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This paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetonitrile catalyzed by iron(III) perchlorate (1), iron(III) chloride (2), iron(III) acetate (3) and a binuclear iron(III) complex with 1,4,7-triazacyclononane (4). The corresponding alkyl hydroperoxides are the main products. Nevertheless in the kinetic study of cyclohexane oxidation, the concentrations of oxygenates (cyclohexanone and cyclohexanol) were measured after reduction of the reaction solution with triphenylphosphine (which converts the cyclohexyl hydroperoxide to the cyclohexanol). Methane and ethane can be also oxidized with TONs up to 30 and 70, respectively. Chloride anions added to the oxidation solution with 1 activate the perchlorate iron derivative in acetonitrile, whereas the water as additive inactivates 2 in the H 2 O 2 decomposition process. Pyrazine-2-carboxylic acid (PCA) added to the reaction mixture decreases the oxidation rate if 1 or 2 are used as catalysts, whereas compounds 3 and 4 are active as catalysts only in the presence of small amount of PCA. The investigation of kinetics and selectivities of the oxidations demonstrated that the mechanisms of the reactions are different. Thus, in the oxidations catalyzed by the 1, 3 PCA and 4 PCA systems the main oxidizing species is hydroxyl radical, and the oxidation in the presence of 2 as a catalyst has been assumed to proceed (partially) with the formation of ferryl ion, (Fe IV O) 2 . In the oxidation catalyzed by the 4 PCA system (TONs attain 240) hydroxyl radicals were generated in the rate-determining step of monomolecular decomposition of the iron diperoxo adduct containing one PCA molecule. A kinetic model of the process which satisfactorily describes the whole set of experimental data was suggested. The constants of supposed equilibriums and the rate constant for the decomposition of the iron diperoxo adduct with PCA were estimated.
This paper describes an investigation of the alkane oxidation with hydrogen peroxide in acetonitrile catalyzed by iron(III) perchlorate (1), iron(III) chloride (2), iron(III) acetate (3) and a binuclear iron(III) complex with 1,4,7-triazacyclononane (4). The corresponding alkyl hydroperoxides are the main products. Nevertheless in the kinetic study of cyclohexane oxidation, the concentrations of oxygenates (cyclohexanone and cyclohexanol) were measured after reduction of the reaction solution with triphenylphosphine (which converts the cyclohexyl hydroperoxide to the cyclohexanol). Methane and ethane can be also oxidized with TONs up to 30 and 70, respectively. Chloride anions added to the oxidation solution with 1 activate the perchlorate iron derivative in acetonitrile, whereas the water as additive inactivates 2 in the H 2 O 2 decomposition process. Pyrazine-2-carboxylic acid (PCA) added to the reaction mixture decreases the oxidation rate if 1 or 2 are used as catalysts, whereas compounds 3 and 4 are active as catalysts only in the presence of small amount of PCA. The investigation of kinetics and selectivities of the oxidations demonstrated that the mechanisms of the reactions are different. Thus, in the oxidations catalyzed by the 1, 3 PCA and 4 PCA systems the main oxidizing species is hydroxyl radical, and the oxidation in the presence of 2 as a catalyst has been assumed to proceed (partially) with the formation of ferryl ion, (Fe IV O) 2 . In the oxidation catalyzed by the 4 PCA system (TONs attain 240) hydroxyl radicals were generated in the rate-determining step of monomolecular decomposition of the iron diperoxo adduct containing one PCA molecule. A kinetic model of the process which satisfactorily describes the whole set of experimental data was suggested. The constants of supposed equilibriums and the rate constant for the decomposition of the iron diperoxo adduct with PCA were estimated.
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BACKGROUND As one of the common VOCs, toluene is not only hazardous to human health, leading to respiratory disease, cancers, but also harmful to the environment, causing destruction of the ozone layer, photochemical smog and global warming. Catalytic oxidation is one of the most advanced technologies for eliminating VOCs and can convert VOCs to benign components such as carbon dioxide (CO2) and water. As catalysts are important in the catalytic process, finding highly active, low cost catalysts is critical. Metal phthalocyanine(MPc) has potential practical value and wide application prospects as catalysts for its uniquely high catalytic activity and selectivity. Thus, four monolithic catalysts were prepared by impregnating MPc onto cordierite honeycomb. RESULTS Characterization by scanning electron microscopy, X‐ray diffraction, Fourier transform infrared and energy‐dispersive X‐ray spectroscopy showed that the metal phthalocyanines were successfully loaded on the cordierite honeycomb. A fixed‐bed reactor was used to examine the catalytic oxidation effects of metal phthalocyanine species, catalyst amount, feed concentration, feed flow and temperature on toluene. The result showed that the catalytic activity of phthalocyanine iron (FePc) to toluene was better than other three MPcs. The optimal reaction conditions were 120 mg catalyst, 6.3 × 10−3 mol m−3feed concentration and 250 mL min−1 feed flow. The conversion of toluene increased with increasing temperature. CONCLUSION FePc/C also had a good catalytic oxidation effect on different aromatic hydrocarbon compounds (benzene and 1,4‐dimethyl‐benzene). The oxidation products of the catalytic system were CO2 and H2O, which met the requirements of green chemistry. FePc/C is a promising catalytic material because it has high catalytic activity and can be operated in simple conditions, such as low temperatures. © 2022 Society of Chemical Industry (SCI).
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