LAUSR

Incorporating the charge transfer medium between semiconductor and cocatalyst accelerates the separation of photogenerated charges, enhancing the photoelectrochemical water oxidation performance. However, the structure regulation of cocatalyst in situ generated by the transfer medium is usually neglected, which would alter the injection efficiency of photogenerated holes. Besides, more relevant technologies are necessary to investigate the intrinsic action of each part on water oxidation. Herein, a novel triadic photoanode is designed rationally, involving Ti‐doped hematite (Ti‐Fe2O3) core, nitrogen‐doped carbon (CN) interlayer, and Ce‐doped NiFe‐LDH (NFC) shell. The results like single‐molecule fluorescence and short‐pulse transient photocurrent experiments reveal CN not only employs as a hole transfer layer to facilitate bulk charge transfer and suppress back recombination, but also polishes up the OH− absorption in conjunction action with NFC. Furthermore, CN exhibits an additional functionality by inducing oxygen vacancies and more Ce4+ in NFC to further raise the injection efficiency, expediting the generation of O2 from absorbed OH−. Consequently, NFC/CN/Ti‐Fe2O3 presents a significantly higher photocurrent density than NFC/Ti‐Fe2O3, accomplishing a photocurrent density of 2.87 mA cm−2 at 1.23 V versus RHE. The design of the multiple‐functional CN exhibits a strategic approach for regulating the reactant absorption and photogenerated hole transfer, thereby enhancing the water oxidation performance.