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The triphasic interaction of gases with electrode surfaces immersed in aqueous electrolyte is crucial in electrochemical technologies (fuel cells, batteries, sensors). Some microporous materials modify this interaction locally via triphasic storage capacity for gases in aqueous environments linked to changes in apparent oxygen concentration and diffusivity (as well as activity and reactivity). Here, a nanoparticulate polymer of intrinsic microporosity (PIM-1) in aqueous electrolyte is shown to store oxygen gas and thereby enhance electrochemical signals for oxygen reduction in aqueous media. Oxygen reduction current transient data at platinum disk electrodes suggest that the reactivity of ambient oxygen in aqueous electrolyte (typically D oxygen = 2.8 × 10 -9 m 2 s -1 ; c oxygen = 0.3 mM) is substantially modified (to approximately D app,oxygen = 1.6 (±0.3) × 10 -12 m 2 s -1 ; c app,oxygen = 50 (±5) mM) with important implications for triphasic electrode processes. The considerable apparent concentration of oxygen even for ambient oxygen levels is important. Potential applications in oxygen sensing, oxygen storage, oxygen catalysis, or applications associated with other types of gases are discussed.

Graphitic carbon nitride (g-C 3 N 4 ) is known to photogenerate hydrogen peroxide in the presence of hole quenchers in aqueous environments. Here, the g-C 3 N 4 photocatalyst is embedded into a host polymer of intrinsic microporosity (PIM-1) to provide recoverable heterogenized photocatalysts without loss of activity. Different types of g-C 3 N 4 (including Pt@g-C 3 N 4 , Pd@g-C 3 N 4 , and Au@g-C 3 N 4 ) and different quenchers are investigated. Exploratory experiments yield data that suggest binding of the quencher either (i) directly by adsorption onto the g-C 3 N 4 (as shown for α-glucose) or (ii) indirectly by absorption into the microporous polymer host environment (as shown for Triton X-100) enhances the overall photochemical H 2 O 2 production process. The amphiphilic molecule Triton X-100 is shown to interact only weakly with g-C 3 N 4 but strongly with PIM-1, resulting in accumulation and enhanced H 2 O 2 production due to the microporous polymer host.

A detailed analysis of the basic transport parameters of two triptycene-based polymers of intrinsic microporosity (PIMs), the ultrapermeable PIM-TMN-Trip and the more selective PIM-BTrip, as a function of temperature from 25 to 55 °C, is reported. For both PIMs, high permeability is based on very high diffusion and solubility coefficients. The contribution of these two factors on the overall permeability is affected by the temperature and depends on the penetrant dimensions. Energetic parameters of permeability, diffusivity, and solubility are calculated using Arrhenius-van't Hoff equations and compared with those of the archetypal PIM-1 and the ultrapermeable, but poorly selective poly(trimethylsilylpropyne). This considers, for the first time, the role of entropic and energetic selectivities in the diffusion process through highly rigid PIMs. This analysis demonstrates that how energetic selectivity dominates the gas-transport properties of the highly rigid triptycene PIMs and enhances the strong size-sieving character of these ultrapermeable polymers.

A thin film of Nafion, of approximately 5 μm thickness, asymmetrically deposited onto a 6 μm thick film of poly(ethylene terephthalate) (PET) fabricated with a 5, 10, 20, or 40 μm microhole, is shown to exhibit prominent ionic diode behavior involving cation charge carrier ("cationic diode"). The phenomenon is characterized via voltammetric, chronoamperometric, and impedance methods. Phenomenologically, current rectification effects are comparable to those observed in nanocone devices where space-charge layer effects dominate. However, for microhole diodes a resistive, a limiting, and an overlimiting potential domain can be identified and concentration polarization in solution is shown to dominate in the closed state.

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.

A molecularly rigid polyamine based on a polymer of intrinsic microporosity (PIM-EA-TB) is shown to capture and stabilize platinum nanoparticles during colloid synthesis in the rigid framework. Stabilization here refers to avoiding aggregation without loss of surface reactivity. In the resulting rigid framework with embedded platinum nanoparticles, the volume ratio of platinum to PIM-EA-TB in starting materials is varied systematically from approximately 1.0 to 0.1 with the resulting platinum nanoparticle diameter varying from approximately 4.2 to 3.1 nm, respectively. Elemental analysis suggests that only a fraction of the polymer is "captured" to give nanocomposites rich in platinum. A transition occurs from electrically conducting and electrochemically active (with shorter average interparticle distance) to nonconducting and only partially electrochemically active (with longer average interparticle distance) polymer-platinum composites. The conducting nanoparticle network in the porous rigid macromolecular framework could be beneficial in electrocatalysis and in sensing applications.

Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer-Emmet-Teller (BET) surface area of 1027 m(2)g(-1)), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m(2)g(-1), but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg(-1) (when oxidized) to ca. 147 Fg(-1) (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1-2 μm thick film.

A novel polymer of intrinsic microporosity (PIM) was prepared from a diaminobenzotriptycene monomer using a polymerization reaction based on Tröger's base formation. The polymer (PIM-BTrip-TB) demonstrated an apparent Brunauer, Emmet, and Teller (BET) surface area of 870 m 2 g -1 , good solubility in chloroform, excellent molecular mass, high inherent viscosity and provided robust thin films for gas permeability measurements. The polymer is highly permeable (e.g., P H 2 = 9980; P O 2 = 3290 Barrer) with moderate selectivity (e.g., P H 2 / P N 2 = 11.0; P O 2 / P N 2 = 3.6) so that its data lie over the 2008 Robeson upper bounds for the H 2 /N 2 , O 2 /N 2 , and H 2 /CH 4 gas pairs and on the upper bound for CO 2 /CH 4 . On aging, the polymer demonstrates a drop in permeability, which is typical for ultrapermeable polymers, but with a significant increase in gas selectivities (e.g., P O 2 = 1170 Barrer; P O 2 / P N 2 = 5.4).

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.

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.

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.

The adsorption/desorption of N2 at 77 K and the adsorption from aqueous solution at 298 K of four organic probe molecules of different sizes (phenol, 4-nitrophenol, orange II, naphthol green B) were studied for a phthalocyanine network polymer of intrinsic microporosity (PIM) and for an activated carbon (Darco 20-40 mesh). N2 sorption analysis gave similar surface areas for the PIM and the carbon (610 and 545 m2 g(-1), respectively) but showed differences in pore size distribution, the PIM being essentially microporous (pore size < 2 nm), with a high proportion of ultramicropores (<0.7 nm), while the carbon had a broader pore size distribution, extending into the mesopore region. The carbon acted as an adsorbent for all the organic probe molecules studied, while the PIM was more selective, adsorbing the smaller molecules but rejecting the large dye naphthol green B. The PIM offers selectivity combined with a well-defined chemical structure incorporating catalytic sites.