Urbano Díaz

Catalysis using multifunctional organosiliceous hybrid materials

Organic-inorganic hybrid materials with different levels of structuration and porous hierarchy and one or several types of active sites in the framework can catalyze multistep chemical processes in a one-pot reactor system following a cascade of reaction events. It will show how the different active sites can act in a synergistic or in a consecutive way following a similar functionality model to biological multisite catalysts. Research on this subject for heterogeneous catalysts is still in the beginning stage and very interesting results can be expected if we are able to successfully combine the properties of organic and inorganic catalysts.

Multifunctional Hybrid Organic−Inorganic Catalytic Materials with a Hierarchical System of Well-Defined Micro- and Mesopores

Novel layered zeolitic organic-inorganic materials (MWW-BTEB) have been synthesized by intercalation and stabilization of arylic silsesquioxane molecules between inorganic zeolitic MWW layers. The organic linkers are conformed by two condensed silyl-arylic groups from disilane molecules, such as 1,4-bis(triethoxysilyl)benzene (BTEB), which react with the external silanol groups of the zeolitic layers. The hybrids contain micropores within the inorganic layers and a well-defined mesoporous system in between the organic linkers. An amination post-treatment introduces basic groups in the organic linkers close to the acid sites present in the structural inorganic counterpart. Through this methodology it has been possible to prepare bifunctional acid-base catalysts where the acid sites are of zeolitic nature located in the inorganic building blocks and the basic sites are part of the organic structure. The resultant materials can act as bifunctional catalysts for performing a two-step cascade reaction that involves the catalytic conversion of benzaldehyde dimethylacetal into benzylidene malononitrile.

Layered zeolitic materials: an approach to designing versatile functional solids

Relevant layered zeolites have been considered in this perspective article from the point of view of the synthesis methodologies, materials characterization and catalytic implications, considering the unique physico-chemical characteristics of lamellar materials. The potential of layered zeolitic precursors to generate novel lamellar accessible zeolites through swelling, intercalation, pillarization, delamination and/or exfoliation treatments is studied, showing the chemical, functional and structural versatility exhibited by layered zeolites. Recent approaches based on the assembly of zeolitic nanosheets which act as inorganic structural units through the use of dual structural directing agents, the selective modification of germanosilicates and the direct generation of lamellar hybrid organic-inorganic aluminosilicates are also considered to obtain layered solids with well-defined functionalities. The catalytic applications of the layered zeolites are also highlighted, pointing out the high accessibility and reactivity of active sites present in the lamellar framework.

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

Designing bifunctional acid-base mesoporous hybrid catalysts for cascade reactions

Bifunctional mesoporous hybrid materials, containing both proton sponges and acid groups, have been prepared following different synthetic routes: co-condensation processes (sol–gel or micellar one-pot routes) or post-synthetic grafting of the organic functionalities. 1,8-Bis(dimethylamino)naphthalene (DMAN), a proton sponge with high pKa, was used as an organic functional builder base and 3-mercaptopropyltriethoxysilane (MPTES) as a pendant precursor of sulfonic acids. The bifunctional hybrid materials were extensively characterized and were investigated as heterogeneous catalysts for various one-pot C–C bond-forming cascade reactions such as deacetalization–Knoevenagel condensation or deacetalization–nitroaldol (Henry) reaction.

In situ preparation of a multifunctional chiral hybrid organic-inorganic catalyst for asymmetric multicomponent reactions

A chiral mesoporous organosilica material incorporating a urea based-cinchona derivative and propylamine groups was prepared by a co-condensation method. The multisite solid catalyst efficiently promoted the asymmetric multicomponent reaction of aldehydes, malonates and nitromethane.

Hybrid organic–inorganic catalytic porous materials synthesized at neutral pH in absence of structural directing agents

Non-ordered porous hybrid materials with different distribution of pore sizes have been synthesized from organic–inorganic bridged silsesquioxane precursors using an NH4F catalyzed sol–gel route. This methodology has allowed to obtain high surface area porous materials in absence of structural directing agents or surfactant molecules. A variety of organic linkers, such as benzene, disulfide, diamine, ethane and ethylene groups, were incorporated within the framework, and the effective integration was confirmed by elemental and thermogravimetrical analyses, Raman and NMR spectroscopies. The pore dimensions of the hybrids could be modified, within the mesoporous range, with the NH4F synthesis and the characteristics of the organic linker. Basic catalytic active sites have been introduced in the organic linkers of the hybrid porous materials that are active and selective for Knoevenagel condensations, showing the possibility to heterogenize organic catalysts while preserving their activity and selectivity by means of these porous organic–inorganic hybrids.

Organic–inorganic supramolecular solid catalyst boosts organic reactions in water

Coordination polymers and metal-organic frameworks are appealing as synthetic hosts for mediating chemical reactions. Here we report the preparation of a mesoscopic metal-organic structure based on single-layer assembly of aluminium chains and organic alkylaryl spacers. The material markedly accelerates condensation reactions in water in the absence of acid or base catalyst, as well as organocatalytic Michael-type reactions that also show superior enantioselectivity when comparing with the host-free transformation. The mesoscopic phase of the solid allows for easy diffusion of products and the catalytic solid is recycled and reused. Saturation transfer difference and two-dimensional 1H nuclear Overhauser effect NOESY NMR spectroscopy show that non-covalent interactions are operative in these host–guest systems that account for substrate activation. The mesoscopic character of the host, its hydrophobicity and chemical stability in water, launch this material as a highly attractive supramolecular catalyst to facilitate (asymmetric) transformations under more environmentally friendly conditions.

Hybrid organic–inorganic catalytic mesoporous materials with proton sponges as building blocks

Non-ordered organic-inorganic mesoporous hybrid materials with basic sites have been synthesized following a fluoride-catalysed sol-gel process at neutral pH and low temperatures that avoids the use of structural directing agents (SDAs). Proton sponges have been used as the organic builder of the hybrids, while the inorganic part corresponds to silica tetrahedra. The proton sponges are diamines that exhibit very high basicity and, after functionalization, have been introduced as part of the walls of the mesoporous silica by one-pot synthesis. Several hybrids with different organic loadings have been synthesized and characterized by gas adsorption, thermogravimetric and elemental analysis, solid state MAS-NMR and FTIR spectroscopy. These hybrids show high activity as base catalysts and can be recycled.

Hybrid organic–inorganic structured materials as single-site heterogeneous catalysts

Catalyst selectivity is associated with well-defined homogeneous active sites. Transition metal complexes and organocatalysts are highly active and selective in the homogeneous phase, and their heterogenization by incorporating them into inorganic solid materials allows combining their excellent catalytic activity with improved separation, recovering and recycling properties. In this article, we present the structural characteristics and catalytic properties of hybrid organic–inorganic materials in which the molecular catalysts are part of the inorganic structure, emphasizing the possibilities of periodic mesoporous hybrid materials and coordination polymers as single-site solid catalysts.