Interfacial Charge Transfer Bridge Prolongs Carrier Recombination Lifetimes of CoFe Metal‐Thiolate Framework/Hematite Photoanode for Water Oxidation

Abstract Constructing heterostructural photoanodes is attractive for elevating the photoelectrochemical (PEC) performance, however, it is a long‐standing challenge to achieve highly efficient interfacial charge transfer. Herein, a CoFe metal‐thiolate framework (CoFe MTF)/Fe 2 O 3 photoanode connected by an interfacial Fe─O─N/S bond is designed to modulate the behavior of charge carriers and improve water oxidation performance. It is disclosed that this interfacial bond functions as a direct charge transfer bridge between shallow trap states of Fe 2 O 3 and CoFe MTF, leading to prolonged carrier recombination lifetimes (85 ns for CoFe MTF/Fe 2 O 3 compared to 37 ns for Fe 2 O 3 ) and enhanced charge transfer efficiency. Alternatively, a robust interfacial electric field is established in the CoFe MTF/Fe 2 O 3 p–n heterojunction, facilitating efficient charge transfer. As expected, the CoFe MTF/Fe 2 O 3 photoanode exhibits significant enhancement in water oxidation, resulting in a three‐fold increase in photocurrent density compared to pristine Fe 2 O 3 . This study highlights the significance of designing interfacially bonded heterostructural photoelectrodes to regulate the transfer characters of charge carriers.