Synthesis of Porous BPPO-Based Anion Exchange Membranes for Acid Recovery Via Diffusion Dialysis

Diffusion dialysis (DD) is an anion exchange membrane-based functional separation process used for acid recovery. TMA (trimethylamine) and BPPO (brominated poly (2,6-dimethyl-1,4-phenylene oxide) were utilized in this manuscript to formulate AEMs (anion exchange membranes) for DD (diffusion dialysis) using the phase-inversion technique. FTIR (Fourier transfer infrared) analysis, proton NMR spectroscopy, morphology, IEC (ion exchange capacity), LER (linear expansion ratio), CR (fixed group concentration), WR (water uptake/adsorption), water contact angle, chemical, and thermal stability, were all used to evaluate the prepared membranes. The effect of TMA content within the membrane matrix on acid recovery was also briefly discussed. It was reported that porous AEMs have a WR of 149.6% to 233.8%, IEC (ion exchange capacity) of 0.71 to 1.43 mmol/g, CR (fixed group concentration) that ranged from 0.0046 mol/L to 0.0056 mol/L, LER of 3.88% to 9.23%, and a water contact angle of 33.10° to 78.58°. The UH (acid dialysis coefficients) for designed porous membranes were found to be 0.0043 to 0.012 m/h, with separation factors (S) ranging from 13.14 to 32.87 at the temperature of 25 °C. These observations are comparable to those found in the DF-120B commercial membrane with UH of 0.004 m/h and S of 24.3 m/h at the same temperature (25 °C). This porous membranes proposed in this paper are excellent choices for acid recovery through the diffusion dialysis process.

Aliphatic Anion Exchange Ionomers with Long Spacers and No Ether Links by Ziegler–Natta Polymerization: Properties and Alkaline Stability

In this work we report the synthesis of poly(vinylbenzylchloride-co-hexene) copolymer grafted with N,N-dimethylhexylammonium groups to study the effect of an aliphatic backbone without ether linkage on the ionomer properties. The copolymerization was achieved by the Ziegler–Natta method, employing the complex ZrCl4 (THF)2 as a catalyst. A certain degree of crosslinking with N,N,N′,N′-tetramethylethylenediamine (TEMED) was introduced with the aim of avoiding excessive swelling in water. The resulting anion exchange polymers were characterized by 1H-NMR, FTIR, TGA, and ion exchange capacity (IEC) measurements. The ionomers showed good alkaline stability; after 72 h of treatment in 2 M KOH at 80 °C the remaining IEC of 76% confirms that ionomers without ether bonds are less sensitive to a SN2 attack and suggests the possibility of their use as a binder in a fuel cell electrode formulation. The ionomers were also blended with polyvinyl alcohol (PVA) and crosslinked with glutaraldehyde. The water uptake of the blend membranes was around 110% at 25 °C. The ionic conductivity at 25 °C in the OH− form was 29.5 mS/cm.

Adsorption and Release Characteristics of Purified and Non-Purified Clinoptilolite Tuffs towards Health-Relevant Heavy Metals

The occurrence of health-relevant contaminants in water has become a severe global problem. For treating heavy-metal-polluted water, the use of zeolite materials has been extended over the last decades, due to their excellent features of high ion exchange capacity and absorbency. The aim of this study was to assess the effect of heavy metal uptake of one purified (PCT) and two non-purified clinoptilolite tuffs (NPCT1 and NPCT2) in aqueous solutions on monovalent ions Ni+, Cd+, Cs+, Ba+, Tl+, and Pb+. Experiments were furthermore carried out in artificial gastric and intestinal fluids to mimic human digestion and compare removal efficiencies of the adsorbent materials as well as release characteristics in synthetic gastric (SGF) and intestinal fluids (SIF). Batch experiments show low sorption capacities for Ni+ and Cd+ for all studied materials; highest affinities were found for Ba+ (99–100%), Pb+ (98–100%), Cs+ (97–98%), and Tl+ (96%), depending on the experimental setup for the PCT. For the adsorption experiments with SGF, highest adsorption was observed for the PCT for Pb+, with an uptake of 99% of the lead content. During artificial digestion, it was proven that the PCT did not release Ba+ cations into solution, whereas 13574 ng·g−1 and 4839 ng·g−1 of Ba+ were measured in the solutions with NPCT1 and NPCT2, respectively. It was demonstrated that the purified clinoptilolite tuff is most effective in remediating heavy-metal-polluted water, particularly during artificial digestion (99% of Pb+, 95% of Tl+, 93% of Ba+). In addition, it was shown that the released amount of bound heavy metal ions (e.g., barium) from the non-purified clinoptilolite tuffs into the intestinal fluids was significantly higher compared to the purified product.

