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Dra. Azócar-Ulloa, Laura
Research Outputs
Tetrabutyl ammonium salts of keggin-type vanadium-substituted phosphomolybdates and phosphotungstates for selective aerobic catalytic oxidation of benzyl alcohol
2022, Díaz, Juan, Pizzio, Luis R., Pecchi, Gina, Campos, Cristian H., Azócar-Ulloa, Laura, Briones, Rodrigo, Romero, Romina, Henríquez, Adolfo, Gaigneaux, Eric M., Contreras, David
A series of tetrabutyl ammonium (TBA) salts of V-included Keggin-type polyoxoanions with W (TBA4PW11V1O40 and TBA5PW10V2O40) and Mo (TBA4PMo11V1O40 and TBA5PMo10V2O40) as addenda atoms were prepared using a hydrothermal method. These synthesized materials were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV-Vis diffuse reflectance (DRS UV-Vis), thermogravimetric analysis (TGA), CHN elemental analysis (EA), inductively coupled plasma spectrometry (ICP-MS), and N2 physisorption techniques to assess their physicochemical/textural properties and correlate them with their catalytic performances. According to FT-IR and DRS UV-Vis, (PVXW(Mo)12−XO40)(3+X)− anions are the main species present in the TBA salts. Additionally, CHN-EA and ICP-MS revealed that the desired stoichiometry was obtained. Their catalytic activities in the liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde were studied at 5 bar of O2 at 170 °C. Independently of the addenda atom nature, the catalytic activity increased with the number of V in the Keggin anion structure. For both series of catalysts, TBA salts of polyoxometalates with the highest V-substitution degree (TBA5PMo10V2O40 and TBA5PW10V2O40) showed higher activity. The maximum benzyl alcohol conversions obtained were 93% and 97% using (TBA)5PMo10V2O40 and (TBA)5PW10V2O40 as catalysts, respectively. In all the cases, the selectivity toward benzaldehyde was higher than 99%.
Catalytic Selective Oxidation of β-O-4 Bond in Phenethoxybenzene as a Lignin Model Using (TBA)5[PMo10V2O40] Nanocatalyst: Optimization of Operational Conditions
2023, Díaz, Juan, Luis R. Pizzio, Pecchi, Gina, Campos, Cristian, Azócar-Ulloa, Laura, Briones, Rodrigo, Romero-Troncoso, Eduardo, Méndez-Rivas, Camila, Melín, Victoria, Murillo-Sierra, Juan, Contreras, David
The catalytic oxidation of phenethoxybenzene as a lignin model compound with a β-O-4 bond was conducted using the Keggin-type polyoxometalate nanocatalyst (TBA)5[PMo10V2O40]. The optimization of the process’s operational conditions was carried out using response surface methodology. The statistically significant variables in the process were determined using a fractional factorial design. Based on this selection, a central circumscribed composite experimental design was used to maximize the phenethoxybenzene conversion, varying temperature, reaction time, and catalyst load. The optimal conditions that maximized the phenethoxybenzene conversion were 137 ◦C, 3.5 h, and 200 mg of catalyst. In addition, under the optimized conditions, the Kraft lignin catalytic depolymerization was carried out to validate the effectiveness of the process. The depolymerization degree was assessed by gel permeation chromatography from which a significant decrease in the molar mass distribution Mw from 7.34 kDa to 1.97 kDa and a reduction in the polydispersity index PDI from 6 to 3 were observed. Furthermore, the successful cleavage of the β-O-4 bond in the Kraft lignin was verified by gas chromatography–mass spectrometry analysis of the reaction products. These results offer a sustainable alternative to efficiently converting lignin into valuable products