Effect of gold electronic state on the catalytic performance of nano gold catalysts in n-Octanol Oxidation

This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/MxOy/TiO2 (where MxOy are Fe2O3 or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/MxOy/TiO2 catalysts were prepared by deposition-precipitation...

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Detalles Bibliográficos
Autores: Pakrieva, Ekaterina, Kolobova, Ekaterina, Kotolevich, Yulia, Pascual, Laura, Carabineiro, Sónia. A.C., Kharlanov, Andrey N., Pichugina, Daria, Nikitina, Nadezhda, German, Dmitrii, Zepeda, Trino A., Tiznado Vazquez, Hugo J., Farías, Mario H., Bogdanchikova, Nina, Cortés Corberán, Vicente, Pestryakov, Alexey
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2020
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/212517
Acceso en línea:http://hdl.handle.net/10261/212517
Access Level:acceso abierto
Palabra clave:gold catalysts
n-octanol oxidation
gold active sites
gold electronic state
support modifiers
Metal content
pretreatment atmosphere
DFT
solvent adsorption
acid-base centers
selectivity
Descripción
Sumario:This study aims to identify the role of the various electronic states of gold in the catalytic behavior of Au/MxOy/TiO2 (where MxOy are Fe2O3 or MgO) for the liquid phase oxidation of n-octanol, under mild conditions. For this purpose, Au/MxOy/TiO2 catalysts were prepared by deposition-precipitation with urea, varying the gold content (0.5 or 4 wt.%) and pretreatment conditions (H2 or O2), and characterized by low temperature nitrogen adsorption-desorption, X-ray powder diffraction (XRD), energy dispersive spectroscopy (EDX), scanning transmission electron microscopy-high angle annular dark field (STEM HAADF), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy of CO adsorption, temperature-programmable desorption (TPD) of ammonia and carbon dioxide, and X-ray photoelectron spectroscopy (XPS). Three states of gold were identified on the surface of the catalysts, Au0, Au1+ and Au3+, and their ratio determined the catalysts performance. Based on a comparison of catalytic and spectroscopic results, it may be concluded that Au+ was the active site state, while Au0 had negative effect, due to a partial blocking of Au0 by solvent. Au3+ also inhibited the oxidation process, due to the strong adsorption of the solvent and/or water formed during the reaction. Density functional theory (DFT) simulations confirmed these suggestions. The dependence of selectivity on the ratio of Brønsted acid centers to Brønsted basic centers was revealed.