Self‐Enhancing H 2 Evolution from TiO 2 Nanostructures under Illumination

: Illumination of anatase in an aqueous methanolic solution leads to the formation of Ti3+ sites that are catalytically active for the generation of dihydrogen (H2 ). With increasing illumination time, a light-induced self-amplification of the photocatalytic H2 production rate can be observed. The effect is characterized by electron paramagnetic resonance (EPR) spectroscopy, reflectivity, and photoelectrochemical techniques. Combined measurements of H2 generation rates and in situ EPR spectroscopic observation over the illumination time with AM 1.5G or UV light establish that the activation is accompanied by the formation of Ti3+ states, which is validated through their characteristic EPR resonance at g=1.93. This self-activation and amplification behavior can be observed for anatase nanoparticles and nanotubes.