Oxide catalysts semiconductors

Understanding and controlling oxide surfaces are the key issues for the development of industrial oxide catalysts, but oxide surfaces are in general heterogeneous and complicated, and hence have been little studied so as to put them on a scientific basis by traditional approaches. While studies of the structure of surfaces have focused on metals and semiconductors over the past thirty years, the application of surface science techniques to metal oxides has blossomed only within the last decade[l-3]. 

The air oxidation of 2-methylpropene to methacrolein was investigated at atmospheric pressure and temperatures ranging between 200° and 460°C. over pumice-supported copper oxide catalyst in the presence of selenium dioxide in an integral isothermal flow reactor. The reaction products were analyzed quantitatively by gas chromatography, and the effects of several process variables on conversion and yield were determined. The experimental results are explained by the electron theory of catalysis on semiconductors, and a reaction mechanism is proposed. It is postulated that while at low selenium-copper ratios, the rate-determining step in the oxidation of 2-methylpropene to methacrolein is a p-type, it is n-type at higher ratios. 

Extending the definition of n-type and p-type reactions, as defined by Vol kenshtein (21) to the electron transfer step, it would seem that the only reaction given by Equation 1 is a p-type reaction. This reaction would be accelerated by the increase in the value of free hole concentration. On the other hand, all other reactions besides the one given by Equation 1 are n-type and would be accelerated by the increase in free electron concentration. Hydrocarbon oxidation reactions catalyzed by solid oxides are accompanied by oxidation and reduction of the catalyst and the degree of the stoichiometric disturbance in the semiconductor changes. The catalytic process in the oxidation of 2-methylpropene over copper oxide catalyst in the presence of Se02 can be visualized as ... 

As indicated previously, it is frequently assumed that weakly bound oxygen leads to the complete combustion of hydrocarbons. However, another possible pathway to complete combustion, may involve the activation of an oxide ion (59). Kazanskii 60) studied in detail the elementary steps of the reduction, photoreduction, and reoxidation of the surfaces of oxide catalysts. He reported that upon exposure to light some semiconductor oxides undergo a charge transfer from the O2- ion to the cation, as shown ... 

With the semiconductor oxidation catalyst, however, the surface becomes activated only upon photoexcitation. At low light intensities, the possibility that many holes are formed in the valence band is remote, so that the irradiated semiconductor powder becomes an effective one-electron oxidant. Now if the same chemistry ensues on the photochemically activated TiC>2 surface, then the reaction will proceed as in the bottom route of eqn 9. Thus, the carboxy radical is formed, producing an alkyl radical after loss of carbon dioxide. Since the semiconductor cannot continue the oxidation after the first step, the radical persists, eventually recapturing the conduction band electron, either directly or through the intervention of an intermediate relay, perhaps superoxide. The resulting anion would be rapidly protonated to product. 

We have shown how the band structure of photoexcited semiconductor particles makes them effective oxidation catalysts. Because of the heterogeneous nature of the photoactivation, selective chemistry can ensue from preferential adsorption, from directed reactivity between adsorbed reactive intermediates, and from the restriction of ECE processes to one electron routes. The extension of these experiments to catalyze chemical reductions and to address heterogeneous redox reactions of biologically important molecules should be straightforward. In fact, the use of surface-modified powders coated with chiral polymers has recently been reputed to cause asymmetric induction at prochiral redox centers. As more semiconductor powders become routinely available, the importance of these photocatalysts to organic chemistry is bound to increase. 

Alloys Borates Solid-state Chemistry Carbides Transition Metal Solid-state Chemistry Chalcogenides Solid-state Chemistry Diffraction Methods in Inorganic Chemistry Electronic Structure of Solids Fluorides Solid-state Chemistry Halides Solid-state Chemistry Intercalation Chemistry Ionic Conductors Magnetic Oxides Magnetism of Extended Arrays in Inorganic Solids Nitrides Transition Metal Solid-state Chemistry Noncrystalline Solids Oxide Catalysts in Solid-state Chemistry Oxides Solid-state Chemistry Quasicrystals Semiconductor Interfaces Solids Characterization by Powder Diffraction Solids Computer Modeling Superconductivity Surfaces. 

Nemst equation is not straightforward however whit thermodynamics data one can demonstrate that CeO can act as an efficient oxidation catalyst [33]. According to its ability to "deliver" oxygen, Ce02 is consider as a n-type semiconductor. This type of oxide is generally assumed to have good oxidation properties [7,20]. 

Another area that has been of interest since the development of this field is that of metal oxides. Simple metal oxides such as MgO provide a test bed for new methods. More complex oxides have attracted much interest for their commercially important properties—solid electrolytes, ferroelectrics, catalysts, semiconductors, superconductors, multiferroics. Relatively simple calculations can, for example, track the path of ions through ionic conductors and suggest alternative solids for fuel cells or batteries. Solids with interesting electrical and magnetic properties such as high Tc superconductors and solids showing colossal magnetoresistance (CMR) have been... 

Bockris and co-workers (317-320) conducted systematic studies on a variety of perovskite oxide catalysts in alkaline solutions and found the kinetics of the OER to have no functional dependence on the semiconductor-type properties of these oxides. The kinetics were found to improve with a decrease of magnetic moment, with a decrease of the enthalpy of formation of transition metal hydroxides, and with an increase in the number of d electrons in the transition metal ion. Thus, it has been suggested that, on the series of perovskites, there is a common slow step, OH desorption, with the differing —OH bond strength giving different isotherms and hence b values (i.e.. 

An alternative way to achieve the photodissociation of water consists in the use of aqueous suspensions of powdered or colloidal semiconductors, in general loaded with noble-metal and/or noble-metal-oxide catalysts which act as short-circuited photoelectrolysis cells. Titanium dioxide was certainly (and is still being) the semiconductor most frequently employed in such systems. 

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