Enhancement of ethylbenzene dehydrogenation of perovskite-type BaZrO<inf>3</inf> catalyst by a small amount of Fe substitution in the B-site

Ryo Watanabe, Yoshinori Saito, Choji Fukuhara

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

The purpose of this study was to clarify the effect of a transition metal (Mn, Fe, Co) substitution in the BaZrO<inf>3</inf> catalyst on the performance of ethylbenzene dehydrogenation (EBDH) with steam. The BaZrO<inf>3</inf> catalyst showed a high performance for the EBDH without steam, however the co-feeding of steam produced a significant decrease in the EBDH activity. By partially substituting the Zr site in the BaZrO<inf>3</inf> catalyst with Mn or Fe, the dehydrogenation activity was dramatically improved, while the Co-substituted catalyst showed a significantly low activity. In particular, the Fe substitution of a small percentage from 2 to 4% was effective for the drastic enhancement of the EBDH performance with steam. Comparing the styrene yield over the BaFe<inf>0.02</inf>Zr<inf>0.98</inf>O<inf>3</inf> catalyst with that over the industrial potassium-promoted iron oxide (Fe-K) catalyst, the BaFe<inf>0.02</inf>Zr<inf>0.98</inf>O<inf>3</inf> catalyst produced a higher styrene yield than the Fe-K catalyst. From the ESR measurement, we found that the Fe-substituted BZO catalyst had the defect-dipole (Fe<sup>3+</sup>-V<inf>ox</inf>) in its structure after EBDH with steam. Highly-active BaFe<inf>0.02</inf>Zr<inf>0.98</inf>O<inf>3</inf> catalyst had a large amount of the defect-dipole and therefore an increase of the oxygen mobility. On the other hand, although low-active catalyst had a large amount of the defect-dipole, but the non-uniformity in the environment of the defect-dipole was increased. Such differences might cause a redox property and a performance for EBDH with steam. The drastic change in activity and environment around the oxygen defect by a small amount of Fe substitution is reported for the first time in the field of perovskite catalysts.

Original languageEnglish
Pages (from-to)57-64
Number of pages8
JournalJournal of Molecular Catalysis A: Chemical
Volume404-405
DOIs
Publication statusPublished - 2015 Aug 1
Externally publishedYes

Fingerprint

Ethylbenzene
Dehydrogenation
dehydrogenation
Perovskite
Substitution reactions
substitutes
catalysts
Catalysts
augmentation
Steam
steam
Defects
defects
dipoles
Styrene
styrenes
ethylbenzene
perovskite
Thermodynamic properties
potassium oxides

Keywords

  • BaZrO<inf>3</inf>
  • Dehydrogenation of ethylbenzene
  • Fe-substitution
  • Perovskite oxide catalyst

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry
  • Process Chemistry and Technology

Cite this

Enhancement of ethylbenzene dehydrogenation of perovskite-type BaZrO<inf>3</inf> catalyst by a small amount of Fe substitution in the B-site. / Watanabe, Ryo; Saito, Yoshinori; Fukuhara, Choji.

In: Journal of Molecular Catalysis A: Chemical, Vol. 404-405, 01.08.2015, p. 57-64.

Research output: Contribution to journalArticle

@article{865efc81988b4bdebe3c06a249c99ef4,
title = "Enhancement of ethylbenzene dehydrogenation of perovskite-type BaZrO3 catalyst by a small amount of Fe substitution in the B-site",
abstract = "The purpose of this study was to clarify the effect of a transition metal (Mn, Fe, Co) substitution in the BaZrO3 catalyst on the performance of ethylbenzene dehydrogenation (EBDH) with steam. The BaZrO3 catalyst showed a high performance for the EBDH without steam, however the co-feeding of steam produced a significant decrease in the EBDH activity. By partially substituting the Zr site in the BaZrO3 catalyst with Mn or Fe, the dehydrogenation activity was dramatically improved, while the Co-substituted catalyst showed a significantly low activity. In particular, the Fe substitution of a small percentage from 2 to 4{\%} was effective for the drastic enhancement of the EBDH performance with steam. Comparing the styrene yield over the BaFe0.02Zr0.98O3 catalyst with that over the industrial potassium-promoted iron oxide (Fe-K) catalyst, the BaFe0.02Zr0.98O3 catalyst produced a higher styrene yield than the Fe-K catalyst. From the ESR measurement, we found that the Fe-substituted BZO catalyst had the defect-dipole (Fe3+-Vox) in its structure after EBDH with steam. Highly-active BaFe0.02Zr0.98O3 catalyst had a large amount of the defect-dipole and therefore an increase of the oxygen mobility. On the other hand, although low-active catalyst had a large amount of the defect-dipole, but the non-uniformity in the environment of the defect-dipole was increased. Such differences might cause a redox property and a performance for EBDH with steam. The drastic change in activity and environment around the oxygen defect by a small amount of Fe substitution is reported for the first time in the field of perovskite catalysts.",
keywords = "BaZrO<inf>3</inf>, Dehydrogenation of ethylbenzene, Fe-substitution, Perovskite oxide catalyst",
author = "Ryo Watanabe and Yoshinori Saito and Choji Fukuhara",
year = "2015",
month = "8",
day = "1",
doi = "10.1016/j.molcata.2015.04.010",
language = "English",
volume = "404-405",
pages = "57--64",
journal = "Journal of Molecular Catalysis A: Chemical",
issn = "1381-1169",
publisher = "Elsevier",

