Microporous Poly Research Articles

Uranium removal from contaminated groundwater using goethite-loaded composite microporous membrane

In this study, we have coupled adsorption and membrane separation for the removal of uranium from contaminated groundwater in environmentally relevant conditions at low energy requirements. The study mainly focuses on elucidating uranium [U(VI)] adsorption mechanisms using surface complexation modeling approach in a novel goethite-loaded composite microfiltration membrane (GLM). The experiments involved immobilizing goethite nanorods in a microporous (0.22 μm pore size) poly (vinylidene fluoride) (PVDF) membrane. The effect of varying goethite loading and hydraulic residence time on U(VI) removal was investigated at field-relevant pH (i.e. pH 8.5). U(VI) adsorption (i.e. 4.95 μg·mg−1) was optimum at a goethite loading of 1.20 mg·cm−2. The effect of varying hydraulic residence time had no impact on U(VI) removal which was also confirmed via performing batch adsorption kinetic experiments. GLM membrane loaded at 1.2 mg·cm−2 could treat 275 L of U(VI) contaminated water having 200 μg of U L−1 below WHO drinking water limit (i.e. 30 μg of U L−1) with 1 m2 of membrane surface area at a maximum adsorption capacity of 6.12 μg·mg−1. Varying the pH of aqueous solution, containing U(VI) from pH 4.0 to pH 10.0, showed a significant impact on uranium uptake ranging from 0.7 μg·mg−1 to 2.63 μg·mg−1 by the composite membrane. The adsorption mechanism of uranium onto goethite was explained via the formation of bidentate surface complexes using the Surface Complexation Model (SCM). The results of batch pH edge experiments and SCM have been compared with pH experiments performed using GLM. The results of SCM predicted the batch pH edge experiment within a RMSE of 0.055. The trend of U(VI) removal in membrane experiments was observed to be similar to that of batch pH edge experiments and was well predicted by the SCM model. Our results show that the novel goethite-loaded membrane has the potential for effective removal of uranium with a lower specific energy consumption.

Tertiary-Amine-Functional Poly(arylene ether)s for Acid-Gas Separations.

Competitive sorption enables the emergent phenomenon of enhanced CO2-based selectivities for gas separation membranes when using microporous polymers with primary amines. However, strong secondary forces in these polymers through hydrogen bonding results in low solvent solubility, precluding standard solution processing approaches to form these polymers into membrane films. Herein, we circumvent these manufacturing constraints while maintaining competitive-sorption enhancements by synthesizing eight representative microporous poly(arylene ether)s (PAEs) with tertiary amines. High-pressure H2S, CO2, and CH4 sorption isotherms were collected for these samples to demonstrate enhanced affinity for acid gases relative to the unfunctional control polymer. Although competitive sorption was observed for all samples, improvements were less pronounced than for primary-amine-functional analogs. For H2S-based separations, the benefits of competitive sorption offset decreases in selectivity due to plasticization. This detailed study helps to elucidate the role of tertiary amines for acid gas separations in solution-processable microporous PAEs.

Ketone-based conjugated microporous poly(aniline)s for the ultradeep separation of heavy metal ions

The heavy-metal contamination of aquatic environments presents imminent threat. Herein, we report a class of dual-heteroatomic conjugated microporous poly(aniline)s showing high-affinity separation performance toward heavy metals. The prepared keto-CMPA shows monolayer adsorption capacity for Hg (II) as high as 980 mg g−1 according to the Langmuir model, and ultra-rapid kinetic with h reaching 30.41 mg g−1 that could be described by the pseudo-second-order model. It maintains excellent stability across six reuses under harsh conditions, and furthermore demonstrates ultradeep separation efficiency that could adsorb almost all of heavy metals to ppb level with low usage. For further industrialization, a competent adsorption device was developed to remove heavy metals down to 1 ppb with a remarkable breakthrough over 20,000 BV. Characterizations and DFT calculation showed that the triangular synergistic region formed by the N-O-sites in the singular CMPA structure provided a feasible binding energy to enable the above impressive performance.

Polymer scaffolds delineate healthy from diseased states at sites distal from the pancreas in two models of type 1 diabetes.

