Photo-electrochemical oxidation

Augustynski J (1988) Aspects of Photo-Electrochemical and Surface Behaviour of Titanium (IV) Oxide. 69 1-61... 

Platinum-loaded Ti02 systems can be considered as a short-circuited photo-electrochemical cell where the Ti02 semiconductor electrode and metal Pt counterelectrode are brought into contact [159]. Light irradiation can induce electron-hole (e -h +) pair formation and surface oxidation and also reduction reactions on each Pt/Ti02 particle (Figure 4.11). These powder-based systems lack the advantage of... 

While the exploration of the implications of irradiated semiconductor surfaces for organic chemistry have only recently been attempted, there now exists a growing body of experiments illustrative of their power (283). A typical example of the contrasting oxidative reactivity observed on irradiated semiconductor surfaces can be seen in the different product distributions obtained by oxidation of 1,1-diphenylethylene photo-electrochemically on Ti02, electrochemically on Pt (an inert electrode material), and with thermal single electron transfer catalysts in homogeneous solution, eq. 89 (284) ... 

Augustynski, J. Aspects of Photo-Electrochemical and Surface Behavior of Titanium(lV) Oxide. Vol. 69, pp. 1-61. 

Augustynski J. Aspects of photo-electrochemical and surface behaviour of titanium (IV) oxide. Struct Bond 1988 69 1-61. 

The photoelectro-Fenton method [98] complements the photo-Fenton and electro-Fenton reactions. In the latter, a potential is applied between two electrodes immersed in a solution containing Fenton reagent and the target compound. The recent study of the herbicide 2,4,5-T, performed in an undivided cell with a Pt anode and an 02-diffusion cathode, showed that the photo-electrochemical process was more powerful than the electro-Fenton process, which can yield only about 60-65% of decontamination. The electro-Fenton method provides complete destruction of all reaction intermediates, except oxalic acid, which, as already mentioned, forms stable complexes with Fe3+ that remain in the solution. The fast photodecarboxylation of such Fe(III)-oxalate complexes by UV fight explains the highest oxidative ability of the photoelectro-Fenton treatment, which allows a fast and total mineralization of highly concentrated acidic aqueous solutions of 2,4,5-T at low current and temperature. A similar behavior was found for the herbicide 3,6-dichloro-2-methoxybenzoic acid [99]. 

The observation of products at intermediate oxidation level in the photocatalytic reactions of hydrocarbons is consistent with a surface-bound radical intermediate [157]. Photocatalytic isotope exchange between cyclopentane and deuterium on bifunctional platinum/titanium dioxide catalysts indicates the importance of weakly adsorbed pentane at oxide sites. The platinum serves to attract free electrons, decreasing the efficiency of electron-hole recombination, and to regenerate the surface oxide after exchange. Much better control of the exchange is afforded with photo-electrochemical than thermal catalysis. 

Although photoelectrochemistry has been known as a field for over thirty years, its full impact on organic synthesis has yet to be revealed. This article has dealt with a variety of examples that show how chemical conversions can be induced by photo-electrochemical activation of light-sensitive semiconductor surfaces. Photoexcitation causes the promotion of an electron from the valence band to the conduction band, thus producing a surface-confined electron-hole pair. The charges represented by this pair are then trapped by interfacial electron transfer. The oxidized and reduced... 

---