Polymerization Procedure Research Articles

Scintillating iron imprinted polymers (Sc-Fe-IIP): Novel material for 55Fe selective recognition

In the coming years, numerous nuclear power plants are expected to reach the end of their operational lifespans, leading to a substantial increase in the demand for analyses during the decommissioning process. Of particular concern is 55Fe, a fission product originating from neutron activation of stable iron. The conventional methods for determining 55Fe using liquid scintillation are known for being time-consuming, complex, and involving multiple steps to eliminate interferences. In this work, the first scintillating imprinted polymer for 55Fe has been developed (Sc-Fe-IIP). Several tests have been conducted to define the polymerization procedure, the components of the polymer, and their proportions, making it possible to combine selective retention and scintillation capabilities for 55Fe determination in one material. The optimum Sc-Fe-IIP is composed of styrene, divinylbenzene, and vinyl phosphonic acid, together with a complex of Fe with acrylic acid and scintillation fluorescence solutes. The iron capacity is up to 17 mg per gram of Sc-Fe-IIP, and the selectivity is 95 %, with reduced retention of copper (4 %) and no retention of nickel or cobalt. Regarding scintillation capabilities, the Sc-Fe-IIP showed a detection efficiency of 4.90 %.

Mechanically Tough Polymer Electrolyte Membranes Prepared By Radiation-Induced Graft Polymerization of Poly (ether ether ketone) Film

The development of state-of-the-art polymer electrolyte membranes is indispensable for solid polymer fuel cells. To make a desired membrane, we have reported the radiation-induced graft polymerization (RGP) method in our previous studies, which is a fascinating technique with great advantages of low-cost fabrication and imparting new functionality via graft polymers to commercially available substrate polymer films, whose excellent mechanical/thermal properties are maintained. Among various substrate polymers, poly (ether ether ketone) (PEEK) is regarded as the most promising aromatic hydrocarbon material for the long life-time operation requirement of fuel cells due to its excellent mechanical stability and high gas barrier property at high temperature. However, graft polymerization on PEEK substrate is rather difficult. To successfully obtain PEEK-based polymer electrolyte membranes with suitably-balanced properties, we have extensively investigated the graft polymerization and irradiation conditions. In this work, we will report the synthesis of both PEEK-based proton- and anion-exchange membranes (PEEK-PEMs and PEEK-AEMs, respectively), and the fuel cell performance using these two types of membranes.1)RGP for making PEEK-PEMs and PEEK-AEMs. The PEEK base films used for RGP was previously immersed in (1, 4-dioxane) DOX at 50°C for 18 hours as a solvent annealing treatment. Ethyl styrene sulfonate (ETSS) and chloromethyl styrene (CMS) are used as precursors for PEMs and AEMs, respectively (Scheme 1).For the synthesis of PEEK-PEMs, the solvent-annealed PEEK films were pre-irradiated with 60Co ϒ-ray at room temperature in argon atmosphere with a total dose 160 kGy. Then the samples were immersed in ETSS/DOX solution (1/1 v/v) at 80°C under the argon atmosphere. The resultant grafted-PEEK membranes has a grafting degree (GD) of 150%. After hydrolysis treatment, the final PEEK-PEM shows an ion-exchange capacity (IEC) of 2.5 mmol/g and a proton conductivity of 0.1 S/cm at 25 °C. For the synthesis of PEEK-AEMs, the same irradiation and polymerization procedures as in the synthesis of PEEK-PEMs were performed, by using CMS as monomers instead of ETSS. The CMS-grafted PEEK with high GD of 66% was obtained in tetraethylenglycol as a solvent. The grafted PEEK was converted to AEM by treating in trimethylamine with a quaternization degree of 76%. The obtained AEM has an IEC of 1.7 mmol/g and an anion conductivity of 0.128 S/cm at 60°C. The mechanical strength and elongation of the resulting PEEK-PEM at 80°C and 100%RH were measured to be 22 MPa and 50%, respectively, which are superior to those of Nafion (10 MPa and 200%, respectively). PEEK-AEM also shows good mechanical strength and elongation of 94 MPa and 18%, respectively, at room temperature and 70% RH.2)Fuel cell performance evaluation. Fuel cell test using PEEK-PEMs and AEMs was carried out according to previous reports [1]. The membrane was sandwiched by anode and cathode electrodes (Pt or Pt/Ru loading 0.5 mg/cm2) and hot-pressed, and then obtained membrane/electrodes assembly (MEA) was then set into a 5 cm2 fuel cell for testing. The cell was fed with pure hydrogen and oxygen gases at a flow rate of 0.05 L/min each to the anode and cathode, respectively, under atmosphere pressure. The cell condition was 80°C and 100%RH.Fuel cell test with an MEA incorporating 16 μm PEEK-PEM shows a good performance of an open circuit of 0.9 V and a power density of 860 mW/cm2 at a current density of 2240 mA/cm2 (Figure 1(a)). Using the PEEK-g-AEM membrane, it shows an open circuit voltage value of more than 0.9 V and a power density of 673 mW/cm2 at a current density of 1199 mA/cm2 (Figure 1(b)). As described above, utilizing radiation-induced graft polymerization, we have for the first time successfully developed two types of polymer electrolyte membranes, PEEK-PEM and PEEK-AEM, using the mechanically tough and chemically stable aromatic hydrocarbon polymer PEEK as the substrate.[1] J. Chen, et al. J.Membr. Sci. 2008, 319, 1-4. Figure 1

