Soutenance publique de thèse de doctorat en Sciences chimiques - Amélie MAERTENS

Porous silicates embedding single-sites as active catalysts for the sustainable conversion of biomass derivatives: Unveiling the role of the Brønsted/Lewis acid balance

Jury

Prof. Benoît CHAMPAGNE (UNamur), président
Prof. Carmela APRILE (UNamur), secrétaire
Prof. Eric GAIGNEAUX (UCLouvain)
Prof. Sonia FIORILLI (Politecnico di Torino)
Prof. Wouter MARCHAL (UHasselt)

Abstract

Heterogeneous acid catalysts became over the years essential to our modern industrial world. Among the possible forms of solid materials with acidic properties, porous silica-based structures embedding active single-sites showed highly promising catalytic activity for various reactions. The insertion of heteroelements inside the SiO₂ network is known to introduce a combination of Brønsted and Lewis acid sites which depends on the nature of the element and influences the catalytic properties of the solid. The present thesis investigates the link between the Brønsted/Lewis acid balance introduced by different elements (Al, Ga, In, Ti, Zr, Hf) inserted or finely dispersed in/onto the structure of extra-small silica nanospheres and the catalytic performances of the solids for two distinct biomass derivatives valorization reactions (i.e. conversion of glycerol to solketal and of ethyl levulinate to γ-valerolactone).

The optimizations of the syntheses were particularly focusing on the insertion of the element inside the SiO₂ matrix to maximize the number of acid sites. In-depth characterizations were conducted on the different substituted nanospheres to probe their morphological, structural, and textural features. A special attention was dedicated to the characterization of the surface acidity. These results were put into perspective with the catalytic performances of the materials. At the end of the investigations, we were able to explain the difference in terms of catalytic activity between the different studied solids and identify the optimal acid properties for the targeted reactions. The stability and recyclability of the best working solids were also assessed, an acute tuning of reaction conditions enabled to reach significatively high conversions, and their performances were tested in challenging conditions (i.e. close to crude feedstock).

The knowledge unveiled through these investigations will give precious insight to design new silica-based catalysts with the appropriate acidity for a wide variety of acid-catalyzed reactions.

 

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