A Microporous Poly(Arylene Ether) Platform for Membrane-Based Gas Separation.

Membrane-based gas separations are crucial for an energy-efficient future. However, it is difficult to develop membrane materials that are high-performing, scalable, and processable. Microporous organic polymers (MOPs) combine benefits for gas sieving and solution processability. Herein, we report membrane performance for a new family of microporous poly(arylene ether)s (PAEs) synthesized via Pd-catalyzed C-O coupling reactions. The scaffold of these microporous polymers consists of rigid three-dimensional triptycene and stereocontorted spirobifluorene, endowing these polymers with micropore dimensions attractive for gas separations. This robust PAE synthesis method allows for the facile incorporation of functionalities and branched linkers for control of permeation and mechanical properties. A solution-processable branched polymer was formed into a submicron film and characterized for permeance and selectivity, revealing lab data that rivals property sets of commercially available membranes already optimized for much thinner configurations. Moreover, the branching motif endows these materials with outstanding plasticization resistance, and their microporous structure and stability enables benefits from competitive sorption, increasing CO2 /CH4 and (H2 S+CO2 )/CH4 selectivity in mixture tests as predicted by the dual-mode sorption model. The structural tunability, stability, and ease-of-processing suggest that this new platform of microporous polymers provides generalizable design strategies to form MOPs at scale for demanding gas separations in industry.

Rational Design of Bifunctional Microporous Organic Polymers Containing Anthracene and Triphenylamine Units for Energy Storage and Biological Applications.

In this study, we synthesized two conjugated microporous polymers (CMPs), An-Ph-TPA and An-Ph-Py CMPs, using the Suzuki cross-coupling reaction. These CMPs are organic polymers with p-conjugated skeletons and persistent micro-porosity and contain anthracene (An) moieties linked to triphenylamine (TPA) and pyrene (Py) units. We characterized the chemical structures, porosities, thermal stabilities, and morphologies of the newly synthesized An-CMPs using spectroscopic, microscopic, and N2 adsorption/desorption isotherm techniques. Our results from thermogravimetric analysis (TGA) showed that the An-Ph-TPA CMP displayed better thermal stability with Td10 = 467 °C and char yield of 57 wt% compared to the An-Ph-Py CMP with Td10 = 355 °C and char yield of 54 wt%. Furthermore, we evaluated the electrochemical performance of the An-linked CMPs and found that the An-Ph-TPA CMP had a higher capacitance of 116 F g-1 and better capacitance stability of 97% over 5000 cycles at 10 A g-1. In addition, we assessed the biocompatibility and cytotoxicity of An-linked CMPs using the MTT assay and a live/dead cell viability assay and observed that they were non-toxic and biocompatible with high cell viability values after 24 or 48 h of incubation. These findings suggest that the An-based CMPs synthesized in this study have potential applications in electrochemical testing and the biological field.

2,2'-Biphenol-based Ultrathin Microporous Nanofilms for Highly Efficient Molecular Sieving Separation.

Organic solvent nanofiltration (OSN) is an emerging membrane separation technology, which urgently requires robust, easily processed, OSN membranes possessing high permeance and small solutes-selectivity to facilitate enhanced industrial uptake. Herein, we describe the use of two 2,2'-biphenol (BIPOL) derivatives to fabricate hyper-crosslinked, microporous polymer nanofilms through IP. Ultra-thin, defect-free polyesteramide/polyester nanofilms (≈5 nm) could be obtained readily due to the relatively large molecular size and ionized nature of the BIPOL monomers retarding the rate of the IP. The enhanced microporosity arises from the hyper-crosslinked network structure and monomer rigidity. Specifically, the amino-BIPOL/PAN membrane exhibits extraordinary permselectivity performances with molecular weight cut-off as low as 233 Da and MeOH permeance of ≈13 LMH/bar. Precise separation of small dye mixtures with similar M.W. based on both their charge and molecular size are achieved.

All-in-One: Sensing, Adsorptive Removal, and Photocatalytic Degradation of Nitro-Explosive Contaminants by Microporous Polycarbazole Polymer.

