G. V. Kornienko

Use of aqueous hydrogen peroxide solutions prepared by cathodic reduction of oxygen for indirect oxidation of chemical substances in situ: Achievements and prospects

The achievements and prospects in the use of aqueous hydrogen peroxide solutions prepared by cathodic reduction of oxygen in carbon black gas-diffusion and graphite electrodes for indirect oxidation of organic and inorganic substrates in situ are analyzed. Specific examples demonstrate the efficiency of using hydrogen peroxide solutions for in situ indirect electrocatalytic oxidation of organic and inorganic substrates to target products (indirect electrochemical synthesis), for decomposition (mineralization) of organic and inorganic pollutants in industrial waters and wastewaters, and for preparation of organic peroxy acids and inorganic peroxy solvates.

Indirect Electrooxidation of Organic Substrates by Hydrogen Peroxide Generated in an Oxygen Gas-Diffusion Electrode

Indirect electrooxidation of phenol, formaldehyde, and maleic acid in cells with and without a cation-exchange membrane, with a platinum anode and a gas-diffusion carbon black cathode, which generates hydrogen peroxide from molecular oxygen, proceeds with high efficiency and various oxidation depths, which depend on the intermediate nature: the process involving HO2- occurs selectively and yields target products, while the formation of HO2· and HO· leads to the destruction of organic compounds to CO2 and H2O.

Indirect electrochemical oxidation of aliphatic alcohols to carboxylic acids by active oxygen forms in aqueous media

Indirect electrochemical oxidation of aliphatic alcohols (butanol, hexanol, nonanol, decanol) to the corresponding carboxylic acids by active oxygen forms (AOFs) generated in situ in electrochemical cells from O2, H2O2, H2O is carried out in aqueous electrolyte using anodes of lead dioxide, a nickel oxide electrode, and boron-doped diamond electrode (BDDE). It is found that selectivity of the process of indirect electrosynthesis of carboxylic acids depends on the chemical nature of the anode material and structure of the initial alcohol and is determined by the conditions of AOF generation. Coupled electrosynthesis with simultaneous in situ generation of AOFs on the cathode and anode occurs more effectively with formation of the corresponding carboxylic acids.

Electrochemical oxidation of phenol on boron-doped diamond electrode

The process of phenol oxidation on a boron-doped diamond electrode (BDD) is studied in acidic electrolytes under different conditions of generation of active oxygen forms (AOFs). The scheme of phenol oxidation known from the literature for other electrode materials is confirmed. Phenol is oxidized through a number of intermediates (benzoquinone, carboxylic acids) to carbon dioxide and water. Comparative analysis of phenol oxidation rate constants is performed as dependent on the electrolysis conditions: direct anodic oxidation, with oxygen bubbling, and addition of H2O2. A scheme is confirmed according to which active radicals (OH·, HO2·, HO2−) are formed on a BDD anode that can oxidize the substrate which leads to formation of organic radicals interacting with each other and forming condensation products. Processes with participation of free radicals (chain-radical mechanism) play an important role in electrochemical oxidation on BDD. Intermediates and polymeric substances (polyphenols, quinone structures, and resins) are formed. An excess of the oxidant (H2O2) promotes a more effective oxidation of organic radicals and accordingly inhibition of the condensation process.

Graphitized carbon materials for electrosynthesis of Н2О2 from О2 in gas-diffusion electrodes

New graphitized carbon materials: technical carbon N220, С140, and СН85 (Omsktekhuglerod) were studied as catalysts of electrosynthesis of alkaline solutions of hydrogen peroxide from oxygen in gasdiffusion electrodes (GDEs). The kinetic parameters of oxygen reduction in alkaline solution and the capacity of gas-diffusion electrodes based on technical carbon N220, С140, and СН85 were determined. Data on the kinetics of hydrogen peroxide accumulation were obtained at different current densities. The fraction of current γ spent on the reduction of oxygen to hydrogen peroxide was determined. The rate constants of hydrogen peroxide decomposition under the given conditions were calculated.

Indirect electrosynthesis of peracetic acid using hydrogen peroxide generated in situ in a gas diffusion electrode

Indirect electrochemical oxidation of acetic to peracetic acid in aqueous solutions using hydrogen peroxide generated in situ from O2 in a gas diffusion electrode was studied. The use of sulfuric acid and ammonium molybdate as catalysts accelerated the formation of peracetic acid during the electrolysis, and the use of both catalysts allowed us to prepare 0.02 M solutions. The limiting stage of the electrosynthesis of peracetic acid was the chemical interaction of the substrate with the generated H2O2. The desired product mainly formed during the storage of the reaction mixture after the electrosynthesis. In electrolytes with more than 3.5 M acetic acid, the electrochemical activity of the gas-diffusion cathode decreased.

Nonanol-1 oxidation on nickel oxide electrode with the involvement of active oxygen forms

The process of nonanol-1 oxidation is studied on the nickel oxide electrode with the use of chemically bound active oxygen forms (AOF) electrochemically generated in situ from O2, H2O2, and H2O. The effect of electrolysis conditions (AOF generation schemes, current density, passed charge) on the yield of pelargonic acid is studied. The oxidation proceeds most efficiently at the current density of 5–10 mA cm−2 as the theoretical charge is passed in the paired electrolysis mode. The current efficiency with respect to pelargonic acid is 83.7%; the substance yield is 83.8%. In addition to pelargonic acid, several oxidation side-products are found in the electrolyte. Their content increases with the increase in the charge passed as a result of further oxidation of pelargonic acid.

Indirect electrochemical oxidation of aniline in acid electrolyte with active oxygen species

Kinetics and selectivity of the aniline oxidation on a boron-doped diamond electrode and lead dioxide anode (Pb/PbO2) in an acid electrolyte were studied under various generation conditions of active oxygen species. The resulting kinetic dependences can be described by a pseudo-first-order equation. The apparent rate constants of the process were determined for two electrolysis modes: direct anodic oxidation and oxidation with addition of hydrogen peroxide. UV spectroscopy was used to determine that the aniline destruction process occurs via formation of a number of intermediate products (benzoquinone, carboxylic acids). It was shown that the aniline destruction process can occur with a rather high efficiency (~80–90%) on the electrode types under study.

Redox-mediated oxidation of cyclohexanone to adipic acid on oxide-nickel anode, with active forms of oxygen involved

Redox-mediated oxidation of cyclohexanol to adipic acid on a porous anode with higher nickel oxides was studied, including the process involving active oxygen species (AOS) in situ generated from hydrogen peroxide and molecular oxygen in an alkaline electrolyte. It was found that the current efficiency by adipic acid grows upon addition of AOS. The selectivity of cyclohexanol oxidation to adipic acid depends on the current density, quantity of passed electricity, and method of AOS generation. It is demonstrated that use of AOS enables oxidation of cyclohexanol with a selectivity of adipic acid formation of up to 89% and its single-stage synthesis with a current efficiency of 50.2% at a current density of 22 mA cm−2 and passing the theoretically required quantity of electricity.

Indirect electrochemical destructive oxidation of aromatic compounds with reactive oxygen species

The indirect destructive electrooxidation of benzene, phenol, and N-methyl-p-aminophenol with active oxygen species generated in situ from O2, H2O2, and H2O in aqueous solutions with various pH values has been carried out using different cell designs with Pt, Pb/PbO2, and Ru-Ti oxide anodes. The indirect oxidation of the aromatic compounds mineralizes them into CO2 and H2O or converts them into simple monocarboxylic or dicarboxylic acids, which can be utilized by microorganisms in subsequent biotreatment.