Electrochromism Based on Reflective Color of Conductive Polymers

Some solid films of organic dyes, such as methylene blue, show a metallic luster. We are interested in the electrochromism of metallic luster and its reflected color from non-metallic materials. It has already been reported that 3-methoxythiophene polymers obtained by chemical and electrochemical synthesis show metallic luster. It was believed that this electrochemical polymerization could only produce a polymer product with high reflectance by slowly sweeping the applied potential, but a metallic luster was achieved by using a different electrolytic polymerization procedure. A constant potential is applied at which the monomer polymerizes, followed by a constant potential at which the polymer product obtained on the electrode is reduced. A polymer film that showed a green metallic luster in a reduced state and a red metallic luster in an oxidized state was obtained by repeating these potentiostatic electropolymerization procedures. We call this method as multi-step potentiostatic polymerization. These color tones were obtained when no light was transmitted through the polymer film, and we believe that they are caused by reflection on the surface of the polymer film. For reference, when white light was transmitted through the polymer film obtained, red color was observed in the reduced state and blue color was observed in the oxidized state. This is electrochromism based on transmitted color, which is well known as polythiophene electrochromism. By performing electrochromism with metallic luster, it becomes possible to apply it to switchable Mirror mirrors.

Development of Sustainable, Environment-Friendly Protein-Based Proton Exchange Membranes for Fuel Cells and Water Electrolyzers

In the twenty-first century, proton-exchange membrane fuel cells (PEMFCs) and water electrolyzers (PEMWEs) represent promising technologies for clean and efficient power generation. Proton exchange membranes (PEMs) are the key components in PEMFCs and PEMWEs. Currently, all proton exchange membranes (PEMs) employed in PEMFCs or PEMWEs are based on synthetic primarily sulfonated polymers. While these synthetic polymers have good proton conductivity, they are expensive and raise environmental concerns. As a result, there is growing interest in identifying suitable alternatives that are cost-effective, sustainable, and environmentally friendly. Biopolymers, which are naturally occurring alternatives to synthetic polymers, are linked by covalent bonds and include cellular components such as proteins, nucleotides, lipids, and polysaccharides. Proteins derived from sustainable sources offer potential advantages for polymer production due to their ability to self-heal and their higher water transport capabilities, particularly in fast-growing plants like cannabis, soybean, corn. In this study, we aim to: (i) develop proton exchange membranes based on plant-based proteins, (ii) fabricate membrane electrode assemblies (MEAs) with the protein membranes and assess their performance as PEM fuel cells and water electrolyzers, and (iii) optimize the polymerization procedures to comply with green chemistry principles and ensure high proton conductivity at temperatures ranging from 80°C to 150°C, making them suitable for use in PEMFCs and PEMWEs.

