In Situ Synthesis of α‑Fe₂O₃/Fe₃O₄ Heterojunction Photoanode via Fast Flame Annealing for Enhanced Charge Separation and Water Oxidation

Hematite (α-Fe₂O₃) is a promising photoanode material in photoelectrochemical (PEC) water splitting. To further improve the catalytic activity, a reasonable construction of heterojunction and surface engineering can effectively improve the photoanode PEC water-splitting performance via improving bulk carrier transport and interfacial charge-transfer efficiency. As Fe₃O₄ has an excellent conductivity and a suitable energy band position, α-Fe₂O₃/Fe₃O₄ heterojunction can be an ideal structure to improve the activity of α-Fe₂O₃. However, only few studies have been reported on α-Fe₂O₃/Fe₃O₄ heterojunctions as photoanodes. In this work, a holey nanorod Fe₂O₃/Fe₃O₄ heterojunction photoanode with oxygen vacancies was fabricated using a rapid and facile flame reduction treatment. Compared with pure Fe₂O₃, the water oxidation performance of the Fe₂O₃/Fe₃O₄ photoanode is improved by ninefold at 1.23 V_RHE. Our study revealed that the porous nanorod structure providing more active sites and oxygen vacancies as the hole transfer medium, together improve the interface charge transfer performance of the photoanode. At the same time, Fe₃O₄ can form a Fe₂O₃/Fe₃O₄ heterojunction to improve the carrier separation efficiency. More importantly, Fe₃O₄ can serve as active sites, solving the slow water oxidation kinetic problem of hematite to enhance the catalytic activity. Our work shows that when flame acts on precursors containing oxygen or hydroxide, it is easy to form compounds with different microstructures or compositions in situ.