Highly monodisperse spherical 3 nm Pd–Cu alloy nanoparticles (NPs) were synthesized in high yield through the coreduction of [Pd(acac)2] (acac=acetylacetonate) and [Cu(acac)2] in nonhydrolytic solutions by using trioctylamine and oleic acid. The relative compositions of Pd and Cu could be tuned by controlling the molar ratios between the metal precursors in the raw solutions. The carbon-supported Pd–Cu NPs (Pd–Cu/C) were chemically dealloyed by acetic acid washing, which resulted in the formation of porous structures. The prepared Pd–Cu/C catalysts exhibited at least threefold enhancement of Pd mass activities compared with a commercial Pd/C catalyst toward formic acid oxidation in an acidic medium, and also showed outstanding electrocatalytic stabilities. The improved electrocatalytic properties of the Pd–Cu NPs are attributed to the presence of a large number of active sites on their surfaces owing to their small particle sizes and chemically dealloyed porous structures.
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