Efficient Exciton Dissociation through the Edge Interfacial State in Metal Halide Perovskite-Based Photocatalysts

Metal halide perovskites (MHPs) with superior optoelectronic properties have recently been actively pursued as catalysts in heterogeneous photocatalysis. Dissociating excitons into charge carriers holds the key to enhancing the photocatalytic performance of MHP-based photocatalysts, especially for those with strong quantum-confinement effects. However, attaining efficient exciton dissociation has been rather challenging. Herein, we propose a novel concept that the edge interfacial state can trigger anisotropic electron transfer to promote exciton dissociation. By taking Cs₄PbBr₆/TiO₂ mesocrystal heterojunction as a proof-of-concept, we demonstrate that the unique interfacial state at the edge of the system is generated by the defect-mediated chemical interaction and acts as a trap state, which brings on a directionally favored electron transfer from the center to edge regions, thereby significantly enhancing the desired exciton dissociation. Consequently, such a system achieves an excellent performance in photocatalytic CO₂ reduction. This paradigmatic work sheds light on the excitonic aspects for rational design of advanced photocatalysts toward high performance.