Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La0.8Ba0.2MnO3-δ Perovskites under Anaerobic Conditions

Hikaru Saito; Hirofumi Seki; Yukiko Hosono; Takuma Higo; Jeong Gil Seo; Shun Maeda; Kunihide Hashimoto; Shuhei Ogo; Yasushi Sekine

doi:10.1021/acs.jpcc.9b06475

Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La_0.8Ba_0.2MnO_3-δ Perovskites under Anaerobic Conditions

Hikaru Saito, Hirofumi Seki, Yukiko Hosono, Takuma Higo, Jeong Gil Seo, Shun Maeda, Kunihide Hashimoto, Shuhei Ogo, Yasushi Sekine

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2 Citations (Scopus)

Abstract

Dehydrogenation of ethane over perovskite oxide catalysts was investigated using the redox of perovskites and H₂O as an oxidizing agent. The La_0.8Ba_0.2MnO_3-δ (LBMO) perovskite showed a high catalytic activity for dehydrogenation of ethane. Periodic dry (without H₂O)-wet (with H₂O) operation tests revealed that dehydrogenation of ethane in the presence of H₂O over LBMO proceeded via the Mars-van Krevelen (MvK) mechanism. Under the wet condition with D₂O instead of H₂O, D₂ formation was verified, demonstrating that reactive lattice oxygens in LBMO contributed to the dehydrogenation reaction and that they were regenerated by water. Isotopic transient tests with H₂ ¹⁸O and in situ X-ray absorption fine structure measurements revealed that the reduction and oxidation of Mn in LaMnO₃ and LBMO occurred under the reaction atmosphere and that the partial replacement of the La sites with Ba improved the redox ability of Mn, resulting in its high activity. Furthermore, temperature-programmed reduction under H₂ elucidated that the reduction of Mn³⁺ to Mn²⁺ was promoted by Ba doping. The LBMO perovskite showed the very high activity for dehydrogenation of ethane in the presence of H₂O via the MvK mechanism by virtue of the high redox properties of Mn.

Original language	English
Journal	Journal of Physical Chemistry C
DOIs	https://doi.org/10.1021/acs.jpcc.9b06475
Publication status	Accepted/In press - 2019 Jan 1

ASJC Scopus subject areas

Electronic, Optical and Magnetic Materials
Energy(all)
Physical and Theoretical Chemistry
Surfaces, Coatings and Films

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Saito, H., Seki, H., Hosono, Y., Higo, T., Seo, J. G., Maeda, S., Hashimoto, K., Ogo, S., & Sekine, Y. (Accepted/In press). Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La_0.8Ba_0.2MnO_3-δ Perovskites under Anaerobic Conditions. Journal of Physical Chemistry C. https://doi.org/10.1021/acs.jpcc.9b06475

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title = "Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La0.8Ba0.2MnO3-δ Perovskites under Anaerobic Conditions",

abstract = "Dehydrogenation of ethane over perovskite oxide catalysts was investigated using the redox of perovskites and H2O as an oxidizing agent. The La0.8Ba0.2MnO3-δ (LBMO) perovskite showed a high catalytic activity for dehydrogenation of ethane. Periodic dry (without H2O)-wet (with H2O) operation tests revealed that dehydrogenation of ethane in the presence of H2O over LBMO proceeded via the Mars-van Krevelen (MvK) mechanism. Under the wet condition with D2O instead of H2O, D2 formation was verified, demonstrating that reactive lattice oxygens in LBMO contributed to the dehydrogenation reaction and that they were regenerated by water. Isotopic transient tests with H2 18O and in situ X-ray absorption fine structure measurements revealed that the reduction and oxidation of Mn in LaMnO3 and LBMO occurred under the reaction atmosphere and that the partial replacement of the La sites with Ba improved the redox ability of Mn, resulting in its high activity. Furthermore, temperature-programmed reduction under H2 elucidated that the reduction of Mn3+ to Mn2+ was promoted by Ba doping. The LBMO perovskite showed the very high activity for dehydrogenation of ethane in the presence of H2O via the MvK mechanism by virtue of the high redox properties of Mn.",

author = "Hikaru Saito and Hirofumi Seki and Yukiko Hosono and Takuma Higo and Seo, {Jeong Gil} and Shun Maeda and Kunihide Hashimoto and Shuhei Ogo and Yasushi Sekine",

year = "2019",

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doi = "10.1021/acs.jpcc.9b06475",

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T1 - Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La0.8Ba0.2MnO3-δ Perovskites under Anaerobic Conditions

AU - Saito, Hikaru

AU - Seki, Hirofumi

AU - Hosono, Yukiko

AU - Higo, Takuma

AU - Seo, Jeong Gil

AU - Maeda, Shun

AU - Hashimoto, Kunihide

AU - Ogo, Shuhei

AU - Sekine, Yasushi

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Dehydrogenation of ethane over perovskite oxide catalysts was investigated using the redox of perovskites and H2O as an oxidizing agent. The La0.8Ba0.2MnO3-δ (LBMO) perovskite showed a high catalytic activity for dehydrogenation of ethane. Periodic dry (without H2O)-wet (with H2O) operation tests revealed that dehydrogenation of ethane in the presence of H2O over LBMO proceeded via the Mars-van Krevelen (MvK) mechanism. Under the wet condition with D2O instead of H2O, D2 formation was verified, demonstrating that reactive lattice oxygens in LBMO contributed to the dehydrogenation reaction and that they were regenerated by water. Isotopic transient tests with H2 18O and in situ X-ray absorption fine structure measurements revealed that the reduction and oxidation of Mn in LaMnO3 and LBMO occurred under the reaction atmosphere and that the partial replacement of the La sites with Ba improved the redox ability of Mn, resulting in its high activity. Furthermore, temperature-programmed reduction under H2 elucidated that the reduction of Mn3+ to Mn2+ was promoted by Ba doping. The LBMO perovskite showed the very high activity for dehydrogenation of ethane in the presence of H2O via the MvK mechanism by virtue of the high redox properties of Mn.

AB - Dehydrogenation of ethane over perovskite oxide catalysts was investigated using the redox of perovskites and H2O as an oxidizing agent. The La0.8Ba0.2MnO3-δ (LBMO) perovskite showed a high catalytic activity for dehydrogenation of ethane. Periodic dry (without H2O)-wet (with H2O) operation tests revealed that dehydrogenation of ethane in the presence of H2O over LBMO proceeded via the Mars-van Krevelen (MvK) mechanism. Under the wet condition with D2O instead of H2O, D2 formation was verified, demonstrating that reactive lattice oxygens in LBMO contributed to the dehydrogenation reaction and that they were regenerated by water. Isotopic transient tests with H2 18O and in situ X-ray absorption fine structure measurements revealed that the reduction and oxidation of Mn in LaMnO3 and LBMO occurred under the reaction atmosphere and that the partial replacement of the La sites with Ba improved the redox ability of Mn, resulting in its high activity. Furthermore, temperature-programmed reduction under H2 elucidated that the reduction of Mn3+ to Mn2+ was promoted by Ba doping. The LBMO perovskite showed the very high activity for dehydrogenation of ethane in the presence of H2O via the MvK mechanism by virtue of the high redox properties of Mn.

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