RESUMEN

The catalytic conversion of renewable feedstocks into chemicals is pursued as a means to sustainably fulfil future societal needs. Due to the oxygen-rich nature of bio-derived substrates, isomerisation, transfer-hydrogenation and retro-aldol reactions have emerged as relevant transformations to produce commodity chemicals and polymer building blocks. In this context, porous materials containing Lewis-acid metals (e.g., Al, Ga, Sn, Ti, Zr) play an important role. Among these, tin-containing zeolites have demonstrated superior catalytic properties which have mainly been attributed to their hydrophobicity and crystallinity. This review evaluates the versatility and the scalability of bottom-up and top-down approaches to introduce Lewis-acid functionalities in zeolitic matrices. A precise characterisation is shown to be crucial to determine the structure, acidity and environment of the sites introduced. In this regard, we highlight the limitations of conventional techniques and the advantages of analytical and modelling tools recently applied to gain an improved understanding of these solids. Thereafter, property-performance relations and important aspects for the industrial amenability of new synthetic routes are exemplified through case studies. Finally, we put forward the need for gathering deeper knowledge of the site location, surface properties and stability to aid the design of next-generation Lewis-acid catalysts.

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RESUMEN

Desilication of commercial MFI-type (ZSM-5) zeolites in solutions of alkali metal hydroxides is demonstrated to generate highly selective heterogeneous catalysts for the aqueous-phase isomerization of biobased dihydroxyacetone (DHA) to lactic acid (LA). The best hierarchical ZSM-5 sample attains a LA selectivity exceeding 90 %, which is comparable to that of the state-of-the-art catalyst (i.e., the Sn-beta zeolite); this optimized hierarchical catalyst is recyclable over three runs. The Lewis acid sites, which are created through desilication along with the introduction of mesoporosity, are shown to play a crucial role in the formation of the desired product; these cannot be achieved by using other post-synthetic methods, such as steaming or impregnation of aluminum species. Desilication of other metallosilicates, such as Ga-MFI, also leads to high LA selectivity. In the presence of a soluble aluminum source, such as aluminum nitrate, alkaline-assisted alumination can introduce these unique Lewis acid centers in all-silica MFI zeolites. These findings highlight the potential of zeolites in the field of biomass-to-chemical conversion, and expand the applicability of desilication for the generation of selective catalytic centers.

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RESUMEN

The current work presents an unprecedented direct observation of macropore formation in the spontaneous self-assembly process to obtain hierarchical meso/macroporous metal oxides made possible with the help of an unusual titanium alkoxide.