Piezoelectric-Effect-Enhanced Full-Spectrum Photoelectrocatalysis in p–n Heterojunction

Photoelectrochemical (PEC) water splitting offers a promising strategy for converting solar energy to chemical fuels. Herein, a piezoelectric-effect–enhanced full-spectrum photoelectrocatalysis with multilayered coaxial titanium dioxide/barium titanate/silver oxide (TiO₂/BTO/Ag₂O) nanorod array as the photoanode is reported. The vertically grown nanorods ensure good electron conductivity, which enables fast transport of the photogenerated electrons. Significantly, the insertion of a piezoelectric BaTiO₃ (BTO) nanolayer at the p-type Ag₂O and n-type TiO₂ interface created a polar charge-stabilized electrical field. It maintains a sustainable driving force that attract the holes of TiO₂ and the electrons of Ag₂O, resulting in greatly increased separation and inhibited recombination of the photogenerated carriers. Furthermore, Ag₂O as a narrow bandgap semiconductor has a high ultraviolet–visible–near infrared (UV–vis–NIR) photoelectrocatalytic activity. The TiO₂/BTO/Ag₂O, after poling, successfully achieves a prominent photocurrent density, as high as 1.8 mA cm⁻² at 0.8 V versus Ag/Cl, which is about 2.6 times the TiO₂ nanorod photoanode. It is the first time that piezoelectric BaTiO₃ is used for tuning the interface of p-type and n-type photoelectrocatalyst. With the enhanced light harvesting, efficient photogenerated electron–hole pairs' separation, and rapid charge transfer at the photoanode, an excellent photoelectrocatalytic activity is realized.