Intermetallic Synergy in PdCuCo Catalysts Boosts C─C Bond Cleavage of Polyalcohol Electrooxidation

Abstract Multi‐metallic catalysts with specific structures play a crucial role in enhancing the selectivity and activity of chemical reactions. However, challenges such as unfavorable alcohol adsorption on catalysts, CO poisoning, and high free energy barriers during oxidation processes pose significant obstacles to catalysts' ability to cleave C─C bonds for complete alcohol oxidation. Here, a series of PdCuCo metalene electrocatalysts is reported, wherein varying intermetallic interactions among Pd, Cu, and Co effectively modulate the alcohol oxidation pathway. Notably, the catalyst Pd_0.15Cu_0.35Co₂, synthesized by galvanic replacement of Cu and Pd on a metallic Co surface, delivers remarkably high activity for electrocatalytic oxidation of ethylene glycol and glycerol in alkaline electrolytes (9.7 and 10.9 A mg⁻¹_Pd, respectively), both of which are much better than reported electrocatalysts and broadly applicable to various alcohols. High performance is assigned to the structural advantages of the material and the synergistic effects of multiple metals. This synergy not merely enhances the surface electronics, fostering the creation of exclusive active sites, but also facilitates the oxidative cleavage of stable C─C bond for efficient oxidation of alcohols.