Electrocatalytic activity of alkyne-functionalized AgAu alloy nanoparticles for oxygen reduction in alkaline media.

1-Dodecyne-functionalized AgAu alloy nanoparticles were synthesized by chemical reduction of metal salt precursors at varied initial feed ratios. Transmission electron microscopic measurements showed that the nanoparticles were all rather well dispersed with the average core diameter in the narrow range of 3 to 5 nm. X-ray photoelectron spectroscopic studies confirmed the formation of AgAu alloy nanoparticles with the gold concentration ranging from approximately 25 at% to 55 at%. Consistent results were obtained in UV-vis spectroscopic measurements where the nanoparticle surface plasmon resonance red-shifted almost linearly with increasing gold concentrations. The self-assembly of 1-dodecyne ligands on the nanoparticle surface was manifested in infrared spectroscopic measurements. Importantly, the resulting nanoparticles exhibited apparent electrocatalytic activity for oxygen reduction in alkaline media, and the performance was found to show a volcano variation in the Au content in the alloy nanoparticles, with the best performance observed for the samples with ca. 35.5 at% Au. The enhanced catalytic activity, as compared to pure Ag nanoparticles or even commercial Pt/C catalysts, was accounted for by the unique metal-ligand interfacial bonding interactions as well as alloying effects that increased metal-oxygen affinity.