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

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.