Interface Modulation of rGO/Bi 0 /BiOCl Enables Efficient Electron Utilization for CO 2 Photoreduction

ABSTRACT Engineering interfacial electronic structure is critical for enhanced charge utilization and product selectivity in photocatalytic CO 2 reduction toward multi‐electron hydrocarbon products. Herein, we report a one‐step glycerol‐assisted solvothermal strategy to construct ternary catalyst rGO/Bi 0 /BiOCl, in which oxygen vacancies and in‐situ formed Bi 0 nanodomains are intimately integrated with a conductive rGO network. Comprehensive spectroscopic and electrochemical analyses along with in situ EPR and DRIFTS results under CO 2 + H 2 O conditions indicate that rGO incorporation not only improves CO 2 adsorption but also alters electron distribution and interfacial charge‐transfer dynamics. While defect‐rich BiOCl with Bi 0 enables CO 2 activation, electron accumulation at vacancy sites limits further reduction. In contrast, the rGO/Bi 0 /BiOCl interface facilitates continuous electron extraction and redistribution, preventing charge stagnation and supporting sustained activation of surface intermediates for deeper hydrogenation. This transition from localized electron trapping to dynamic electron utilization enables enhanced selectivity (92%) toward CH 4 and C 2 H 4 and exhibits a 12‐fold increase in CH 4 photoreduction activity compared to pristine water made BiOCl. This work establishes a design principle for coupling defects with conductive interfaces and identify roles of rGO and Bi 0 in driving CO 2 reduction to hydrocarbons.