Reduction Polymerization of CO2 with Phenylene Silanes Catalyzed by Single Component B(C6F5)3.

CO2 is an abundant C1 resource but a green-house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers-Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane-co-silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step-growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.

Reduction Polymerization of CO2 with Phenylene Silanes Catalyzed by Single Component B(C6F5)3

AbstractCO2 is an abundant C1 resource but a green‐house gas and chemically inert. Thus, its utilization has been a promising but challenging project. Herein, we report the unprecedented polymerization of CO2 and C6H4(SiMe2H)2 using B(C6F5)3 alone under mild conditions to give poly(silphenylene siloxane) accompanied by releasing CH4. The copolymerization can be extended to comonomers of phenylene silanes bearing functional groups. Moreover, it combines with Piers‐Rubinsztajn reaction to establish a tandem polymerization system to achieve super thermal resistant poly(siloxane‐co‐silphenylene siloxane)s. Density functional theory reveals that B(C6F5)3 is activated by silanes to form free HB(C6F5)2, which is the true active species for CO2 reducing to borylformate, the rate controlling step of the polymerization procedure. The subsequent multiple reductions of borylformate to CH4 and the step‐growth to poly(silphenylene siloxane)s can be fulfilled by both B(C6F5)3 and HB(C6F5)2, and the former shows a slightly higher activity. This work opens a new avenue of utilizing CO2 to fabricate polysiloxanes that is unable to access using current manners.

The Kinetics of Polymer Brush Growth in the Frame of the Reaction Diffusion Front Formalism.

We studied the properties of a reaction front that forms in irreversible reaction-diffusion systems with concentration-dependent diffusivities during the synthesis of polymer brushes. A coarse-grained model of the polymerization process during the formation of polymer brushes was designed and investigated for this purpose. In this model, a certain amount of initiator was placed on an impenetrable surface, and the "grafted from" procedure of polymerization was carried out. The system consisted of monomer molecules and growing chains. The obtained brush consisted of linear chains embedded in nodes of a face-centered cubic lattice with excluded volume interactions only. The simulations were carried out for high rafting densities of 0.1, 0.3, and 0.6 and for reaction probabilities of 0.02, 0.002, and 0.0002. Simulations were performed by means of the Monte Carlo method while employing the Dynamic Lattice Liquid model. Some universal behavior was found, i.e., irrespective of reaction rate and grafting density, the width of the reaction front as well as the height of the front show for long times the same scaling with respect to time. During the formation of the polymer layer despite the observed difference in dispersion of chain lengths for different grafting densities and reaction rates at a given layer height, the quality of the polymer layer does not seem to depend on these parameters.

Laser ablation and chemical vapor deposition to prepare a nanostructured PPy layer on the Ti surface

Abstract The deposition of polypyrrole (PPy) on a Ti surface is commonly employed to enhance the material’s properties for different applications such as supercapacitors, biomedicine, and corrosion resistance. Instead of complex or costly polymerization procedures for the PPy synthesis on the Ti metal surface, we utilized the effect of a simple and inexpensive laser ablation of the Ti surface in the open-air environment to prepare a hydrophilic TiO2 surface. In this condition, a thin PPy layer with remarkable nanostructures such as nanorings (∼80 nm) and nanotubes (∼245 nm) was deposited on a selective and desired pattern of ablated Ti areas through the chemical vapor deposition process using ferric chloride (FeCl3) solution as a pyrrole oxidizer. Raman and X-ray photoelectron spectroscopy (XPS) analyses confirmed the PPy formation on the Ti surface. The creation of these nanostructures was due to the micro/nanomorphology of the ablated Ti substrate. Water contact angle (WCA) measurements indicated the hydrophobic behavior of the PPy/Ti surface by the aging effect after 24 weeks with the change of WCA from 20° to 116°. The change in the surface chemical composition upon adsorption of airborne organic compounds with the long-term storage of PPy/Ti surface in air was studied by the XPS test.

