L. N. Polyanskii

Cooperative interactions of metal nanoparticles in the ion-exchange matrix with oxygen dissolved in water

The kinetics of the reduction of molecular oxygen dissolved in water with nanocomposites consisting of an ion-exchange matrix and copper nanoparticles deposited in it in various amounts was studied. As the metal content in the polymer increased, the amount of reduced oxygen initially increased and then reached the limiting value. At a certain metal content, ionization of individual particles with formation of metal counterions changes to the oxidation of particles assembly giving layers of oxide products. The mechanism changes at the percolation threshold of the electron conductivity of the nanocomposite and determines the maximum amount of absorbed oxygen.

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.

Redox sorption of oxygen on a layered cathode-polarized nanocomposite metal-ion exchanger

The redox sorption of molecular oxygen from a flow of deionized water onto a cathode-polarized granular layer of nanocomposite copper-ion exchanger is considered. A mathematical description of it in terms of external diffusion is given. In contrast to better-known approaches, conditions are created that are as close as possible to the limiting diffusion current; this effect can be achieved by dividing the granular layer into shallow layers, each of which is then polarized with a near-limiting current. This allows water to be obtained with a particular value of deoxygenation close to the theoretically calculated value in stationary sorption membrane electrolyzers equipped with a unit containing a nanocomposite copper-ion exchanger. It is established that the lower deoxygenation value relative to the one calculated from the limiting current is associated with the additional reduction of oxygen with copper nanoparticles.

A macrokinetic model of redox sorption on metal–ion exchanger nanocomposites at electrochemical polarization

A conceptual macrokinetic model of redox sorption on metal–ion exchanger nanocomposites upon electrochemical polarization is formulated and a corresponding mathematical model is constructed. The solution to a multi-point boundary value problem for the concentration of a sorbed substance (oxygen) is given. The concentration front of the sorbed substance is characterized by a concentration gradient in the near-surface layer of the solution, by layers of the products of metal oxidation in the composite forming due to both external and internal diffusion transfer, and by chemical and electrochemical reactions at the interphase boundaries. A considerable reduction in the concentration gradient of the sorbate in layers of the products of oxidation of metal and the growth of the diffusion layer of the solution with polarizing currents weaker than the limiting diffusion current are noted.

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.

Redox sorption in metal–ion-exchanger nanocomposites upon electrochemical polarization

A conjugated macrokinetic problem is solved for two moving boundaries of chemical reactions during redox sorption in metal–ion-exchange nanocomposites under conditions of current flow. Numerical solutions to the multipoint boundary value problem indicate that the impact of the current includes a slowing of front migration associated with distinct stages of the chemical reaction between metal nanoparticles and oxygen due to electrochemical reduction, a reduced surface concentration of the active sorbate (oxygen), and an increased degree of redox sorption. An increase in the contribution from the electrochemical component and a transition to external diffusion control are observed as the current density grows.

Sorption-membrane system for deep deoxygenation of water

We have studied the redox sorption of oxygen from flowing distilled water in a multistage sorptionmembrane cell with a metal (Cu)–sulfo cation exchanger (KU-23 in the H+ form) granular nanocomposite in the cathode compartment and a sulfo cation exchanger (KU-23 in the H+ form) in the anode compartments separated by a cation-exchange membrane (MC-40 in the H+ form). It is shown that the redox sorption of oxygen on the granular nanocomposite bed polarized with a current which is less than the limiting external diffusion one is complicated by internal steps (oxygen diffusion in the polymer matrix pores and the chemical oxidation of metal nanoparticles) and proceeds with a mixed diffusion-kinetic control. In the mode of limiting diffusion current polarization, the contribution of internal stages decreases and the process becomes steady due to the transition into the external diffusion region. A theoretical calculation shows that the process performed in series-connected multistage cells with polarization of each stage in the mode of limiting external diffusion current allows obtaining water with a dissolved oxygen content of <10 ppb.

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.

Electroreduction of oxygen on metal (Au, Cu)-ion exchanger nanocomposites in the diffusion mode

The kinetics of the electroreduction of oxygen in the diffusion mode on single granules of nanocomposites consisting of dispersed particles of the metal (Au, Cu) of the nanometer size and macroporous sulfonic cation-exchanger matrix KU-23 is studied. No noticeable effect of the factors of size of the metal component and ion exchange over the matrix on the external diffusion current of oxygen reduction is observed. The drop in current observed in a number of cases is due to a transition to the mixed external and internal kinetics as a result of the macroporous structure of the matrix and the chemical activity of nanoparticles of the metal component.