V. A. Krysanov

The stabilization of nanodisperse silver in a sulfo cation exchanger

Silver-ion exchanger (electron ion exchanger, EI) composites with equivalent silver and hydrogen counterion contents were prepared by chemical deposition. Microscopic and X-ray data showed that silver nanoparticles and their ensembles isolated from each other and stabilized by a polymeric matrix were formed. Contact of Ag0-EI in the H+ form with solutions of silver salts caused the occurrence of two processes, ion exchange and metal recrystallization. These processes were interrelated because they involved one common particle, the silver counterion. Recrystallization proceeded by the electron-ion mechanism, but, because of matrix isolation of silver particles, electron transfer occurred inside separate structural elements (ensembles of particles) rather than over the whole composite volume. The transfer of silver ions largely occurred over ionogenic matrix centers, which substantially decreased their mobility. The low electronic conductivity of the composite and limited mobility of counterions were charge stabilization factors, which hindered recrystallization and, along with matrix stabilization, contributed to the retention of nanosized silver particles.

Electroreduction of molecular oxygen on dispersed copper in an ion-exchange matrix

Electrochemical reduction of molecular oxygen was studied on a [dispersed copper]-[macroporous KU-23 15/100S sulfocation exchanger with various metal concentrations] composite electrode. It was found that a high proton concentration in the ion-exchange matrix causes a decrease in the oxygen reaction overvoltage. The nanostructured state of copper particles causes stabilization of the intermediate product, i.e., hydrogen peroxide. Using the rotating disk electrode method, it was detected that the process is limited by external diffusion of oxygen to composite grains. The oxygen reaction is mostly concentrated on the grain surface and surface layers; oxygen is reduced in the bulk due to dispersed copper oxidation.

Copper electrodeposition into ion-exchange materials

Electrodeposition of copper into spherical granules of ion-exchange materials KU-23 and KU-2 out of acid sulfate solutions is studied by a method of cyclic voltammetry. It is discovered that the discharge of copper ions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of ions localized at fixed groups [RSO3−]. The cyclic voltammogram exhibits an additional cathodic peak in the potential region corresponding to the reduction of single-charged copper ions that form as a result of their accumulation inside pores of the ion-exchange matrix during anodic dissolution of metal deposited previously. It is fixed microscopically that the process of deposition begins at the graphite substrate/ion-exchanger interface and passes into bulk upon the formation of an electron-conducting layer saturated with copper. Preliminary saturation of the ion-exchanger by copper deposited chemically facilitates uniform electrodeposition of copper over the entire volume of pores of the ion-exchange matrix.

Contribution from the ion-exchange factor to the potential of a copper-containing electron-ion exchanger

The process of formation of the electrode potential of EI-21 electron-ion exchanger, composed of ultrafine copper particles and KU-23 sulfocationite, was studied. The potentials of a EI-21 powdery electrode with a platinum lead in copper(II) sulfate solutions of various concentrations (0.005–1.0 M) were measured using currentless-mode potentiometry. The potential of this electrode first shifted by 0.02–0.15 V in the negative direction with respect to a compact copper electrode, after which the shift eventually decreased to −0.010 ± 0.003 V. It was demonstrated that the time evolution of the potential is determined by the interplay of electron and ion exchange. When EI-21 is placed onto a platinum lead, the role of the potential-determining reaction passes from Cu2+ + e− ⇄ Cu+ to Cu2+ + 2e− ⇄ Cu. At the same time, H+-Cu2+ ion exchange gives rise to a change in the ratio of the concentration of copper(II) ions in the internal and external solutions. The Donnan potential, which arises at the boundary between the electron-ion exchanger and the external solution, maintains a high concentration of copper(II) ions in the internal solution, a factor that facilitates the recrystallization of the particle distributed over the bulk of the exchanger. The process of recrystallization slows down with time to such an extent that the electrode potential stops changing, remaining at a level close to the equilibrium potential of the Cu2+/Cu pair. It was concluded that the internal stability of the system makes the potential of the EI-21 electrode sensitive to the dispersity of the metal component and the concentration of potential-determining metal ions in the external solution.