A novel electropolymerized molecularly imprinted dual-mode sensor for bisphenol AF detection in pond mud

Recently, bisphenol AF (BPAF) as most commonly used bisphenol A analogs had the increasing higher level in the environment with unknown risks. Herein, a synchronous dual-mode sensor had been established based on differential pulse voltammetry (DPV) and electrochemiluminescence (ECL) for the detection of BPAF in pond mud. Firstly, the sensing molecularly imprinted polymer (MIP) films were prepared by electrochemical polymerization procedure with 3,4-ethoxylene dioxy thiophene (EDOT) as the functional monomer, BPAF as the template molecule and MXene as the supporting electrolyte. Due to unique characters of PEDOT and MXene, the constructed MIP films were stable and highly conductive. Meanwhile, zinc-doped bismuth sulfide quantum dots (Zn-Bi2S3 QDs) were synthesized as a nano-emitter to generate strong ECL signals in the MIP film. In the sensing process, a pulsed voltage applied to the PEDOT/MXene MIP film to generate both DPV and ECL signals for simultaneous dual-mode detection. Additionally, the liquid-liquid extraction with deep eutectic solvent (menthol: octanol 1:1) was used for the pre-concentration of the BPAF in the pond mud. Based on the sensing system, the ECL and DPV response showed the good linear relationships with the concentration of BPAF with the ranges of 0.01 μM–50 μM and 0.1 μM–50 μM and the detection limits of 0.0060 μM and 0.059 μM, respectively.

Boosting visible-light-promoted photodegradation of norfloxacin by S-doped g-C3N4 grafted by NiS as robust photocatalytic heterojunctions

As a result of industrial expansion and ill-considered exploitation of resources, serious environmental issues have recently emerged that have led to damage to the ecosystem. In particular, antibiotics, such as norfloxacin (NOR) have emerged as highly hazardous contaminants resulting from the increased use of these drugs worldwide. Photocatalysis-based degradation using heterojunctions has become almost the only way to permanently and eco-friendly degrade these pollutants. Herein, noble metal-free nanohybrids composed of S-doped g-C3N4 grafted by NiS (denoted as NiS/SCN) have been fabricated via hydrothermal and one-step polymerization (at 550 °C) procedures. The photocatalytic activity of 3 %NiS/SCN photocatalyst was almost 6- and 20-times as high as SCN and NiS, respectively, achieving 96.2 % NOR degradation within 90 min. The recommended photocarriers transfer pathway was suggested and supported experimentally. Considerably, loading a small amount of NiS cocatalyst over S-doped g-C3N4 boosted performance in addition to efficient reusability. This increased photocatalytic activity can be attributed to the fact that doping g-C3N4 with sulfur can reduce the bandgap and thus broaden the response range to visible-light, and the effective effect of Schottky junction can significantly improve the separation rate of electron-hole pairs. Accordingly, the constructed NiS/SCN nanocomposites are potential candidates for photocatalysis processes, particularly visible-light-induced degradation of organic pollutants.

