Clays and catalysis: a promising future

This paper summarizes the main data appeared in the last years on the oxidative dehydrogenation (ODH) of short chain alkanes on supported vanadium oxide catalysts. The acid-base character of metal oxide support influences the dispersion of vanadium on the surface of the support, as well as the nature of the vanadium species. The reducibility and structure of surface vanadium oxide species and the acid-base character of catalysts, in addition to their catalytic properties in the ODH of C2–C4 alkanes, strongly depend on the metal oxide used as support and the vanadium loading. In this way, it appears that tetrahedral V5+-species are active and selective sites in the ODH of C2–C4 alkanes. The effect of the coordination number and aggregation state of surface vanadium oxide species, and the presence of acid/base sites on the catalytic behavior of supported vanadium oxide catalysts are discussed. It is concluded that these are important factors that must be considered to develop selective catalysts in ODH reactions.

Oxidative dyhydrogenation of short chain alkanes on supported vanadium oxide catalysts

This review is focused on the use of solid Lewis acids to promote catalytic oxidations. While the concept of using Lewis acids to promote the reaction of organic substrates with oxidizing reagents is widely accepted in homogeneous catalysis, this concept has not become evident and generally used in heterogeneous catalysis until recent days. Certainly the development of new Lewis acid solids active and selective for catalytic oxidations is an urgent need and a challenging scientific target for some substrates especially using environmentally friendly oxidants. Since the replacement of current stoichiometric oxidations for the production of fine chemicals by environmentally benign catalytic oxidations is one of the major tasks in green chemistry, solid Lewis acids are called to play a crucial role to accomplish this goal. In the review, we will see the still important role that stoichiometric oxidations play in our daily life, and how they are being substituted by catalytic oxidations. At this point, three general mechanisms in which Lewis acids are involved will be described, and the material has been organized starting from homogeneous and ending with solid catalysts for heterogeneous oxidations. A bridge between the two will be established by presenting catalytic systems that can fill the gap between the two systems helping to rationalize the nature of the catalytic active sites in solid systems. This review is obviously focused on solid oxidation catalysts, and the core of the review is organized to show the evolution from the simplest strategy for heterogeneizing homogeneous catalysts, i.e., supporting the active species on large surface area solids, to the more elaborate ones in which the active sites are part of the solid structure. Given the importance of metallosilicates, and more specifically titanosilicates, as catalysts in commercial processes, special attention has been paid to these types of materials. Although sufficient references are provided to early seminal work, special emphasis has been given to most recent contributions to this area, particularly of the last 10 years. Patent literature has also been extensively covered in this review. Examples to illustrate the concepts have been selected among recent publications, and an effort has been made to present a series of commercial and near commercial processes based on catalytic oxidations. Finally, two * E-mail: acorma@itq.upv.es. 3837 Chem. Rev. 2002, 102, 3837−3892

Lewis acids as catalysts in oxidation reactions: from homogeneous to heterogeneous systems.

Hydrotalcite-like anionic clays (HTs; or layered double hydroxides, LDHs) can be used as precursors to mixed oxides, but their catalytic potential reaches much further. This review demonstrates that HTs can be successfully applied in a broad spectrum of organic reactions, with advantages such as improved activity, selectivity, metal dispersion, less waste production, and an improved recuperation of immobilized catalysts. HTs can be used in the as-synthesized form or after different pretreatments. The HT as such is a solid base or, depending on the elemental composition of its octahedral layers, may have redox properties. Specific metals can be incorporated either as a cation in the octahedral layer or as an anion via exchange. The anion-exchange strategy is especially successful in the context of heterogenizing homogeneous catalysts. A particular advantage for base catalysis is that the number and strength of the basic sites can be tuned precisely to a specific reaction. HTs are excellent materials to des...

A. Dejoz

Papers

Influence of the acid-base character of supported vanadium catalysts on their catalytic properties for the oxidative dehydrogenation of n-butane