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A Comparative Study on Physiochemical, Thermomechanical, and Electrochemical Properties of Sulfonated Poly(Ether Ether Ketone) Block Copolymer Membranes with and without Fe₃O₄ Nanoparticles.

ABSTRACT: The composite structure, good porosity, and electrochemical behavior of proton exchange membranes (PEMs) are important characteristics, which can improve the performance of polymer electrolyte fuel cells (PEFCs). In this study, we designed and synthesized an XY block copolymer via a polycondensation reaction that contains sulfonated poly(ether ether ketone) (SPEEK) (X) as a hydrophilic unit and a fluorinated oligomer (Y) as a hydrophobic unit. The prepared XY block copolymer is composed of Fe₃O₄ nanoparticles to create composite architecture, which was subsequently treated with a 1 M H₂SO₄ solution at 70 °C for 1 h to eliminate Fe₃O₄ and generate a pores structure in the membrane. The morphological, physiochemical, thermomechanical, and electrochemical properties of bare XY, XY/Fe₃O₄-9 and XY(porous)-9 membranes were measured and compared in detail. Compared with XY/Fe₃O₄-9 composite, the proton conductivity of XY(porous)-9 membrane was remarkably enhanced as a result of the existence of pores as nano-conducting channels. Similarly, the XY(porous)-9 membrane exhibited enhanced water retention and ion exchange capacity among the prepared membranes. However, the PEFC power density of XY(porous)-9 membrane was still lower than that of XY/Fe₃O₄-9 membrane at 60 °C and 60% relative humidity. Also, the durability of XY(porous)-9 membrane is found to be lower compared with pristine XY and XY/Fe₃O₄-9 membranes as a result of the hydrogen crossover through the pores of the membrane.

SUBMITTER: Kim AR

PROVIDER: S-EPMC6473931 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Composite Sulfonated Polyether-Ether Ketone Membranes with SBA-15 for Electrochemical Energy Systems.

Project description:The aim of this work is the evaluation of a Sulfonated Poly Ether-Ether Ketone (S-PEEK) polymer modified by the addition of pure Santa Barbara Amorphous-15 (SBA-15, mesoporous silica) and SBA-15 previously impregnated with phosphotungstic acid (PWA) fillers (PWA/SBA-15) in order to prepare composite membranes as an alternative to conventional Nafion® membranes. This component is intended to be used as an electrolyte in electrochemical energy systems such as hydrogen and methanol Proton Exchange Membrane Fuel Cell (PEMFC) and Electrochemical Hydrogen Pumping (EHP). The common requirements for all the applications are high proton conductivity, thermomechanical stability, and fuel and oxidant impermeability. The morphology of the composite membranes was investigated by Scanning Electron Microscopy- Energy Dispersive X-ray Spectroscopy (SEM-EDS) analysis. Water Uptake (Wup), Ion Exchange Capacity (IEC), proton conductivity, methanol permeability and other physicochemical properties were evaluated. In PEMFC tests, the S-PEEK membrane with a 10 wt.% SBA-15 loading showed the highest performance. For EHP, the inclusion of inorganic materials led to a back-diffusion, limiting the compression capacity. Concerning methanol permeability, the lowest methanol crossover corresponded to the composites containing 5 wt.% and 10 wt.% SBA-15.

| S-EPMC7178128 | biostudies-literature

Nanocomposite Based on Functionalized Gold Nanoparticles and Sulfonated Poly(ether ether ketone) Membranes: Synthesis and Characterization.

Project description:Gold nanoparticles, capped by 3-mercapto propane sulfonate (Au-3MPS), were synthesized inside a swollen sulfonated poly(ether ether ketone) membrane (sPEEK). The formation of the Au-3MPS nanoparticles in the swollen sPEEK membrane was observed by spectroscopic and microscopic techniques. The nanocomposite containing the gold nanoparticles grown in the sPEEK membrane, showed the plasmon resonance ?max at about 520 nm, which remained stable over a testing period of three months. The size distribution of the nanoparticles was assessed, and the sPEEK membrane roughness, both before and after the synthesis of nanoparticles, was studied by AFM. The XPS measurements confirm Au-3MPS formation in the sPEEK membrane. Moreover, AFM experiments recorded in fluid allowed the production of images of the Au-3MPS@sPEEK composite in water at different pH levels, achieving a better understanding of the membrane behavior in a water environment; the dynamic hydration process of the Au-3MPS@sPEEK membrane was investigated. These preliminary results suggest that the newly developed nanocomposite membranes could be promising materials for fuel cell applications.

| S-EPMC5503356 | biostudies-literature

Hydration, Prediction of the pK a, and Infrared Spectroscopic Study of Sulfonated Polybenzophenone (SPK) Block-Copolymer Hydrocarbon Membranes and Comparisons with Nafion.

