The kinetics of N2O electroreduction in the absence and presence of methanol was studied between 295 and 333 K on polycrystalline Pt and Pd electrodes in 0.1M NaOH. In the absence of methanol the reduction of N2O on Pd is more facile than on Pt as shown by the approximately four times lower apparent activation energy and lower Tafel slope (Pt: 0.111 +/- 0.019Vdec(-1), Pd: 0.084 +/- 0.007V dec(-1) at 295K). Two different electroreduction mechanisms are proposed for Pt and Pd with and without participation of underpotential deposited hydrogen, respectively. The selectivity of Pt and Pd electrodes toward both N2O electroreduction and methanol (0.5 and 1 M) oxidation at 295 K was also investigated. Pt based electrocatalysts are promising candidates for the anode of a mixed reactant CH3OH-N2O fuel cell due to inhibition of N2O reduction by chemisorbed methanol. Pd on the other hand is a selective cathode electrocatalyst since N2O reduction takes place fairly actively in the presence of 1M methanol, while methanol oxidation is inhibited. (C) 2011 Elsevier Ltd. All rights