Ferroelectric Polarization-Enhanced Photoelectrochemical Water Splitting in TiO₂-BaTiO₃ Core-Shell Nanowire Photoanodes

The performances of heterojunction-based electronic devices are extremely sensitive to the interfacial electronic band structure. Here we report a largely enhanced performance of photoelectrochemical (PEC) photoanodes by ferroelectric polarization-endowed band engineering on the basis of TiO₂/BaTiO₃ core/shell nanowires (NWs). Through a one-step hydrothermal process, a uniform, epitaxial, and spontaneously poled barium titanate (BTO) layer was created on single crystalline TiO₂ NWs. Compared to pristine TiO₂ NWs, the 5 nm BTO-coated TiO₂ NWs achieved 67% photocurrent density enhancement. By numerically calculating the potential distribution across the TiO₂/BTO/electrolyte heterojunction and systematically investigating the light absorption, charge injection and separation properties of TiO₂ and TiO₂/BTO NWs, the PEC performance gain was proved to be a result of the increased charge separation efficiency induced by the ferroelectric polarization of the BTO shell. The ferroelectric polarization could be switched by external electric field poling and yielded PEC performance gain or loss based on the direction of the polarization. This study evidence that the piezotronic effect (ferroelectric or piezoelectric potential-induced band structure engineering) holds great promises in improving the performance of PEC photoelectrodes in addition to chemistry and structure optimization.