Project description:We used long-range-corrected density functional theory to investigate the hydration, pK a values, and harmonic vibrational spectroscopy of sulfonated polybenzophenone (SPK) block-copolymer hydrocarbon membranes to ascertain the reasons why this gives comparable or higher proton conductivities against Nafion over a wide range of humidity. It was found that a minimum of three water molecules are required for proton dissociation in both membranes. From natural population analysis, it was noticed that the proton dissociation of SPK membranes is nearly comparable to Nafion at relatively low water content. Next, we explored the applicability of the appropriate treatment for pK a and proton's energy with a benchmark set (AKB) scheme to compute the pK a values for these membranes. These results indicate that the proton dissociative abilities of sulfonic acid groups of the SPK membrane are higher than those of Nafion. This could be one of the reasons for the SPK membrane to show higher proton conductivities at high relative humidity. Furthermore, the effect of hydration on the proton conductivity of membranes illustrates that asymmetric stretching of the SO3 - mode was in agreement with Nafion ones but opposite trends were found in the case of symmetric stretching of the SO3 - mode upon hydration.

| S-EPMC8655912 | biostudies-literature

Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug.

Project description:We introduce the use of block copolymer membranes for an emerging application, "drug capture". The polymer is incorporated in a new class of biomedical devices, referred to as ChemoFilter, which is an image-guided temporarily deployable endovascular device designed to increase the efficacy of chemotherapy-based cancer treatment. We show that block copolymer membranes consisting of functional sulfonated polystyrene end blocks and a structural polyethylene middle block (S-SES) are capable of capturing doxorubicin, a chemotherapy drug. We focus on the relationship between morphology of the membrane in the ChemoFilter device and efficacy of doxorubicin capture measured in vitro. Using small-angle X-ray scattering and cryogenic scanning transmission electron microscopy, we discovered that rapid doxorubicin capture is associated with the presence of water-rich channels in the lamellar-forming S-SES membranes in aqueous environment.

| S-EPMC4989249 | biostudies-literature

Alleviating the Mechanical and Thermal Degradations of Highly Sulfonated Poly(Ether Ether Ketone) Blocks via Copolymerization with Hydrophobic Unit for Intermediate Humidity Fuel Cells.

Project description:In this contribution, sulfonated poly(ether ether ketone) (SPEEK) is inter-connected using a hydrophobic oligomer via poly-condensation reaction to produce SPEEK analogues as PEMs. Prior sulfonation is performed for SPEEK to avoid random sulfonation of multi-block copolymers that may destroy the mechanical toughness of polymer backbone. A greater local density of ionic moieties exist in SPEEK and good thermomechanical properties of hydrophobic unit offer an unique approach to promote the proton conductivity as well as thermomechanical stability of membrane, as verify from AC impedance and TGA. The morphological behavior and phase variation of membranes are explored using FE-SEM and AFM; the triblock (XYX) membranes exhibits a nano-phase separated morphology. Performance of PEFC integrated with blend and block copolymer membranes is determined at 60 °C under 60% RH. As a result, the triblock (XYX) membrane has a high power density than blend (2X1Y) membrane.

| S-EPMC6401815 | biostudies-other

Reconstitution of the membrane protein OmpF into biomimetic block copolymer-phospholipid hybrid membranes.

Project description:Structure and function of many transmembrane proteins are affected by their environment. In this respect, reconstitution of a membrane protein into a biomimetic polymer membrane can alter its function. To overcome this problem we used membranes formed by poly(1,4-isoprene-block-ethylene oxide) block copolymers blended with 1,2-diphytanoyl-sn-glycero-3-phosphocholine. By reconstituting the outer membrane protein OmpF from Escherichia coli into these membranes, we demonstrate functionality of this protein in biomimetic lipopolymer membranes, independent of the molecular weight of the block copolymers. At low voltages, the channel conductance of OmpF in 1 M KCl was around 2.3 nS. In line with these experiments, integration of OmpF was also revealed by impedance spectroscopy. Our results indicate that blending synthetic polymer membranes with phospholipids allows for the reconstitution of transmembrane proteins under preservation of protein function, independent of the membrane thickness.

| S-EPMC4979867 | biostudies-literature

Facilitated Structure Formation in Isoporous Block Copolymer Membranes upon Controlled Evaporation by Gas Flow.

