Anion exchange membrane with viologen moiety as anion exchange groups and generation of photo-induced electrical potential from the membrane

An anion exchange membrane with a viologen moiety was prepared by the reaction of a film of chloromethylated polysulfone and 4,4′-bipyridine. The anion exchange membrane showed a high electrical resistance and a high transport number of anions due to the development of high crosslinking by the diamine. After the membrane had been swollen with ethylene glycol, photo-voltage and photo-current (82 mV, 410 nA at 200 kΩ load, 160 μm thick membrane) were generated from the membrane upon photo-irradiation.     

Fundamental studies of a new series of anion exchange membranes: membrane preparation and characterization

Chemical cross-linking anion exchange series membranes were prepared from linear engineering plastics poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) by conducting the processes of bromination and amination at both benzyl and aryl positions. Compared with the traditional technologies, the membrane route described in this paper has cancelled the chloromethylation process and thus, given up the use of chloromethyl methyl ether, which has been considered as a potential harmful toxicity material. The ion exchange capacity, water content, membrane potential and transport number of membranes were studied. The results show that the membrane properties are significantly affected by the bromination processes: benzyl-substitution will enhance the ion exchange capacity and water content, while the aryl-substitution will decrease the water content with approximately unchanged ion exchange capacity. By properly balancing them, a series of membranes can be obtained to comply with different industrial requirements, such as diffusional dialysis, electrodialysis, and water splitting processes.     

Interaction between anionic polyelectrolytes and anion exchange membranes and change in membrane properties

Electrodialytic transport properties of anion exchange membranes were measured after formation of anionic polyelectrolyte layers on the membrane surfaces: relative transport number of various anions to chloride ions, current efficiency and apparent diffusion coefficients of neutral molecules. The anionic polyelectrolyte layers were formed by immersing the membrane into an aqueous solution of polycondensation product of sodium naphthalene sulfonate and formaldehyde or polystyrene sulfonic acid.

The change in the relative transport number between anions was remarkable in the anion exchange membrane with high ion exchange capacity by forming the layer. Results were: the relative transport number of sulfate ions to chloride ions decreased and those of nitrate ions to chloride ions, fluoride ions to chloride ions and bromide ions to chloride ions increased compared with the corresponding membrane. Although the apparent diffusion coefficient of neutral molecules suggested clogging of the membrane pores by the polyelectrolyte, anions with higher hydrated ionic diameter were able to permeate through the membrane easily. This means that difference of electrostatic repulsion force against two anions is effective on the change in the relative transport number of anions.     

Preparation and properties of anion exchange membranes having pyridinium or pyridinium derivatives as anion exchange groups

Anion exchange membranes with pyridinum groups and various pyridinium derivative groups were prepared from a copolymer membrane composed of chloromethylstyrene and divinylbenzene, and pyridine and pyridine derivatives. The anion exchange membranes obtained showed excellent electrochemical properties in electrodialysis. The transport numbers of sulfate ions, bromide ions, nitrate ions, and fluoride ions relative to chloride ions were evaluated in connection with the species of a substituent and the position of the substituent in the pyridinium groups. In general, when a hydrophilic substituent (methanol groups) existed at the 2-position of the pyridinium groups, nitrate ions and bromide ions, which are less hydrated, permeated through the membranes with difficulty, and sulfate ions permeated selectively through the membranes. On the other hand, when hydrophobic groups, for example, ethyl groups, existed at the 2-position of the pyridinium groups, bromide ions and nitrate ionspermeated selectively through the membranes and fluoride ions had difficulty permeating through the membranes. The carbon number of the alkyl chain of 4-alkyl pyridinium groups also affected permeation of nitrate ions and bromide ions due to the change in hydrophilicity of the membranes. Though the hydration of the anions and the species of the substituent at the 2-position of the pyridinium groups were related to selective permeation of the anion through the membranes, permeation of sulfate ions was not as sensitive to the hydrophilicity of the membranes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 49–58, 1998     