A highly multitasking 3D polycarbazole based microporous organic polymer (ACzMOP) is rationally prepared via a low-cost FeCl3 catalyzed polymerization route utilizing a newly developed Td -symmetric adamantane core tetracarbazolic monomer. The nitrogen-rich ACzMOP integrated with photo-redox active electron-rich π-conjugated polycarbazole modules featuring large BET surface area of 1568 m 2  g -1 , pore volume of 1.58 cc g -1 , excellent physicochemical stability, and strong fluorescence in both aqueous and solid phases. Aqueous suspension including ACzMOP coated paper strip is highly responsive to the aqueous solution of nitroaromatics especially 2,4-dinitrotoluene, an unavoidable intermediate of 2,4,6-trinitrotoluene contamination, with ultra-trace level detection capability (up to 0.32 ppb). The thin layer of solid polymer is capable of detecting nitroaromatic vapors, especially nitrotoluenes in a very sensitive manner. Moreover, the polymer exhibit record uptake of nitrotoluenes and nitrophenols with maximum uptake capability up to 510 mg g -1  setting a new benchmark among known porous materials. The polymer efficiently degrades toxic 4-nitrophenol to the value-added 4-aminophenol precursor (TOF = 0.143 h -1 ) via photocatalytic pathway. For the very first time, ACzMOP as a single material system is capable of efficiently sensing and removing all sorts of nitroaromatic contaminations with regenerability under mild washing/vacuum conditions.

Designing Internal Hierarchical Porous Networks in Polymer Monoliths that Exhibit Rapid Removal and Photocatalytic Degradation of Aromatic Pollutants.

This paper describes the preparation of 3D polymer monoliths containing internal hierarchical porosity. The porous networks are fabricated based on Pickering high-internal-phase emulsions (HIPEs) stabilized by microporous ß-cyclodextrin-based polymer particles (CDPs) as the emulsifier; CDPs are facilely synthesized by the polyaddition reactions without the need for catalysts. The designed Pickering agents enable to form a bicontinuous internal phase in 8:2 cyclohexane-water v/v, and the oil droplets in the continuous water phase is found to be fairly stable up to 1 month. Furthermore, the addition of acrylamide and N,N'-methylenebis(acrylamide) results in polymer networks after in situ thermal polymerization at 60 °C in the water phase, and the monoliths include both interconnected macropores from the HIPE template and micro- and mesopores from the CDPs embedded at the interface. The porous monoliths rapidly absorb a variety of solvents taking advantage of multiscale porosity and amphiphilicity. Furthermore, the materials can be efficiently used for the removal of aromatic pollutants and then reused after washing and drying without the deterioration of performance. Also, they exhibit high photocatalytic capability and good recyclability as being used as a catalytic support when embedded with titanium dioxide (TiO2 ).

Band Structure Engineering of Schiff-Base Microporous Organic Polymers for Enhanced Visible-Light Photocatalytic Performance.

Schiff-base networks (SBNs), as typical examples of nitrogen-doped microporous organic polymers (MOPs), exhibit promising application prospects owing to their stable properties and tunable chemical structures. However, their band structure engineering, which plays a key role in optical properties, remains elusive due to the complicated mechanisms behind energy level adjustment. In this work, a series of SBNs are fabricated by tailoring the ratio of p-phthalaldehyde and o-phthalaldehyde in the Schiff-base chemistry reaction with melamine, resulting in a straightforward as well as continuous tuning of their band gaps ranging from 4.4 to 1.4 eV. Consequently, SBNs can be successfully used as photocatalysts with excellent visible-light photocatalytic activity even under metal-free conditions. Significantly, electronic structures of SBNs are systematically studied by electrochemical and spectroscopic characterizations, demonstrating that the enhanced performance is ascribed to proper band structure and improved charge separation ability. More importantly, in combination with theoretical calculations, the band structure regulation mechanism and band structure-photocatalytic property relationship are deeply disclosed. The results obtained from this study will not only furnish SBN materials with excellent performance for solar energy conversion, but also open up elegant protocols for the molecular engineering of MOPs with desirable band structures.

Synthesis of Nitrogen-Rich Polymers by Click Polymerization Reaction and Gas Sorption Property.

