This review provides insight into the different aspects and challenges associated with the realization of sustainable solar hydrogen production systems on a practical large scale.

A hematite photoanode showing a stable, record-breaking performance of 4.32 mA/cm2 photoelectrochemical water oxidation current at 1.23 V vs. RHE under simulated 1-sun (100 mW/cm2) irradiation is reported. This photocurrent corresponds to ca. 34% of the maximum theoretical limit expected for hematite with a band gap of 2.1 V. The photoanode produced stoichiometric hydrogen and oxygen gases in amounts close to the expected values from the photocurrent. The hematitle has a unique single-crystalline “wormlike” morphology produced by in-situ two-step annealing at 550°C and 800°C of β-FeOOH nanorods grown directly on a transparent conducting oxide glass via an all-solution method. In addition, it is modified by platinum doping to improve the charge transfer characteristics of hematite and an oxygen-evolving co-catalyst on the surface.