Electrochemical Dealloying-Assisted Surface-Engineered Pd-Based Bifunctional Electrocatalyst for Formic Acid Oxidation and Oxygen Reduction

Synthesis of non-Pt bifunctional electrocatalyst for the anodic oxidation of liquid fuel and cathodic reduction of oxygen is of great interest in the development of energy conversion devices. We demonstrate a facile room-temperature synthesis of surface-engineered trimetallic alloy nanoelectrocatalyst based on Co, Cu, and Pd by thermodynamically favorable transmetallation reaction and electrochemical dealloying. The quasi-spherical CoxCuyPdz trimetallic catalysts were synthesized by the thermodynamically favorable reaction of K2PdCl4 with sheetlike ComCun bimetallic alloy nanostructure. The surface engineering of CoxCuyPdz was achieved by electrochemical dealloying. The surface-engineered alloy electrocatalyst exhibits excellent bifunctional activity toward formic acid oxidation reaction (FAOR) and oxygen reduction reaction (ORR) at same pH. The elemental composition and lattice strain control the electrocatalytic performance. The elemental composition-dependent compressive strain weakens the adsorption of oxygen-containing species and favors the facile electron transfer for FAOR and ORR. The engineered alloy electrocatalyst of Co0.02Cu13.8Pd86.18 composition is highly durable and delivers high mass-specific activity for ORR and FAOR. It delivers mass-specific activities of 1.50 and 0.202 A/mgPd for FAOR and ORR, respectively, in acidic pH. The overall performance is superior to that of as-synthesized Pd and dealloyed bimetallic Co2.7Pd97.3 and Cu5.61Pd94.39 nanoelectrocatalysts.