Synthesis of a Multi-Template Molecular Imprinted Bulk Polymer for the Adsorption of Non-Steroidal Inflammatory and Antiretroviral Drugs

In this paper, we report the synthesis of a multi-template molecularly imprinted polymer (MIP) to target and extract naproxen, ibuprofen, diclofenac, emtricitabine, tenofovir disoproxil, and efavirenz from wastewater bodies. A bulk polymerization procedure was used to synthesize the MIP and non-imprinted polymer (NIP). The specific recognition sites for each target were obtained through the removal of the imprinted targeted compounds. The interaction of antiretroviral drugs (ARVs) and non-steroidal anti-inflammatory drugs (NSAIDs) compounds with the MIP was studied under various conditions such as pH, mass, concentration, and time factors. The results demonstrated the optimum conditions were 55 mg of MIP, pH 7.0, a concentration of 5 mg L−1, and a contact time of 10 min. For every compound studied, the extraction efficiencies for ARVs and NSAIDs in aqueous solutions was >96%. The adsorption capacity for the MIP was >0.91 mg·g−1. Adsorption obeys a second-order rate, and the Freundlich model explains the adsorption isotherm data. This study demonstrated that the synthesized multi-template MIP has huge potential to be employed for the removal of ARVs and NSAIDs from the environment as well as in drug purification or recovery processes.

Bimetal Pyrophosphate of CoNiP2O7@polypyrrole Nanocomposite‐ Based Electrode for Hybrid Supercapacitor Applications

A significant challenge in the realm of asynchronous capacitors is the development of innovative electrode materials with improved electrochemical behaviour and increased cycles. In this article, a new method is proposed for the facile synthesis of bi metal pyrophosphate anchored on polypyrrole (CoNiP2O7/NF@PPy) utilizing the hydrothermal and polymerization procedures. Cobalt nickel pyrophosphate nanoarrays are created, and they are successfully used as an electrode material for supercapacitors. The novelty of this work, a novel electrode of binder free mixed metal pyrophosphate (CoNiP2O7) composited to conducting polymer of polypyrrole is developed. Then, the prepared CoNiP2O7/NF CoNiP2O7/NF@PPy electrodes capacitive and diffusive mechanism discussed by using Trassati method. In electrochemical experiments, the CoNiP2O7/NF@PPy composite showed considerably enhanced specific capacity (1202 mAhg−1), which is much greater than that of pure CoNiP2O7/NF (819 mAhg−1). Additionally, the hybrid supercapacitor (CoNiP2O7/NF@PPy//AC) device manufactured had the highest energy density of 94.6 Wh kg−1. These findings indicate that this composite is a promising option for electrochemical capacitors.

Polyethylene Glycol Cross-Linked Hydrogel for Drug Absorption Properties

ABSTRACT Three-dimensional polymeric networks called hydrogels have drawn a lot of interest in a variety of biomedical applications because of their distinctive qualities, like high water content and biocompatibility. Hydrogels can be strengthened mechanically and become more stable via cross-linking. In this study, we described the synthesis and characterization of a cross-linked hydrogel made of polyethylene glycol (PEG) capable of absorbing drug. The hydrogel was created by using a polymerization procedure to cross-link PEG chains. In order to allay this worry, we added particular functional groups to the hydrogel matrix that had a strong affinity for glutaraldehyde. These functional groups made it easier for excess glutaraldehyde to be absorbed and sequestered inside the hydrogel, lowering its cytotoxic potential. After incubation with the hydrogel, the residual glutaraldehyde concentration in solution was measured in order to assess the glutaraldehyde absorption potential.

Reverse Engineering of Radical Polymerizations by Multi-Objective Optimization.

Reverse engineering is applied to identify optimum polymerization conditions for the synthesis of polymers with pre-defined properties. The proposed approach uses multi-objective optimization (MOO) and provides multiple candidate polymerization procedures to achieve the targeted polymer property. The objectives for optimization include the maximal similarity of molar mass distributions (MMDs) compared to the target MMDs, a minimal reaction time, and maximal monomer conversion. The method is tested for vinyl acetate radical polymerizations and can be adopted to other monomers. The data for the optimization procedure are generated by an in-house-developed kinetic Monte-Carlo (kMC) simulator for a selected recipe search space. The proposed reverse engineering algorithm comprises several steps: kMC simulations for the selected recipe search space to derive initial data, performing MOO for a targeted MMD, and the identification of the Pareto optimal space. The last step uses a weighted sum optimization function to calculate the weighted score of each candidate polymerization condition. To decrease the execution time, clustering of the search space based on MMDs is applied. The performance of the proposed approach is tested for various target MMDs. The suggested MOO-based reverse engineering provides multiple recipe candidates depending on competing objectives.

