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Information × Registration Number 0222U001732, 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. popup.stage_title Head Pokutsa Oleksandr P, Registration Date 02-02-2022 Organization Department of Physical and Chemistry of Combustible Fossils LM Litvinenko of the National Academy of Sciences of Ukraine popup.description2 As a result of research: (і) the influence of activator (oxalic acid, ОА) at the kinetics of cyclohexane oxidation by H2O2 catalyzed with VО(асас)2 and process mechanism was studied. The last one is stipulated by ОА as well as the salt of the later with initial VО(асас)2 (VО(oxalate)) dissociation. That leads to decreasing the overall electric resistance 1/G of the reaction mixture and is the essence of OA activating impact. As follows from the electronic spectroscopy and cyclic voltammetry, together with 1/G alteration, the replacement of the weak field ligands (асас) of VО(асас)2 by the middle field ones (oxalates) strengthens the cation-ligand bonds and prevents the irreversible catalyst oxidation. In the absence of ОА, the 1/G value was several times higher than in ОА + VО(асас)2 case. The last feature correlate well with noticeably higher process efficiency in presence of ОА. Experimental data and DFT calculation of the main quantum-chemical parameters (catalyst d-d-levels splitting, HOMO-LUMO gap, Gibbs energy) revealed that the process efficiency relates with modification of metalocomplex outer-sphere electronic shelves and may lead to generation of metalperoxo species VО(η2-О2). On the other hand, oxalate-anions, besides decreasing of 1/G, may facilitate Н2О2 interaction with catalyst cations. Ultimately, that results in process productivity increasing; (іі) the impact of specific and unspecific solvation, structural factors as well as intermediate state parameters at the rate constants of oxidation of nitrogen-contained compounds by peroxoacids was investigated. The results of these studies were published in 4 papers of national and international journals and presented at 4 national and international Conferences. Product Description popup.authors Dutka Volodymyr S Zaborovskiy Andriy B Midyana Halyna H Maksym Dariya S popup.nrat_date 2022-03-09 Close