Pd/C nanocatalyst with high turnover frequency (TOP) for hydrogen generation from the formic acid (FA)-sodium formate (SF) mixtures was prepared via an ex situ reduction of PdCl2 used formate in the presence of citric acid. The morphology and property of the Pd/C catalyst before and after decomposition of FA-SF mixture were characterised using transmission electron microscopy, high-resolution transmission electron microscopy, Xray photoelectron spectroscopy, energy dispersive spectroscopy, X-ray diffractometer and Fourier transform infrared spectrometer. Over this Pd/C catalyst, a TOP of 228.3 h(-1) was observed for a FA-SF mixture with a FA/SF ratio of 1:9. The observed TOP was the highest ever reported for heterogeneous Pd/C catalysts. The deactivation of the Pd/C catalyst was attributed to desorption of citric acid, reduction of Pd-II content and adsorption of CO. Washing and drying could partially recover the activity of the Pd/C catalyst. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.