Robust Ruthenium Catalysts Supported on Mesoporous Cyclodextrin-Templated TiO2-SiO2 Mixed Oxides for the Hydrogenation of Levulinic Acid to γ-Valerolactone

• Published in: International journal of molecular sciences Vol. 22; no. 4; p. 1721
• Main Authors: Decarpigny, Cédric, Noël, Sébastien, Addad, Ahmed, Ponchel, Anne, Monflier, Eric, Bleta, Rudina
• Format: Journal Article
• Language: English
• Published: Basel MDPI AG 09.02.2021; MDPI
• Subjects: Activated carbon; Biomass; Catalysis; Catalysts; Chemical Sciences; Colloids; Crystals; Cyclodextrins; High resolution electron microscopy; Hydrogenation; Levulinic acid; Light scattering; Mixed oxides; Morphology; Nanocrystals; Nanoparticles; Oxides; Photon correlation spectroscopy; Poloxamers; randomly methylated β-cyclodextrin; Ru catalyst; Ruthenium; Ruthenium oxide; Scanning transmission electron microscopy; Self-assembly; Silicon dioxide; sol-gel; Titanium dioxide; Transmission electron microscopy; X ray powder diffraction; X-ray diffraction; β-Cyclodextrin; γ-valerolactone; sol-gelmixed oxides; γ; aqueous phase hydrogenation; randomly methylated β; cyclodextrin; valerolactone; Ru catalyst; levulinic acid
• ISSN: 1422-0067; 1661-6596; 1422-0067
• DOI: 10.3390/ijms22041721

In this paper, we present a versatile template-directed colloidal self-assembly method for the fabrication in aqueous phase of composition-tuned mesoporous RuO2@TiO2-SiO2 catalysts. Randomly methylated β-cyclodextrin/Pluronic F127 supramolecular assemblies were used as soft templates, TiO2 colloids as building blocks, and tetraethyl orthosilicate as a silica source. Catalysts were characterized at different stages of their synthesis using dynamic light scattering, N2-adsorption analysis, powder X-ray diffraction, temperature programmed reduction, high-resolution transmission electron microscopy, high-angle annular bright-field and dark-field scanning transmission electron microscopy, together with EDS elemental mapping. Results revealed that both the supramolecular template and the silica loading had a strong impact on the pore characteristics and crystalline structure of the mixed oxides, as well as on the morphology of the RuO2 nanocrystals. Their catalytic performance was then evaluated in the aqueous phase hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) under mild conditions (50 °C, 50 bar H2). Results showed that the cyclodextrin-derived catalyst displayed almost quantitative LA conversion and 99% GVL yield in less than one hour. Moreover, this catalyst could be reused at least five times without loss of activity. This work offers an effective approach to the utilization of cyclodextrins for engineering the surface morphology of Ru nanocrystals and pore characteristics of TiO2-based materials for catalytic applications in hydrogenation reactions.