Intrinsically Microporous Polymer Nanosheets for High-Performance Gas Separation Membranes.

Microporous polymer nanosheets with thicknesses in the range 3-5 nm and with high apparent surface area (Brunauer-Emmett-Teller surface area 940 m2 g-1 ) are formed when the effectively bifunctional (tetrafluoro) monomer used in the preparation of the prototypical polymer of intrinsic microporosity PIM-1 is replaced with an effectively tetrafunctional (octafluoro) monomer to give a tightly crosslinked network structure. When employed as a filler in mixed-matrix membranes based on PIM-1, a low loading of 0.5 wt% network-PIM-1 nanosheets gives rise to enhanced CO2 permeability and CO2 /CH4 selectivity, compared to pure PIM-1.

The fabrication of ultrathin films and their gas separation performance from polymers of intrinsic microporosity with two-dimensional (2D) and three-dimensional (3D) chain conformations.

The expansion of the use of polymeric membranes in gas separation requires the development of membranes based on new polymers with improved properties and their assessment under real operating conditions. In particular, the fabrication of ultrathin films of high performance polymers that can be used as the selective layer in composite membranes will allow large reductions in the amount of the expensive polymer used and, hence, the cost of membrane fabrication. In this contribution, two polymers of intrinsic microporosity (PIMs) with very different chain configurations (two-dimensional, 2D, chains or conventional contorted three-dimensional, 3D, conformation) have been compared in their ability to form ultrathin films, showing the relevance of polymer design to obtain compact and defect-free films. Monolayers of the 2D polymer PIM-TMN-Trip can be efficiently deposited onto poly[1-(trimethylsilyl)-1-propyne] (PTMSP) to obtain composite membranes with a CO2/N2 selectivity similar to that of the corresponding thick membranes of the same PIM using only a small fraction of the selective polymer (less than 0.1%).

Toward an Understanding of the Microstructure and Interfacial Properties of PIMs/ZIF-8 Mixed Matrix Membranes.

A study integrating advanced experimental and modeling tools was undertaken to characterize the microstructural and interfacial properties of mixed matrix membranes (MMMs) composed of the zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) and two polymers of intrinsic microporosity (PIM-1 and PIM-EA-TB). Analysis probed both the initial ZIF-8/PIM-1 colloidal suspensions and the final hybrid membranes. By combination of dynamic light scattering (DLS) and transmission electron microscopy (TEM) analytical and imaging techniques with small-angle X-ray scattering (SAXS), the colloidal suspensions were shown to consist mainly of two distinct kinds of particles, namely, polymer aggregates of about 200 nm in diameter and densely packed ZIF-8-NP aggregates of a few 100 nm in diameter with a 3 nm thick polymer top-layer. Such aggregates are likely to impart the granular texture of ZIF-8/PIMs MMMs as shown by SEM-XEDS analysis. At the molecular scale, modeling studies showed that the surface coverage of ZIF-8 NPs by both polymers appears not to be optimal with the presence of microvoids at the interfaces that indicates only a moderate compatibility between the polymer and ZIF-8. This study shows that the microstructure of MMMs results from a complex interplay between the ZIF-8/PIM compatibility, solvent, surface chemistry of the ZIF-8 NPs, and the physicochemical properties of the polymers such as molecular structure and rigidity.

The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing.

Efficient reactions between fluorine-functionalised biphenyl and terphenyl derivatives with catechol-functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the size and substituent bulk of the terminal groups, a number of soluble compounds with apparent BET surface areas in excess of 600 m(2) g(-1) are produced. The efficiency of OMIM structural units for generating microporosity is in the order: propellane>triptycene>hexaphenylbenzene>spirobifluorene>naphthyl=phenyl. The introduction of bulky hydrocarbon substituents significantly enhances microporosity by further reducing packing efficiency. These results are consistent with findings from previously reported packing simulation studies. The introduction of methyl groups at the bridgehead position of triptycene units reduces intrinsic microporosity. This is presumably due to their internal position within the OMIM structure so that they occupy space, but unlike peripheral substituents they do not contribute to the generation of free volume by inefficient packing.

Triptycene-based Organic Molecules of Intrinsic Microporosity.

