Precise molecular sieving of ethylene from ethane using triptycene-derived submicroporous carbon membranes.

Replacement or debottlenecking of the extremely energy-intensive cryogenic distillation technology for the separation of ethylene from ethane has been a long-standing challenge. Membrane technology could be a desirable alternative with potentially lower energy consumption. However, the current key obstacle for industrial implementation of membrane technology is the low mixed-gas selectivity of polymeric, inorganic or hybrid membrane materials, arising from the similar sizes of ethylene (3.75 Å) and ethane (3.85 Å). Here we report precise molecular sieving and plasticization-resistant carbon membranes made by pyrolysing a shape-persistent three-dimensional triptycene-based ladder polymer of intrinsic microporosity with unparalleled mixed-gas performance for ethylene/ethane separation, with a selectivity of ~100 at 10 bar feed pressure, and with long-term continuous stability for 30 days demonstrated. These submicroporous carbon membranes offer opportunities for membrane technology in a wide range of notoriously difficult separation applications in the petrochemical and natural gas industry.

Defect Engineering in Metal-Organic Frameworks Towards Advanced Mixed Matrix Membranes for Efficient Propylene/Propane Separation.

Highly permselective and durable membrane materials have been sought for energy-efficient C3 H6 /C3 H8 separation. Mixed-matrix membranes (MMMs) comprising a polymer matrix and metal-organic frameworks (MOFs) are promising candidates for this application; however, rational matching of filler-matrix is challenging and their separation performances need to be further improved. Here, we propose a novel strategy of "defect engineering" in MOFs as an additional degree of freedom to design advanced MMMs. MMMs incorporated with defect-engineered MOFs exhibit exceptionally high C3 H6 permeability and maintained C3 H6 /C3 H8 selectivity, especially with enhanced stability under industrial mixed-gas conditions. The gas transport, sorption, and material characterizations reveal that the defect sites in MOFs provide the resulting MMMs with not only ultrafast diffusion pathways but also favorable C3 H6 sorption by forming complexation with unsaturated open metal sites, confirmed by in situ FT-IR studies. Most importantly, the concept is also valid for different polymer matrices and gas pairs, demonstrating its versatile potential in other fields.

Finely Tuned Submicroporous Thin-Film Molecular Sieve Membranes for Highly Efficient Fluid Separations.

Polymeric membranes with increasingly high permselective performances are gaining a significant role in lowering the energy burden and improving the environmental sustainability of complex chemical separations. However, the commercial deployment of newly designed materials with promising intrinsic properties for fluid separations has been stalled by challenges associated with fabrication and scale up of low-cost, high-performance, defect-free thin-film composite (TFC) membranes. Here, a facile method to fabricate next-generation TFC membranes using a bridged-bicyclic triptycene tetra-acyl chloride (Trip) building block with a large fraction of finely tuned structural submicroporosity (pore size < 4 Å) is demonstrated. The TFCs exhibit superb potential for removal of small (≈200 g mol-1 ) organic microcontaminants from organic solvent streams by showing both improved rejection and permeance in organic systems compared to current state-of-the-art commercial membranes. The TFCs also display unprecedented properties for desalination applications with performance located far above the current water permeance/sodium chloride rejection trendline. The strategy of using highly contorted triptycene building blocks with well-defined interconnected internal free volume elements establishes a scalable, generalized approach to fabricate highly selective, submicroporous TFC membranes for a wide variety of challenging energy-intensive fluid separations.

Ultraselective glassy polymer membranes with unprecedented performance for energy-efficient sour gas separation.

