Atomic‐Bridge Engineered Mo–Cl–Cu Initiates d ‐Band Center Modulation and Non‐Equilibrium Carrier Kinetics in S‐Scheme Heterojunctions for Enhanced Photoredox Catalysis

ABSTRACT Modulating non‐equilibrium carrier dynamics is a long‐standing pursuit at the nexus of materials physics and chemistry. Constructing strongly coupled heterojunction interfaces via terminal group engineering offers a compelling route to achieve this goal. Herein, we report a fluoride‐free etching strategy to selectively terminate MoB MBene with chloride (Cl) groups. These Cl terminals serve as charge‐regulating bridges upon coupling with CuO nanosheets, forming a Mo–Cl–Cu atomic linkage within the resultant S‐scheme heterojunctions. This atomic bridge profoundly enhances the built‐in electric field (BIEF) at the interface, enabling the directional transfer of non‐equilibrium carriers, prolonging their lifetime, while simultaneously modulating the d ‐band center. This synergistic modulation yields a superior photocatalyst for concurrent biomass valorization and CO 2 reduction, achieving a CO evolution rate of 78.75 µmol g −1 h −1 (a 56.8‐fold increase over the precursor) and retaining over 90% of its initial activity after 30 cycles. This work underscores terminal‐group‐enabled atomic bridging as a pivotal design principle for developing efficient and durable S‐scheme photocatalytic systems.