Decoration of chitosan microspheres with inorganic oxide clusters: Rational design of hierarchically porous, stable and cooperative acid–base nanoreactors

• Published in: Journal of catalysis 2010-07, Vol.273 (2), p.147-155
• Main Authors: Kadib, Abdelkrim El, Molvinger, Karine, Bousmina, Mosto, Brunel, Daniel
• Format: Article
• Language: English
• Subjects: Acids; Bifunctional materials; Catalysis; Chemical Sciences; Chemistry; Chitosan microspheres; Colloidal state and disperse state; Cooperative catalysis; Exact sciences and technology; General and physical chemistry; Inorganic chemistry; Nanoscience; Porous materials; Supercritical drying; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2010.05.010

Mimicking enzyme action in solid materials: the cohabitation in close proximity of NH 2 from chitosan and acidic inorganic oxide in the replicated hybrid microsphere leads to cooperative action in catalysis. One of the fundamental enzymatic catalyst assets, which is the most difficult to engineer in synthetic systems, is the coexistence of multifunctional sites and their synergetic cooperation. In this work, an efficient approach toward cooperative acid–base materials using natural matrices is proposed. Taking advantages from chitosan polysaccharide as nano-assembling system and on the supercritical drying technique to preserve their porosity, the mutual interactions between different glucosamine units and the Lewis acidic precursors (Ti, Zr, Al, Sn) allowed the preparation of hierarchically porous microspheres in which well-separated amino groups from chitosan are replicated with highly dispersed acidic inorganic oxides. This decoration at the nano-scale entails a notable improvement on the hydrothermal stability of the resulting organic–inorganic hybrid materials. The resulting acid–base hybrid materials are assessed for three carbon–carbon forming reactions (Henry condensation, Michael addition and jasminaldehyde synthesis) and systematically compared to the pure acidic inorganic oxide and basic chitosan microspheres. The bifunctional materials displayed interesting catalytic activity and selectivity, with respect to monofunctional ones, witnessing thus on the cooperative effect attainable in chitosan@inorganic oxide microspheres.