Strong Interfacial Interaction in Polarized Ferroelectric Heterostructured Nanosheets for Highly Efficient and Selective Photocatalytic CO2 Reduction

Abstract Heterojunctions are sustainable solutions for the photocatalytic CO 2 reduction reaction (CO 2 RR) by regulating charge separation behavior at the interface. However, their efficiency and product selectivity are severely hindered by the inflexible and weak built‐in electric field and the electronic structure of the two phases. Herein, ferroelectric‐based heterojunctions between polarized bismuth ferrite (BFO(P)) and CdS are constructed to enhance the interfacial interactions and catalytic activity. The intrinsic polarization field depending on the ferroelectric state causes significant electrostatic potential difference and energy‐band bending. This helps overcome the unsatisfactory redox potential that differs from the classical catalytic mechanism, and synergy from the heterostructure facilitates effective separation and transfer of photogenerated charges with an extended lifetime (>20 ns) and significantly enhanced photovoltage (1002 times that of BFO). The optimized charge carrier dynamics allow the heterojunction to achieve a much higher CO yield compared to state‐of‐the‐art ferroelectric‐based photocatalysts, and 85.46 and 23.47 times higher than those of pristine CdS and BFO, respectively. Moreover, it maintains an impressive 100% product selectivity together with excellent repeatability and cycling. This work not only sheds light on how a strong inherent polarity promotes the performance of heterojunction photocatalysts but also provides new insights for designing efficient photocatalytic CO 2 RR.