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

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

Confinement of Candida Antarctica Lipase B in a Multifunctional Cyclodextrin-Derived Silicified Hydrogel and Its Application as Enzymatic Nanoreactor

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Oxidation of 2,5-diformfylfuran to 2,5-furandicarboxylic acid catalyzed by Candida antarctica Lipase B immobilized in a cyclodextrin-templated mesoporous silica. The critical role of pore characteristics on the catalytic performance

International audienceHypothesisPorous silica has been extensively used as suitable carrier for the immobilization of various enzymes. Randomly Methylated β-Cyclodextrin (RaMeβCD) has surface active properties and very high solubility in water and could therefore be used as template in the fabrication of silica particles with tunable pore size.ExperimentsSilica particles were prepared by sol-gel process in alkaline medium with and without use of RaMeβCD. Lipase Bfrom Candida antarctica (CALB) was either incorporated within the pores of RaMeβCD-derived support or covalently attached on the surface of CD-free silica particles and its catalytic performance was assayed in the oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA). Enzymatic reactors were characterized by N2-adsorption analysis, small angle XRD, TG/DSC experiments, ATR-FTIR spectroscopy, HR-TEM and LSCM, while reaction products were determined based on 1H NMR spectroscopy combined with HPLC.FindingsResults showed that the use of RaMeβCD as structure directing agent led to mesoporous silica composed of uniform 8 nm-sized particles with 11 nm-sized mesopores compatible with the dimensions of CALB (3.0 nm × 4.0 nm × 5.0 nm). Incorporation of CALB within the pores of RaMeβCD-derived silica caused almost a two-fold increase in specific activity after 7 h at 40 °C when compared to lipase immobilized on the surface of CD-free silica particles (33.2 μmol g−1 min−1vs. 14.4 μmol g−1 min−1). Moreover, the RaMeβCD-derived biocatalyst demonstrated enhanced operational stability during the recycling experiments, retaining more than 90% of its initial activity after five 24 h-reaction cycles. These findings open up new avenues for future research on the use of cyclodextrins in the development of enzyme-based nanoreactors

Effect of Functional Group on the Catalytic Activity of Lipase B from Candida antarctica Immobilized in a Silica-Reinforced Pluronic F127/α-Cyclodextrin Hydrogel

International audienceSurface modification plays a key role in the fabrication of highly active and stable enzymatic nanoreactors. In this study, we report for the first time the effect of various functional groups (epoxy, amine, trimethyl, and hexadecyl) on the catalytic performance of lipase B from Candida antarctica (CALB) incorporated within a monolithic supramolecular hydrogel with multiscale pore architecture. The supramolecular hydrogel formed by host-guest interactions between α-cyclodextrin (α-CD) and Pluronic F127 was first silicified to provide a hierarchically porous material whose surface was further modified with different organosilanes permitting both covalent anchoring and interfacial activation of CALB. The catalytic activity of nanoreactors was evaluated in the liquid phase cascade oxidation of 2,5-diformylfuran (DFF) to 2,5-furandicarboxylic acid (FDCA) under mild conditions. Results showed that high FDCA yields and high efficiency conversion of DFF could be correlated with the ability of epoxy and amine moieties to keep CALB attached to the carrier, while the trimethyl and hexadecyl groups could provide a suitable hydrophobic-hydrophilic interface for the interfacial activation of lipase. Cationic cross-linked β-CD was also evaluated as an enzyme-stabilizing agent and was found to provide beneficial effects in the operational stability of the biocatalyst. These supramolecular silicified hydrogel monoliths with hierarchical porosity may be used as promising nanoreactors to provide easier enzyme recovery in other biocatalytic continuous flow processes

Bioprocesses for the Biodiesel Production from Waste Oils and Valorization of Glycerol

The environmental context causes the use of renewable energy to increase, with the aim of finding alternatives to fossil-based products such as fuels. Biodiesel, an alternative to diesel, is now a well-developed solution, and its production from renewable resources makes it perfectly suitable in the environmental context. In addition, it is biodegradable, non-toxic and has low greenhouse gas emissions: reduced about 85% compared to diesel. However, the feedstock used to produce biodiesel competes with agriculture and the application of chemical reactions is not advantageous with a “green” process. Therefore, this review focuses only on bioprocesses currently taking an important place in the production of biodiesel and allow high yields, above 90%, and with very few produced impurities. In addition, the use of waste oils as feedstock, which now accounts for 10% of feedstocks used in the production of biodiesel, avoids competition with agriculture. To present a complete life-cycle of oils in this review, a second part will focus on the valorization of the biodiesel by-product, glycerol. About 10% of glycerol is generated during the production of biodiesel, so it should be recovered to high value-added products, always based on bioprocesses. This review will also present existing techniques to extract and purify glycerol. In the end, from the collection of feedstocks to the production of CO2 during the combustion of biodiesel, this review presents the steps using the “greener” possible processes

Bioprocesses for the Biodiesel Production from Waste Oils and Valorization of Glycerol

The environmental context causes the use of renewable energy to increase, with the aim of finding alternatives to fossil-based products such as fuels. Biodiesel, an alternative to diesel, is now a well-developed solution, and its production from renewable resources makes it perfectly suitable in the environmental context. In addition, it is biodegradable, non-toxic and has low greenhouse gas emissions: reduced about 85% compared to diesel. However, the feedstock used to produce biodiesel competes with agriculture and the application of chemical reactions is not advantageous with a “green” process. Therefore, this review focuses only on bioprocesses currently taking an important place in the production of biodiesel and allow high yields, above 90%, and with very few produced impurities. In addition, the use of waste oils as feedstock, which now accounts for 10% of feedstocks used in the production of biodiesel, avoids competition with agriculture. To present a complete life-cycle of oils in this review, a second part will focus on the valorization of the biodiesel by-product, glycerol. About 10% of glycerol is generated during the production of biodiesel, so it should be recovered to high value-added products, always based on bioprocesses. This review will also present existing techniques to extract and purify glycerol. In the end, from the collection of feedstocks to the production of CO2 during the combustion of biodiesel, this review presents the steps using the “greener” possible processes

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

International audienceIn 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