Membrane-based separation of combined acid gases carbon dioxide and hydrogen sulfide from natural gas streams has attracted increasing academic and commercial interest. These feeds are referred to as "sour," and herein, we report an ultra H2S-selective and exceptionally permeable glassy amidoxime-functionalized polymer of intrinsic microporosity for membrane-based separation. A ternary feed mixture (with 20% H2S:20% CO2:60% CH4) was used to demonstrate that a glassy amidoxime-functionalized membrane provides unprecedented separation performance under challenging feed pressures up to 77 bar. These membranes show extraordinary H2S/CH4 selectivity up to 75 with ultrahigh H2S permeability >4000 Barrers, two to three orders of magnitude higher than commercially available glassy polymeric membranes. We demonstrate that the postsynthesis functionalization of hyper-rigid polymers with appropriate functional polar groups provides a unique design strategy for achieving ultraselective and highly permeable membrane materials for practical natural gas sweetening and additional challenging gas pair separations.

Synthesis and Gas-Permeation Characterization of a Novel High-Surface Area Polyamide Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene: Towards Polyamides of Intrinsic Microporosity (PIM-PAs).

A triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diamino-triptycene (TMDAT), was used for the synthesis of a novel solution-processable polyamide obtained via polycondensation reaction with 4,4'-(hexafluoroisopropylidene)bis(benzoic acid) (6FBBA). Molecular simulations confirmed that the tetrasubstitution with ortho-methyl groups in the triptycene building block reduced rotations around the C⁻N bond of the amide group leading to enhanced fractional free volume. Based on N2 sorption at 77 K, 6FBBA-TMDAT revealed microporosity with a Brunauer⁻Emmett⁻Teller (BET) surface area of 396 m² g-1; to date, this is the highest value reported for a linear polyamide. The aged 6FBBA-TMDAT sample showed moderate pure-gas permeabilities (e.g., 198 barrer for H2, ~109 for CO2, and ~25 for O2) and permselectivities (e.g., αH2/CH4 of ~50) that position this polyamide close to the 2008 H2/CH4 and H2/N2 upper bounds. CO2⁻CH4 mixed-gas permeability experiments at 35 °C demonstrated poor plasticization resistance; mixed-gas permselectivity negatively deviated from the pure-gas values likely, due to the enhancement of CH4 diffusion induced by mixing effects.

Experimental Mixed-Gas Permeability, Sorption and Diffusion of CO2-CH4 Mixtures in 6FDA-mPDA Polyimide Membrane: Unveiling the Effect of Competitive Sorption on Permeability Selectivity.

The nonideal behavior of polymeric membranes during separation of gas mixtures can be quantified via the solution-diffusion theory from experimental mixed-gas solubility and permeability coefficients. In this study, CO2-CH4 mixtures were sorbed at 35 °C in 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA)-m-phenylenediamine (mPDA)-a polyimide of remarkable performance. The existence of a linear trend for all data of mixed-gas CO2 versus CH4 solubility coefficients-regardless of mixture concentration-was observed for 6FDA-mPDA and other polymeric films; the slope of this trend was identified as the ratio of gas solubilities at infinite dilution. The CO2/CH4 mixed-gas solubility selectivity of 6FDA-mPDA and previously reported polymers was higher than the equimolar pure-gas value and increased with pressure from the infinite dilution value. The analysis of CO2-CH4 mixed-gas concentration-averaged effective diffusion coefficients of equimolar feeds showed that CO2 diffusivity was not affected by CH4. Our data indicate that the decrease of CO2/CH4 mixed-gas diffusion, and permeability selectivity from the pure-gas values, resulted from an increase in the methane diffusion coefficient in mixtures. This effect was the result of an alteration of the size sieving properties of 6FDA-mPDA as a consequence of CO2 presence in the 6FDA-mPDA film matrix.

High-Pressure CO2 Sorption in Polymers of Intrinsic Microporosity under Ultrathin Film Confinement.

