In situ Ni-doping during cathodic electrodeposition of hematite for excellent photoelectrochemical performance of nanostructured nickel oxide-hematite p-n junction photoanode

Highlights: • NiO-hematite p-n junction photoanodes were fabricated via an in situ Ni-doping. • The fundamental mechanism of Ni²⁺ ions involved was elucidated. • The optimum Ni dopant was 25 M% for the highest photocurrent density. • It exhibited an excellent photoelectrochemical performance of 7-folds enhancement. - Abstract: Nanostructured nickel oxide-hematite (NiO/α-Fe₂O₃) p-n junction photoanodes synthesized from in situ doping of nickel (Ni) during cathodic electrodeposition of hematite were successfully demonstrated. A postulation model was proposed to explain the fundamental mechanism of Ni²⁺ ions involved, and the eventual formation of NiO on the subsurface region of hematite that enhanced the potential photoelectrochemical water oxidation process. Through this study, it was found that the measured photocurrent densities of the Ni-doped hematite photoanodes were highly dependent on the concentrations of Ni dopant used. The optimum Ni dopant at 25 M% demonstrated an excellent photoelectrochemical performance of 7-folds enhancement as compared to bare hematite photoanode. This was attributed to the increased electron donor density through the p-n junction and thus lowering the energetic barrier for water oxidation activity at the optimum Ni dopant concentration. Concurrently, the in situ Ni-doping of hematite has also lowered the photogenerated charge carrier transfer resistance as measured using the electrochemical impedance spectroscopy. It is expected that the fundamental understanding gained through this study is helpful for the rational design and construction of highly efficient photoanodes for application in photoelectrochemical process.