Quantum Dot Based Heterostructures for Unassisted Photoelectrochemical Hydrogen Generation

TiO₂ hollow nanowires (HNWs) and nanoparticles (NPs) constitute promising architectures for QDs sensitized photoanodes for H₂ generation. We sensitize these structures with CdS/CdSe quantum dots by two different methods (chemical bath deposition, CBD and succesive ionic layer adsorption and reaction, SILAR) and evaluate the performance of these photoelectrodes. Remarkable photocurrents of 4 mA·cm and 8 mA·cm^?2 and hydrogen generation rates of 40 ml·cm^?2·day^?1 and 80 ml·cm^?2·day^?1 have been obtained in a three electrode configuration with sacrificial hole scavengers (Na₂S and Na₂SO₃), for HNWs and NPs respectively, which is confirmed through gas analysis. More importantly, autonomous generation of H₂ (20 ml·cm^?2·day^?1 corresponding to 2 mA·cm^?2 photocurrent) is obtained in a two electrode configuration at short circuit under 100 mW·cm^?2 illumination, clearly showing that these photoanodes can produce hydrogen without the assistance of any external bias. To the best of the authors' knowledge, this is the highest unbiased solar H₂ generation rate reported for these of QDs based heterostructures. Impedance spectroscopy measurements show similar electron density of trap states below the TiO₂ conduction band while the recombination resistance was higher for HNWs, consistently with the much lower surface area compared to NPs. However, the conductivity of both structures is similar, in spite of the one dimensional character of HNWs, which leaves some room for improvement of these nanowired structures. The effect of the QDs deposition method is also evaluated. Both structures show remarkable stability without any appreciable photocurrent loss after 0.5 hour of operation. The findings of this study constitute a relevant step towards the feasibility of hydrogen generation with wide bandgap semiconductors/quantum dots based heterostructures.