Engineering Sub‐Nanometer Hafnia‐Based Ferroelectrics to Break the Scaling Relation for High‐Efficiency Piezocatalytic Water Splitting

Abstract Reversible control of ferroelectric polarization is essential to overcome the heterocatalytic kinetic limitation. This can be achieved by creating a surface with switchable electron density; however, owing to the rigidity of traditional ferroelectric oxides, achieving polarization reversal in piezocatalytic processes remains challenging. Herein, sub‐nanometer‐sized Hf 0.5 Zr 0.5 O 2 (HZO) nanowires with a polymer‐like flexibility are synthesized. Oxygen K‐edge X‐ray absorption spectroscopy and negative spherical aberration‐corrected transmission electron microscopy reveal an orthorhombic ( Pca2 1 ) ferroelectric phase of the HZO sub‐nanometer wires (SNWs). The ferroelectric polarization of the flexible HZO SNWs can be easily switched by slight external vibration, resulting in dynamic modulation of the binding energy of adsorbates and thus breaking the “scaling relationship” during piezocatalysis. Consequently, the as‐synthesized ultrathin HZO nanowires display superb water‐splitting activity, with H 2 production rate of 25687 µmol g −1 h −1 under 40 kHz ultrasonic vibration, which is 235 and 41 times higher than those of non‐ferroelectric hafnium oxides and rigid BaTiO 3 nanoparticles, respectively. More strikingly, the hydrogen production rates can reach 5.2 µmol g −1 h −1 by addition of stirring exclusively.