Benzyl Alcohol Oxidation on Carbon-Supported Pd Nanoparticles: Elucidating the Reaction Mechanism

Experiments were conducted on the liquid‐phase oxidation of benzyl alcohol over Pd nanoparticles, with the aim of determining the operative chemical reaction. Experiments were conducted in a batch reactor with para‐xylene as the solvent and continuous gas purging of the headspace. The following expe...

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Bibliographic Details
Published in:ChemCatChem 2014-12, Vol.6 (12), p.3464-3473
Main Authors: Savara, Aditya, Chan-Thaw, Carine E., Rossetti, Ilenia, Villa, Alberto, Prati, Laura
Format: Article
Language:English
Subjects:
adsorption
Alcohol
alcohols
Chemical industry
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
oxidation
palladium
reaction mechanisms
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Summary:Experiments were conducted on the liquid‐phase oxidation of benzyl alcohol over Pd nanoparticles, with the aim of determining the operative chemical reaction. Experiments were conducted in a batch reactor with para‐xylene as the solvent and continuous gas purging of the headspace. The following experimental parameters were varied: the initial benzyl alcohol concentration, the oxygen partial pressure in the headspace, and the reactor temperature. From trends in the concentration profiles and integrated production of each product, it was determined that there are two primary reaction paths: A) an alkoxy pathway leading to toluene, benzaldehyde, and benzyl ether, and B) a carbonyloxyl pathway (“neutral carboxylate”) leading to benzoic acid, benzene, and benzyl benzoate. From the mechanism elucidated, it is clear that the coverages of atomic hydrogen, atomic oxygen, and surface hydroxyls must be accounted for to achieve a complete description of the quantitative kinetics. Two key intermediates are involved in the catalytic liquid‐phase oxidation of benzyl alcohol. An alkoxy intermediate is proposed for the route to benzyl aldehyde, toluene, and benzyl ether. A carbonyloxyl intermediate is proposed for the route to benzoic acid, benzene, and benzyl benzoate.
ISSN:1867-3880
1867-3899
DOI:10.1002/cctc.201402552