Piezocatalysis,converting mechanical vibration into chemical energy,h as emerged as ap romising candidate for water-splitting technology.H owever,t he efficiency of the hydrogen production is quite limited. We herein report welldefined 10 nm BaTiO 3 nanoparticles (NPs) characterized by al arge electro-mechanical coefficient which induces ah igh piezoelectric effect. Atomic-resolution high angle annular dark field scanning transmission electron microscopy(HAADF-STEM) and scanning probe microscopy(SPM) suggests that piezoelectric BaTiO 3 NPs displayac oexistence of multiple phases with lowe nergy barriers and polarization anisotropy which results in ahigh electro-mechanical coefficient. Landau free energy modeling also confirms that the greatly reduced polarization anisotropyf acilitates polarization rotation. Employing the high piezoelectric properties of BaTiO 3 NPs,w e demonstrate an overall water-splitting process with the highest hydrogen production efficiency hitherto reported, with aH 2 production rate of 655 mmol g À1 h À1 ,whichcould rival excellent photocatalysis system. This study highlights the potential of piezoelectric catalysis for overall water splitting.

Monodispersed ferroelectric BaTiO3 nanoparticles are synthesized as a model system to investigate the effect of ferroelectricity on a photocatalytic process. The results demonstrate that ferroelectricity can directly affect the photocatalytic activity due to promotion of the separation of photo-excited carriers by spontaneous polarization in ferroelectric materials. Moreover, Ag nanoparticles are attached on these BaTiO3 to further improve the photocatalytic property.

Developing nano‐ferroelectric materials with excellent piezoelectric performance for piezocatalysts used in water splitting is highly desired but also challenging, especially with respect to reaching large piezo‐potentials that fully align with required redox levels. Herein, heteroepitaxial strain in BaTiO3 nanoparticles with a designed porous structure is successfully induced by engineering their surface reconstruction to dramatically enhance their piezoelectricity. The strain coherence can be maintained throughout the nanoparticle bulk, resulting in a significant increase of the BaTiO3 tetragonality and thus its piezoelectricity. Benefiting from high piezoelectricity, the as‐synthesized blue‐colored BaTiO3 nanoparticles possess a superb overall water‐splitting activity, with H2 production rates of 159 μmol g−1 h−1, which is almost 130 times higher than that of the pristine BaTiO3 nanoparticles. Thus, this work provides a generic approach for designing highly efficient piezoelectric nanomaterials by strain engineering that can be further extended to various other perovskite oxides, including SrTiO3, thereby enhancing their potential for piezoelectric catalysis.

A simplified one-pot solid-state reaction has been developed to synthesize (1 − x)BaTiO3–xCoFe2O4 composites, which can enhance the magnetodielectric interaction between different phases.