Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming

A combined experimental and theoretical study

Donghai Mei, Vassiliki Alexandra Glezakou, Vanessa Lebarbier, Libor Kovarik, Haiying Wan, Karl O. Albrecht, Mark Gerber, Roger Rousseau, Robert A. Dagle

Research output: Contribution to journalArticle

50 Citations (Scopus)

Abstract

In this work, we present a combined experimental and theoretical investigation of stable MgAl2O4-supported Rh and Ir catalysts for the steam methane reforming (SMR) reaction. Catalytic SMR performance for a series of noble metal catalysts supported on MgAl 2O4 spinel has been evaluated at 873-1123 K. The turnover rate at 873 K follows the order: Pd > Ir > Pt ∼ Rh > Ru > Ni. However, Rh and Ir are found to have the best combination of activity and stability for SMR in the presence of simulated biomass-derived syngas where highly dispersed ∼2 nm Rh and ∼1 nm Ir clusters are identified on the MgAl2O4 spinel support. Scanning Transmission Electron Microscopy (STEM) images show that this excellent dispersion is maintained even under high-temperature conditions (e.g., at 1123 K in the presence of steam), while larger particle sizes of Rh and particularly Ir are observed when supported on Al2O3. These observations are further confirmed by ab initio molecular dynamic (AIMD) simulations, which find that ∼1 nm Rh and Ir particles (50-atom cluster) bind strongly to the MgAl 2O4 surface via a redox process. The strong metal-support interaction between the spinel support and Rh or Ir helps anchor the metal clusters and reduce the tendency to form larger particle sizes. Density functional theory (DFT) calculations suggest that these supported smaller Rh and Ir particles have a lower work function than larger more bulk-like ones, which enables them to activate both water and methane more effectively than larger particles, yet have a minimal influence on the relative stability of coke precursors. In addition, theoretical mechanistic studies are used to probe the relationship between structure and reactivity. Consistent with the experimental observations, our theoretical modeling results also suggest that the small spinel-supported Ir catalyst is more active than the counterpart Rh catalyst for SMR.

Original languageEnglish
Pages (from-to)11-23
Number of pages13
JournalJournal of Catalysis
Volume316
DOIs
Publication statusPublished - 2014

Fingerprint

Steam reforming
steam
methane
spinel
catalysts
Catalysts
Catalyst supports
Particle size
Reforming reactions
Precious metals
Metals
Anchors
Coke
synthesis gas
coke
Density functional theory
Molecular dynamics
metal clusters
biomass
Methane

Keywords

  • Ab initio molecular dynamics
  • Iridium
  • Methane steam reforming
  • Rhodium
  • Spinel

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming : A combined experimental and theoretical study. / Mei, Donghai; Glezakou, Vassiliki Alexandra; Lebarbier, Vanessa; Kovarik, Libor; Wan, Haiying; Albrecht, Karl O.; Gerber, Mark; Rousseau, Roger; Dagle, Robert A.

In: Journal of Catalysis, Vol. 316, 2014, p. 11-23.

Research output: Contribution to journalArticle

Mei, Donghai ; Glezakou, Vassiliki Alexandra ; Lebarbier, Vanessa ; Kovarik, Libor ; Wan, Haiying ; Albrecht, Karl O. ; Gerber, Mark ; Rousseau, Roger ; Dagle, Robert A. / Highly active and stable MgAl2O4-supported Rh and Ir catalysts for methane steam reforming : A combined experimental and theoretical study. In: Journal of Catalysis. 2014 ; Vol. 316. pp. 11-23.
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abstract = "In this work, we present a combined experimental and theoretical investigation of stable MgAl2O4-supported Rh and Ir catalysts for the steam methane reforming (SMR) reaction. Catalytic SMR performance for a series of noble metal catalysts supported on MgAl 2O4 spinel has been evaluated at 873-1123 K. The turnover rate at 873 K follows the order: Pd > Ir > Pt ∼ Rh > Ru > Ni. However, Rh and Ir are found to have the best combination of activity and stability for SMR in the presence of simulated biomass-derived syngas where highly dispersed ∼2 nm Rh and ∼1 nm Ir clusters are identified on the MgAl2O4 spinel support. Scanning Transmission Electron Microscopy (STEM) images show that this excellent dispersion is maintained even under high-temperature conditions (e.g., at 1123 K in the presence of steam), while larger particle sizes of Rh and particularly Ir are observed when supported on Al2O3. These observations are further confirmed by ab initio molecular dynamic (AIMD) simulations, which find that ∼1 nm Rh and Ir particles (50-atom cluster) bind strongly to the MgAl 2O4 surface via a redox process. The strong metal-support interaction between the spinel support and Rh or Ir helps anchor the metal clusters and reduce the tendency to form larger particle sizes. Density functional theory (DFT) calculations suggest that these supported smaller Rh and Ir particles have a lower work function than larger more bulk-like ones, which enables them to activate both water and methane more effectively than larger particles, yet have a minimal influence on the relative stability of coke precursors. In addition, theoretical mechanistic studies are used to probe the relationship between structure and reactivity. Consistent with the experimental observations, our theoretical modeling results also suggest that the small spinel-supported Ir catalyst is more active than the counterpart Rh catalyst for SMR.",
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AU - Kovarik, Libor

AU - Wan, Haiying

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AU - Gerber, Mark

AU - Rousseau, Roger

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