Abstract
“Black” TiO2 nanotube arrays (TNTAs) of different darkness are formed by thermal reduction of anodic TiO2 nanotube layers in H2 atmosphere at different temperatures (300–500 °C), and their (photo-)electrochemical properties are studied by IPCE spectroscopy, transient photocurrent measurements, IMPS, PEIS, CV, and Mott-Schottky analysis. Hydrogenation of the TNTAs leads to the enhancement of their IPCE (by up to 1.5 times), despite increased recombination losses at anodic potentials. Reduced TNTAs demonstrate a “metallic” behavior by a characteristic frequency response of their impedance and phase angle, reduced charge transfer resistance at anodic bias, increased double layer capacitance, and remarkably increased donor densities (up to 7.25 × 1023 cm−3). The observed alterations in the properties of TNTAs after hydrogenation are ascribed to the formation of defects and TiHx.