Boosting the electrocatalytic activity of Pd/C by Cu alloying: Insight on Pd/Cu composition and reaction pathway

Tuning composition of Pd-based bimetallic electrocatalysts of high stability and durability is of great importance in energy-related reactions. This study reports the remarkable electrocatalytic performance of carbon-supported bimetallic Pd-Cu alloy nanoparticles (NPs) towards formic acid oxidation (FAO) and oxygen reduction reaction (ORR). Among various bimetallic compositions, Pd₃Cu/C alloy NPs exhibits the best FAO and ORR activity. During FAO reaction, Pd₃Cu/C alloy NPs exhibits a peak with a current density of 28.33 mA cm^-2 and a potential of 0.2 V (vs. Ag/AgCl) which is higher than that of the other PdCu compositions and standard 20 wt% Pd/C catalyst. Meanwhile, the onset potential (-0.09 V), half-wave potential (-0.18 V), limiting current density at 1600 rpm (-4.9 mA cm^-2) and Tafel slope (64 mV dec^-1) values of Pd₃Cu/C alloy NPs validate its superiority over the conventional 20 wt% Pt/C catalyst for ORR. Experimental and DFT studies have confirmed that the enhanced activity can be attributed to the electronic effect that arises after Cu alloying which causes a downshift of Pd d-band center and structural effect that produces highly dispersed NPs over the carbon matrix with high electrochemically active surface area.