Composite Nanostructures of TiO2 and ZnO for Water Splitting Application: Atomic Layer Deposition Growth and Density Functional Theory Investigation

The commercialization of solar fuel devices requires the development of novel engineered photoelectrodes for water splitting applications which are based on redundant, cheap, and environmentally friendly materials. In the current study, a combination of titanium dioxide (TiO2) and zinc oxide (ZnO) onto nanotextured silicon is utilized for a composite electrode with the aim to overcome the individual shortcomings of the respective materials. The properties of conformal coverage of TiO2 and ZnO layers are designed on the atomic scale by the atomic layer deposition technique. The resulting photoanode shows not only promising stability but also nine times higher photocurrents than an equivalent photoanode with a pure TiO2 encapsulation onto the nanostructured silicon. Density functional theory calculations indicate that segregation of TiO2 at the ZnO surfaces is favorable and leads to the stabilization of the ZnO layers in water environments. In conclusion, the novel designed composite material constitutes a promising base for a stable and effective photoanode for the water oxidation reaction. A novel photoanode for water oxidation based on a composite TiO2‐ZnO encapsulation engineered for stabilized photo­electroactivity of the nanostructured silicon substrate is developed. Density functional theory is applied to obtain realistic structural models of the TiO2‐ZnO composite on the atomic scale and the way in which the configurational modifications lead to a better performance of the electrodes is investigated.