six-connected nodes through the linear ditopic alkyne linker. In compound PRP-3, the 3,4-dibromothiophene molecule was added to the reaction mixture to introduce the thiophene ring as a ditopic linker.…”

Section: Resultsmentioning

confidence: 99%

“…The observed N 2 sorption isotherm for PRP-3,4 can be classified as type IVlike character demonstrating H2-type hysteresis. 37 This behavior is common among porous organic polymers and can be associated with swelling of the polymers rather than taken to indicate presence of mesoporosity inside the material. 37 In PRP-5, the heteroleptic Ru(NCS) 2 (bpy) 2 coordination cluster was utilized for its known photoactivity, 38 and resulted in a microporous polymer with fully reversible, type-I N 2 sorption isotherm (BET surface area of 349 m 2 /g).…”

Section: Resultsmentioning

confidence: 99%

“…37 This behavior is common among porous organic polymers and can be associated with swelling of the polymers rather than taken to indicate presence of mesoporosity inside the material. 37 In PRP-5, the heteroleptic Ru(NCS) 2 (bpy) 2 coordination cluster was utilized for its known photoactivity, 38 and resulted in a microporous polymer with fully reversible, type-I N 2 sorption isotherm (BET surface area of 349 m 2 /g). The pore size distribution in PRP-5 is remarkable as it indicates uniform and narrow distribution at ranges of 5, 10 and 15 Å (SI).The reduced apparent surface area of PRP-5 relative to the rest of the reported compounds here can be attributed to the reduced number of extension points (four brominated aromatic carbons as compared to six in the earlier examples) from which polymer growth and inter-chain linkage commenced.…”

Section: Resultsmentioning

confidence: 99%

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Porous–Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

Haikal

Wang

Hassan

et al. 2016

ACS Appl. Mater. Interfaces

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Abstract.A number of permanently porous polymers containing Ru(bpy) n photosensitizer or a cobaloxime complex, as a protonreduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multi-topic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity towards hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited state lifetime of the covalently-immobilized Ru(bpy) 3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy) n or the cobaloxime complexes.

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Microporous Organic Polymers for Methane Storage

Cited by 367 publications

References 31 publications

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates

Design and synthesis of novel carbazole–spacer–carbazole type conjugated microporous networks for gas storage and separation

Porous–Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

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