Transport of acetylcholine in a membrane

A laminate model of the cleft-plus-postsynaptic membrane structure of the neuromuscular junction was studied. In order to prepare a model of the postsynaptic membrane, the properties of acetylcholine (Ach) receptor-rich vesicles purified from Torpedo fish were measured. Immobilization of vesicles was demonstrated by various methods, in particular, by investigating collagen and carrageenan matrices as models of the fluidfilled fibrous matrix of the cleft. It was found that a laminated system employing a liquid membrane-containing vesicle suspension, together with a swollen collagen membrane, is an appropriate model for examining important transport/reception aspects of the cleft-plus-postsynaptic membrane structure. Combined transport with immobilization of Ach in the liquid membrane system was elucidated and effective diffusivities in the vesicle suspension layer were calculated. Effective diffusivities of the composite system simulating the cleft and the postsynaptic membrane were evaluated as well. These data illustrate the importance of penetrant immobilization in retarding the diffusion process during neurotransmission.     

Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange

The formation reaction and the intercalation of adenosine triphosphate (ATP) were studied for hydrotalcite (HT), a layered double hydroxide (LDH) of magnesium and aluminum. Hydrotalcite with nitrate ions in the interlayer (HT-NO(3)) was formed (A) by dropwise addition of a solution of magnesium and aluminum nitrates (pH ca. 3) to a sodium hydroxide solution (pH ca. 14) until the pH decreased from 14 to 10 and (B) by dropwise addition of the NaOH solution to the solution of magnesium and aluminum nitrates with pH increasing from 3 to 10. The precipitate obtained with method B was contaminated with aluminum hydroxide and the crystallinity of the product was low, possibly because aluminum hydroxide precipitates at pH 4 or 5 and remains even after HT-NO(3) forms at pH above 8. With method A, however, the precipitate was pure HT-NO(3) with increased crystallinity, since the solubility of aluminum hydroxide at pH above and around 10 is high as dissolved aluminate anions are stable in this high pH region, and there was no aluminum hydroxide contamination. The formed HT-NO(3) had a composition of [Mg(0.71)Al(0.29)(OH)(2)](NO(3))(0.29).0.58H(2)O. To intercalate ATP anions into the HT-NO(3), HT-NO(3) was dispersed in an ATP solution at pH 7. It was found that the interlayer nitrate ions were completely exchanged with ATP anions by ion exchange, and the interlayer distance expanded almost twice with a free space distance of 1.2 nm. The composition of HT-ATP was established as [Mg(0.68)Al(0.32)(OH)(2)](ATP)(0.080)0.88H(2)O. The increased distance could be explained with a calculated molecular configuration of the ATP as follows: An ATP molecule is bound to an interlayer surface with the triphosphate group, the adenosine group bends owing to its bond angles and projects into the interlayer to a height of 1 nm, and the adenosine groups aligned in the interlayer support the interlayer distance.     

Industrial recovery of mixed acid (HF + HNO3) from the titanium spent leaching solutions by diffusion dialysis with a new series of anion exchange membranes

The results of the development of the industrial diffusion dialysis technology and the unit based on it for mixed acid recovery from titanium metal processing have been considered. Mixed acid can be selectively separated from the spent liquor contained mainly HNO₃, HF and titanium ions by diffusion dialysis using a new series of anion exchange membranes. The results showed that this separation is seriously affected by the membrane water content and ion exchange capacity (IEC). Some titanium complex anion (TiF₆)²⁻ give rise to the difficulty in separation so that the best separation efficiency does not occur at the cases of high water content and IEC of membranes. By controlling the membrane preparation conditions (bromination content and position), a desired membrane for this system has been obtained with both relatively high acid recovery ratio and acid/titanium selectivity.

Economic estimation was conducted based on an industrial diffusion dialyser with 499 sheets of 1600 mm×800 mm membrane and the practical runs parameters: process quantity 2400 m³ per year, total acid recovery ratio 85%. The results showed that the investment could be recovered within 5 months. After 5 years’ run, one such dialyser can bring about CN$ 4.3 million profits besides the significant environmental benefits.     

