Improving the catalytic activity of Pt-Rh/C towards ethanol oxidation through the addition of Pb

•PtRhPb/C catalysts were synthesised using a simple chemical reduction method.•The addition of Pb to PtRh improves the electrocatalytic activity towards the EOR.•XANES data corroborate the existence of the bifunctional mechanism promoted by Pb.•The Pt3RhPb/C presented the highest CO2 and CH3COOH production at lower potentials.•Pb promotes non-selective oxidation rather than a driven CO2 production.