Vulcan XC-72Rcarbon supported Pd nanoparticles was obtained in a NH3-mediated polyol process without any protective agent and characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM) techniques. The added NH3 species is found to have a strong complex ability to Pd, which not only avoids the formation of Pd hydroxide precipitate resulted from Pd hydrolysis, but also restrains the further complete reduction of Pd. Temperature-programmed reduction equipped with a mass spectrometry (TPR-MS) is employed to study the reductive behavior of unreduced Pd complex in Pd/C catalyst and the results show that the post-treatment in a reductive atmosphere at higher temperature is needed to ensure the complete reduction of Pd. XRD patterns show the heat-treated Pd/C sample in a reductive atmosphere has a face centered cubic crystal structure and TEM image indicates that the dispersion of Pd nanoparticles on the carbon support is uniform and in a narrow particle size range. Thermodynamic data analysis is carried out to elucidate the possible reaction pathway for the preparation of Pd/C catalyst in this process. The obtained Pd/C catalyst shows high activity to formic acid oxidation and high selectivity to oxygen reduction reaction (ORR) with the presence of methanol. (c) 2007 Elsevier B.V. All rights reserved.