Retention of some glucosinolates in anion exchange chromatography. Part I: Qualitative study on a silica-trialkylammonium exchanger

Summary The retention and separation of glucosinolates, as organic anions, were studied on a silica-based strong anion exchanger under isocratic elution conditions. All glucosinolates carry the same functional ionic group (-OSO ₃ ^– ), however they do not have the same retention in anion exchange chromatography. The plots of capacity factors of organic anions versus the reciprocal of eluent ion concentration show good linearity. From the slope and y-intercept data the major retention mechanisms are interpreted as ion exchange and reversed-phase interactions. The effects of nature and concentration of the eluent ion and the influence of organic modifier addition to the aqueous buffered mobile phase are also investigated. Direct and indirect UV detection were used.Our results open the way for the development of new systems for intact glucosinolate analysis which are easier to use than the present ion-pairing chromatographic method.     

Extraction chromatography of common anions in liquid-liquid anion exchange systems. Part. III. Monobasic aliphatic organic acids and their sodium salts as eluants

Summary The chromatographic behaviour of anions on paper strips treated with tri-n-octylamine (TOA) salts or Aliquat 336 and developed with aqueous solutions of acetic, formic, monochloroacetic or trifluoroacetic acids and their sodium salts was investigated. Liquid-liquid extraction of organic acids by 0.1 M solution of TOA in benzene as well as the anion exchange between benzene solutions of TOA salts or Aliquat 336 (in acetate form) in benzene and aqueous solutions of sodium halides was also studied. It was found that extraction increases in the following order of the acids: CH₃COOOH<HCOOH<CH₂CICOOH<CF₃COOH; the relative affinity of organic anions to the quaternary alkyl-ammonium cation also increase in a similar order. The extraction of acid in excess over the amount necessary to neutralize the amine was observed for all four acids. The R_F values of anions investigated depend markedly on the type of organic acids or their salts and their concentration in the mobile phase. Halide ions are more strongly retained on paper treated with Aliquat 336 as compared with TOA salts. The chromatographic systems investigated offer many possibilities to separate various anion mixtures.Parts and II: refs. [1, 2].     

Transport properties of thermally responsive anion exchange membranes containing N‐isopropylacrylamide in electrodialysis

Anion exchange membranes containing N‐isopropylacrylamide as a component were prepared, and their electrochemical properties were examined. The membranes were crosslinked with ethylene glycol dimethacrylate and contained weakly basic or strongly basic anion exchange groups. The dependence of electrochemical properties of the membranes (electrical resistance, transport number of anions, water content, and reduced osmotic flux) on temperature was completely different from those of the anion exchange membrane without N‐isopropylacrylamide. For example, the reduced osmotic flux decreased with increasing temperature until 40°C, and the transport number of chloride ions increased with increasing temperature from 25.0°C, although those of the conventional membrane monotonously increased or decreased. The transport numbers of various anions relative to chloride ions in electrodialysis were evaluated at a different temperature. Although the transport numbers between anions did not change appreciably in the conventional membrane with temperature, those of the anion exchange membranes with N‐isopropylacrylamide changed with a temperature dependent on the hydration degree of anions: permeation of less‐hydrated anions such as nitrate and bromide ions compared with chloride ions increased with increasing temperature, and that of strongly hydrated anions such as sulfate and fluoride ions decreased with increasing temperature. This is based on the increase or decrease in uptake of the anions in the membrane with the change in temperature because hydrophilicity of the membranes changes with temperature due to the apparent aggregation of isopropyl groups in the membranes. And the change in electrochemical properties and transport numbers of various anions relative to chloride ions with temperature was completely reversible with increasing or decreasing temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 793–804, 1999     

Simultaneous recovery of EDTA and lead(II) from their chelated solutions using a cation exchange membrane

Factors affecting the efficiency of electrochemical recovery of EDTA and Pb(II) from their chelated solutions were systematically examined using a cation exchange membrane Neosepta CM-1. The catholyte contained an equimolar amount of Pb(II) and EDTA, and the anolyte contained 0.1 M NaNO₃. The iridium oxide coated on titanium (IrO₂/Ti) and stainless steel were used as anode and cathode, respectively. Experiments were carried out at different current densities (46.3–185 A/m²), initial catholyte pH values (1.47–6.02) and Pb(II) concentrations (0.005–0.03 M). An economically feasible current efficiency and recovery percentages of Pb(II) and EDTA could be achieved if the concentration of the chelated Pb(II) was sufficiently high.     

