Steady-state redox sorption of oxygen dissolved in water on granular layers of copper-ion-exchange nanocomposites

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Abstract

The process of redox sorption of oxygen dissolved in water on cathodically polarized granular layers of copper-ion-exchange nanocomposites depending on the water flow rate and the value of polarizing current is studied. It is observed that initially the amount of absorbed oxygen exceeds the amount of leaked electricity. With time, the chemical activity of the nanocomposite decreases, and oxygen continues to be sorbed and further recovered mainly due to the current component of the process. Simultaneous increase in the water flow rate and the strength of the limiting current is concluded to have a favorable effect on the rate of oxygen uptake. Maintaining the constancy of the water supply mode and the respective current strength ensures a stationary course of diffusion, chemical, and electrochemical stages. Successive stages of external diffusive oxygen transfer to the surface of nanocomposite grains, intra-diffusive oxygen transfer along the grain pores and chemical oxidation of copper nanoparticles to oxides characteristic of the final sources are found to be compensated by the stages of electroreduction of oxygen from surface adsorbed complexes and regeneration of oxidation products into metallic copper nanoparticles. The nanocomposite is a continuous source of newly reduced metal particles and contributes to the oxygen redox sorption process reaching the stationary mode. Unlike the nonpolarizable granular layer, the oxygen concentration remains at a low constant level under the conditions of the maximum admissible electric current applied.

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T. A. Kravchenko

Voronezh State University

Author for correspondence.
Email: krav280937@yandex.ru
Russian Federation, Voronezh

O. A. Kozaderov

Voronezh State University

Email: krav280937@yandex.ru
Russian Federation, Voronezh

D. D. Vakhnin

Voronezh State University

Email: krav280937@yandex.ru
Russian Federation, Voronezh

I. A. Golovin

Voronezh State University

Email: krav280937@yandex.ru
Russian Federation, Voronezh

A. E. Martynov

Voronezh State University

Email: krav280937@yandex.ru
Russian Federation, Voronezh

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2. Fig. 1. Schematic diagram of a seven-stage electrodeoxygenator with granular NC packing in the cathode chamber for removing oxygen dissolved in water: K – cathodes, A – anodes, MK-40 – membrane, Lewatit K2620(Na+) – granulated sulfocation exchanger, Cu0∙Lewatit K2620(Na+) – nanocomposite, R – resistors with variable resistance, Rj – resistance of the j-stage, Ij – current strength at the j-stage.

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3. Fig. 2. Kinetic dependences of the concentration of oxygen dissolved in water C (a) and the relative concentration of oxygen C/C0 (b) in water at the outlet of the cathode-polarized granular layer of the Cu0·Lewatit K2620(Na+) nanocomposite in a single-stage electrolyzer with different water flow rates u, cm/s: 1– 0.33; 2– 0.50. Curves: 1, 2 – oxygen concentration C0 at the inlet to the granular layer; 1ʹ, 2ʹ – oxygen concentration C at the exit from the granular layer, 3 – relative oxygen concentration at the exit.

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4. Fig. 3. Time dependences of the quantity Q(a) and the rate dQ/dt(b) of oxygen absorption from water by a granular layer of Cu0·Lewatit K2620(Na+) nanocomposite in a single-stage electrolyzer with different water flow rates u, cm/s: 1– 0.33; 2– 0.50. Curves: 1, 2 – total amount of absorbed oxygen; 1ʹ, 2ʹ – amount of oxygen absorbed due to current.

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5. Fig. 4. Kinetic dependences of the concentration of oxygen C dissolved in water (a) and the relative concentration of oxygen C/C0 (b) in water at the outlet of the cathodically polarized granular layer of Cu0·LewatitK2620(Na+) nanocomposite in a seven-stage electrolyzer with different water flow rates u, cm/s: 1– 0.33; 2– 0.50. Curves: 1, 2 – oxygen concentration C0 at the inlet to the granular layer; 1ʹ, 2ʹ – oxygen concentration C at the exit from the granular layer, 3 – relative oxygen concentration at the exit.

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6. Fig. 5. Time dependences of the quantity Q (a) and the rate dQ/dt (b) of oxygen absorption from water by a granular layer of Cu0·Lewatit K2620(Na+) nanocomposite in a seven-stage electrolyzer with different water flow rates u, cm/s: 1 – 0.33; 2 – 0.50. Curves 1, 2 – total amount of absorbed oxygen; 1ʹ, 2ʹ – amount of oxygen absorbed due to current.

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7. Fig. 6. Micrographs of sections of grains of the Cu0∙Lewatit K2620 nanocomposite during electroreduction of oxygen dissolved in water with the maximum permissible current (I/Ilim ≈ 1); a – initial state, b – I/Ilim ≈ 1.

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8. Fig. 7. Spatial diagram of the oxygen reduction process on a cathodically polarized copper-ion-exchange nanocomposite: A – anode, M – ion-exchange membrane, K – cathode. The line above the symbol indicates belonging to the ion-exchange matrix.

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