ABSTRACT
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.
ABSTRACT
Herein, we report the synthesis and bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities of a CuOx-CeO2/C electrocatalyst (EC) with rich oxide-oxide and oxide-carbon interfaces. It not only demonstrates a smaller Tafel slope (65 mV dec-1) and higher limiting current density (-5.03 mA cm-2) but also exhibits an onset potential (-0.10 V vs Ag/AgCl) comparable to that of benchmark Pt/C. Besides undergoing the favorable direct four-electron ORR pathway, it unveils a loss of 23% of its initial current after 6 h of a stability test and a negative shift of 4 mV in the half-wave potential after the accelerated durability test compared to the corresponding current loss of 28% and negative shift of 20 mV for Pt/C. It also reveals remarkable OER activity in an alkaline medium with a low onset potential (0.20 V) and a smaller Tafel slope (177 mV dec-1). The bifunctional ORR/OER activity of CuOx-CeO2/C EC can be ascribed to the synergistic effects, its unique structure with enriched oxygen vacancies owing to the presence of Ce4+/Ce3+, robust oxide-oxide and oxide-carbon heterointerfaces, and homogeneous dispersion of oxides over the carbon bed, which facilitates faster electronic conduction.
