Self‐Driven Interfacial Assembly of MIL‐68 MOFs on Group‐III Nitride Nanorod Arrays for Constructing Efficient Photoanodes

Abstract The development of highly efficient and stable photoelectrochemical (PEC) systems remains a critical challenge for solar‐driven water splitting and pollutant degradation. Herein, a novel strategy is reported for the self‐driven interfacial assembly of MIL‐68‐type metal–organic frameworks (MOFs) on group III‐nitride nanorods (InN and GaN) to construct high‐performance photoanodes. Through in situ solvothermal growth facilitated by surface metal cluster anchoring, MIL‐68 (In/Ga) layers are uniformly coated on III‐nitride nanorods, forming tightly bonded heterojunctions with significantly reduced interfacial resistance. The resulting InN/MIL‐68 (In) heterostructure demonstrates a remarkable photocurrent density of 13.19 mA cm −2 at 1.23 V versus RHE and an ABPE of 3.74%, representing a 19‐fold enhancement over pristine InN. Furthermore, the GaN/MIL‐68 (Ga) system achieves 94% degradation of Rhodamine B under visible‐light irradiation without sacrificial agents. Theoretical calculations and operando characterizations reveal a direct Z‐scheme charge transfer mechanism, enabling efficient spatial separation of redox species and enhanced generation of reactive oxygen species. This work provides a generalizable approach for constructing MOF/semiconductor heterostructures and highlights the potential of surface‐cluster‐assisted MOF assembly for advancing solar energy conversion and environmental remediation technologies.