Supported Molecular Catalysis Immobilized Catalysts

Redox and Chemical Catalysis at Monolayer and Multilayer Coated Electrodes 

There are a number of ways of attaching a monolayer of redox molecules to an electrode surface.10 Multilayered films can be obtained by deposition of a polymer containing redox centers. These may be attached to the polymer backbone covalently, electrostatically, or coordinatively if the redox center contains a transition metal. 

FIGURE 4.10. Catalysis at monolayer and multilayer electrode coatings. 

Although cyclic voltammetry could fruitfully be applied to the kinetic analysis of these catalytic systems, it has mostly been investigated by means of rotating disk electrode voltammetry (Section 1.3.2). The simplest case is that of an irreversible catalytic reaction at a monolayer coating. The next section is devoted to the analysis of these systems by the two techniques. 

Catalysis at multilayered electrode coatings is then addressed. Besides the rate of the catalytic reaction within the film and the diffusion of the substrate and products between the bulk of the bathing solution and the film-solution interface, the current response depends on two additional factors permeation of the substrate through the film, and transport of electrons through the film. Analysis of the first of these factors also involves a discussion of the inhibition of the electrode electron transfer that the presence of a film on the electrode surface may cause, whether the electrode is covered by a monolayer or by a thicker film. This discussion also addresses the important case where inhibition is due to deposition onto the electrode surface of one of the reaction products. 

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When combined with the isolation and reactivity studies of the patterned aminosilica (7), the increased activity of the patterned catalysts provide further evidence that the patterning technique developed allows for the synthesis of aminosilicas which behave like isolated, single-site materials (although a true single site nature has not been proven). As the olefin polymerization catalysts supported by the patterned materials show a marked improvement over those materials supported on traditional aminosilicas, these patterned materials should be able to improve supported small molecular catalysis as well. Future improvements in catalysis with immobilized molecular active sites could be realized if this methodology is adopted to prepare new catalysts with isolated, well-defined, single-site active centers. 

Blanco, R.M., Terreros, P., Fernandez-Perez, M., Otero, C. and az-Gonzalez, G. (2004) Functionalization of mesoporous silica for lipase immobilization Characterization of the support and the catalysts. Journal of Molecular Catalysis B-Enzymatic, 30, 83-93. 

The use of polymeric coatings in catalysis is mainly restricted to the physical and sometimes chemical immobilization of molecular catalysts into the bulk polymer [166, 167]. The catalytic efficiency is often impaired by the local reorganization of polymer attached catalytic sites or the swelling/shrinking of the entire polymer matrix. This results in problems of restricted mass transport and consequently low efficiency of the polymer-supported catalysts. An alternative could be a defined polymer coating on a solid substrate with equally accessible catalytic sites attached to the polymer (side chain) and uniform behavior of the polymer layer upon changes in the environment, such as polymer brushes. 

In microporous supports or zeolites, catalyst immobilization is possible by steric inclusion or entrapment of the active transition metal complex. As catalyst retention requires the encapsulation of a relatively large complex into cages only accessible through windows of molecular dimensions, the term ship-in-a-bottle has been coined for this methodology. Intrinsically, the size of the window not only determines the retention of the complex, but also limits the substrate size that can be used. The sensitivity to diffusion limitations of zeolite-based catalysis remains unchanged with the ship-in-a-bottle approach. In many cases, complex deformation upon heterogenization may occur. 

Abstract Immobilized metallic and bimetallic complexes and clusters on oxide or zeolite supports made from well-defined molecular organometaUic precursors have drawn wide attention because of their novel size-dependent properties and their potential applications for catalysis. It is speculated that nearly molecular supported catalysts may combine the high activity and selectivity of homogenous catalysts with the ease of separation and robustness of operation of heterogeneous catalysts. This chapter is a review of the synthesis and physical characterization of metaUic and bimetallic complexes and clusters supported on metal oxides and zeohtes prepared from organometaUic precursors of well-defined molecularity and stoichiometry. 

New types of mesoporous molecular sieves (their first synthesis opened a new subfield of molecular sieve chemistry) have been prepared over the last ten years by new synthetic approaches, different from those known for zeolites. The variety of the synthetic procedures described and the differences in the textural properties due to different synthetic procedures, as well as to the high temperature treatment, give evidence that mesoporous molecular sieves of different chemical compositions are very interesting materials not only in materials science. They could be important also for the application as heterogeneous catalysis, support for immobilization of homogeneous catalysts, adsorbents or materials for synthesis of new types of inclusion compounds. 

Although the oxidation of tertiary phosphines by these catalytic processes has minimal useful application, it needs to be considered as a problematic side reaction in homogeneous catalysis. Much effort is being currently expended to immobilize platinum metal phosphine complexes on heterogenized tertiary phosphine supports, and irreversible oxidation at phosphorus on these supports effectively destroys the supported catalyst. Recent observations that the compound Rh6(CO)i6 catalyzes the oxidation of tertiary phosphines correlate with the report that phosphine oxidation occurs with molecular oxygen on Rh6(CO)i6 bound to diphenylphosphino-functionalized poly(styrenedivinylbenzene). Thus, in order to use these phosphinated polymer-supported rhodium catalysts, one needs either to rigorously exclude oxygen, or to find a way to inhibit the simultaneous catalyzed phosphine oxidation. 

Another way in which catalysis can be achieved using solid materials is to use them as supports for other catalysts such as metal salts. In this way a catalytic species is held immobile on the solid phase. This means that with amorphous solids a highly dispersed layer of catalyst is created and with lamella or porous solids the catalyst is held in a restricted space. The combination of the catalyst and the restriction of molecular movement brought about by the solid can give powerful control over reactive species. 

Recently, immobilization of salen-based catalysts has been demonstrated both on solid supports [83] and on dendritic molecular frameworks, which allow for en-antioselective catalysis with good to excellent ee over several cycles [84]. 

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