Four Organic Molecules of Intrinsic Microporosity (OMIMs) were prepared by fusing triptycene-based components to a biphenyl core. Due to their rigid molecular structures that cannot pack space efficiently, these OMIMs form amorphous materials with significant microporosity as demonstrated by apparent BET surface areas in the range of 515-702 m(2) g(-1). Bulky cyclic 1',2',3',4'-tetrahydro-1',1',4',4'-tetramethylbenzo units placed on the triptycene termini are especially efficient at enhancing microporosity.

Characterizing the structure of organic molecules of intrinsic microporosity by molecular simulations and X-ray scattering.

The design of a new class of materials, called organic molecules of intrinsic microporosity (OMIMs), incorporates awkward, concave shapes to prevent efficient packing of molecules, resulting in microporosity. This work presents predictive molecular simulations and experimental wide-angle X-ray scattering (WAXS) for a series of biphenyl-core OMIMs with varying end-group geometries. Development of the utilized simulation protocol was based on comparison of several simulation methods to WAXS patterns. In addition, examination of the simulated structures has facilitated the assignment of WAXS features to specific intra- and intermolecular distances, making this a useful tool for characterizing the packing behavior of this class of materials. Analysis of the simulations suggested that OMIMs had greater microporosity when the molecules were the most shape-persistent, which required rigid structures and bulky end groups. The simulation protocol presented here allows for predictive, presynthesis screening of OMIMs and similar complex molecules to enhance understanding of their structures and aid in future design efforts.

Laser chemosensor with rapid responsivity and inherent memory based on a polymer of intrinsic microporosity.

This work explores the use of a polymer of intrinsic microporosity (PIM-1) as the active layer within a laser sensor to detect nitroaromatic-based explosive vapors. We show successful detection of dinitrobenzene (DNB) by monitoring the real-time photoluminescence. We also show that PIM-1 has an inherent memory, so that it accumulates the analyte during exposure. In addition, the optical gain and refractive index of the polymer were studied by amplified spontaneous emission and variable-angle ellipsometry, respectively. A second-order distributed feedback PIM-1 laser sensor was fabricated and found to show an increase in laser threshold of 2.5 times and a reduction of the laser slope efficiency by 4.4 times after a 5-min exposure to the DNB vapor. For pumping at 2 times threshold, the lasing action was stopped within 30 s indicating that PIM-1 has a very fast responsivity and as such has a potential sensing ability for ultra-low-concentration explosives.

Nitrogen and hydrogen adsorption by an organic microporous crystal.

Quick on the uptake: Following its identification during a targeted search, the intriguing crystal structure of 3,3',4,4'-tetra(trimethylsilylethynyl)biphenyl was investigated. Simple removal of the included solvent provides an organic crystal with an open microporous structure that has a striking similarity to that of zeolite A (see picture). Reversible adsorption of nitrogen and hydrogen gases at 77 K confirms that the microporosity is permanent.

Novel spirobisindanes for use as precursors to polymers of intrinsic microporosity.

The synthesis of novel spirobisindane-based monomers for the preparation of polymers of intrinsic microporosity (PIMs) with bulky, rigid substituents is described. Polymers derived from monomers containing spiro-linked fluorene substituents display enhanced solubility and microporosity due to additional frustration of packing in the solid state.

A triptycene-based polymer of intrinsic microposity that displays enhanced surface area and hydrogen adsorption.

A novel triptycene-based polymer of intrinsic microporosity (Trip-PIM) displays enhanced surface area (1065 m2 g(-1)) and reversibly adsorbs 1.65% hydrogen by mass at 1 bar/77 K and 2.71% at 10 bar/77 K.

Polymers of intrinsic microporosity (PIMs): bridging the void between microporous and polymeric materials.

Novel types of microporous material are required for chemoselective adsorptions, separations and heterogeneous catalysis. This concept article describes recent research directed towards the synthesis of polymeric materials that possess microporosity that is intrinsic to their molecular structures. These polymers (PIMs) can exhibit analogous behaviour to that of conventional microporous materials, but, in addition, may be processed into convenient forms for use as membranes. The excellent performance of these membranes for gas separation and pervaporation illustrates the unique character of PIMs and suggests immediate technological applications.

Polymers of intrinsic microporosity (PIMs): robust, solution-processable, organic nanoporous materials.

Microporous materials can be derived directly from soluble polymers whose randomly contorted shapes prevent an efficient packing of the macromolecules in the solid state.