Oxidation catalysts, tunable electronic

Surfactant-based synthesis of mesoporous metal oxides and metal sulfides emerged about four years after the initial report of MCM-41 [21-36]. High surface area and thermally robust mesoporous metal oxides and sulfides represent a new class of materials with diverse opportunities for the development of improved fuel and solar cells, batteries, membranes, chemical delivery vehicles, heavy metal sponges, sensors, magnetic devices and new catalysts. All of these applications could benefit from tailorable Bronsted and Lewis acidity and basicity, flexible oxidation states, and tunable electronic, optical and magnetic properties. 

Transition metal complexes functioning as redox catalysts are perhaps the most important components of an ATRP system. (It is, however, possible that some catalytic systems reported for ATRP may lead not only to formation of free radical polymer chains but also to ionic and/or coordination polymerization.) As mentioned previously, the transition metal center of the catalyst should undergo an electron transfer reaction coupled with halogen abstraction and accompanied by expansion of the coordination sphere. In addition, to induce a controlled polymerization process, the oxidized transition metal should rapidly deactivate the propagating polymer chains to form dormant species (Fig. 11.16). The ideal catalyst for ATRP should be highly selective for atom transfer, should not participate in other reactions, and should deactivate extremely fast with diffusion-controlled rate constants. Finther, it should have easily tunable activation rate constants to meet sped c requirements for ATRP monomers. For example, very active catalysts with equilibrium constants K > 10 for styrenes and acrylates are not suitable for methacrylates. 

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