Porous Hybrid Materials for Catalysis and Energy applications

Abstract

Porous materials have exhibited some remarkable performances in wide range of applications such as in the field of catalysis, gas adsorption, water treatment, bio- imaging, drugs delivery and energy applications. This is due to the pore characteristic of these materials. In fact, their properties depend mainly on the pore size, pore morphology and pore size distribution. The knowledge of understanding the effect of chemical nature of porous materials on the heterogeneous catalysis has significantly increased since last decades resulting in the increase in the development of innovative porous nano-hybrid materials. Scientists have integrated inorganic and organic materials to generate new structures with unique properties. A significant enhancement in their properties have been observed compared to their single components. This research work focuses on the design and tailoring of innovative hybrid materials with intrinsic porosity based on well studied single components for catalysis and energy applications. The first example is represented by the impregnation technique of gold nanoclusters (Au NCs) inside the pores of mesoporous silica nanoparticles (MSNs). The performance of Au NCs/ MSN as catalyst was evaluated by the epoxidation reaction of styrene. It shows a remarkable catalytic activity, high selectivity towards styrene epoxide (74%) and high conversion of styrene (88%). We have also investigated the self-assembly of polyoxomolybdates (P2Mo5O23) and cyclodextrins (CDs) as molecular building blocks (MBBs) through the bridging

effect of counter cations (Na+, K+, and Cs+). This assembly has resulted in the formation of seven different crystals to give seven crystal structures of POM-CD MOFs. These novel porous hybrid frameworks with intrinsic porosity and tunable porosity have been well studied and characterized using different techniques. Interestingly, one of these structures (K-PMo-γ-CD) was obtained in good yield (70 % based on γ-CD), and was therefore selected to further study the catalytic performance of this type of the hybrid organic-inorganic structures (POM-CD MOFs). The ketalization process of cyclohexanone with glycol using K-PMo-γ-CD as catalysts, have been chosed as module reaction for this study. Our results showed that the material give the best catalytic performance, which reached its maximum conversion of 99.94 %, at 100oC.

Finally, the scope of our research have been extended by combining another porous macrocycle, a trianglamine (TA), with the metal cluster complex system (polyoxometalate). This hybrid framework (POM-TA) have been well designed and synthesized based on molecular recognition. A detailed characterization shows that the POM-TA material has high surface area that suggests that it can be suitable as catalyst for some industrial processes. Our research on such organic-inorganic hybrid frameworks represents a promising enrichment in the field of heterogeneous catalysis. This is largely due to the possibility of combining different molecular building blocks to form a hybrid framework with improved properties such as intrinsic porosity, large surface area, and tunable structural properties.