Project description:The conventional fabrication of isoporous membranes via the evaporation-induced self-assembly of block copolymers in combination with non-solvent induced phase separation (SNIPS) is achieved under certain environmental conditions. In this study, we report a modification in the conventional fabrication process of (isoporous) flat sheet membranes in which the self-assembly of block copolymers is achieved by providing controlled evaporation conditions using gas flow and the process is introduced as gSNIPS. This fabrication approach can not only trigger and control the microphase separation but also provides isoporous structure formation in a much broader range of solution concentrations and casting parameters, as compared to fabrication under ambient, uncontrolled conditions. We systematically investigated the structure formation of the fabrication of integral asymmetric isoporous membranes by gSNIPS. A quantitative correlation between the evaporation conditions (causing solvent evaporation and temperature drop) and the self-assembly of block copolymers beginning from the top layer up to a certain depth, orientation of pores in the top layer and the substructure morphology has been discussed empirically.

| S-EPMC7281245 | biostudies-literature

Polymer Nanodiscs: Discoidal Amphiphilic Block Copolymer Membranes as a New Platform for Membrane Proteins.

Project description:Lipid nanodiscs are playing increasingly important roles in studies of the structure and function of membrane proteins. Development of lipid nanodiscs as a membrane-protein-supporting platform, or a drug targeting and delivery vehicle in general, is undermined by the fluidic and labile nature of lipid bilayers. Here, we report the discovery of polymer nanodiscs, i.e., discoidal amphiphilic block copolymer membrane patches encased within membrane scaffold proteins, as a novel two-dimensional nanomembrane that maintains the advantages of lipid nanodiscs while addressing their weaknesses. Using MsbA, a bacterial ATP-binding cassette transporter as a membrane protein prototype, we show that the protein can be reconstituted into the polymer nanodiscs in an active state. As with lipid nanodiscs, reconstitution of detergent-solubilized MsbA into the polymer nanodiscs significantly enhances its activity. In contrast to lipid nanodiscs that undergo time- and temperature-dependent structural changes, the polymer nanodiscs experience negligible structural evolution under similar environmental stresses, revealing a critically important property for the development of nanodisc-based characterization methodologies or biotechnologies. We expect that the higher mechanical and chemical stability of block copolymer membranes and their chemical versatility for adaptation will open new opportunities for applications built upon diverse membrane protein functions, or involved with drug targeting and delivery.

| S-EPMC5680229 | biostudies-literature

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Design of Block-Copolymer Nanoporous Membranes for Robust and Safer Lithium-Ion Battery Separators.

Project description:Lithium-ion batteries (LIBs) suffer from unsatisfied performance and safety risks mainly because of the separators. Herein, a block copolymer (BCP) composed of robust and electrolyte-affinitive polysulfone (PSF) and Li+-affinitive polyethylene glycol (PEG) is rationally designed to prepare a new type of LIB separator. The copolymer is subjected to selective swelling, producing nanoporous membranes with PEG chains enriched along the pore walls. Intriguingly, when used as LIB separators, thus-produced BCP membranes efficiently integrate the merits of both PSF and PEG chains, endowing the separators thermal resistance as high as 150 °C and excellent wettability. Importantly, the nanoporous separator is able to close the pores with a temperature of 125 °C, offering the battery a thermal shutdown function. The membrane exhibits ultrahigh electrolyte uptake up to 501% and a prominent ionic conductivity of 10.1 mS cm-1 at room temperature. Batteries assembled with these membranes show excellent discharge capacity and C-rate performance, outperforming batteries assembled from other separators including the extensively used Celgard 2400. This study demonstrates a facile strategy, selective swelling of block copolymer, to engineer high-performance and safer LIB separators, which is also applicable to produce advanced copolymer-based separators for other types of batteries.

| S-EPMC8025019 | biostudies-literature

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