Oxidation reactions, semiconductor

Standard 50%—most suitable for industrial bleaching, processing, pollution abatement, and general oxidation reactions. Semiconductor Reg. Seg, 50%—conforms to ACS and Semi Specs, for water etching and cleaning, and applications requiring low residues,... 

The charge carriers may reduce or oxidize the semiconductor itself leading to decomposition. This poses a serious problem for practical photoelectrochemical devices. Absolute thermodynamic stability can be achieved if the redox potential of oxidative decomposition reaction lies below the valence band and the redox potential of the reductive decomposition reaction lies above the conduction band. In most cases, usually one or both redox potentials lie within the bandgap. Then the stability depends on the competition between thermodynamically possible reactions. When the redox potentials of electrode decomposition reactions are thermodynamically more favored than electrolyte redox reactions, the result is electrode instability, for example, ZnO, Cu20, and CdS in an aqueous electrolyte. 

A comparative study of oxides which were closely related, but had different electrical properties, showed that both n- and p-type semiconduction promoted the oxidation reaction, forming CO as the major carbon-containing product. In a gas mixture which was 30% methane, 5% oxygen, and 65% helium, reacted at 1168 K the coupling reactions were best achieved with the electrolyte Lao.9Sro.1YO 1.5 and the /i-lype semiconductor Lao.sSro MntL A and the lily pe semiconductor LaFeo.sNbo.2O1 a produced CO as the major oxidation product (Alcock et al., 1993). The two semiconductors are non-stoichiometric, and the subscript 3 — x varies in value with the oxygen pressure and temperature. Again, it is quite probable that the surface reactions involve the formation of methyl radicals and O- ions. 

An alternative approach involves using two semiconductor electrodes, with the oxidation reaction occurring at an n-type semiconductor (Ti02) and the reduction reaction occurring at a p-type semiconductor (GaP) (Figure 11.10). 

In the simplest case where the oxidation reaction of a semiconductor material (42a) proceeds exclusively through the valence band and the reaction of reduction of the Ox component of the solution exclusively through the conduction band (see Fig. 13a), corrosion kinetics is limited by minority carriers for either type of conductivity. In fact, it can be seen from Fig. 12 that icorr(p) = i"m(p) and 1 ( ) = ipim(n), where ijj are the limiting currents of minority carriers (symbols in parentheses denote the type of conductivity of a sample under corrosion). Since the corrosion rate is limited by the supply of minority carriers to the interface, it appears to be rather low in darkness. The values of [Pg.283]

I For the case of copper, a mixture of cuprous and cupric oxides is present on the copper surface which acts as a defect semiconductor. Therefore, electrons can readily be transported from copper to its oxide surface allowing oxidation to continue at the metal oxide/adhesive interface ls. This continued oxidation reaction which involves the base metal can interfere with adhesion between the oxide and the adhesive. Hence, the underlying metal atoms can effect the adhesion forces in some cases 171... 

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 ... 

Figure 4.11 explains how the loaded metal can act as catalyst for both the reductive and oxidative reactions. The essential point is that the barrier height at the metal/semiconductor interface is changeable by the principle of Fig. 4 10 or other mechanisms. Thus, when the band bending is weak, photoexcited electrons mostly enter the metal and the metal acts as a catalyst for a reductive reaction (Fig. 4.11(A)). On the other hand, when the band bending is strong, the holes in the valence band mostly enter the metal and the metal acts as a catalyst for an oxidative reaction (Fig. 4.11(B)). The prevalence of one over the other depends on the magnitude of the band bending, i.e., on the relative rates of reaction of the electrons and holes at the metal-free semiconductor surface.

Electrochemical reactions at metal electrodes can occur at their redox potential if the reaction system is reversible. In cases of semiconductor electrodes, however, different situations are often observed. For example, oxidation reactions at an illuminated n-type semiconductor electrode commence to occur at around the flat-band potential Ef j irrespective of the redox potential of the reaction Ergdox Efb is negative of Ere 0 (1 2,3). Therefore, it is difficult to control the selectivity of the electrochemical reaction by controlling the electrode potential, and more than one kind of electrochemical reactions often occur competitively. The present study was conducted to investigate factors which affect the competition of the anodic oxidation of halide ions X on illuminated ZnO electrodes and the anodic decomposition of the electrode itself. These reactions are given by Eqs 1 and 2, respectively ... 

A semiconductor suitable for an efficient photo-oxidation reactions of environmental relevance should fulfil several requirements. Its bandgap should allow the use of solar radiation, ie the catalyst has to absorb in the visible or near-UV light region. The redox potentials of 0H7H20 and 02/02 couples should lie within this bandgap ( 0H./H20 = 2.8V [62], E°02/0.- = -0.16V [63]) in order to facilitate... 

Zhang XV, Ellery SP, Friend CM, et al. Photodriven reduction and oxidation reactions on colloidal semiconductor particles Implications for prebiotic synthesis. J Photochem Photobiol A Chem 2007 185 301-11. 

The method nearest to electronic device fabrication is the nanoscale processing based on the anodic oxidation of semiconductors and metals. The following electrochemical reactions proceed after applying voltage between the probe and the substrate in the column of adsorbed water generated at the region between them in the air as shown in Fig. 17. 

The driving force of the electron transfer process in the interface is the difference of energy between the levels of the semiconductor and the redox potential of the species close to the particle surface. The thermodynamically possible processes occurring in the interface are represented in Fig. 9 the photogenerated holes give rise to the D -> D + oxidative reaction while the electrons of the conduction band lead to the A -> A reductive process. The most common semiconductors present oxidative valence bands (redox potentials from +1 to + 3.5 V) and moderately reductive conduction bands (+ 0.5 to - 1.5 V) [115]. Thus, in the presence of redox species close or adsorbed to the semiconductor particle and under illumination, simultaneous oxidation and reduction reactions can take place in the semiconductor-solution interface. 

A varying and much more complex mechanistic situation exists in heterogeneous photocatalysis (Fig. 5-13). With respect to the transient oxygen species, comparable overall oxidation reactions are usually observed, but the set of primary reactive oxygen species is slightly different. It is commonly assumed, that superoxide radical anions and hydroxyl radicals are the primary species formed after photogeneration of the electron-hole pair of a semiconductor catalyst in the presence of water and air (Serpone, 1996). In the presence of ozone, ozonide radical anions or are formed by fast electron transfer reaction of superoxide radical anions with O3 molecules. The combination Ti02-03-UV/VIS is called photocatalytic ozonation (Kopf et al., 2000). For example, it was applied for the decomposition of tri-chloroethene in the gas phase (Shen and Kub, 2002). 

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