Type 1 diabetes (T1D) prevention is currently limited by the lack of diagnostic tools able to identify disease before autoimmune destruction of the pancreatic β cells. Autoantibody tests are used to predict risk and, in combination with glucose dysregulation indicative of β cell loss, to determine administration of immunotherapies. Our objective was to remotely identify immune changes associated with the disease, and we have employed a subcutaneously implanted microporous poly(e-caprolactone) (PCL) scaffold to function as an immunological niche (IN) in two models of T1D. Biopsy and analysis of the IN enables disease monitoring using transcriptomic changes at a distal site from autoimmune destruction of the pancreas, thereby gaining cellular level information about disease without the need for a biopsy of the native organ. Using this approach, we identified gene signatures that stratify healthy and diseased mice in both an adoptive transfer model and a spontaneous onset model of T1D. The gene signatures identified herein demonstrate the ability of the IN to identify immune activation associated with diabetes across models.

A 3D bioreactor model to study osteocyte differentiation and mechanobiology under perfusion and compressive mechanical loading

Osteocytes perceive and process mechanical stimuli in the lacuno-canalicular network in bone. As a result, they secrete signaling molecules that mediate bone formation and resorption. To date, few three-dimensional (3D) models exist to study the response of mature osteocytes to biophysical stimuli that mimic fluid shear stress and substrate strain in a mineralized, biomimetic bone-like environment. Here we established a biomimetic 3D bone model by utilizing a state-of-art perfusion bioreactor platform where immortomouse/Dmp1-GFP-derived osteoblastic IDG-SW3 cells were differentiated into mature osteocytes. We evaluated proliferation and differentiation properties of the cells on 3D microporous scaffolds of decellularized bone (dBone), poly(L-lactide-co-trimethylene carbonate) lactide (LTMC), and beta-tricalcium phosphate (β-TCP) under physiological fluid flow conditions over 21 days. Osteocyte viability and proliferation were similar on the scaffolds with equal distribution of IDG-SW3 cells on dBone and LTMC scaffolds. After seven days, the differentiation marker alkaline phosphatase (Alpl), dentin matrix acidic phosphoprotein 1 (Dmp1), and sclerostin (Sost) were significantly upregulated in IDG-SW3 cells (p = 0.05) on LTMC scaffolds under fluid flow conditions at 1.7 ml/min, indicating rapid and efficient maturation into osteocytes. Osteocytes responded by inducing the mechanoresponsive genes FBJ osteosarcoma oncogene (Fos) and prostaglandin-endoperoxide synthase 2 (Ptgs2) under perfusion and dynamic compressive loading at 1 Hz with 5 % strain. Together, we successfully created a 3D biomimetic platform as a robust tool to evaluate osteocyte differentiation and mechanobiology in vitro while recapitulating in vivo mechanical cues such as fluid flow within the lacuno-canalicular network. Statement of significanceThis study highlights the importance of creating a three-dimensional (3D) in vitro model to study osteocyte differentiation and mechanobiology, as cellular functions are limited in two-dimensional (2D) models lacking in vivo tissue organization. By using a perfusion bioreactor platform, physiological conditions of fluid flow and compressive loading were mimicked to which osteocytes are exposed in vivo. Microporous poly(L-lactide-co-trimethylene carbonate) lactide (LTMC) scaffolds in 3D are identified as a valuable tool to create a favorable environment for osteocyte differentiation and to enable mechanical stimulation of osteocytes by perfusion and compressive loading. The LTMC platform imitates the mechanical bone environment of osteocytes, allowing the analysis of the interaction with other cell types in bone under in vivo biophysical stimuli.

Unconventional extraction of uranium from seawater through microenvironment-specific conjugated microporous poly(aniline)s

The sustainability of uranium-based nuclear energy relies on the development of quick and effective uranium adsorbents. Herein, we propose a facile post-synthetic technique by grafting amino-functional groups onto the fluorenone-functionalized conjugated microporous poly(aniline)s (CMPs) network to acquire a novel class of N decorated polymers for uranium capture. By leveraging the abundant N sites and microenvironment-containing molecular structure, CMPA-F-BDA showcases excellent UO22+ adsorption performance with fast adsorption kinetic with initial adsorption rate up to 43.78 mg g−1 min−1, Langmuir adsorption capacity of 443 mg g−1 and exceptional adsorption selectivity of Kd = 1.3 × 107 mL g−1 even in the serious presence of competitive cations. Additionally, CMPA-F-BDA could treat up to 18.5 L g−1 of low-concentration uranium solution (1 mg L−1) and actual seawater, removing 87.9% of uranium from 10 L of seawater, and has excellent reusability. This study demonstrates the bright future of CMPs for the extraction of low-concentration uranium.

Formation of Microporous Poly Acrylonitrile-Co-Methyl Acrylate Membrane via Thermally Induced Phase Separation for Immiscible Oil/Water Separation.