Ultrathin microporous polymer films are pertinent to the development and further spread of nanotechnology with very promising potential applications in molecular separations, sensors, catalysis, or batteries. Here, we report high-pressure CO2 sorption in ultrathin films of several chemically different polymers of intrinsic microporosity (PIMs), including the prototypical PIM-1. Films with thicknesses down to 7 nm were studied using interference-enhanced in situ spectroscopic ellipsometry. It was found that all PIMs swell much more than non-microporous polystyrene and other high-performance glassy polymers reported previously. Furthermore, chemical modifications of the parent PIM-1 strongly affected the swelling magnitude. By investigating the behavior of relative refractive index, nrel, it was possible to study the interplay between micropores filling and matrix expansion. Remarkably, all studied PIMs showed a maximum in nrel at swelling of 2-2.5% indicating a threshold point above which the dissolution in the dense matrix started to dominate over sorption in the micropores. At pressures above 25 bar, all PIMs significantly plasticized in compressed CO2 and for the ones with the highest affinity to the penetrant, a liquidlike mixing typical for rubbery polymers was observed. Reduction of film thickness below 100 nm revealed pronounced nanoconfinement effects and resulted in a large swelling enhancement and a quick loss of the ultrarigid character. On the basis of the partial molar volumes of the dissolved CO2, the effective reduction of the Tg was estimated to be ∼200 °C going from 128 to 7 nm films.

Synthesis of Highly Gas-Permeable Polyimides of Intrinsic Microporosity Derived from 1,3,6,8-Tetramethyl-2,7-diaminotriptycene.

A simple synthetic route to a novel sterically hindered triptycene-based diamine, 1,3,6,8-tetramethyl-2,7-diaminotriptycene (TMDAT), and its use in the preparation of high molecular weight polyimides of intrinsic microporosity (PIM-PIs) are reported. The organosoluble TMDAT-derived polyimides displayed high Brunauer-Emmett-Teller surface areas ranging between 610 and 850 m2 g-1 and demonstrated excellent thermal stability of up to 510 °C. Introduction of the rigid three-dimensional paddlewheel triptycene framework and the tetramethyl-induced restriction of the imide bond rotation resulted in highly permeable polyimides with moderate gas-pair selectivity. The best performing polyimide made from TMDAT and a triptycene-based dianhydride showed gas transport properties located between the 2008 and 2015 polymer permeability/selectivity trade-off curves with H2 and O2 permeabilities of 2858 and 575 barrer combined with H2/N2 and O2/N2 selectivities of 24 and 4.8, respectively, after 200 days of physical aging.

Mixed-Penetrant Sorption in Ultrathin Films of Polymer of Intrinsic Microporosity PIM-1.

Mixed-penetrant sorption into ultrathin films of a superglassy polymer of intrinsic microporosity (PIM-1) was studied for the first time by using interference-enhanced in situ spectroscopic ellipsometry. PIM-1 swelling and the concurrent changes in its refractive index were determined in ultrathin (12-14 nm) films exposed to pure and mixed penetrants. The penetrants included water, n-hexane, and ethanol and were chosen on the basis of their significantly different penetrant-penetrant and penetrant-polymer affinities. This allowed studying microporous polymer responses at diverse ternary compositions and revealed effects such as competition for the sorption sites (for water/n-hexane or ethanol/n-hexane) or enhancement in sorption of typically weakly sorbing water in the presence of more highly sorbing ethanol. The results reveal details of the mutual sorption effects which often complicate comprehension of glassy polymers' behavior in applications such as high-performance membranes, adsorbents, or catalysts. Mixed-penetrant effects are typically very challenging to study directly, and their understanding is necessary owing to a broadly recognized inadequacy of simple extrapolations from measurements in a pure component environment.

Synthesis and Characterization of a Novel Microporous Dihydroxyl-Functionalized Triptycene-Diamine-Based Polyimide for Natural Gas Membrane Separation.

An intrinsically microporous polyimide is synthesized in m-cresol by a one-pot high-temperature condensation reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and newly designed 2,6 (7)-dihydroxy-3,7(6)-diaminotriptycene (DAT1-OH). The 6FDA-DAT1-OH polyimide is thermally stable up to 440 °C, shows excellent solubility in polar solvents, and has moderately high Brunauer-Teller-Emmett (BET) surface area of 160 m2 g-1 , as determined by nitrogen adsorption at -196 °C. Hydroxyl functionalization applied to the rigid 3D triptycene-based diamine building block results in a polyimide that exhibits moderate pure-gas CO2 permeability of 70 Barrer combined with high CO2 /CH4 selectivity of 50. Mixed-gas permeation studies demonstrate excellent plasticization resistance of 6FDA-DAT1-OH with impressive performance as potential membrane material for natural gas sweetening with a CO2 permeability of 50 Barrer and CO2 /CH4 selectivity of 40 at a typical natural gas well partial pressure of 10 atm.

