Engineering Polarization in the Ferroelectric Electrocatalysts to Boost Water Electrolysis

Abstract Water splitting is the most important process for making green hydrogen. The positive effects of ferroelectric polarization in various kinds of water splitting are well recognized, but the study of electrocatalytic water splitting is still in its infancy. Herein, a family of intrinsic ferroelectrics with a flexible tetragonal tungsten bronze structure is chosen to accommodate oxygen evolution reaction (OER) active sites together with its freedom for tuning the ferroelectric polarization. It is found that the OER performance is positively correlated with the ferroelectric polarization, with a significant reduction in the overpotential of ≈40 mV at 10 mA cm −2 , coming from two trade‐off effects, i.e., enhancement of the surface adsorption and band tilting for fast electron transfer. This study not only fills the gap between electrocatalytic water splitting and the band structure but also proposes ferroelectric polarization as a powerful tool to enhance water splitting for clean hydrogen in several ways.