An interconnected sponge structure and porous surface poly (acrylonitrile-co-methyl acrylate) (P(AN-MA)) microfiltration membranes (MF) were fabricated via thermally induced phase separation (TIPS) by using caprolactam (CPL), and acetamide (AC) as the mixed diluent. When the ternary system was composed of 15 wt.% P(AN-MA), 90 wt.% CPL, and 10 wt.% AC and formed in a 25 °C air bath, the membrane exhibited the highest water flux of 8107 L/m2·h. The P(AN-MA) membrane contained hydrophobic groups (-COOCH3) and hydrophilic groups (-CN), leading it to exhibit oleophobic properties underwater and hydrophobic properties in oil. The membrane demonstrates efficient separation of immiscible oil/water mixtures. The pure water flux of the petroleum ether/water mixture measured 870 L/m2·h, and the pure oil flux of the petroleum tetrachloride/water mixture measured 1230 L/m2·h under the influence of gravity. Additionally, the recovery efficiency of diluents through recrystallization was 85.3%, significantly reducing potential pollution and production costs.

Intrinsic microporous poly(phenyl-alkane)s with pendent piperazinium for high performance anion exchange membrane fuel cells

Exploring anion exchange membranes (AEMs) with high conductivity and satisfactory stability is very meaningful for the advancement of alkaline fuel cells. Herein, a novel class of intrinsic microporous AEMs with pendent piperazinium are systematically fabricated for alkaline fuel cell performance testing. Contorted and rigid spirobisindane backbone structure expands the free volume of AEMs, inducing broad and interconnected ion transport channels. This unique feature endows membranes a leading advantage for the efficient transmission of hydroxide ions. Consequently, the prepared membrane displays excellent normalized hydroxide conductivity of 78.99 mS g cm−1 mmol−1 at 80 °C. Meanwhile, the hydroxide conductivity degrades by only 8.3 % after treatment in 1 M NaOH for 1000 h at 80 °C. Moreover, the peak power density of H2/O2 single cell employing this membrane exhibits 1.06 W cm−2 at 80 °C and the cell can preserve 93.0 % of its initial voltage after operating for 18 h.

Selective Adsorption Behavior of Sulfuric Acid Oxidized and Doped Conjugated Microporous Poly(aniline)s toward Lead Ions in an Aqueous Environment.

The coexistence of lead, zinc, and copper ions in wastewater constitutes an environmental challenge of pressing concern. This research delves into the preparation of innovative oxidation-doped conjugated microporous poly(aniline) frameworks, exploring their prospective efficacy in regulating lead ion adsorption from aqueous solutions. H2SO4-CMPTA demonstrates the capability to reach adsorption equilibrium within 15 min at a lead concentration of 50 ppm. Even at a lead concentration of 20 ppm, it still efficaciously attenuates these levels to sub-10 ppb, a value surpassing extant standard. H2SO4-CMPTA retains over 78.8% adsorption efficiency after six cycles. Analytical characterization coupled with computational calculations suggests that sulfate-coordinated nitrogen cationic structure plays a crucial role in adsorption. A deeper investigation reveals the cardinal role of electrostatic attraction and exclusive chelation adsorption underpinning the efficient capture of lead ions by doped sulfate ions. Intriguingly, in a mixed heavy metal solution containing lead, zinc, and copper ions, H2SO4-CMPTA exhibits an initial predilection toward zinc ions, yet an eventual ion-exchange adsorption gravitating toward lead ions was discerned, governed by the latter's superior binding energy. Our study elucidates a promising material as an efficacious tool for the remediation of aquatic environments tainted with lead contaminants.

Microporous Fluorescent Poly(D,L-lactide) Acid-Carbon Nanodot Scaffolds for Bone Tissue Engineering Applications.

