Effects of La2O3 on the mixed higher alcohols synthesis from syngas over co catalysts: A combined theoretical and experimental study

Vanessa M. Lebarbier, Donghai Mei, Do Heui Kim, Amity Andersen, Jonathan L. Male, Johnathan E. Holladay, Roger Rousseau, Yong Wang

Research output: Contribution to journalArticle

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Abstract

The promoting role of lanthanum oxide (La2O3) in the catalytic synthesis of mixed higher (C2-C6) alcohols from syngas on Co-based catalysts was investigated using a combination of in situ and ex situ X-ray diffraction (XRD), photoelectron spectroscopy (XPS), catalyst reactivity performance studies, and ab initio molecular dynamics (AIMD) simulations. XRD measurements show that doping with La (0.5 wt %) onto activated carbon (AC) supported Co catalyst enhances the Co2C phase formation, whereas the Co2C phase formation is largely suppressed on alumina supported Co catalyst. A strong correlation of the selectivity toward alcohols with the ratio of Co2C/Co particles present in the catalysts was observed. AIMD simulations suggest that on AC supports La exists as an oxide phase in the form of small clusters in the vicinity of Co particles. It was found that Co2C formation is energetically favorable, especially for smaller Co particles because of the formation of surface carbide. Theoretical mechanistic studies indicate that oxygenated hydrocarbons can be formed on these catalysts by multiple routes involving the formation of CHxO and CHxCO species at the interface between the La2O 3 phase and Co/Co2C. A detailed comparison with previous findings in the literature as well as discussion of the implications of these results upon the improvement of the selectivity of these catalysts toward higher alcohols is presented.

Original languageEnglish
Pages (from-to)17440-17451
Number of pages12
JournalJournal of Physical Chemistry C
Volume115
Issue number35
DOIs
Publication statusPublished - Sep 8 2011

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synthesis gas
alcohols
Alcohols
catalysts
Catalysts
synthesis
Catalyst selectivity
activated carbon
Activated carbon
Molecular dynamics
selectivity
Lanthanum oxides
molecular dynamics
lanthanum oxides
X ray diffraction
Aluminum Oxide
Computer simulation
Photoelectron spectroscopy
Hydrocarbons
diffraction

ASJC Scopus subject areas

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

Cite this

Effects of La2O3 on the mixed higher alcohols synthesis from syngas over co catalysts : A combined theoretical and experimental study. / Lebarbier, Vanessa M.; Mei, Donghai; Kim, Do Heui; Andersen, Amity; Male, Jonathan L.; Holladay, Johnathan E.; Rousseau, Roger; Wang, Yong.

In: Journal of Physical Chemistry C, Vol. 115, No. 35, 08.09.2011, p. 17440-17451.

Research output: Contribution to journalArticle

Lebarbier, Vanessa M. ; Mei, Donghai ; Kim, Do Heui ; Andersen, Amity ; Male, Jonathan L. ; Holladay, Johnathan E. ; Rousseau, Roger ; Wang, Yong. / Effects of La2O3 on the mixed higher alcohols synthesis from syngas over co catalysts : A combined theoretical and experimental study. In: Journal of Physical Chemistry C. 2011 ; Vol. 115, No. 35. pp. 17440-17451.
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