Polarization switching-controlled oxygen evolution and reduction reactions for ferroelectric single-atom catalysts

Unlike conventional single-atom catalysts (SACs), ferroelectric materials provide a novel approach to controlling catalytic activity through ferroelectric polarization switching. Herein, utilizing ab initio calculations, we investigated the effect of the polarization switching on the catalytic activities of oxygen reduction (ORR) and oxygen evolution reactions (OER) in ferroelectric SACs with transition-metal atoms anchored on the ferroelectric In₂Se₃ monolayer. The polarization switching not only enables effective control of the reaction overpotentials but also the corresponding potential limiting steps, thereby activating and enhancing catalytic performance. Notably, reorienting the polarization direction at the specific reaction step can reactivate the stuck catalytic reduction and further improve the activity of specific TM-In₂Se₃ with poor catalytic activity in both upward and downward polarization. Multilevel corrections involving overpotentials, orbital populations, and d-band centers demonstrate that the modulation of catalytic activity through polarization switching originates from the adjustable d-band centers of the supported metal atoms. These findings demonstrate that ferroelectricity switching is a highly promising avenue for improving OER and ORR activity.