How Do Organic Vapors Swell Ultrathin Films of Polymer of Intrinsic Microporosity PIM-1?

Dynamic sorption of ethanol and toluene vapor into ultrathin supported films of polymer of intrinsic microporosity PIM-1 down to a thickness of 6 nm are studied with a combination of in situ spectroscopic ellipsometry and in situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm, three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to that of thicker films. Second, at low penetrant activities (below 0.3p/p0), films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite a similar swelling magnitude. Third, for the ultrathin films, the onset of the dynamic penetrant-induced glass transition Pg has been found to shift to higher values, indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the superglassy PIM-1 at the substrate surface leads to an arrested, even more rigid, and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics, and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion, the surface seems to plasticize earlier than the bulk, and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.

How Much Do Ultrathin Polymers with Intrinsic Microporosity Swell in Liquids?

As synthetic membrane materials, polymers with intrinsic microporosity (PIMs) have demonstrated unprecedented permeation and molecular-separation properties. Here, we report the swelling characteristics of submicron-thick supported films of spirobisindane-based PIMs, PIM-1 and PIM-6FDA-OH, for six organic solvents and water using in situ spectroscopic ellipsometry. Surprisingly, PIMs swell significantly in most organic solvents, with swelling factors (SF = hswollen/hdry) as high as 2.5. This leads to the loss of the ultrarigid character of the polymer and produces equilibrated liquid-like swollen films. Filling of the excess frozen-in fractional free volume with liquid was discovered next to swelling-induced polymer matrix dilation. Water hardly swells the polymer matrix, but it penetrates into the intrinsic microporous structure. This study is the first to provide fundamental swelling data for PIMs, leading to better comprehension of their permeation properties. Such an understanding is indispensable for applications such as solvent filtration, natural-gas separation, and ion retention in flow batteries.

Synthesis and Effect of Physical Aging on Gas Transport Properties of a Microporous Polyimide Derived from a Novel Spirobifluorene-Based Dianhydride.

A novel generic method is reported for the synthesis of a spirobifluorene-based dianhydride (SBFDA). An intrinsically microporous polyimide was obtained by polycondensation reaction with 3,3'-dimethylnaphthidine (DMN). The corresponding polymer (SBFDA-DMN) exhibited good solubility, excellent thermal stability, as well as significant microporosity with high BET surface area of 686 m2/g. The O2 permeability of a methanol-treated and air-dried membrane was 1193 Barrer with a moderate O2/N2 selectivity of 3.2. The post-treatment history and aging conditions had great effects on the membrane performance. A significant drop in permeability coupled with an increase in selectivity was observed after long-term aging. After storage of 200 days, the gas separation properties of SBFDA-DMN were located slightly above the latest Robeson upper bounds for several gas pairs such as O2/N2 and H2/N2.

Fine-Tuned Intrinsically Ultramicroporous Polymers Redefine the Permeability/Selectivity Upper Bounds of Membrane-Based Air and Hydrogen Separations.

Intrinsically ultramicroporous (<7 Å) polymers represent a new paradigm in materials development for membrane-based gas separation. In particular, they demonstrate that uniting intrachain "rigidity", the traditional design metric of highly permeable polymers of intrinsic microporosity (PIMs), with gas-sieving ultramicroporosity yields high-performance gas separation membranes. Highly ultramicroporous PIMs have redefined the state-of-the-art in large-scale air (e.g., O2/N2) and hydrogen recovery (e.g., H2/N2, H2/CH4) applications with unprecedented molecular sieving gas transport properties. Accordingly, presented herein are new 2015 permeability/selectivity "upper bounds" for large-scale commercial membrane-based air and hydrogen applications that accommodate the substantial performance enhancements of recent PIMs over preceding polymers. A subtle balance between intrachain rigidity and interchain spacing has been achieved in the amorphous microstructures of PIMs, fine-tuned using unique bridged-bicyclic building blocks (i.e., triptycene, ethanoanthracene and Tröger's base) in both ladder and semiladder (e.g., polyimide) structures.

