Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2).

Several of the multiple applications of titanium dioxide nanomaterials are directly related to the introduction or generation of charge carriers in the oxide. Thus, electrochemistry plays a central role in the understanding of the factors that must be controlled for the optimization of the material for each application. Herein, the main conceptual tools needed to address the study of the electrochemical properties of TiO(2) nanostructured electrodes are reviewed, as well as the electrochemical methods to prepare and modify them. Particular attention is paid to the dark electrochemical response of these nanomaterials and its direct connection with the TiO(2) electronic structure, interfacial area and grain boundary density. The physical bases for the generation of currents under illumination are also presented. Emphasis is placed on the fact that the kinetics of charge-carrier transfer to solution determines the sign and value of the photocurrent. Furthermore, methods for extracting kinetic information from open-circuit potential and photocurrent measurements are briefly presented. Some aspects of the combination of electrochemical and spectroscopic measurements are also dealt with. Finally, some of the applications of TiO(2) nanostructured samples derived from their electrochemical properties are concisely reviewed. Particular attention is paid to photocatalytic processes and, to a lesser extent, to photosynthetic reactions as well as to applications related to energy from the aspects of both saving (electrochromic layers) and accumulation (batteries). The use of TiO(2) nanomaterials in solar cells is not covered, as a number of reviews have been published addressing this issue.

The interaction of photogenerated charges with molecular oxygen was investigated on TiO2 nanocrystals by means of paramagnetic resonance (EPR) spectroscopy. Compared to photoactivation experiments in vacuum at P < 10(-6) mbar and T = 140 K, the presence of O2 enhances the concentration of persistently trapped electron and hole centres--by a factor of ten--due to the formation of adsorbed O2- species. The photoadsorption of oxygen was also tracked quantitatively by pressure measurements, and the number of trapped charges, hole centres and O2- was found to correspond to ten electron-hole pairs per TiO2 nanocrystal. Conversely, in experiments at P < 10(-6) mbar with one trapped electron-hole pair per particle, charge separation is not persistent and completely reversible with respect to temperature. Heating to 298 K causes the total annihilation of photogenerated and trapped charges.

For monocrystalline TiO2 electrodes, capacitive currents are observed at potentials that are negative enough to induce the filling of conduction band states. Nanoparticulate electrodes exhibit, apart from these currents, an additional pair of capacitive peaks at more positive potentials, which can be attributed to charge traps in the band gap. We have taken advantage of the well-defined morphology and crystal structure of three different types of rutile electrodes to investigate the nature of these band gap states. In particular, nanostructured films composed of oriented wires, films of randomly distributed nanoparticles, and smooth single crystals have been used. The analysis of the cyclic voltammetry response reveals a strong dependence of the trap state concentration on the morphological structure of the films. On the basis of results concerning the surface modification of the electrodes, we propose a model with a location of these band gap states at grain boundaries. We report, furthermore, on a new procedure to prepare hierarchically organized nanostructures by direct deposition of nanowires onto nanoparticulate films in aqueous solutions at low temperature. From a practical point of view, this procedure allows for a systematic tuning of the inner surface area and the porosity of the original samples.