Electronic Structure of Pure and N-Doped TiO2 Nanocrystals by Electrochemical Experiments and First Principles Calculations

Optical and electrochemical characterizations are carried out in conjunction with first-principles calculations on pure and N-doped titania nanocrystals. These are prepared in laboratory with initial doping concentrations of triethylamine in the range of 0.1−0.5 N/Ti molar ratio. Diffuse reflectance UV−vis spectra of N-doped samples present a significant absorption in the visible region. The flatband potential ( E fb ) of pure and nitrogen-doped TiO 2 (−0.6 ± 0.2 V vs NHE) is determined by impedance spectroscopy (Mott−Schottky plots) and the quasi-Fermi level, n E F * (−0.67̅V vs NHE) by photovoltage measurements as a function of the suspension pH in the presence of an electrochemical probe (methylviologen, MV 2+ ). Theoretical density of electronic states calculations, where several N doping versus vacancy combinations are taken into consideration, together with the optical and electrochemical experiments allow us to draw a detailed picture of the electronic features of the doped samples.