Metal oxides, interfacial electron

The addition of a second species can cause a decrease in charge recombination and an increase in the TiOz photocatalytic efficiency. Such behavior was examined by loading a series of species on the surface or into the crystal lattice of photocatalysts inorganic ions [148-152], noble metals [153,154], and other semiconductor metal oxides [155], It was thus proven that modifications produced by these species can change semiconductor surface properties by altering interfacial electron-transfer events and thus the photocatalytic efficiency. 

A more complicated model situation is demanded if one thinks of the equivalent circuit for an electrode covered with an oxide film. One might think of A1 and the protective oxide film that grows upon it during anodic polarization. One has to allow for the resistance of the solution, as before. Then there is an equivalent circuit element to model the metal oxide/solution interface, a capacitance and interfacial resistance in parallel. The electrons that enter the oxide by passing across the interfacial region can be shown to go to certain surface states (Section 6.10.1.8) on the oxide surface, and they must be represented. Finally, on the way to the underlying metal, the electron... 

It is often assumed that, to a first approximation, the electronic interactions between the surface and the adsorbate can be understood in terms of weak interactions between the electronic structures of the two components, which are assumed not to change significantly on adsorption compared to their separate properties. The first sections of this chapter therefore deal with relevant aspects of the electronic structure of the adsorbates and the metal oxides by themselves. In the final section, interfacial interactions are discussed. 

Interfacial electron transfer between a metal and an excited sensitizer, A -L- B where B represents a metal electrode, may be reductive, whereby the electron transfers from the conduction band of the metal to the singly occupied HOMO state of the excited adsorbed molecules, thus resulting in A -L-B and a cathodic photocurrent at the electrode. Alternatively, it may be an oxidative process, wherein the electron is transferred from the adsorbate to the metal, so resulting in A+-L-B and an anodic photocurrent at the electrode. 

Fig. 5. (a) Bulk electronic concentration at the metal—oxide interface and electron-hole concentration at the oxide—oxygen interface associated with equilibrium interfacial reactions, (b) Electronic energy-level diagram illustrating the dielectric (or semiconducting) nature of the oxide, with the possibility of electron transport (e.g. by tunneling or thermal emission) from the metal to fill O levels at the oxide—oxygen interface to create a potential difference, VM, across the oxide. 

Not only must we consider the ionic defects produced by the interfacial reactions, but equally important in a description of metal oxidation are the electronic defects produced by the interfacial reactions. This is illustrated schematically in Fig. 5. The parent metal constitutes a ready source... 

Dang X. and Hupp J. T. (1999), Interfacial charge-transfer pathways evidence for Mareus-type inverted electron transfer in metal oxide semiconductor/inorganic dye systems , J. Chem. Soc. 121, 8399-8400. 

When the polymer flhn is oxidized, its electronic conductivity can exceed the ionic conductivity due to mobile counterions. Then, the film behaves as a porous metal with pores of limited diameter and depth. This can be represented by an equivalent circuit via modified Randles circuits such as those shown in Figure 8.4. One Warburg element, representative of linear finite restricted diffusion of dopants across the film, is also included. The model circuit includes a charge transfer resistance, associated with the electrode/fllm interface, and a constant phase element representing the charge accumulation that forms the interfacial double... 

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