Local electric field engineering via ferroelectric substrates for enhanced oxygen reduction reaction on single-atom catalysts

Environmental factors at electrochemical interfaces, such as the local electric field, are widely recognized as critical determinants of catalytic performance, which could strongly influence reaction pathways and kinetics. However, strategies that leverage these effects to precisely control catalytic activity are limited. In this study, using grand canonical potential density functional theory, we demonstrate that combining single-atom catalysts (SACs) with ferroelectric substrates is a powerful solution. The modified local electric field significantly weakens the adsorption of the *OH intermediate in the oxygen reduction reaction (ORR) on the FeN₄–C catalyst. By establishing a physical model, we reveal that the local electric field is primarily modified by surface charges induced by the applied potential and the intrinsic dipole moment of the substrate. Our findings highlight the significant role of local electric fields in tailoring catalytic mechanism, and pave the way for a promising substate engineering approach in the rational design of high-performance electrocatalytic devices.