}

TY - JOUR

T1 - Enhancement of ethylbenzene dehydrogenation of perovskite-type BaZrO3 catalyst by a small amount of Fe substitution in the B-site

AU - Watanabe, Ryo

AU - Saito, Yoshinori

AU - Fukuhara, Choji

PY - 2015/8/1

Y1 - 2015/8/1

N2 - The purpose of this study was to clarify the effect of a transition metal (Mn, Fe, Co) substitution in the BaZrO3 catalyst on the performance of ethylbenzene dehydrogenation (EBDH) with steam. The BaZrO3 catalyst showed a high performance for the EBDH without steam, however the co-feeding of steam produced a significant decrease in the EBDH activity. By partially substituting the Zr site in the BaZrO3 catalyst with Mn or Fe, the dehydrogenation activity was dramatically improved, while the Co-substituted catalyst showed a significantly low activity. In particular, the Fe substitution of a small percentage from 2 to 4% was effective for the drastic enhancement of the EBDH performance with steam. Comparing the styrene yield over the BaFe0.02Zr0.98O3 catalyst with that over the industrial potassium-promoted iron oxide (Fe-K) catalyst, the BaFe0.02Zr0.98O3 catalyst produced a higher styrene yield than the Fe-K catalyst. From the ESR measurement, we found that the Fe-substituted BZO catalyst had the defect-dipole (Fe3+-Vox) in its structure after EBDH with steam. Highly-active BaFe0.02Zr0.98O3 catalyst had a large amount of the defect-dipole and therefore an increase of the oxygen mobility. On the other hand, although low-active catalyst had a large amount of the defect-dipole, but the non-uniformity in the environment of the defect-dipole was increased. Such differences might cause a redox property and a performance for EBDH with steam. The drastic change in activity and environment around the oxygen defect by a small amount of Fe substitution is reported for the first time in the field of perovskite catalysts.

AB - The purpose of this study was to clarify the effect of a transition metal (Mn, Fe, Co) substitution in the BaZrO3 catalyst on the performance of ethylbenzene dehydrogenation (EBDH) with steam. The BaZrO3 catalyst showed a high performance for the EBDH without steam, however the co-feeding of steam produced a significant decrease in the EBDH activity. By partially substituting the Zr site in the BaZrO3 catalyst with Mn or Fe, the dehydrogenation activity was dramatically improved, while the Co-substituted catalyst showed a significantly low activity. In particular, the Fe substitution of a small percentage from 2 to 4% was effective for the drastic enhancement of the EBDH performance with steam. Comparing the styrene yield over the BaFe0.02Zr0.98O3 catalyst with that over the industrial potassium-promoted iron oxide (Fe-K) catalyst, the BaFe0.02Zr0.98O3 catalyst produced a higher styrene yield than the Fe-K catalyst. From the ESR measurement, we found that the Fe-substituted BZO catalyst had the defect-dipole (Fe3+-Vox) in its structure after EBDH with steam. Highly-active BaFe0.02Zr0.98O3 catalyst had a large amount of the defect-dipole and therefore an increase of the oxygen mobility. On the other hand, although low-active catalyst had a large amount of the defect-dipole, but the non-uniformity in the environment of the defect-dipole was increased. Such differences might cause a redox property and a performance for EBDH with steam. The drastic change in activity and environment around the oxygen defect by a small amount of Fe substitution is reported for the first time in the field of perovskite catalysts.

KW - BaZrO<inf>3</inf>

KW - Dehydrogenation of ethylbenzene

KW - Fe-substitution

KW - Perovskite oxide catalyst

UR - http://www.scopus.com/inward/record.url?scp=84928161717&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84928161717&partnerID=8YFLogxK

U2 - 10.1016/j.molcata.2015.04.010

DO - 10.1016/j.molcata.2015.04.010

M3 - Article

VL - 404-405

SP - 57

EP - 64

JO - Journal of Molecular Catalysis A: Chemical

JF - Journal of Molecular Catalysis A: Chemical

SN - 1381-1169

ER -