Rational Design Combining Morphology and Charge-Dynamic for Hematite/Nickel−Iron Oxide Thin-Layer Photoanodes: Insights into the Role of the Absorber/Catalyst Junction

Water oxidation represents the anodic reaction in most of the photoelectrosynthetic setups for artificial photosynthesis developed so far. The efficiency of the overall process strongly depends on the joint exploitation of good absorber domains and interfaces with minimized recombination pathways. To this end, we report on the effective coupling of thin-layer hematite with amorphous porous nickel-iron oxide catalysts prepared via pulsed laser deposition. The rational design of such composite photoelectrodes leads to the formation of a functional adaptive junction, with enhanced photoanodic properties with respect to bare hematite. Electrochemical impedance spectroscopy has contributed to shed light on the mechanisms of photocurrent generation, confirming the reduction of recombination pathways as the main contributor to the improved performances of the functionalized photoelectrodes. Our results highlight the importance of the amorphous catalysts' morphology, as dense and electrolyte impermeable layers hinder the pivotal charge compensation processes at the interface. The direct comparison with all-iron and all-nickel catalytic counterparts further confirms that control over the kinetics of both hole transfer and charge recombination, enabled by the adaptive junction, is key for the optimal operation of this kind of semiconductor/catalyst interfaces.