Microporous organic polymers (MOPs) are promising materials for gas sorption because of their intrinsic and permanent porosity, designable framework, and low density. The introduction of nitrogen-rich building block in MOPs will greatly enhance the gas sorption capacity. Here, we report the synthesis of MOPs from the 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine unit and aromatic azides linkers by click polymerization reaction. Fourier transform infrared (FTIR) and solid-state 13C CP-MAS (Cross Polarization-Magic Angle Spinning) NMR confirm the formation of the polymers. CMOP-1 and CMOP-2 exhibit microporous networks with a BET (Brunauer⁻Emmett⁻Teller) surface area of 431 m²·g-1 and 406 m²·g-1 and a narrow pore size distribution under 1.2 nm. Gas sorption isotherms including CO2 and H2 were measured. CMOP-1 stores a superior CO2 level of 1.85 mmol·g-1 at 273 K/1.0 bar, and an H2 uptake of up to 2.94 mmol·g-1 at 77 K/1.0 bar, while CMOP-2, with its smaller surface area, shows a lower CO2 adsorption capacity of 1.64 mmol·g-1 and an H2 uptake of 2.48 mmol·g-1. In addition, I2 vapor adsorption was tested at 353 K. CMOP-1 shows a higher gravimetric load of 160 wt%. Despite the moderate surface area, the CMOPs display excellent sorption ability for CO2 and I2 due to the nitrogen-rich content in the polymers.

Nanoscale Fluorescent Metal-Organic Framework@Microporous Organic Polymer Composites for Enhanced Intracellular Uptake and Bioimaging.

Polymer-modified metal-organic frameworks combine the advantages of both soft polymers and crystalline metal-organic frameworks (MOFs). It is a big challenge to develop simple methods for surface modification of MOFs. In this work, MOF@microporous organic polymer (MOP) hybrid nanoparticles (UNP) have been synthesized by epitaxial growth of luminescent boron-dipyrromethene (BODIPYs)-imine MOPs on the surface of UiO-MOF seeds, which exhibit low cytotoxicity, smaller size distribution, well-retained pore integrity, and available functional sites. After folic acid grafting, the enhanced intracellular uptake and bioimaging was validated.

BILP-19-An Ultramicroporous Organic Network with Exceptional Carbon Dioxide Uptake.

Porous benzimidazole-based polymers (BILPs) have proven to be promising for carbon dioxide capture and storage. The polarity of their chemical structure in combination with an inherent porosity allows for adsorbing large amounts of carbon dioxide in combination with high selectivities over unpolar guest molecules such as methane and nitrogen. For this reason, among purely organic polymers, BILPs contain some of the most effective networks to date. Nevertheless, they are still outperformed by competitive materials such as metal-organic frameworks (MOFs) or metal doped porous polymers. Here, we report the synthesis of BILP-19 and its exceptional carbon dioxide uptake of up to 6 mmol•g-1 at 273 K, making the network comparable to state-of-the-art materials. BILP-19 precipitates in a particulate structure with a strongly anisotropic growth into platelets, indicating a sheet-like structure for the network. It exhibits only a small microporous but a remarkable ultra-microporous surface area of 144 m2•g-1 and 1325 m2•g-1, respectively. We attribute the exceptional uptake of small guest molecules such as carbon dioxide and water to the distinct ultra-microporosity. Additionally, a pronounced hysteresis for both guests is observed, which in combination with the platelet character is probably caused by an expansion of the interparticle space, creating additional accessible ultra-microporous pore volume. For nitrogen and methane, this effect does not occur which explains their low affinity. In consequence, Henry selectivities of 123 for CO2/N2 at 298 K and 12 for CO2/CH4 at 273 K were determined. The network was carefully characterized with solid-state nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, thermal gravimetry (TG) and elemental analyses as well as physisorption experiments with Ar, N2, CO2, CH4 and water.

Mini-review on the novel synthesis and potential applications of carbazole and its derivatives.

