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Title: Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles

Abstract

Six products are formed from benzyl alcohol oxidation over Pd nanoparticles using O2 as the oxidant: benzaldehyde, toluene, benzyl ether, benzene, benzoic acid, and benzyl benzoate. Three experimental parameters were varied here: alcohol concentration, oxygen concentration, and temperature. Microkinetic modeling using a mechanism published recently with surface intermediates was able to produce all 18 trends observed experimentally with mostly quantitative agreement. Approximate analytical equations derived from the microkinetic model for isothermal conditions reproduced the isothermal trends and provided insight. The most important activation energies are Ea2=57.9 kJ mol₋1, Ea5=129 kJ mol₋1, and Ea6=175 kJ mol₋1, which correspond to alcohol dissociation, alkyl hydrogenation, and the reaction of alkyl species with alkoxy species. Upper limits for other activation energies were identified. The concepts of a sticking coefficient and steric factor in solution were applied.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
  2. Univ. degli Studi di Milano (Italy). Dipartimento di Chimica
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1295106
Alternate Identifier(s):
OSTI ID: 1401220
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Journal Volume: 8; Journal Issue: 15; Journal ID: ISSN 1867-3880
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alcohols; kinetics; molecular modeling; oxidation; palladium

Citation Formats

Savara, Aditya, Rossetti, Ilenia, Chan-Thaw, Carine E., Prati, Laura, and Villa, Alberto. Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles. United States: N. p., 2016. Web. doi:10.1002/cctc.201600368.
Savara, Aditya, Rossetti, Ilenia, Chan-Thaw, Carine E., Prati, Laura, & Villa, Alberto. Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles. United States. doi:10.1002/cctc.201600368.
Savara, Aditya, Rossetti, Ilenia, Chan-Thaw, Carine E., Prati, Laura, and Villa, Alberto. Thu . "Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles". United States. doi:10.1002/cctc.201600368. https://www.osti.gov/servlets/purl/1295106.
@article{osti_1295106,
title = {Microkinetic Modeling of Benzyl Alcohol Oxidation on Carbon-Supported Palladium Nanoparticles},
author = {Savara, Aditya and Rossetti, Ilenia and Chan-Thaw, Carine E. and Prati, Laura and Villa, Alberto},
abstractNote = {Six products are formed from benzyl alcohol oxidation over Pd nanoparticles using O2 as the oxidant: benzaldehyde, toluene, benzyl ether, benzene, benzoic acid, and benzyl benzoate. Three experimental parameters were varied here: alcohol concentration, oxygen concentration, and temperature. Microkinetic modeling using a mechanism published recently with surface intermediates was able to produce all 18 trends observed experimentally with mostly quantitative agreement. Approximate analytical equations derived from the microkinetic model for isothermal conditions reproduced the isothermal trends and provided insight. The most important activation energies are Ea2=57.9 kJ mol₋1, Ea5=129 kJ mol₋1, and Ea6=175 kJ mol₋1, which correspond to alcohol dissociation, alkyl hydrogenation, and the reaction of alkyl species with alkoxy species. Upper limits for other activation energies were identified. The concepts of a sticking coefficient and steric factor in solution were applied.},
doi = {10.1002/cctc.201600368},
journal = {ChemCatChem},
number = 15,
volume = 8,
place = {United States},
year = {Thu Jul 14 00:00:00 EDT 2016},
month = {Thu Jul 14 00:00:00 EDT 2016}
}

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