Fe2O3–TiO2 Nano‐heterostructure Photoanodes for Highly Efficient Solar Water Oxidation

Harnessing solar energy for the production of clean hydrogen by photo­electrochemical water splitting represents a very attractive, but challenging approach for sustainable energy generation. In this regard, the fabrication of Fe₂O₃–TiO₂ photoanodes is reported, showing attractive performances [≈2.0 mA cm⁻² at 1.23 V vs. the reversible hydrogen electrode in 1 M NaOH] under simulated one‐sun illumination. This goal, corresponding to a tenfold photoactivity enhancement with respect to bare Fe₂O₃, is achieved by atomic layer deposition of TiO₂ over hematite (α‐Fe₂O₃) nanostructures fabricated by plasma enhanced‐chemical vapor deposition and final annealing at 650 °C. The adopted approach enables an intimate Fe₂O₃–TiO₂ coupling, resulting in an electronic interplay at the Fe₂O₃/TiO₂ interface. The reasons for the photocurrent enhancement determined by TiO₂ overlayers with increasing thickness are unraveled by a detailed chemico‐physical investigation, as well as by the study of photo­generated charge carrier dynamics. Transient absorption spectroscopy shows that the increased photoelectrochemical response of heterostructured photoanodes compared to bare hematite is due to an enhanced separation of photogenerated charge carriers and more favorable hole dynamics for water oxidation. The stable responses obtained even in simulated seawater provides a feasible route in view of the eventual large‐scale generation of renewable energy.