To the question of oxidation on the surface of oxides: temperature- programmed oxidation of cyclohexanol
No. 33 (2022), CONTENTS
No. 33 (2022)

To the question of oxidation on the surface of oxides: temperature- programmed oxidation of cyclohexanol

CONTENTS
https://doi.org/10.15407/kataliz2022.33.001
Published October 26, 2022
Volodymyr V. Brei
Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine
Svitlana I. Levytska
Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine
Svitlana V. Prudius
Institute for Sorption and Problems of Endoecology of the National Academy of Sciences of Ukraine, 13 General Naumov Str., Kyiv 03164, Ukraine
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Keywords

heterogeneous catalysis, oxidation on oxides, supported catalysts, mixed oxides

How to Cite

Brei, V. V., Levytska, S. I., & Prudius, S. V. (2022). To the question of oxidation on the surface of oxides: temperature- programmed oxidation of cyclohexanol. Catalysis and Petrochemistry, (33), 1-9. https://doi.org/10.15407/kataliz2022.33.001
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Abstract

Temperature-programmed reaction (TPR) method with mass spectrometric control of the products was used to study of cyclohexanol oxidation into cyclohexanone on individual and mixed oxides supported by γ-Al2O3 and silica gel. In the TPR profiles the temperature of a maximum rate of cyclohexanone formation varies from 125°C for MoO3/Al2O3 to 235°C for less active CuO/Al2O3. The catalytic activity of individual oxides decreases in the order MoO3/Al2O3> V2O5/SiO2 > Fe2O3/Al2O3 > Bi2O5/Al2O3 > TiO2/SiO2 ≈ СeO2/Al2O3 > TiO2/Al2O3 > SnO2/Al2O3. As "reactive" oxygen in our TPR experiment was supplied only from oxide lattice, oxide activity is determined by different energy of the surface Me – O bonds. The approach to search for mixed active oxides based on decreasing coordination number of O2- ions is proposed, that confirmed by the example of CuO-WO3/Al2O3 catalyst. The mixed supported oxides, especially CuOCrO3/Al2O3, CuO-MoO3/Al2O3, MoO3-SnO2/Al2O3 and Bi2O3–SnO2/Al2O3, are more active in С6Н12О + 1/2О2 → С6Н10О + Н2О oxidation. The synthesized CuO-CrO3/Al2O3 catalyst provides cyclohexanone formation without side   cyclohexanol dehydration and can be used for the oxidation of ethylene glycol – methanol mixture into methyl glycolate. CuO-Cr2O3/Al2O3 with a spinel structure of CuCr2O4 ([CuO4] 6− tetrahedra, Cu2+ sp3-hybridization) is more active in cyclohexanol oxidation than CuO/Al2O3 with flat [CuO4] 6−squares, Cu2+ dsp2-hybridization. This is explained by the lower energy of Cu-O bonds at sp3-hybridization of Cu2+ ions.

https://doi.org/10.15407/kataliz2022.33.001
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