Beyond Tradition: A MOF-On-MOF Cascade Z-Scheme Heterostructure for Augmented CO2 Photoreduction

Abstract

Metal–organic frameworks (MOFs) are rigorously investigated as promising candidates for CO₂ capture and conversion. MOF-on-MOF heterostructures integrate bolstered charger carrier separation with the intrinsic advantages of MOF components, exhibiting immense potential to substantially escalate the efficiency of photocatalytic CO₂ reduction (CO₂RR). However, the structural and compositional complexity poses significant challenges to the controllable development of these heterostructures. Herein, a conventional MOF-on-MOF nanocomposite is readily optimized from a type II heterojunction to a state-of-the-art cascade Z-scheme configuration via the encapsulation of Pt nanoparticles (Pt NPs), establishing synergistic MOF-MOF and metal-MOF heterojunctions with reinforced built-in electric field. A cascade electron flow is thus propelled, vigorously separating the photogenerated charge carriers and profoundly extending their lifetimes. Collectively, the photocatalytic activity of the cascade Z-scheme is drastically promoted, exhibiting a nearly quintuple enhancement in the CO production rate over the original type II heterostructure. Moreover, the anti-sintering capacity of the developed nanocomposite is unveiled, elucidating its simultaneously improved activity and stability. These findings present unprecedented regulation over the configuration of a MOF-on-MOF heterojunction, substantially enriching the fundamental understanding and rational design strategies of composite materials.