Synergistic Effect of Polarization‐Induced Electric Field and Electronic Perturbation on Pd x Co y Bimetallic Catalysts for Enhancing Formic Acid Electrooxidation

Formic acid electrooxidation (FAO) on Pd involves multiple electron‐transfer steps and strong adsorption of intermediates, making the reaction highly sensitive to interfacial properties. Here, we design a FAO catalyst that integrates a polarization‐induced electric field (PEF) with Pd–Co alloys to regulate the interfacial electron‐transfer kinetics and electronic structure of Pd aiming to accelerate the interface charge transfer and optimize the adsorption bond strength. Pd x Co y alloyed nanoparticles are supported on carbon‐coated tetragonal BaTiO 3 (TBT@SC), where the ferroelectric polarization of TBT provides the PEF. Physical and electrochemical analysis proves that the PEF accelerates the charge transfer at electrode/electrolyte interface, and promotes kinetics of the electron‐transfer to form HCOO* and *COOH from HCOOH, i.e., the rate‐determining step of FAO. Compared with the non‐PEF catalyst (3.7 mA cm −2 ), the PEF‐assisted catalyst delivers a markedly enhanced FAO activity of 8.2 mA cm −2 . Meanwhile, tuning the Pd/Co atomic ratio with the presence of PEF enables electronic perturbation of Pd active sites to balance the intermediate adsorption and FAO activity. Moreover, the PEF suppresses Co dissolution and mitigates Pd 0 depletion during operation, leading to improved durability. This work highlights an interfacial engineering strategy via PEF‐assisted electronic modulation to design high‐performance FAO catalysts.