Abstract

AbstractConstructing an internal electric field (IEF) within the hematite (Fe2O3) photoanode for highly efficient water oxidation performance with facilitated charge transfer and separation remains still a significant challenge. Unlike the conventional approach of creating interfacial electric fields through heterojunction design by introducing another semiconductor, a novel strategy is proposed for engineering localized n‐p homojunctions on the surface of Fe2O3 photoanode using gradient Zn2+ doping strategy. By implementing this approach, the inherent n‐type characteristics of Fe2O3 can be transformed into p‐type, thereby facilitating the formation of an n‐p junction with robust IEF, which enables more efficient charge separation and transfer. Additionally, the gradient Zn2+ doping is accompanied by the generation of oxygen vacancies, which further improves the charge transfer efficiency and accelerates water oxidation kinetics. As expected, the photocurrent density of optimized Fe2O3 photoanode at 1.23 V versus reversible hydrogen electrode is ≈2.6‐fold that of Fe2O3. This work provides a novel perspective on the design of localized n‐p homojunction within photoanodes for achieving high solar energy conversion efficiency.

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