The effect of the counter anion on the transport of thiourea in a PVC-based polymer inclusion membrane using Capriquat as carrier

This paper describes the effect of four counter anions (CH₃COO⁻, Cl⁻, NO₃⁻, ClO₄⁻) of the trioctylmethylammonium (TOMA) cation on the rate of solvent extraction of thiourea and its transport across poly(vinyl chloride) (PVC)-based polymer inclusion membranes (PIMs). The membranes also contained 2-nitrophenyl octyl ether (NPOE) as the plasticizer while chloroform was used as diluent in the solvent extraction studies. It is demonstrated that the counter anion affects substantially the rate of membrane transport and the degree of extraction follows the order: CH₃COO⁻ > Cl⁻ > NO₃⁻ ? ClO₄⁻. The transport rate is negligible for the perchlorate anion. This order is consistent with thiourea interacting with the counter anion through hydrogen bonding to form a heteroconjugate anion.     

Influence of operating conditions on the rejection of cobalt and lead ions in aqueous solutions by a nanofiltration polyamide membrane

The potential use of nanofiltration polyamide membrane for removing cobalt and lead ions from wastewater was investigated. Rejection experiments were conducted with Pb(NO₃)₂ and Co(NO₃)₂ in both single-salt solutions and mixtures. Experimental rejection rates were corrected for concentration polarization phenomenon by means of film theory. The structural features of the membrane (pore radius and thickness-to-porosity ratio) were first estimated from the fitting of glucose rejection rates. Its surface charge properties were then investigated in single-salt solutions at pH values between 3 and 7. Rejection of both heavy metal ions was found to be influenced by operating conditions such as permeate flux, solution pH and feed salt concentration. In single-salt solutions, rejection of lead was higher than that of cobalt at pH ≥ 5. This behavior may be explained by (i) higher normalized volume charge density in the Pb(NO₃)₂ than in the Co(NO₃)₂ solution and (ii) lower ionic strength of the Pb(NO₃)₂ solution as compared with the Co(NO₃)₂ solution. At pH < 5, the dielectric exclusion would be more important for Co(NO₃)₂ than for Pb(NO₃). Lead rejection was almost the same in both single-salt solutions and ternary mixtures, whereas cobalt rejection was strongly affected by the presence of lead. Cobalt was found to be rejected much more than lead in mixtures at equal mass concentrations, the difference between rejections of the two cations being greater as pH increased.     

Transport properties of protic ionic liquids,pure and in aqueous solutions: Effects of the anion and cation structure

Ionic conductivities of twelve protic ionic liquids (PILs) and their mixtures with water over the whole composition range are reported at 298.15 K and atmospheric pressure. The selected PILs are the pyrrolidinium-based PILs containing nitrate, acetate or formate anions; the formate-based PILs containing diisopropylethylammonium, amilaminium, quinolinium, lutidinium or collidinium cations; and the pyrrolidinium alkylcarboxylates, [Pyrr][C_nH_2n+1COO] with n = 5–8. This study was performed in order to investigate the influence of molecular structures of the ions on the ionic conductivities in aqueous solutions. The ionic conductivities of the aqueous solutions are 2–30 times higher than the conductivities of pure PILs. The maximum in conductivity varies from ww=0.41 ??to ??0.74$w_w=0.41\text{\hspace{0.17em}??}\text{to}\text{\hspace{0.17em}??}0.74$ and is related to the nature of cations and anions. The molar conductance and the molar conductance at infinite dilution for (PIL + water) solutions are then determined. Self-diffusion coefficients of the twelve protic ionic liquids in water at infinite dilution and at 298.15 K are calculated by using the Nernst–Haskell, the original and the modified Wilke–Chang equations. These calculations show that similar values are obtained using the modified Wilke–Chang and the Nernst–Haskell equations. Finally, the effective hydrodynamic (or Stokes) radius of the PILs was determined by using the Stokes–Einstein equation. A linear relationship was established in order to predict this radius as a function of the anion alkyl chain length in the case of the pyrrolidinium alkylcarboxylates PILs.     