Microporous organic polymers (MOPs) are a new type of porous materials, which have advantages of synthetic diversity, chemical and physical stability, microporous size controllability, etc. MOPs indicate broad applications in various fields such as heterogeneous catalysis, gas adsorption, separation, and storage. In recent years, MOPs have attracted an enormous attention in greenhouse gas capture due to their great potential in physisorptive gas storage. Carbazole and its derivatives have been studied extensively as Metal-Organic Polyhedra (MOPs) building blocks due to their unique structural features and versatile functionalization possibilities. This paper systematically reviews the synthesis, characterization and application of carbazole-based polymers, and relationship of structures and properties of these polymers. The application of the polymers in carbon dioxide (CO2) capture field is analysed taking advantage of their adjustable microporous structure and electron rich properties. This review also provides novel insights regarding functional polymer materials that have high ability of greenhouse gas capture and absorbing selectivity will be obtained by reasonable molecular design and efficient synthesis.

Porous Triptycene Network Based on Tröger's Base for CO2 Capture and Iodine Enrichment.

A three-dimensional rigid "six-connected" porous triptycene network based on Tröger's base (TB-PTN) was synthesized by using triptycenes as connectors and Tröger's base as linkers. With characteristics of a high surface area of 1528 m2 g-1, nitrogen-enriched groups, and superior thermal stability, TB-PTN displays a high CO2 uptake of 22.3 wt % (273 K, 1 bar) and excellent iodine vapor adsorption (240 wt %).

Polyacetylene-type networks prepared by coordination polymerization of diethynylarenes: new type of microporous organic polymers.

Microporous organic polymers (MOP) of a new type have been synthesised in high yields by a simple coordination polymerization of 1,3-diethynylbenzene, 1,4-diethynylbenzene and 4,4'-diethynylbiphenyl catalysed by [Rh(cod)acac] and [Rh(nbd)acac] complexes. The new MOPs are non-swellable polyacetylene-type conjugated networks consisting of ethynylaryl-substituted polyene main chains that are crosslinked by arylene linkers. Prepared MOP samples have a mole fraction of branching units (by (13)C CP/MAS NMR) from 0.30 to 0.47 and exhibit the BET (Brunaer-Emmett-Teller) surface up to 809 m(2) g(-1) and hydrogen uptake up to 0.69 wt% (77 K, H2 pressure 750 torr).

Selective Adsorption and Separation of Xylene Isomers and Benzene/Cyclohexane with Microporous Organic Polymers POP-1.

The separation of chemical substances with analogous chemical structures and physical properties remains a great challenge. In this work, triptycene-like microporous organic polymers (MOPs), POP-1, was synthesized via choosing 1,4-dimethoxybenzene (DMB) and triptycene as external cross-linkers and building blocks, respectively, and POP-1 was employed to separate xylene isomers and benzene (Bz)/cyclohexane (Cy). Results show that POP-1 has a higher uptake for m-xylene (0.29 g/g) and Bz (1.02 g/g); more intriguingly, their complete separation can be realized within 0.6 min using a column packed with POP-1. The interaction between POP-1 networks and adsorbates was also investigated using theoretical (density functional theory together with noncovalent interaction analysis) and experimental (inverse gas chromatography) approaches. Especially, both results present a good agreement, that is, weak interactions such as CH/π interactions play a dominant role in defining the separation performance of POP-1 for xylene isomers and Bz/Cy mixtures. Our findings suggest that MOPs may open up a new route for separating the chemicals that are similar in structure and size.

Facile preparation of microporous organic polymers functionalized macroporous hydrophilic resin for selective enrichment of glycopeptides.

A macroporous adsorption resin (MAR) with ∼10 µm diameter was synthesized by seed-swelling polymerization and further modified with a layer of microporous organic polymers (MOP) by "one-pot" solvothermal reaction. The resulting MAR@MOP exhibited high specific surface area of 131.3 m2/g, which was higher than that of pristine MAR (57.8 m2/g). The contact angle also decreased from 58.8° (MAR) to 24° (MAR@MOP), indicating that the MOP was successfully grafted onto the surface of MAR. The chemical composition of MAR@MOP was confirmed by Fourier-transform infrared spectroscopy, 13C NMR and element analysis. The enrichment efficiency of MAR@MOP to glycopeptides was demonstrated by trapping N-linked glycopeptides from tryptic digests of human immunoglobulin G (IgG), horseradish peroxidase (HRP) and bovine fetuin. Furthermore, 879 unique N-glycosylation sites in 811 unique glycopeptides sequence mapped to 516 N-glycosylated proteins were identified in three replicate analyses of proteins extracted from mouse liver. Therefore, this hydrophilic MOP-coated adsorbent would be applied in the enrichment and identification of low-abundance N-linked glycopeptides in complicated biological samples.

