Dynamic Electron–Hole Shuttle at Atomic Interfaces for Solar‐Driven H ₂ O ₂ and Benzaldehyde Coproduction

ABSTRACT Harnessing solar energy to produce value‐added chemicals simultaneously requires the critical step of spatially separating redox processes. However, conventional photocatalysts remain fundamentally constrained by sluggish charge dynamics and irreversible recombination. Here, we propose an atomic‐level interfacial shuttle mechanism in sub‐nanometer gold cluster‐anchored nickel manganite (H‐NiMn 2 O 4‐β /Au 0.5 NCs), which couples dynamic electron–hole separation with Ni 3+ /Ni 2+ redox cycling. Ultrafast transient absorption spectroscopy indicates electron transfer occurring within 3.06 ps, mediated by an Au–O–Ni coordination interface. In this system, Ni 3+ functions as a transient electron trap, undergoing rapid reduction to Ni 2+ and subsequently transferring electrons to adjacent Au clusters, accelerating charge kinetics by 22.16‐fold. This atomic‐scale electron relay selectively steers 2e − oxygen reduction by balancing *OOH intermediate stabilization and desorption, yielding H 2 O 2 at 1.00 mmol g −1 h −1 . Simultaneously, hole accumulation on lattice oxygen drives α–H abstraction, enabling photooxidation of benzyl alcohol to benzaldehyde (14.59 mmol g −1 h −1 ). This work presents a dynamic dual‐site catalysis model, offering atomic‐level insight into interfacial charge management for solar‐driven redox transformations.