Том 57, № 4 (2017)

A novel type of ion-selective membranes based on Nafen^TM alumina nanofibers coated with carbon is proposed. The membranes are produced by filtration of a Nafen nanofiber suspension through a porous support followed by drying and sintering. A thin carbon layer (up to 2 nm) is deposited on the nanofibers by chemical vapor deposition (CVD). Its formation is confirmed by the results of Raman spectroscopy and visually observed in TEM images. According to low temperature nitrogen adsorption experiments, the formation of carbon layer leads to decreasing pore size (the maximum of pore size distribution shifts from 28 to 16 nm) and the corresponding decrease of porosity (from 75 to 62%) and specific surface area (from 146 to 107 m²g^–1). The measurement of membrane potential in an electrochemical cell has shown that the deposition of carbon on the membrane results in high ionic selectivity. In an aqueous KCl solution, the membranes display high anion selectivity with anion and cation transference numbers of 0.94 and 0.06, respectively. The fixed-charge density of membrane has been determined by fitting the experimental data using the Teorell–Meyer–Sievers model. It has been found that the membrane fixed-charge density increases with increasing electrolyte concentration. Possible applications of the membranes produced include nanofiltration, ultrafiltration, and separation of charged species in mixtures. The formation of a conductive carbon layer on the pore surface can be employed for fabricating membranes with switchable ion-transport selectivity.

Hybrid ion-exchange membranes of MF-4SK brand containing hydrated silica and zirconia nanoparticles with sulfonic acid-functionalized surface have been synthesized. The effect of modification on the properties of materials in the proton and potassium forms and the characteristics of potentiometric sensors based on these materials have been studied. It has been found that membrane modification leads to an increase in the ionic conductivity compared with that of the unmodified MF-4SK sample and, in some cases, to a decrease in diffusion permeability. Variations in the cation transport selectivity provided by the modification of MF-4SK membrane have made it possible to decrease the sensitivity of sensors to interfering hydronium cations in an acid medium and increase the sensitivity to amino acid anions and zwitterions in an alkaline medium. Optimum membrane compositions for the determination of histidine cations at pH < 7 and the simultaneous determination of potassium cations and methionine zwitterions and anions at pH > 7 have been selected.

Polyacrylonitrile (PAN) membranes with the rejection coefficients of bovine serum albumin (M_w = 69000 Da) up to 97% have been developed. The effect of IR irradiation of PAN membranes at temperatures to 180°С has been studied for the first time. It has been found that the IR modification of the membranes at 120°С for 5 min makes PAN insoluble in a wide range of organic solvents. The test PAN membranes were obtained from PAN solutions in dimethyl sulfoxide (DMSO) with different polymer concentrations in casting solution. The morphology and filtration characteristics of the membranes are almost unaffected by the treatment. The permeability of the membranes to DMSO, dimethylformamide (DMF), dimethylacetamide (DMAA), and N-methyl-2-pyrrolidone (NMP) has been measured. It has been demonstrated that the IR-treated PAN membranes can be used for filtering the above solvents, although the initial polymer is soluble in these solvents. These membranes can also be used as supports of chemically resistant nanofiltration membranes for aprotic solvents.