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

Research output: Contribution to journalArticle

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.

Original languageEnglish
JournalJournal of Physical Chemistry C
DOIs
Publication statusAccepted/In press - 2019 Jan 1

Fingerprint

Ethane
Dehydrogenation
perovskites
dehydrogenation
ethane
mars
Perovskite
X ray absorption
Oxidants
Oxides
catalytic activity
Catalyst activity
Thermodynamic properties
fine structure
Doping (additives)
Oxygen
catalysts
atmospheres
Oxidation
oxidation

ASJC Scopus subject areas

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

Cite this

Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La0.8Ba0.2MnO3-δ Perovskites under Anaerobic Conditions. / Saito, Hikaru; Seki, Hirofumi; Hosono, Yukiko; Higo, Takuma; Seo, Jeong Gil; Maeda, Shun; Hashimoto, Kunihide; Ogo, Shuhei; Sekine, Yasushi.

In: Journal of Physical Chemistry C, 01.01.2019.

Research output: Contribution to journalArticle

Saito, Hikaru ; Seki, Hirofumi ; Hosono, Yukiko ; Higo, Takuma ; Seo, Jeong Gil ; Maeda, Shun ; Hashimoto, Kunihide ; Ogo, Shuhei ; Sekine, Yasushi. / Dehydrogenation of Ethane via the Mars-van Krevelen Mechanism over La0.8Ba0.2MnO3-δ Perovskites under Anaerobic Conditions. In: Journal of Physical Chemistry C. 2019.
@article{41b85285513b4923b994288b379c0e78,
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",
month = "1",
day = "1",
doi = "10.1021/acs.jpcc.9b06475",
language = "English",
journal = "Journal of Physical Chemistry C",
issn = "1932-7447",
publisher = "American Chemical Society",

}

TY - JOUR

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.

UR - http://www.scopus.com/inward/record.url?scp=85073831493&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85073831493&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.9b06475

DO - 10.1021/acs.jpcc.9b06475

M3 - Article

AN - SCOPUS:85073831493

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

ER -