International Journal of Hydrogen Energy, Vol.39, No.22, 11547-11556, 2014
Methanol and ethanol oxidation on carbon supported nanostructured Cu core Pt-Pd shell electrocatalysts synthesized via redox displacement
Six different carbon-supported Cu core Pt-Pd shell (Cu@Pt-Pd) catalysts have been successfully synthesized by the galvanic replacement of Cu atoms by Pt4+ and Pd2+ ions at room temperature and their electrocatalytic activity for methanol and ethanol oxidation have been evaluated in acid media. Cu@Pt-Pd core shell nanoparticles with a narrow size distribution and an average diameter in the range of 3.1-3.5 nm were generated onto the carbon support. The compositional and the structural analysis of the as-prepared materials pointed out that the nanoparticles are formed by a Cu rich core covered by a Pt-Pd rich shell due to the interdiffusion of the metals after the galvanic replacement reaction. The electrocatalytic properties of the Cu@Pt-Pd electrodes in the electro-oxidation of methanol and ethanol was found to be dependent on the electrochemical surface area, lattice strain of the surface, composition and thickness of the Pt-Pd shell surrounding the Cu core. The optimum catalyst composition to obtain the best performance for methanol and ethanol electro-oxidation was determined to be Pt0.59Pd0.324Cu0.167/C (6.2 wt.% Pt, 2.2 wt.% Pd and 0.7 wt.% Cu). This catalyst has a greatly enhanced mass activity, lower onset potential and poisoning rate, and higher turnover number in the MOR and EOR reactions compared to a commercial Pt0.51Ru0.49/C (20 wt.% Pt and 10 wt.% Ru). Consequently, this simple preparation method is a viable approach to making a highly active catalyst with low platinum content for application in direct alcohol fuel cells (DAFCs). Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.