Hydrocarbon Oxidation Depth: H2O2/Cu2Cl4•2DMG/CH3CN System

被引：1

作者：

Shchapin, Igor Yu ^{[1
,2
]}

Nekhaev, Andrey, I ^{[3
]}

Ramazanov, Dzhamalutdin N. ^{[3
]}

Al-Yusufi, Mohammed ^{[4
]}

Samoilov, Vadim O. ^{[3
]}

Maximov, Anton L. ^{[3
]}

机构：

[1] DI Mendeleev Univ Chem Technol Russia, Dept High Energy Chem & Radioecol, Miusskaya Ploshchad 9, Moscow 125047, Russia

[2] Branch Joint Stock Co United Rocket & Space Corp, Sci Res Inst Space Device Engn, Aviamotornaya St 53, Moscow 111024, Russia

[3] Russian Acad Sci, AV Topchiev Inst Petrochem Synth, Leninsky Prospect 29, Moscow 119991, Russia

[4] Leibniz Inst Catalysis LIKAT, Dept Heterogeneous Catalyt Proc, Albert Einstein Str 29A, D-18059 Rostock, Germany

来源：

CATALYSTS | 2022年 / 12卷 / 04期

关键词：

hydrocarbons; catalytic oxidation; Cu(II) complex; dimethylglyoxime; hydrogen peroxide; CH3CN; oxidation depth; adiabatic ionization potential; DFT calculations; MOLECULAR PHOTOELECTRON-SPECTROSCOPY; ULTRAVIOLET-ABSORPTION-SPECTRA; SELECTIVE CATALYTIC-OXIDATION; IONIZATION ENERGIES; CRYSTAL-STRUCTURE; HYDROGEN-PEROXIDE; AEROBIC OXIDATION; COPPER CATALYST; GAS-PHASE; N-OXIDES;

D O I：

10.3390/catal12040409

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The oxidation of hydrocarbons of different structures under the same conditions is an important stage in the study of the chemical properties of both the hydrocarbons themselves and the oxidation catalysts. In a 50% H2O2/Cu2Cl4 center dot 2DMG/CH3CN system, where DMG is dimethylglyoxime (Butane-2,3-dione dioxime), at 50 degrees C under the same or similar conditions, we oxidized eleven RH hydrocarbons of different structures: mono-, bi- and tri-cyclic, framework and aromatic. To compare the composition of the oxidation products of these hydrocarbons, we introduced a new quantitative characteristic, "distributive oxidation depth D(O), %" and showed the effectiveness of its application. The adiabatic ionization potentials (AIP) and the vertical ionization potentials (VIP) of the molecules of eleven oxidized and related hydrocarbons were calculated using the DFT method in the B3LYP/TZVPP level of theory for comparison with experimental values and correlation with D(O). The same calculations of AIP were made for the molecules of the oxidant, solvent, DMG, related compounds and products. It is shown that component X, which determines the mechanism of oxidation of hydrocarbons RH with AIP(Exp) >= AIP(X) = 8.55 +/- 0.03 eV, is a trans-DMG molecule. Firstly theoretically estimated experimental values of AIP(trans-DMG) = 8.53 eV and AIP(cis-DMG) = 8.27 eV.

引用

页数：26

共 110 条

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