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.

Ferroelectrics are promising candidate materials for electrocaloric refrigeration. Materials with a large electrocaloric effect (ECE) near room temperature and a broad working temperature range are getting closer to practical applications. However, the enhanced ECE is always achieved under high electric field, which limits their wide cooling applications. In this paper, the phase diagram of lead-free BaHf x Ti 1-x O 3 (BHT) ferroelectric ceramics was established. A large ECE under relatively low electric field (ΔE=10 kV/cm) is firstly reported in BHT ferroelectric ceramics. The direct temperature change (ΔT=0.35 °C under 10 kV/cm) in BHT ceramics is comparable with those reported in the literature under high electric fields. Meanwhile, the electrocaloric efficiency (ΔT/ΔE=0.35 K mm kV-1 under 10 kV/cm) is thirteen percent higher than the best value reported previously under high electric field (ΔE=145 kV/cm). We demonstrate that the ECE can be greatly enhanced by tuning the composition of the lead-free BHT ceramics to its first-order phase transition (FPT), invariant critical point (ICP) or diffuse phase transition (DPT). It is shown that the enhancement in ECE is strongly dependent on the nature of structural phase transition and electric field coupling effect, which has been confirmed by both the indirect and direct ECE measurements. A phenomenological explanation based on Landau model was also proposed to understand this phenomenon. Our findings in this work may provide a better understanding and design methodology for developing more practically useful electrocaloric materials.

BT-13CH exhibits a large electrocaloric effect over a broad temperature range because of multiphase coexistence (MPC) with diffuse phase transition (DPT) character.

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.