In this study, we introduce novel microporous poly(D,L-lactide) acid-carbon nanodot (PLA-CD) nanocomposite scaffolds tailored for potential applications in image-guided bone regeneration. Our primary objective was to investigate concentration-dependent structural variations and their relevance to cell growth, crucial aspects in bone regeneration. The methods employed included comprehensive characterization techniques such as DSC/TGA, FTIR, rheological, and degradation assessments, providing insights into the scaffolds' thermoplastic behavior, microstructure, and stability over time. Notably, the PLA-CD scaffolds exhibited distinct self-fluorescence, which persisted after 21 days of incubation, allowing detailed visualization in various multicolor modalities. Biocompatibility assessments were conducted by analyzing human adipose-derived stem cell (hADSC) growth on PLA-CD scaffolds, with results substantiated through cell viability and morphological analyses. hADSCs reached a cell viability of 125% and penetrated throughout the scaffold after 21 days of incubation. These findings underscore the scaffolds' potential in bone regeneration and fluorescence imaging. The multifunctional nature of the PLA-CD nanocomposite, integrating diagnostic capabilities with tunable properties, positions it as a promising candidate for advancing bone tissue engineering. Our study not only highlights key aspects of the investigation but also underscores the scaffolds' specific application in bone regeneration, providing a foundation for further research and optimization in this critical biomedical field.

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.

A Microporous Poly(Arylene Ether) Platform for Membrane‐Based Gas Separation**

AbstractMembrane‐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 (H2S+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.

Wettability tunable conjugated microporous poly(aniline)s for long-term, rapid and ppb level sequestration of Hg(II)

Wettability tunable conjugated microporous poly(aniline)s for long-term, rapid and ppb level sequestration of Hg(II)

Application of Ionized Intrinsic Microporous Poly(phenyl-alkane)s as Alkaline Ionomers for Anion Exchange Membrane Water Electrolyzers

Application of Ionized Intrinsic Microporous Poly(phenyl-alkane)s as Alkaline Ionomers for Anion Exchange Membrane Water Electrolyzers

Nitrogen-doped microporous carbons as highly efficient adsorbents for CO2 and Hg(II) capture

Nitrogen-doped microporous carbon, which features a uniquely tunable porosity, exhibits promisingly high adsorption prospects in the greenhouse gas capture and water treatment. Herein, we propose a series of novel N-doped microporous carbons (CMPAn-C1000), and precisely tune their porosities via a direct pyrolysis of rigid conjugated microporous poly(aniline)s (CMPAn, n = 1, 2, 3) with pore size difference in a molecular level, as achieved by simply tuning their linkers with varying sizes, planarity, and symmetry. The CMPA3-C1000, with a satisfactory amount of nitrogen heteroatoms, high SBET of ∼800 m2 g−1, and large ultra-micropore volume of 0.25 cm3 g−1, has excellent CO2 capture ability (i.e., 5.1 mmol g−1 at 273 K, 1 atm) and Hg(II) adsorption performance (i.e., Qe = 571 mg g−1; k2 = 0.0031 g mg−1 min−1), respectively. CMPA3-C1000 might perform chemisorption towards Hg(II), according to calculations using density functional theory and experimental data; nitrogen atoms in porous carbon contributed to this excellent Hg(II) adsorption.

Sulfuric acid-doped conjugated microporous poly(aniline)s enabled unconventional Hg (II) adsorption from aqueous solution

New strategies are required to modify adsorbents that possess numerous accessible chelating sites with high utilization, in order to achieve both rapid uptake and high capacity for the contaminants, which are still urgently needed. This study introduces a novel integration of a conjugated microporous polymer (CMP) material with conventional polyaniline, representing the first instance of such a combination. By amalgamating the doping properties of polyaniline with the highly stable structure and extensive microporous attributes of CMP, we achieve a synergistic effect. The conjugated microporous polyaniline is subjected to a concentrated sulfuric acid modification (SD-CMPA), enabling simultaneous oxidation, doping, and pore channel modification in a single step. The resulting SD-CMPA exhibits a record-breaking maximum adsorption capacity for Hg2+, reaching as high as 1720 mg·g−1, as well as a benchmark distribution coefficient of 2.5 × 108 mL·g−1. Moreover, it demonstrates robust reusability, retaining over 96% of its adsorption capacity for at least six cycles. These remarkable features enable the achievement of ultra-deep-water purification to 0.452 ppb in an effective manner. The impressive performance of SD-CMPA can be attributed to the abundance of nitrogen-containing groups, particularly the tertiary amine nitrogen in the material skeleton, as supported by X-ray photoelectron spectroscopy and density functional theory calculations. The results presented in this study demonstrate the exceptional potential of SD-CMPA for high-performance environmental remediation.

