Photo-Electro-Oxidation of Alcohols on Titanium Dioxide Thin Film Electrodes

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INQUIMAE-DQIAQF, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, 1428 Buenos Aires, Argentina, and Unidad de Actividad Química, Comisión Nacional de Energía Atómica, Avenida del Libertador 8250, 1429 Buenos Aires, Argentina
Cite this: J. Phys. Chem. B 1999, 103, 26, 5505–5511
Publication Date (Web):June 11, 1999
Copyright © 1999 American Chemical Society
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The photo-electro-oxidation on titanium dioxide film electrodes of methanol, 2-propanol, and tert-butyl alcohol has been studied by measuring the transient photocurrents observed during the early stages of illumination. Transients and steady-state photocurrents, measured at different applied potentials and methanol concentrations, were compared with model predictions. The numerical solution of the differential equations corresponding to methanol photo-electro-oxidation, as well as the advanced experimental evidence, supports the hypothesis that surface hole trapping as −OH mediates the charge transfer to methanol. Formation of −OH accounts for the high initial photocurrents, its rapid decay being due to recombination. The rate of oxidation of methanol is then determined by the rate of reaction between −OH and CH3OH located in the interfacial region. The oxidation of CH2OH to CH2O, through the injection of an electron into the conduction band (current doubling), gives rise to an increase in photocurrent; steady state values are later attained. As a consequence, a minimum transient is observed. The minimum is marginally observable in tert-butyl alcohol solutions, in line with the properties of the respective radicals.

 Universidad de Buenos Aires.

 E-mail:  [email protected]


 Corresponding authors.


 Comisión Nacional de Energía Atomica.

 E-mail:  [email protected]

 E-mail:  [email protected]


 E-mail:  [email protected]

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