期刊
JOURNAL OF CATALYSIS
卷 317, 期 -, 页码 114-125出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jcat.2014.06.010
关键词
Selective hydrogenation; Benzoic acid; Benzyl alcohol; CeO2; CeO2-ZrO2; Supported Au catalysts
The gas-phase hydrogenation of benzoic acid was studied over Au supported on CeO2 and Ce0.62Zr0.38O2 (CZ). HAADF-STEM has established formation of nanoscale (mean = 1.5-2 nm) Au particles, which is consistent with CO adsorption measurements. Incorporation of Au facilitated partial support reduction during TPR to 573 K where the presence of Zr increased oxygen mobility, resulting in a greater degree of Ce4+ reduction (to Ce3+ in Au/CZ, as demonstrated by oxygen storage capacity and XPS measurements. Hydrogenation of an aqueous benzoic acid feed generated benzaldehyde and benzyl alcohol with a higher rate over Au/CZ that is attributed to the action of oxygen vacancies, which activate the carboxyl function for hydrogen attack. A parallel/consecutive kinetic model has been applied to quantify catalytic selectivity. A concerted (single step) conversion is proposed for Au/CeO2 that involves bridging interaction of the benzoate with Ce cations and Au nanoparticles with hydrogen addition. A stepwise conversion on Au/CZ is achieved via a Mars and van Krevelen mechanism with benzoic acid activation at an oxygen vacancy and reaction with surface hydrogen to generate benzaldehyde as a reactive intermediate that is converted to benzyl alcohol via nucleophilic C = O attack. Switching from an aqueous to ethanolic feed increased rate due to greater oxygen vacancy availability with higher selectivity to benzaldehyde and appreciable toluene formation over Au/CZ. (C) 2014 Elsevier Inc. All rights reserved.
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