Unveiling the Synergy of Interfacial Contact and Defects in α‐Fe₂O₃ for Enhanced Photo‐Electrochemical Water Splitting

Abstract Photo‐electrochemical (PEC) water splitting is a promising method for converting solar energy into clean energy, but the mechanism of improving PEC efficiency through the interfacial contact and defect strategy remains highly controversial. Herein, reduced graphene oxide (rGO) and oxygen vacancies are introduced into α‐Fe₂O₃ nanorod (NR) arrays using a simple spin‐coating method and acid treatment. The resultant oxygen vacancy–α‐Fe₂O₃/rGO‐integrated system exhibits a higher photocurrent, four times than the pristine α‐Fe₂O₃. It is well evidenced that the electronic interface interaction between α‐Fe₂O₃ and rGO is boosted with the oxygen vacancies, facilitating electron transfer from α‐Fe₂O₃ to rGO. Moreover, the oxygen vacancies not only create interband states in α‐Fe₂O₃ that can trap photogenerated holes and thus facilitate charge separation but significantly also strengthen the adsorption of oxidative intermediates and reduce the energy barrier of rate‐determining step during oxygen evolution reaction (OER). This study demonstrates an rGO–oxygen vacancy synergistic interfacial contact and defect modification approach to design semiconducting photocatalysts for high‐efficiency solar energy capture and conversion. The generated principle is expected to be extendable to another material system.