Palladium-copper bimetallic surfaces as electrocatalysts for the ethanol oxidation in an alkaline medium

•Surface-modified Pd/C by Cuupd and alloyed Pd-Cu/C nanocatalysts were prepared.•Activity for ethanol oxidation reaction was investigated in an alkaline electrolyte.•Addition of Cu to Pd enhanced its activity, regardless of the type of the catalyst.•Pd-Cu /C was superior during potentiostatic short time stability test.•Bifunctional and electronic effect contributed to good performance of the nanoalloy. Two types of Cu-modified Pd catalysts supported on high area carbon were prepared: Pd nanoparticles modified with a sub-monolayer of underpotentially deposited Cu (Cu@Pd/C) and Pd-Cu alloy nanoparticles (Pd-Cu/C), and examined for the ethanol oxidation reaction (EOR) in alkaline solution. The catalysts were characterized by energy-dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy, as well as cyclic voltammetry. As reference catalysts, Pd/C and Pt/C were used. The electrochemically active surface area of all samples was determined from COads and Cuupd desorption and Pd oxide reduction, and used to assess their intrinsic activity for EOR. Intimate contact of Pd with Cu atoms enhanced its activity, regardless of the type of bimetal catalyst. The atomic Pd:Cu ratio between 2:1 and 4:1 appears to be optimal for high activity. The most active catalyst under the potentiodynamic conditions was Cu@Pd/C with θ(Cu) = 0.21,although Pd-Cu/C was superior during the potentiostatic test. All bimetallic catalysts surpassed Pd/C in mass activity. The EOR activity of Pt/C was higher compared to Pd-based catalysts at low potentials, both in terms of specific and mass activity, but with a significant decline over a 30-min potentiostatic stability test.