Improved performance of polyamide nanofiltration membrane embedded with zeolite beta

In this study, zeolite beta nanoparticles were incorporated into an interfacial polymerization procedure for the fabrication of thin film nanocomposites (TFNs). The successful introduction of zeolite beta into the polyamide (PA) selective layer was confirmed by surface attenuated total reflection infrared spectroscopy (ATR-FTIR), and x-ray photoelectron spectroscopy (XPS). The introduction of porous structured zeolite beta improved the water flux and rejection rate of the TFN membrane compared to the PA thin film composite (TFC) membrane. A quantitative performance coefficient is further proposed in this work, comprehensively considering the flux and rejection rate to evaluate the performance of TFNs. For five salt solutions, we found that the TFN0.3 membrane with 0.3 wt% of zeolite particles had a high coefficient of performance. With the help of zeolite particles, the TFN0.3 membrane achieved a high flux of 92.53 L/(m2·h) under an operating pressure of 5 bar. For ion separation from binary solutions, the TFN0.2 membrane with 0.2 wt% zeolite content was a better choice for a wide range of binary mixtures, which is because the addition of zeolite beta resulted in smaller pore sizes, the strongest zeta potential, and the thickest thickness (scanning electron microscope, SEM determined) of the TFN0.2 membrane. All these factors contribute to the selectivity of the TFN0.2 membrane. Our study provides an efficient and cost-effective method to simultaneously improve the permeability and rejection of nanofiltration membranes, facilitating the development of nanofiltration for water recovery.

SYNTHESIS AND CHARACTERIZATION OF MOLECULAR IMPRINTED POLYMERS FOR PHENYLBUTAZONE EXTRACTION

Phenylbutazone is a pharmaceutical substance often added to rheumatic herbs. However, because of the complexity of the matrix caused by the presence of compounds in herbal medicines, the determination of phenylbutazone requires a time-consuming sample preparation process prior to analysis. This study was conducted to develop a specific sorbent that can be used to prepare phenylbutazone in herbal medicine. The performance of phenylbutazone Molecularly Imprinted Polymer (MIP) was evaluated using three distinct porogens (ethanol, methanol, and methanol-chloroform (1:1)) and two polymerization procedures (bulk and precipitation). According to the results of the polymer optimization, the polymer generated by precipitation in methanol-chloroform (1:1) has good sorbent characteristics. FTIR physical characterization revealed complete polymerization. The bulk procedure produces a more physically stable sorbent than the precipitation method does. Keywords: MIP Performance Evaluation, Phenylbutazone Molecular Imprinted Polymer, Polymer Imprinting Factor

Block-copolymer-armed star polyampholyte with pH- and temperature-tunable supramolecular nanostructures for enhanced dye adsorption

The present investigation involves the synthesis of a series of block-copolymer-armed polyampholyte star polymers with sensitivity to changes in pH and temperature. The polymers are prepared using poly(2-hydroxyethyl methacrylate) core, while the arms are composed of a block copolymers consisting of acrylic acid and 2-(dimethylamino)ethyl methacrylate. The synthesis process involves a three-stage polymerization procedure utilizing reversible addition fragmentation chain transfer. The synthesized structures undergo characterization, and their self-assembly behavior is examined in relation to the adsorption of methylene blue, methyl orange, and the concurrent adsorption of both dyes. The development of spherical electrostatic complexes with varying diameters are seen as a consequence of pH variation. The present study investigates the impact of various parameters, including time, block location in the arms, pH, molecular weight, self-assembly effects, dye concentration, and temperature, on the process of adsorption. The study elucidates the adsorption phenomenon by examining its kinetics, thermodynamics, and adsorption isotherms. The findings of the study reveal that the greatest percentages of methylene blue adsorption are seen under alkaline pH conditions, whereas the most adsorption of methyl orange occurres under acidic pH conditions. The adsorption process by star-block polymers may be characterized as a spontaneous and endothermic mechanism, including heterojunction and multilayer adsorption. The polymers show promise for water purification applications due to their ability to simultaneously adsorb two dyes and their sensitivity to temperature and pH.

