Abstract
Some material properties depend not only on synthesis and processing parameters, but may furthermore significantly change during operation. This is particularly true for high surface area materials. We used a combined electrochemical and spectroscopic approach to follow the changes of the photoelectrocatalytic activity and of the electronic semiconductor properties of mesoporous TiO2 films upon charge transfer reductive doping. Shallow donors (i.e. electron/proton pairs) were introduced into the semiconductor by the application of an external potential or, alternatively, by band gap excitation at open circuit conditions. In the latter case the effective open circuit doping potential depends critically on electrolyte composition (e.g. the presence of electron or hole acceptors). Transient charge accumulation (electrons and protons) in nanoparticle electrodes results in a photocurrent enhancement which is attributed to the deactivation of recombination centers. In nanotube electrodes the formation of a space charge layer results in an additional decrease of charge recombination at positive potentials. Doping is transient in nanoparticle films, but turns out to be stable for nanotube arrays.