Designed synthesis of nanostructured ZrO2 as active support for glycerol valorization reaction

• Published in: Ceramics international 2023-01, Vol.49 (2), p.1764-1778
• Main Authors: Pedro S Nascimento, João, Martins, Antonio J., de Cássia F Bezerra, Rita, Bertoldo, Gabriela M., Oliveira, Alcineia C., Bezerra, João R., Araujo, Rinaldo S., Lang, Rossano, Otubo, Larissa, Rodríguez-Aguado, E., Rodríguez-Castellón, E.
• Format: Article
• Language: English
• Subjects: CuO; DFT; Glycerol; Nanoparticles; Nanostructured ZrO2
• ISSN: 0272-8842; 1873-3956
• DOI: 10.1016/j.ceramint.2022.09.140

Designed synthesis of nanostructured ZrO2 as support for glycerol valorization reaction was investigated. The nanocasting route was used to obtain the ZrO2 support possessing well-dispersed Cu and Zn nanoparticles. The solids were fully characterized by High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Electron paramagnetic resonance (EPR), N2-physisorption isotherms, Temperature-programmed desorption of ammonia (NH3-TPD), Scanning electron microscopy coupled to energy dispersive spectroscopy (SEM-EDS) and Fourier transform infrared (FTIR) spectroscopy measurements. The resultant CuZn/ZrO2 catalyst presented here was distinguished by its unique mesostructured features and defective sites formation. The promotional effect of Cu nanoparticles on the activity illustrated that the formation of active acid sites of medium to strong strength can be modulated by adding a second metal to the catalyst. All these properties provided active solids for acetalization of glycerol with aldehydes and ketones due to the interaction between the active centers and the nanostructured support. Density functional theory (DFT) calculation showed the most favorable mechanistic route of low energy for biofuel additives production.