Enhanced Charge Transfer by Passivation Layer in 3DOM Ferroelectric Heterojunction for Water Oxidation in HCO₃⁻/CO₂ System

Abstract Photoelectrochemical carbon dioxide conversion to fuels such as carbon monoxide, methanol, and ethylene exhibits great potential to solve energy issues. Unfortunately, CO₂ conversion efficiency is still low due to violent charge recombination at the photoanode. Herein, a novel 3D macroporous ferroelectric heterojunction composed of BiFeO₃ and LiNbO₃ is developed by a template‐assisted sol–gel method, aiming at facilitating charge transfer kinetics. As expected, a tremendous enhancement of photocurrent density (300 times vs bare planar BiFeO₃ film) and charge transfer efficiency (up to 76%) is obtained in the HCO₃⁻/CO₂ system without any cocatalyst. The photoelectrochemical performance is switchable by poling to form a depolarization electric field. Photoelectrochemical impedance spectroscopy reveals that the charge transfer resistance decreases due to the synergistic effect of BiFeO₃ 3D macroporous skeleton and LiNbO₃ passivation layer by tuning surface states. These results suggest a novel strategy for enhancing photoelectrochemical water oxidation as the anodic reaction of CO₂ reduction.