Promising Potential of Eugenol (Clove) Based Organic Membrane for Polymer Electrolyte Membrane Fuel Cell

Fuel cell is one of alternative method to replace fossil fuel energy. The important component of fuel cell is a membrane that used for separating cathode and anode also as a proton conductor. The purpose of this research is to produce polymer electrolyte membrane from poly (eugenol sulfonate) (PES) as polymer matrix, characterize the resulting membrane analysis using ionic properties analysis by calculating ionic conductivity using impedance spectroscopy, ion exchange capacity (IEC), solvent absorption analysis by calculating water uptake and methanol permeability, and studying mechanism Proton transport that occurs on the membrane. This research was initiated by making polymer of PES, and then fabrication and characterization of electrolytic polymer membrane. The formed membrane has an optimal proton conductivity of 0.00095 S.cm-1 with PES composition of 22% (wt).

Evaluation of power generation and treatment efficiency of dairy wastewater in microbial fuel cell using TiO2 – SPEEK as proton exchange membrane

The aim of this study is to synthesis SPEEK composite proton exchange membrane with the addition of TiO2 nanofillers for microbial fuel cell application. SPEEK composite membrane with varying weight percentage of TiO2 (2.5, 5, 7.5 and 10%) was prepared to study the effect of TiO2 concentration on membrane performance. Synthesized composite membranes were subjected to various characterization studies such as FT-IR, XRD, Raman spectroscopy; TGA, UTM and SEM. Physico-chemical properties of membrane such as water uptake capacity, ion exchange capacity and thickness were also analyzed. 5% TiO2 – SPEEK composite membrane exhibited the higher water uptake capacity value and Ion exchange capacity value of 31% and 1.71 meq/g respectively. Performance of the MFC system with TiO2 – SPEEK membranes were evaluated and compared with the pristine SPEEK and Nafion membrane. 5% TiO2 – SPEEK membrane produced the higher power density (1.22 W/m2) and voltage (0.635 V) than the other membranes investigated. Efficacy of MFC in wastewater treatment was evaluated based on the chemical oxygen demand (COD), total organic carbon content and turbidity. Biofilm growth over the surface of the electrodes was also analyzed using scanning electron microscopy.

Sulfonated Polyimide Membranes Derived from a Novel Sulfonated Diamine with Pendant Benzenesulfonic Acid for Fuel Cells

For improving the hydrolytic stability of sulfonated polyimides consisting of five membered anhydrides, novel sulfonated polyimides (NSPIs) were prepared via polymerization of 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), with a novel diamine monomer with a pendant sulfonic acid group and 4,4-oxydianiline. Water uptake of this NSPI with an excellent film-forming ability was almost equal to that of Nafion® 117, while their ion exchange capacity (IEC) was 22% higher than Nafion® 117. The loss in weight decreased by 53% and loss in IEC decreased by 66% compared to that of Nafion® 117; both were used to quantitatively measure hydrolytic stability, and radical oxidative stability also increased by 75% when compared with Nafion® 117. Mechanically, this NSPI was superior, and its proton conductivity was higher than Nafion® 117 at elevated temperatures. All these improvements were due to the introduction of this pendant group. Taken together, we herein report a promising renewable energy source based on SPIs capable of displaying proton conductivity and enhanced hydrophilicity.

Modelling and simulation of the ion exchange process for Zn2+(aq) removal using zeolite NaY

The treatment of water contaminated by toxic metals using ion exchange with zeolites is becoming attractive due to its low capital costs and high potential for removal capacity. Mathematical modelling of this process allows for operational control and estimation of the ability to remove these metals. In this work, the kinetic modelling was performed based on finite bath experimental data, with Intraparticle Diffusion (IPD) and External Liquid Film Mass Transfer (MTEF) models. The models Thomas (TH), Yoon-Nelson (YN) and Solid Film Mass Transfer (MTSF) were used to estimate the saturation time, ion exchange capacity and sizing variables of a fixed bed column. For the finite bath system, the results showed that the mass transfer was better represented by the IPD phenomenon. The breakthrough curve obtained by the Aspen Adsorption (MTSF) model presented the best fit, compared with experimental data, with R2≥0.9923. The average ion exchange capacities calculated for MTSF, TH and YN were respectively 2.22, 2.12 and 2.07 meq Zn2+(aq)/ g of zeolite. The model simulated with Aspen Adsorption was also used to analyze the continuous system behaviour, by varying the height of the bed. It was observed that increasing the height, the saturation time and ion exchange capacity also increase, while reducing the height makes axial dispersion the predominant mass transfer phenomenon, which reduces the diffusion of Zn2+(aq) ions.

