Displacement of hexanol by the hexanoic acid overoxidation product in alcohol oxidation on a model supported palladium nanoparticle catalyst

Avram M. Buchbinder, Natalie A. Ray, Junling Lu, Richard P. Van Duyne, Peter C Stair, Eric Weitz, Franz M. Geiger

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

This work characterizes the adsorption, structure, and binding mechanism of oxygenated organic species from cyclohexane solution at the liquid/solid interface of optically flat alumina-supported palladium nanoparticle surfaces prepared by atomic layer deposition (ALD). The surface-specific nonlinear optical vibrational spectroscopy, sum-frequency generation (SFG), was used as a probe for adsorption and interfacial molecular structure. 1-Hexanoic acid is an overoxidation product and possible catalyst poison for the aerobic heterogeneous oxidation of 1-hexanol at the liquid/solid interface of Pd/Al 2O 3 catalysts. Single component and competitive adsorption experiments show that 1-hexanoic acid adsorbs to both ALD-prepared alumina surfaces and alumina surfaces with palladium nanoparticles, that were also prepared by ALD, more strongly than does 1-hexanol. Furthermore, 1-hexanoic acid adsorbs with conformational order on ALD-prepared alumina surfaces, but on surfaces with palladium particles the adsorbates exhibit relative disorder at low surface coverage and become more ordered, on average, at higher surface coverage. Although significant differences in binding constant were not observed between surfaces with and without palladium nanoparticles, the palladium particles play an apparent role in controlling adsorbate structures. The disordered adsorption of 1-hexanoic acid most likely occurs on the alumina support, and probably results from modification of binding sites on the alumina, adjacent to the particles. In addition to providing insight on the possibility of catalyst poisoning by the overoxidation product and characterizing changes in its structure that result in only small adsorption energy changes, this work represents a step toward using surface science techniques that bridge the complexity gap between fundamental studies and realistic catalyst models.

Original languageEnglish
Pages (from-to)17816-17823
Number of pages8
JournalJournal of the American Chemical Society
Volume133
Issue number44
DOIs
Publication statusPublished - Nov 9 2011

Fingerprint

Hexanols
Aluminum Oxide
Palladium
Nanoparticles
Alcohols
Adsorption
Oxidation
Catalysts
Acids
Alumina
Atomic layer deposition
Adsorbates
Poisons
Molecular Structure
Poisoning
hexanoic acid
Catalyst poisoning
Spectrum Analysis
Vibrational spectroscopy
Binding Sites

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Displacement of hexanol by the hexanoic acid overoxidation product in alcohol oxidation on a model supported palladium nanoparticle catalyst. / Buchbinder, Avram M.; Ray, Natalie A.; Lu, Junling; Van Duyne, Richard P.; Stair, Peter C; Weitz, Eric; Geiger, Franz M.

In: Journal of the American Chemical Society, Vol. 133, No. 44, 09.11.2011, p. 17816-17823.

Research output: Contribution to journalArticle

Buchbinder, Avram M. ; Ray, Natalie A. ; Lu, Junling ; Van Duyne, Richard P. ; Stair, Peter C ; Weitz, Eric ; Geiger, Franz M. / Displacement of hexanol by the hexanoic acid overoxidation product in alcohol oxidation on a model supported palladium nanoparticle catalyst. In: Journal of the American Chemical Society. 2011 ; Vol. 133, No. 44. pp. 17816-17823.
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