Co and Ni Ratio Modulation‐Derived Electron Deficient Pd Trimetallic Catalysts for Enhanced Formic Acid Electrooxidation

PdCoNi trimetallic catalysts attracted extensive interest in direct formic acid fuel cells due to high poisoning resistance and high activity for formic acid electro‐oxidation (FAO). Herein, a series of Pd 0.75 Co x Ni y /C alloys with a modulated ratio of Co and Ni are synthesized to investigate the effect of Co and Ni content on the electronic structure of Pd for FAO. The physical analysis demonstrated that the introduction of Co and Ni induces the lattice strain effect compared to monometallic Pd catalysts. As a consequence of fixing the total amount of Co and Ni, the strain effect is restricted, and the electronic perturbation of Pd is successfully regulated by varying the ratio of Co and Ni in Pd 0.75 Co x Ni y /C trimetallic alloys. Pd loses more electrons, the bond strength of Pd−H is weakened, and FAO activity is enhanced first and then decreased as the Co content increases. Among the trimetallic catalysts, Pd 0.75 Co 0.125 Ni 0.125 /C trimetallic catalyst exhibits the highest current density of 3.253 mA cm −2 owing to the optimum electronic perturbation and Pd−H bond strength. This work provides a valuable guideline for future studies of Pd‐based trimetallic alloys.