Mixed metal catalysts electronic effect

The experimental results described in this review support the concept that, in certain reactions of the redox type, the interaction between catalysts and supports and its effect on catalytic activity are determined by the electronic properties of metals and semiconductors, taking into account the electronic effects in the boundary layer. In particular, it has been shown that electronic effects on the activity of the catalysts, as expressed by changes of activation energies, are much larger for inverse mixed catalysts (semiconductors supported and/or promoted by metals) than for the more conventional and widely used normal mixed catalysts (metals promoted by semiconductors). The effects are in the order of a few electron volts with inverse systems as opposed to a few tenths of an electron volt with normal systems. This difference is readily understandable in terms of the different magnitude of, and impacts on electron concentrations in metals versus semiconductors. 

The necessity to have more than one component in a catalyst arises from many needs those linked to the polyfunctionality often required for the different steps in a reaction, the need to enhance the rate of some reaction steps, inhibition of unwanted side reactions, provision of adequate thermal stability, to take advantage of observed synergetic effects. From a fundamental point of view, the presence of several metal elements in a common structure permits the adjustment of the local electronic properties, imposes well defined coordinations, limits the extent of oxidation-reduction phenomena, and may stabilize the whole catalyst by retarding sintering. Mixed oxide catalysts are used as such, or as precursors of active catalysts, for a whole range of important industrial processes, a representative selection of which is given in Table 1. 

A related series of mixed-metal face to face porphyrin dimers (192) has been studied by Collman et al.506 A motivation for obtaining these species has been their potential use as redox catalysts for such reactions as the four-electron reduction of 02 to H20 via H202. It was hoped that the orientation of two cofacial metalloporphyrins in a manner which permits the concerted interaction of both metals with dioxygen may promote the above redox reaction. Such a result was obtained for the Co11 /Co" dimer which is an effective catalyst for the reduction of dioxygen electrochemic-ally.507 However for most of the mixed-metal dimers, including a Con/Mnn species, the second metal was found to be catalytically inert with the redox behaviour of the dimer being similar to that of the monomeric cobalt porphyrin. However the nature of the second metal ion has some influence on the potential at which the cobalt centre is reduced. 

Supported metal oxide catalysts are a new class of catalytic materials that are excellent oxidation catalysts when redox surface sites are present. They are ideal catalysts for investigating catalytic molecular/electronic structure-activity selectivity relationships for oxidation reactions because (i) the number of catalytic active sites can be systematically controlled, which allows the determination of the number of participating catalytic active sites in the reaction, (ii) the TOP values for oxidation studies can be quantitatively determined since the number of exposed catalytic active sites can be easily determined, (iii) the oxide support can be varied to examine the effect of different types of ligand on the reaction kinetics, (iii) the molecular and electronic structures of the surface MOj, species can be spectroscopically determined under all environmental conditions for structure-activity determination and (iv) the redox surface sites can be combined with surface acid sites to examine the effect of surface Bronsted or Lewis acid sites. Such fundamental structure-activity information can provide insights and also guide the molecular engineering of advanced hydrocarbon oxidation metal oxide catalysts such as supported metal oxides, polyoxo metallates, metal oxide supported zeolites and molecular sieves, bulk mixed metal oxides and metal oxide supported clays. 

However, the scheme proposed to explain the effect of Ni ions on the codeposition of Mo (Eqs. 42 and 43) leaves some unanswered questions. Equation (39) shows the interaction between two soluble ions, leading to the two-electron reduction of one of them, and the formation of a mixed-metal complex adsorbed on the surface. All these processes cannot happen in a single step, but the authors did not specify what actually is assumed to happen Is [NiCit]- first adsorbed on the surface and then acts as the catalyst for the reduction of Mo04 to M0O2 Or, perhaps, the two ions form a mixed-metal complex in solution, which is subsequently adsorbed and reduced ... 

Catalysts employed in the oxidative production of PA are V205-based compositions which are generally of the monolayer type and are supported on titania (anatase). With such catalysts, selectivities in excess of 80 mole % PA are achieved at essentially complete conversion. The utilization of Sb-V-oxidc-based catalysts supported on anatase improves the PA selectivity. However, little is known about the intrinsic chemical or electronic effects of Sb203 in such catalytic systems, as well as the chemical and physical characterization of the supported Sb-oxide or supported Sb-V-mixed metal oxide [1]. 

Bonding modifiers are employed to weaken or strengthen the chemisorption bonds of reactants and products. Strong electron donors (such as potassium) or electron acceptors (such as chlorine) that are coadsorbed on the catalyst surface are often used for this purpose. Alloying may create new active sites (mixed metal sites) that can greatly modify activity and selectivity. New catalytically active sites can also be created at the interface between the metal and the high-surface-area oxide support. In this circumstance the catalyst exhibits the so-called strong metal-support interaction (SMSI). Titanium oxide frequently shows this effect when used as a support for catalysis by transition metals. Often the sites created at the oxide-metal interface are much more active than the sites on the transition metal. 

Due to their high surface-to-volume ratio and size-dependent electronic properties nanostructured materials like NPs are good as catalysts. NPs of different sizes and structures can show significantly different catalytic activities and thus provides an opportunity to understand the structure-function relationship. NPs prepared usually in ensembles of NPs immobilized on an electrode. Thus the electrocatalytic property result of the average properties of the ensemble. Optimization of the catalyst requires increasing the number of sites available for the reaction to occur, shape and size effect of NP and composition of particles (in case of mixed metal... 

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