Journal of Physical Chemistry B, Vol.107, No.3, 758-768, 2003
Cyclic voltammetry studies of nanoporous semiconductors. Capacitive and reactive properties of nanocrystalline TiO2 electrodes in aqueous electrolyte
Extended networks of nanosized semiconductor particles permeated with an electrolyte display unique electrochemical behaviors. We report on a general investigation of the electrochemical properties of nanoporous electrodes by means of cyclic voltammetry. Models have been developed accounting for the fundamental characteristics of these electrodes: charge accumulation, charge transport, and interfacial charge transfer. These characteristics can be translated into simple electrical equivalents, which allow us to identify and classify the major features of voltammetry response according to the competition of the different processes during a voltammetric scan. A key point for describing the experimental observations is the potential dependence of the intrinsic film capacitance. The physical meaning of this capacitance is discussed in terms of the distribution of electronic states. We describe in detail the numerical simulation methods, and despite the simplicity of our approach, we show that these methods allow for quantitative description of experimental data of nanoporous TiO2 electrodes in aqueous electrolyte, including the determination of the density of states and the absolute energy levels.