Fast formation of strong symmetric poly (vinylidene fluoride) membranes via a modified VIPS method

BackgroundPolymer membranes for microfiltration and membrane distillation should be skinless and symmetric with a bi-continuous structure. To effectively eliminate the inherently formed skin layer and macrovoids in the membrane, proper modifications of preparation parameters are proposed. MethodsSkinless microporous poly(vinylidene fluoride) (PVDF) membranes with a uniform bi-continuous structure were fabricated through phase inversion processes that combine vapor-induced phase separation (40 °C and 70% relative humidity) and non-isothermal immersion precipitation (22 °C) with casting dopes consisting of triethyl phosphate (TEP), PVDF, and a small amount of glycerol, a nonsolvent. Significant findingsIntroduction of glycerol to the dope solution induces a rapid polymer crystallization upon exposure to water vapor. Experimental results demonstrate that a skinless microporous membrane can be obtained with a short vapor exposure time of 1.5 min. Additionally, the synthesized membrane possesses ideal filtration properties, including high hydrophobicity (contact angle = 113° for both surfaces), high porosity (83%), adequate strength (2.4 N/mm2), and suitable pore size (0.12 μm). This membrane also exhibits superb rejection capability (99%) and high permeation flux (450 LMH) for filtration of poly(methyl methacrylate) particles with an average size of 0.15 μm..

Microporous Hematite-Loaded Composite Membrane for Arsenic(III) and Arsenic(V) Removal

In this work, adsorption and membrane separation were combined to remove adsorbable contaminants from water at lower energy requirements. Such an approach was investigated for arsenic (As) removal with hematite nanoparticles (70 ± 20 nm) immobilized in a microporous (0.2 μm pore size) poly(vinylidene fluoride) (PVDF) membrane. Hematite loading and hydraulic residence time with the role of speciation were investigated for As(III) and As(V) removal using hematite-loaded composite membrane (HLCM). During the flow-through filtration, it was observed 50% removal for As(III), while only 15% As(V) was removed at pH 8 with 2.6 mg/cm2 hematite loading, equivalent to uptakes of 5.5 ± 0.8 μgAs(III)/cm2 and 3.9 ± 0.6 μgAs(V)/cm2. Varying the pH from 2 to 12 and, ultimately, As(III, V) speciation showed a significant impact on the uptake, especially for As(V). In this case, increasing the NaCl concentration from 0.58 to 20 g/L hindered the charge attraction. Arsenic uptake increased with increasing the hematite loading from 0.7 to 3.9 mg/cm2, while the impact of the hydraulic residence time (flux) was observed. Arsenic uptake by this composite membrane requires further improvement in terms of adsorption capacity. Increasing the loading of hematite in the membrane or chemical modifications of hematite to achieve enhanced affinity for As(III, V) will be part of further material modification. From the water treatment perspective, the composite membrane potentially provides effective removal with a lower specific energy consumption compared to nanofiltration.

Framing of Poly(arylene-ethynylene) around Carbon Nanotubes and Iodine Doping for the Electrochemical Detection of Dopamine.

Dopamine (DA), an organic biomolecule that acts as both a hormone and a neurotransmitter, is essential in regulating emotions and metabolism in living organisms. The accurate determination of DA is important because it indicates early signs of serious neurological disorders. Covalent organic frameworks (COFs) and metal-organic frameworks (MOFs) have received considerable attention in recent years as promising porous materials with an unrivaled degree of tunability for electrochemical biosensing applications. This study adopted a solvothermal strategy for the synthesis of a conjugated microporous poly(arylene ethynylene)-4 (CMP-4) network using the Sonagashira-Hagihara cross-coupling reaction. To increase the crystallinity and electrical conductivity of the material, CMP-4 was enveloped around carbon nanotubes (CNTs), followed by iodine doping. When used as an electrochemical probe, the as-synthesized material (I2-CMP-CNT-4) exhibited excellent selectivity and sensitivity to dopamine in the phosphate-buffered solution. The detection limits of the electrochemical sensor were 1 and 1.7 μM based on cyclic voltammetry (CV) and differential pulse voltammetry (DPV).

Microporous poly- and monocrystalline diamond films produced from chemical vapor deposited diamond-germanium composites.

We report on a novel method for porous diamond fabrication, which is based on the synthesis of diamond-germanium composite films followed by etching of the Ge component. The composites were grown by microwave plasma assisted CVD in CH4-H2-GeH4 mixtures on (100) silicon, and microcrystalline- and single-crystal diamond substrates. The structure and the phase composition of the films before and after etching were analyzed with scanning electron microscopy and Raman spectroscopy. The films revealed a bright emission of GeV color centers due to diamond doping with Ge, as evidenced by photoluminescence spectroscopy. The possible applications of the porous diamond films include thermal management, surfaces with superhydrophobic properties, chromatography, supercapacitors, etc.