Greener preparation of a flexible material based on macaw palm oil derivatives and CO2

The polymerization procedure reduces the aminolysis drawback found in conventional synthesis for renewable polyhydroxyurethanes. The polymer is from two macaw palm oil derivatives and presents flexible, luminescent, and waterproofing features.

Superacid catalyzed triptycene-based polymer to enhance membrane permeability for molecular sieving of nitrogen over VOC

Superacid catalysis, a suitable method for the synthesis of membrane materials owing to its facile polymerization procedure, has been extensively studied. However, superacid-catalyzed binary coplanar polymer membranes generally exhibit low permeabilities. In this study, a rigid 3D triptycene-based polymer was synthesized by the superacid catalysis of triptycene with trifluoroacetophenone and diphenyl ether to enhance membrane permeability for the molecular sieving of nitrogen over volatile organic compound (VOC). The synthesis of polymers with (CF3PhET) or without triptycene (CF3PhE) was investigated using different characterizations. The triptycene content of the synthesized polymers was optimized based on an analysis of the molecular weight, membrane-forming properties, and separation performance. The separation performances of membranes fabricated using CF3PhE, CF3PhET, and a mixture of CF3PhE and triptycene were compared. Results showed that the introduction of non-coplanar triptycene in the membrane can increase permeability by nearly 60 times due to the enhanced free volume, from 30 Barrer for the CF3PhE membrane to 1755 Barrer for the membrane with 5 ​mol% triptycene content for the separation of a 3 ​mol% nitrogen/cyclohexane mixture at 1 ​L/(m2·min). Furthermore, the rejection remains constant, which provides an effective idea for the synthesis of membrane materials with high performance using superacid catalysis.

An Overview on Polymer-Based Electrolytes with High Ionic Mobility for Safe Operation of Solid-State Batteries

Liquid electrolytes used in commercial Li-ion batteries are generally based on toxic volatile and flammable organic carbonate solvents, thus raising safety concerns in case of thermal runaway. The most striking solution at present is to switch on all solid-state designs exploiting polymer materials, films, ceramics, low-volatile, green additives, etc. The replacement of liquids component with low-flammable solids is expected to improve the safety level of the device intrinsically. Moreover, a solid-state configuration is expected to guarantee improved energy density systems. However, low ionic conductivity, low cation transport properties and issues in cell manufacturing processes must be overcome [1].Electrochemical performance in lab-scale devices can be readily improved using different RTILs or specific low-volatile additives. Here, an overview is offered of the recent developments in our labs on innovative polymer-based electrolytes allowing high ionic mobility, particularly attractive for safe, high-performing, solid-state Li-metal batteries, and obtained by different techniques, including solvent-free UV-induced photopolymerization. Cyclic voltammetry and galvanostatic charge/discharge cycling coupled with electrochemical impedance spectroscopy exploiting different electrode materials (e.g., LFP, Li-rich NMC, LNMO, Si/C) demonstrate specific capacities approaching theoretical values even at high C-rates and stable operation for hundreds of cycles at ambient temperature [2,3]. Direct polymerization procedures on top of the electrode films are also used to obtain an intimate electrode/electrolyte interface and full active material utilization in both half and full-cell architectures. In addition, results of composite hybrid polymer electrolytes [4] and new single-ion conducting polymers [5] are shown, specifically developed to attain improved ion transport and high oxidation stability for safe operation with high voltage electrodes even at ambient conditions.