Oxygen electroreduction on a granulated layer of a copper-containing electron-ion exchanger

The reduction of dissolved oxygen from a flowing aqueous solution of sodium sulfite on a cathodically polarized granulated layer of a copper-containing electron-ion exchanger is studied. It is established that the polarizing current is distributed over the layer height nonuniformly. A peak current corresponding to the oxygen electroreduction is discovered. The peak shifts from the inlet into the granulated layer to the exit out of it, which is connected with the advance of the concentration front and with an increase in ohmic resistance due to partial oxidation of copper centers. The distribution of the polarizing current is analogous to the distribution of the limiting current of the oxygen reduction, which is determined from polarization curves. The reaching of a stationary position of the peak of the polarizing current and the oxygen reduction degree with time testifies to the onset of a stationary state, at which the current turns limiting and the balance between the arrival and electroreduction of oxygen is fulfilled.

Contribution of dimensional factor to the potential of copper-containing electron-ion exchangers

The average size of copper particles in copper-containing electron-ion exchangers is determined with the aid of microscopy and x-ray diffractometry. The results are used to calculate the contribution made by a dimensional factor to the electrode potential. Compared to the potential of compact copper, the potential shift in the negative direction measured experimentally falls within the region of calculated values. The average size of copper particles remains practically unchanged after contact with a copper sulfate solution, testifying to stabilization of an ultradisperse state of copper particles by a polymer matrix.

Stability of Ultradisperse Copper in a Sulfo Cation Exchanger Matrix

The recrystallization of ultradisperse copper chemically deposited onto a sulfo cation exchanger matrix was studied by the potentiometric method. The stationary value of the electrode potential of the copper-sulfo cation exchanger composite was established during a long period of time, which depended on the ionic form of the composite (H+, Cu2+, or Na+), solution composition (CuSO4, H2SO4, and Na2SO4), and solution concentration. Recrystallization was favored by copper(II) counterions, which entered the composite as a result of ion exchange, nonexchange absorption of copper sulfate, or preliminary composite transformation into the Cu2+ form. In the quasi-equilibrium state, the concentration of copper(II) counterions was maintained at a high level by the Donnan interfacial potential. At all the copper(II) sulfate concentrations used, the potential of the Cu2+/Cu ion—metal pair in the ion-exchange matrix remained at virtually the same level, which was indicative of the stable state of copper particles. In the absence of an external source of copper ions, recrystallization was significantly hindered; therefore, the potential exhibited only a slight drift. Copper ions formed in the solution of small crystals were localized in the vicinity of ionogenic matrix centers, which decreased the mobility of these particles as counterions; therefore, the dispersity of particles remained unchanged.

Percolation effects with copper electrodeposition in ion-exchange material

The effect of preliminary doping of sulfo cation-exchange material KU-23 15/100S with a chemically deposited metal (Ag, Cu) on the rate of copper ion electroreduction is investigated. It is shown that the threshold dependence of the reaction current of copper electroreduction on the amount of doped metal is due to the formation of a single percolation cluster in an ion-exchange grain and, as a result, to the appearance of electron conductivity. It is established that preliminary doping changes the nucleation mechanism from a gradual to an instantaneous one. Results from a local X-ray spectral microanalysis provide the basis for concluding that copper electrodeposition is uniform throughout the volume of an ion-exchange grain. The average size of the copper particles formed is 100 nm.

Sorption of Molecular Oxygen by Metal–Ion Exchanger Nanocomposites

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal–ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Percolation effect in dynamics of oxygen redox sorption with metal-ion exchanger nanocomposites

The dynamics of redox sorption of oxygen dissolved in water is investigated on the granular bed of metal-ion exchanger nanocomposites (NCs) with different capacities with respect to metal. The increase in capacity enhances the amount of oxygen absorbed up to a certain extent. Above this limit, the process decelerates, which results in the appearance of a maximum in the dependence of oxygen breakthrough time in the filtrate on the metal content. The limit is related to the transition of particles from the isolated state to the cooperative one and the corresponding change in the mechanism of redox sorption process at the percolation threshold of the electronic conductivity of the NC.