Oxygenates on titanium oxide

Baez, V.B. Graves, J.E. Pletcher, D. (1992) The reduction of oxygen on titanium oxide electrodes. /. Elec-troanal. Chenu, 340(1-2), 273-86. 

Higashimoto S, KitaoN, Yoshida N, Saknra T, Azuma M, Ohue H, Sakata Y (2009) Selective photocatalytic oxidation of benzyl alcohol and its derivatives into corresponding aldehydes by molecular oxygen on titanium dioxide undCT visible light irradiation. J Catal 266 (2) 279-285... 

The iodides of the alkaU metals and those of the heavier alkaline earths are resistant to oxygen on heating, but most others can be roasted to oxide in air and oxygen. The vapors of the most volatile iodides, such as those of aluminum and titanium(II) actually bum in air. The iodides resemble the sulfides in this respect, with the important difference that the iodine is volatilized, not as an oxide, but as the free element, which can be recovered as such. Chlorine and bromine readily displace iodine from the iodides, converting them to the corresponding chlorides and bromides. 

The aforementioned inconsistencies between the paralinear model and actual observations point to the possibility that there is a different mechanism altogether. The common feature of these metals, and their distinction from cerium, is their facility for dissolving oxygen. The relationship between this process and an oxidation rate which changes from parabolic to a linear value was first established by Wallwork and Jenkins from work on the oxidation of titanium. These authors were able to determine the oxygen distribution in the metal phase by microhardness traverses across metallographic sections comparison of the results with the oxidation kinetics showed that the rate became linear when the metal surface reached oxygen... 

The above results on detection of trace concentrations of oxygen by sine oxide films (and titanium oxide films, to a lesser degree), as well as the results on detection of alkyl radicals, which are acceptors of semiconductor electrons, show that the behaviour and electric properties of... 

Heat-flow calorimetry may be used also to detect the surface modifications which occur very frequently when a freshly prepared catalyst contacts the reaction mixture. Reduction of titanium oxide at 450°C by carbon monoxide for 15 hr, for instance, enhances the catalytic activity of the solid for the oxidation of carbon monoxide at 450°C (84) and creates very active sites with respect to oxygen. The differential heats of adsorption of oxygen at 450°C on the surface of reduced titanium dioxide (anatase) have been measured with a high-temperature Calvet calorimeter (67). The results of two separate experiments on different samples are presented on Fig. 34 in order to show the reproducibility of the determination of differential heats and of the sample preparation. 

Fig. 34. Differential heats of adsorption of oxygen at 450°C on the surface of samples of titanium oxide (anatase) which have been previously reduced by carbon monoxide (pco = 70 Torr) at 450°C for 15 hr 67).

Fig. 10-16. Polarization curves for anodic oxygen and cathodic hydrogen redox reactions on an n-type semiconductor electrode of titanium oxide in the dark and in a photoex-cited state i = anodic current in the dark (zero) = anodic current...

Quite recently it was shown that phosphonic esters, trimethylsilyl [124, 143] and alkyl esters [124,143, 145] could also be used to modify the surface of titanium or aluminum oxide in organic solvents at moderate temperatures. Unlike Si-O-C bonds, P-O-C bonds are not easily hydrolyzed, and their cleavage on an oxide surface was unexpected. Most probably, coordination of the phosphoryl oxygen to the surface assists the condensation by increasing the electrophilicity of the P atom, thus facilitating the condensation of P-0-R groups with surface hydroxyls (Scheme 7) [124]. The chemisorption of... 

Fio. 22. Spectra of successive oxides of titanium, showing effect of increased oxygen on amplitude of fine structure, and showing distinction between rutile and anatase. 

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