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Registration Number

0223U001402, 0118U003623 , R & D reports

Title

The oxidation of hydrocarbons and their oxygen-containing oxygen and hydrogen peroxide derivatives to practically important intermediates is evidenced by bio-inspired activators.

Head

Pokutsa Oleksandr P,

Registration Date

28-01-2023

Organization

Department of Physical and Chemistry of Combustible Fossils LM Litvinenko of the National Academy of Sciences of Ukraine

Description

The high promoting ability of oxalic acid (OA) was established on the example of the oxidation of toluene and cyclohexane by O2 and H2O2 catalyzed by VO(acac)2. The core of effect consists of a significant decrease the electrical resistance of the reaction medium. One of the reasons for the observed effect is the increase of the charged particles concentration caused by the dissociation of OA, as well as its salt VO(oxalate)2 formed upon OA interaction with the original VO(acac)2. This leads to decreasing in the total resistance 1/G of the reaction medium and is the essence of the activating effect. Substitution of weak-field ligands (acac), VO(acac)2 with middle-strength field ligands (oxalate) strengthens the cation-ligand bond and extends the life of the catalyst. The effectiveness of the process is also related to the formation of metal-peroxo species VO(η2-O2). On the other hand, as revealed OA and H2O2 additives significantly neutralize the promoting effect of NHPI in the VO(acac)2/(Co(acac)2)/NHPI/O2 catalytic system. For the first time, the kinetic dependencies of the combined effect of light irradiation and activators (NHPI, OA) on the oxidation of toluene catalyzed by V and Co salts in the presence of the photocatalyst Me2Acr+–Mes were investigated. The catalytic effect of nanoparticles of d-metals in zero valency (Ni, Cu, Ag) on the decomposition of H2O2 and the influence of hydroxyl-containing solvents (MeOH, H2O) on this reaction was studied. The peculiarities of quinoline oxidation by peroxodecanoic acid PDK in a number of organic solvents were studied. The parameters of specific and non-specific solvation have the greatest influence on this process. The total reaction rate constants of the acridine oxidation of PDK in various organic solvents (k) and the activation energy (Eak) in various organic media were found. There is a linear relationship between the transition state parameters ΔН≠ and ΔЅ≠, which indicates the presence of a compensation effect.

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Dutka Volodymyr Stepanovych
Zaborovskiy Andriy B
Midyana Halyna H.
Maksym Dariya S