Engineering Sub‐Nanometer Hafnia‐Based Ferroelectrics to Break the Scaling Relation for High‐Efficiency Piezocatalytic Water Splitting
- 15 September 2023
- journal article
- research article
- Published by Wiley in Advanced Materials
- Vol. 35 (42) , e2303018
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 Hf0.5Zr0.5O2 (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 (Pca21) 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 H2 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 BaTiO3 nanoparticles, respectively. More strikingly, the hydrogen production rates can reach 5.2 µmol g−1 h−1 by addition of stirring exclusively.Keywords
Funding Information
- National Natural Science Foundation of China (21776059, 51802076)
- Natural Science Foundation of Hebei Province (B2018208093, B2021208005, B2021208019)
- Australian Research Council
This publication has 51 references indexed in Scilit:
- Determination of the 3D shape of a nanoscale crystal with atomic resolution from a single imageNature Materials, 2014
- Surface Structure-Dependent Molecular Oxygen Activation of BiOCl Single-Crystalline NanosheetsJournal of the American Chemical Society, 2013
- Ferroelectricity in Simple Binary ZrO2 and HfO2Nano Letters, 2012
- Piezopotential‐Driven Redox Reactions at the Surface of Piezoelectric MaterialsAngewandte Chemie International Edition, 2012
- Flexoelectric rotation of polarization in ferroelectric thin filmsNature Materials, 2011
- Direct Water Splitting Through Vibrating Piezoelectric Microfibers in WaterThe Journal of Physical Chemistry Letters, 2010
- Local Phase Decomposition as a Cause of Polarization Fatigue in Ferroelectric Thin FilmsPhysical Review Letters, 2006
- Martensitic Phase Transformation of Isolated HfO2, ZrO2, and HfxZr1 – xO2 (0 < x < 1) NanocrystalsAdvanced Functional Materials, 2005
- Critical thickness for ferroelectricity in perovskite ultrathin filmsNature, 2003
- Atomic-Resolution Imaging of Oxygen in Perovskite CeramicsScience, 2003