Copper Rich Composite Materials Based on Carboxylic Cation Exchangers and Their Thermal Transformation

The effect of a cupric deposit (Cu2+, CuO) on the thermal decomposition of carboxylic cation exchangers (CCEs) is not known, and such studies may have practical significance. CCEs have a very high ion exchange capacity, so an exceptionally large amount of CuO (which is a catalyst) can be precipitated inside them. Two CCEs, macroreticular (Amberlite IRC50) and gel-like (Amberlite IRC86), served as a polymeric support to obtain copper-rich hybrid ion exchangers. Composites with CuO particles inside a polyacrylic matrix (up to 35.0 wt% Cu) were obtained. Thermal analyses under air and under N2 were performed for CCEs in the H+ and Cu2+ form with and without a CuO deposit. The results of sixteen experiments are discussed based on the TG/DTG curves and XRD patterns of the solid residues. Under air, the cupric deposit shifted the particular transformations and the ultimate polymeric matter decomposition (combustion) toward lower temperatures (even about 100–150 °C). Under N2, the reduction of the cupric deposit to metallic copper took place. Unique composite materials enriched in carbonaceous matter were obtained, as the products of polymeric matrix decomposition (free radicals and hydrogen) created an additional amount of carbon char due to the utilization of a certain amount of hydrogen to reduce Cu (II) to Cu0.

Electrospinning of Polyepychlorhydrin and Polyacrylonitrile Anionic Exchange Membranes for Reverse Electrodialysis

The saline gradient present in river mouths can be exploited using ion-exchange membranes in reverse electrodialysis (RED) for energy generation. However, significant improvements in the fabrication processes of these IEMs are necessary to increase the overall performance of the RED technology. This work proposes an innovative technique for synthesizing anion exchange membranes (AEMs) via electrospinning. The AEM synthesis was carried out by applying a high voltage while ejecting a mixture of polyepichlorohydrin (PECH), 1,4-diazabicyclo [2.2.2] octane (DABCO® 33-LV) and polyacrylonitrile (PAN) at room temperature. Different ejection parameters were used, and the effects of various thermal treatments were tested on the resulting membranes. The AEMs presented crosslinking between the polymers and significant fiber homogeneity with diameters between 1400 and 1510 nm, with and without thermal treatment. Good chemical resistance was measured, and all synthesized membranes were of hydrophobic character. The thickness, roughness, swelling degree, specific fixed-charge density and ion-exchange capacity were improved over equivalent membranes produced by casting, and also when compared with commercial membranes. Finally, the results of the study of the electrospinning parameters indicate that a better performance in electrochemical properties was produced from fibers generated at ambient humidity conditions, with low flow velocity and voltage, and high collector rotation velocity.

Fast Bulky Anion Conduction Enabled by Free Shuttling Phosphonium Cations

Highly conductive anion-exchange membranes (AEMs) are desirable for applications in various energy storage and conversion technologies. However, conventional AEMs with bulky HCO3- or Br- as counterion generally exhibit low conductivity because the covalent bonding restrains the tethered cationic group’s mobility and rotation. Here, we report an alternative polyrotaxane AEM with nontethered and free-shuttling phosphonium cation. As proved by temperature-dependent NMR, solid-state NMR, and molecular dynamics simulation, the phosphonium cation possesses a thermally trigged shuttling behavior, broader extension range, and greater mobility, thus accelerating the diffusion conduction of bulky anions. Owing to this striking feature, high HCO3- conductivity of 105 mS cm-1 at 90°C was obtained at a relatively lower ion-exchange capacity of 1.17 mmol g-1. This study provides a new concept for developing highly conductive anion-exchange membranes and will catalyze the exploration of new applications for polyrotaxanes in ion conduction processes.