Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism

Bo Hu, Andrew Bean Getsoian, Neil M. Schweitzer, Ujjal Das, Hacksung Kim, Jens Niklas, Oleg Poluektov, Larry A. Curtiss, Peter C Stair, Jeffrey T. Miller, Adam S. Hock

Research output: Contribution to journalArticle

63 Citations (Scopus)

Abstract

We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 °C. For catalytic propane dehydrogenation, single-site Co2+/SiO2 exhibits selectivities >95% at 550 °C and >90% at 650 °C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co2+ similar to that previously reported for single-site Zn2+/SiO2.

Original languageEnglish
Pages (from-to)24-37
Number of pages14
JournalJournal of Catalysis
Volume322
DOIs
Publication statusPublished - Feb 1 2015

Fingerprint

Propane
Dehydrogenation
dehydrogenation
propane
Silicon Dioxide
Silica
Ions
silicon dioxide
Density functional theory
Paramagnetic resonance
Hydrogen
electron paramagnetic resonance
ions
Gases
selectivity
Chemical activation
fine structure
activation
vapor phases
density functional theory

Keywords

  • Dehydrogenation
  • EXAFS
  • Lewis acid
  • Raman spectroscopy
  • Single-site catalysis

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Hu, B., Bean Getsoian, A., Schweitzer, N. M., Das, U., Kim, H., Niklas, J., ... Hock, A. S. (2015). Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism. Journal of Catalysis, 322, 24-37. https://doi.org/10.1016/j.jcat.2014.10.018

Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism. / Hu, Bo; Bean Getsoian, Andrew; Schweitzer, Neil M.; Das, Ujjal; Kim, Hacksung; Niklas, Jens; Poluektov, Oleg; Curtiss, Larry A.; Stair, Peter C; Miller, Jeffrey T.; Hock, Adam S.

In: Journal of Catalysis, Vol. 322, 01.02.2015, p. 24-37.

Research output: Contribution to journalArticle

Hu, B, Bean Getsoian, A, Schweitzer, NM, Das, U, Kim, H, Niklas, J, Poluektov, O, Curtiss, LA, Stair, PC, Miller, JT & Hock, AS 2015, 'Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism', Journal of Catalysis, vol. 322, pp. 24-37. https://doi.org/10.1016/j.jcat.2014.10.018
Hu, Bo ; Bean Getsoian, Andrew ; Schweitzer, Neil M. ; Das, Ujjal ; Kim, Hacksung ; Niklas, Jens ; Poluektov, Oleg ; Curtiss, Larry A. ; Stair, Peter C ; Miller, Jeffrey T. ; Hock, Adam S. / Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism. In: Journal of Catalysis. 2015 ; Vol. 322. pp. 24-37.
@article{26372e82b2174ad6a93aee82b40dab16,
title = "Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism",
abstract = "We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 °C. For catalytic propane dehydrogenation, single-site Co2+/SiO2 exhibits selectivities >95{\%} at 550 °C and >90{\%} at 650 °C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co2+ similar to that previously reported for single-site Zn2+/SiO2.",
keywords = "Dehydrogenation, EXAFS, Lewis acid, Raman spectroscopy, Single-site catalysis",
author = "Bo Hu and {Bean Getsoian}, Andrew and Schweitzer, {Neil M.} and Ujjal Das and Hacksung Kim and Jens Niklas and Oleg Poluektov and Curtiss, {Larry A.} and Stair, {Peter C} and Miller, {Jeffrey T.} and Hock, {Adam S.}",
year = "2015",
month = "2",
day = "1",
doi = "10.1016/j.jcat.2014.10.018",
language = "English",
volume = "322",
pages = "24--37",
journal = "Journal of Catalysis",
issn = "0021-9517",
publisher = "Academic Press Inc.",

}

TY - JOUR

T1 - Selective propane dehydrogenation with single-site CoII on SiO2 by a non-redox mechanism

AU - Hu, Bo

AU - Bean Getsoian, Andrew

AU - Schweitzer, Neil M.

AU - Das, Ujjal

AU - Kim, Hacksung

AU - Niklas, Jens

AU - Poluektov, Oleg

AU - Curtiss, Larry A.

AU - Stair, Peter C

AU - Miller, Jeffrey T.

AU - Hock, Adam S.

PY - 2015/2/1

Y1 - 2015/2/1

N2 - We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 °C. For catalytic propane dehydrogenation, single-site Co2+/SiO2 exhibits selectivities >95% at 550 °C and >90% at 650 °C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co2+ similar to that previously reported for single-site Zn2+/SiO2.

AB - We report the synthesis, characterization, and catalytic performance for gas phase propane dehydrogenation of single-site Co2+ ions supported on silica. Spectroscopic characterization by resonance Raman, electron paramagnetic resonance, and X-ray near-edge and extended absorption fine structure revealed that tetrahedrally coordinated Co2+ ions are chemisorbed into the trisiloxane rings on the surface of amorphous silica. In situ XAS shows that Co is not oxidized by air nor reduced by hydrogen even at 650 °C. For catalytic propane dehydrogenation, single-site Co2+/SiO2 exhibits selectivities >95% at 550 °C and >90% at 650 °C with stable activity over 24 h. Calculations with hybrid density functional theory support a non-redox mechanism for activation of C-H and H-H bonds by Co2+ similar to that previously reported for single-site Zn2+/SiO2.

KW - Dehydrogenation

KW - EXAFS

KW - Lewis acid

KW - Raman spectroscopy

KW - Single-site catalysis

UR - http://www.scopus.com/inward/record.url?scp=84919400958&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84919400958&partnerID=8YFLogxK

U2 - 10.1016/j.jcat.2014.10.018

DO - 10.1016/j.jcat.2014.10.018

M3 - Article

AN - SCOPUS:84919400958

VL - 322

SP - 24

EP - 37

JO - Journal of Catalysis

JF - Journal of Catalysis

SN - 0021-9517

ER -