Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO2: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

McEntee, Monica; Tang, Wenjie; Neurock, Matthew; Yates, Jr., John T.

doi:10.1021/cs5014255

Title: Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO₂: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids

Journal Article · Fri Dec 12 04:00:00 UTC 2014 · ACS Catalysis

DOI: https://doi.org/10.1021/cs5014255 · OSTI ID:1265447

McEntee, Monica ^[1]; Tang, Wenjie ^[1]; Neurock, Matthew ^[1]; Yates, Jr., John T. ^[1]

Univ. of Virginia, Charlottesville, VA (United States)

Here, the partial oxidation of model C₂–C₄ (acetic, propionic, and butyric) carboxylic acids on Au/TiO₂ catalysts consisting of Au particles ~3 nm in size was investigated using transmission infrared spectroscopy and density functional theory. All three acids readily undergo oxidative dehydrogenation on Au/TiO₂. Propionic and butyric acid dehydrogenate at the C2–C3 positions, whereas acetic acid dehydrogenates at the C1–C2 position. The resulting acrylate and crotonate intermediates are subsequently oxidized to form β-keto acids that decarboxylate. All three acids form a gold ketenylidene intermediate, Au₂C=C=O, along the way to their full oxidation to form CO₂. Infrared measurements of Au₂C=C=O formation as a function of time provides a surface spectroscopic probe of the kinetics for the activation and oxidative dehydrogenation of the alkyl groups in the carboxylate intermediates that form.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Energy Frontier Research Centers (EFRC); Fluid Interface Reactions, Structures and Transport Center (FIRST)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1265447

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 2 Vol. 5; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanistic Insights into the Catalytic Oxidation of Carboxylic Acids on Au/TiO₂: Partial Oxidation of Propionic and Butyric Acid to Gold Ketenylidene through Unsaturated Acids