Application of a cellulose phosphate ion exchange membrane as a binding phase in the diffusive gradients in thin films technique for measurement of trace metals

The technique of diffusive gradients in thin films (DGT) is a newly developed analytical technique capable of measuring in situ concentrations of trace metals in the environment. The technique employs a thin film diffusive hydrogel (with well-defined diffusion properties) in contact with a binding phase capable of binding metal ions of interest. In this work, we demonstrate, for the first time, the use of a commercially available solid ion exchange membrane (Whatman P81) as the binding phase in DGT analysis. The cellulose phosphate-based Whatman P81 membrane is a strong cation exchange membrane. Its performance characteristics as a new binding phase in DGT measurement of Cu²⁺ and Cd²⁺ were systematically investigated. Several advantages over the conventional ion exchange resin-embedded hydrogel binding phases used in DGT were observed including simple preparation, ease of handling, and reusability. The binding capacities of the material to various metal ions were examined both collectively and individually. The binding phase preferentially binds to transition metal ions rather than matrix ions such as potassium, sodium, calcium and magnesium, which are competitive species in natural waters. Within the optimum pH range (pH 4.0-9.0), the maximum non-competitive binding capacities of the membrane for Cu²⁺ and Cd²⁺ were 3.22 and 3.07 μmol cm⁻², respectively. The suitability of the new membrane-based binding phase for DGT applications was validated experimentally. The experimental results demonstrated excellent agreement with theoretically predicted trends. The measurement was not degraded after four consecutive reuses of the cellulose phosphate binding phase.     

The temperature dependence of hydrogen and anion adsorption at a Pt( 100) electrode in aqueous H2SO4 solution

Research on the underpotential deposition of H (upd H) and anion adsorption on Pt( 100) in 0.5 M aqueous H₂SO₄ solution by cyclic voltammetry (CV) indicates that the overall adsorption/desorption charge density is affected strongly by variation of the temperature T, and that it decreases by about 1/3 when T is raised from 293 to 328 K. The sharp peak at 0.375 V vs. RHE assigned to the anion adsorption decreases its potential, current density and charge density. The CV feature assigned to the upd H, a wide shoulder overlapping the sharp peak, also decreases with T augmentation, but the decline of its charge density is less pronounced. The results indicate that the H_upd and anion surface coverages, θ_HAN and θ_AN respectively are strongly temperature-dependent. This behavior may be assigned to lateral repulsive interactions.     

Preparation and characterization of PVDF‐based blend membranes as polymer electrolyte membranes in fuel cells: Study of factor affecting the proton conductivity behavior

There is a huge demand especially for polyvinylidene fluoride (PVDF) and its copolymers to provide high performance solid polymer electrolytes for use as an electrolyte in energy supply systems. In this regard, the blending approach was used to prepare PVDF‐based proton exchange membranes and focused on the study of factor affecting the ir proton conductivity behavior. Thus, a series of copolymers consisting of poly (methyl methacrylate) (PMMA), polyacrylonitrile (PAN), and poly(2‐acrylamido‐2‐methyl‐l‐propanesulfonic acid) (PAMPS) as sulfonated segments were synthesized and blended with PVDF matrix in order to create proton transport sites in PVDF matrix. It was found that addition of PMMA‐co‐PAMPS and PAN‐co‐PAMPS copolymers resulted in a significant increase in porosity, which favored the water uptake and proton transport at ambient temperature. Furthermore, crystallinity degree of the PVDF‐based blend membranes was increased by addition of the related copolymers, which is mainly attributed to formation of hydrogen bonding interaction between PVDF matrix and the synthesized copolymers, and led to a slight decrease in proton conductivity behavior of blend membranes. From impedance data, the proton conductivity of the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes increases to 10 and 8.4 mS cm⁻¹ by adding only 50% of the related copolymer (at 25°C), respectively. Also, the blend membranes containing 30% sulfonated copolymers showed a power density as high as 34.30 and 30.10 mW cm⁻² at peak current density of 140 and 79.45 mA cm⁻² for the PVDF/PMMA‐co‐PAMPS and PVDF/PAN‐co‐PAMPS blend membranes, respectively. A reduction in the tensile strength was observed by the addition of amphiphilic copolymer, whereas the elongation at break of all blend membranes was raised.