Microporous Organic Polymers Based on Hyper-Crosslinked Coal Tar: Preparation and Application for Gas Adsorption.

Hyper-crosslinked polymers (HCPs) are promising materials for gas capture and storage, but high cost and complicated preparation limit their practical application. In this paper, a new type of HCPs (CTHPs) was synthesized through a one-step mild Friedel-Crafts reaction with low-cost coal tar as the starting material. Chloroform was utilized as both solvent and crosslinker to generate a three-dimensional crosslinked network with abundant micropores. The maximum BET surface area of the prepared CTHPs could reach up to 929 m2 g-1 . Owing to the high affinity between the heteroatoms on the coal-tar building blocks and the CO2 molecules, the adsorption capacity of CTHPs towards CO2 reached up to 14.2 wt % (1.0 bar, 273 K) with a high selectivity (CO2 /N2 =32.3). Furthermore, the obtained CTHPs could adsorb 1.27 wt % H2 at 1.0 bar and 77.3 K, and also showed capacity for the capture of high organic vapors at room temperature. In comparison with other reported porous organic polymers, CTHPs have the advantages of low-cost, easy preparation, and high gas-adsorption performance, making them suitable for mass production and practical use in the future.

Exploitation of a microporous organic polymer as a stationary phase for capillary gas chromatography.

Microporous organic polymers (MOPs) have emerged as a new class of functional porous materials with unique characteristics and potential uses in diverse areas. However, the field of MOPs for gas chromatographic (GC) separations has not been well explored. Herein, a MOP namely KAPs-1 was dynamic coated onto a capillary column for the first time. The fabricated column exhibited a nonpolar nature and the column efficiency for n-dodecane was up to 7769 plates m(-1). The KAPs-1 coated column showed high GC separation performance for a series of volatile organic compounds (VOCs) including the challenging ethylbenzene and xylene isomers, which could not be resolved at baseline on the commercial 5% phenyl polysiloxane stationary phase. Moreover, the relative standard deviations for five replicate determinations of the studied analytes were 0.0-0.6%, 0.9-3.2%, 1.1-5.9%, 0.8-3.7% for retention time, peak area, peak height and peak width, respectively. To investigate the interaction between some analytes and the stationary phase, thermodynamic and kinetic parameters were also evaluated. The results of this study show it is very promising to utilize MOPs as stationary phases for capillary GC.

Knitting aromatic polymers for efficient solid-phase microextraction of trace organic pollutants.

A series of knitting aromatic polymers (KAPs) were successfully synthesized using a simple one-step Friedel-Crafts alkylation of aromatic monomers and were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Then, as-synthesized KAPs with large surface areas, unique pore structures and high thermal stability were prepared as solid-phase microextraction (SPME) coatings that exhibited good extraction abilities for a series of benzene compounds (i.e., benzene, toluene, ethylbenzene and m-xylene, which are referred to as BTEX) and polycyclic aromatic hydrocarbons (PAHs). Under the optimized conditions, the methodologies established for the determination of BTEX and PAHs using the KAPs-triPB and KAPs-B coatings, respectively, possessed wide linear ranges, low limits of detection (LODs, 0.10-1.13ngL(-1) for BTEX and 0.05-0.49ngL(-1) for PAHs) and good reproducibility. Finally, the proposed methods were successfully applied to the determination of BTEX and PAHs in environmental water samples, and satisfactory recoveries (93.6-124.2% for BTEX and 77.2-113.3% for PAHs) were achieved. This study provides a benchmark for exploiting novel microporous organic polymers (MOPs) for SPME applications.