Energy-efficient hydrogen separation by AB-type ladder-polymer molecular sieves.

Increases in hydrogen selectivity of more than 100% compared with the most selective ladder polymer of intrinsic microporosity (PIM) reported to date are achieved with self-polymerized A-B-type ladder monomers comprising rigid and three-dimensional 9,10-dialkyl-substituted triptycene moieties. The selectivities match those of materials commercially employed in hydrogen separation, but the gas permeabilities are 150-fold higher. This new polymer molecular sieve is also the most selective PIM for air separation.

On the photophysicochemical properties of selected fluoroquinolones: solvatochromic and fluorescence spectroscopy study.

The photophysicochemical properties of selected fluoroquinolones in different solvents of various physical properties, including polarity and hydrogen bonding ability, were investigated using steady state fluorescence spectroscopy. The solvent-dependant fluorescence emission spectra of selected fluoroquinolones, namely ciprofloxacin (CIPR) and enrofloxacin (ENRO), were employed to gain insights concerning its photophysicochemical properties of interests. Interestingly, fluorescence spectra of the selected drugs exhibited structured emission spectra in nonpolar solvents such as hexane, whereas unstructured spectra were observed in more polar solvents such as alcohols and water. Also, a notable bathochromic shift in λ(max)(em) was observed in fluorescence spectra of both drugs with increasing solvent polarity that resulted in biphasic behavior upon applying the Lippert-Mataga correlation that correspond to general and specific solvent effects. Applying the Lippert-Mataga correlation to the fluorescence spectra of CIPR and ENRO in various solvents was employed to estimate the dipole moment difference between the ground and excited states of them, Δµ(µ(e) - µ(g)), where obtained results revealed the values of 9.4 and 16.2 Debye for the LE and ICT states of ENRO, respectively, and 8.0 and 16.2 Debye for the LE and ICT states of CIPR, respectively. Multiple linear regression analysis (MLRA) based on Kamlet-Taft equating was applied against absorption frequency (ν(abs)), emission frequency (ν(em)), Stokes shift (∆ν), and fluorescence quantum yield (Φ(f)), where obtained results revealed excellent correlation (R: 0.916-0.966) that are consistent with other results considering the effect of solvent polarizability, hydrogen bonding ability, and viscosity on the photophysicochemical properties of the studied fluoroquinolones.

High-performance membranes from polyimides with intrinsic microporosity.

Membranes with high permeability to gases are formed from polyimides with rigid backbones that incorporate a spiro-centre. A route to this new range of high-free-volume polyimides is demonstrated, and exceptional performance is obtained for a polymer containing a dimethyl binaphthyl unit.

The potential of organic polymer-based hydrogen storage materials.

The challenge of storing hydrogen at high volumetric and gravimetric density for automotive applications has prompted investigations into the potential of cryo-adsorption on the internal surface area of microporous organic polymers. A range of Polymers of Intrinsic Microporosity (PIMs) has been studied, the best PIM to date (a network-PIM incorporating a triptycene subunit) taking up 2.7% H(2) by mass at 10 bar/77 K. HyperCrosslinked Polymers (HCPs) also show promising performance as H(2) storage materials, particularly at pressures >10 bar. The N(2) and H(2) adsorption behaviour at 77 K of six PIMs and a HCP are compared. Surface areas based on Langmuir plots of H(2) adsorption at high pressure are shown to provide a useful guide to hydrogen capacity, but Langmuir plots based on low pressure data underestimate the potential H(2) uptake. The micropore distribution influences the form of the H(2) isotherm, a higher concentration of ultramicropores (pore size <0.7 nm) being associated with enhanced low pressure adsorption.

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.