Towards Polymer‐Based Hydrogen Storage Materials: Engineering Ultramicroporous Cavities within Polymers of Intrinsic Microporosity

McKeown, Neil B.; Gahnem, Bader; Msayib, Kadhum J.; Budd, Peter M.; Tattershall, Carin E.; Mahmood, Khalid; Tan, Siren; Book, D. L.; Langmi, Henrietta W.; Walton, Allan

doi:10.1002/anie.200504241

Cited by 428 publications

(293 citation statements)

References 33 publications

Supporting

Mentioning

285

Contrasting

Unclassified

Order By: Relevance

“…16 Recently, Budd and coworkers described a novel class of high free volume polymeric microporous materials termed "polymers of intrinsic microporosity" (PIM) whose rigid and randomly contorted structures decrease chain packing efficiently in the solid state. Hence, these materials have gained considerable attention for use in heterogeneous catalysis, 3,17a membrane separations, 17b, 18 and hydrogen storage 4,[19][20][21] and as adsorbents for organic compounds. 3,22 The most commonly reported such material having high molecular weight, termed PIM-1, is prepared from commercially available 5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane (TTSBI) and 2,3,5,6-tetrafluoroterephthalonitrile (TFTPN) by an efficient double aromatic nucleophilic substitution (S N Ar) polycondensation.…”

Section: Introductionmentioning

confidence: 99%

Polymers of Intrinsic Microporosity Derived from Novel Disulfone-Based Monomers

et al. 2009

View full text Add to dashboard Cite

The synthesis of three novel disulfone-based monomers from readily available hexafluorobenzene and thiols for the preparation of homopolymers and copolymers of intrinsic microporosity (PIMs) is described. The disulfonyl-based PIMs derived from 5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane (TTSBI) with tetrafluoroterephthalonitrile (TFTPN) and disulfone-based monomers were prepared at high temperature (160°C) within 1 h. Three new copolymers (monomer molar ratio of TTSBI and disulfonebased monomers=3:1) show a good combination of properties, such as excellent film-forming characteristics and gas transport properties. Compared with a previously reported microporous nitrile-based homopolymer, referred to as PIM-1, the present sulfone-based copolymers have higher gas selectivities for O 2 /N 2 and CO 2 / N 2 , while showing some reduction in pure-gas permeabilities. The relationship between the structure and gas permeation behavior of the copolymers is discussed.

show abstract

Section: Introductionmentioning

confidence: 99%

Polymers of Intrinsic Microporosity Derived from Novel Disulfone-Based Monomers

et al. 2009

View full text Add to dashboard Cite

show abstract

“…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.…”

mentioning

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

View full text Add to dashboard Cite

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.

show abstract

“…[23] PIMs owe their microporosity (following the definition by the Internation Union of Pure and Applied Chemistry (IUPAC), [24] i.e., pores of dimensions < 2 nm) and high gas permeability to rigid and contorted macromolecular structures that cannot pack space efficiently. [25][26][27][28][29][30] The rigidity is enforced by a fused ring structure and the sites of contortion are provided by spirocentres (i.e., a tetrahedral carbon shared by two rings). For PIM-1 and PIM-7 the spiro-center was introduced by the use of the commercially available 5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethyl-1,1 0 -spirobisindane 1 as monomer.…”

mentioning

confidence: 99%