Highly Dispersed SiOx/Al2O3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites

Aidan R. Mouat, Cassandra George, Takeshi Kobayashi, Marek Pruski, Richard P. Van Duyne, Tobin J Marks, Peter C Stair

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al2O3 surface, functionalizing the surface with "mild" Brønsted acid sites. For liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

Original languageEnglish
Pages (from-to)13346-13351
Number of pages6
JournalAngewandte Chemie - International Edition
Volume54
Issue number45
DOIs
Publication statusPublished - Nov 1 2015

Fingerprint

Aluminum Oxide
Alumina
Catalysts
Cyclohexanols
Lewis Acids
Acids
Carbon Monoxide
Dehydration
Pyridine
Nuclear magnetic resonance spectroscopy
X ray photoelectron spectroscopy
Vapors
Liquids
silanol
Temperature
tetraethoxysilane

Keywords

  • alcohol dehydration
  • atomic layer deposition
  • heterogeneous catalysis
  • silica-alumina
  • solid acid

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Highly Dispersed SiOx/Al2O3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites. / Mouat, Aidan R.; George, Cassandra; Kobayashi, Takeshi; Pruski, Marek; Van Duyne, Richard P.; Marks, Tobin J; Stair, Peter C.

In: Angewandte Chemie - International Edition, Vol. 54, No. 45, 01.11.2015, p. 13346-13351.

Research output: Contribution to journalArticle

Mouat, Aidan R. ; George, Cassandra ; Kobayashi, Takeshi ; Pruski, Marek ; Van Duyne, Richard P. ; Marks, Tobin J ; Stair, Peter C. / Highly Dispersed SiOx/Al2O3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites. In: Angewandte Chemie - International Edition. 2015 ; Vol. 54, No. 45. pp. 13346-13351.
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AU - Van Duyne, Richard P.

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AB - The reaction of γ-alumina with tetraethylorthosilicate (TEOS) vapor at low temperatures selectively yields monomeric SiOx species on the alumina surface. These isolated (-AlO)3Si(OH) sites are characterized by PXRD, XPS, DRIFTS of adsorbed NH3, CO, and pyridine, and 29Si and 27Al DNP-enhanced solid-state NMR spectroscopy. The formation of isolated sites suggests that TEOS reacts preferentially at strong Lewis acid sites on the γ-Al2O3 surface, functionalizing the surface with "mild" Brønsted acid sites. For liquid-phase catalytic cyclohexanol dehydration, these SiOx sites exhibit up to 3.5-fold higher specific activity than the parent alumina with identical selectivity.

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