Active self-supported Pd1Snx catalysts are synthesized by the sacrificial support method. Self-supported Pd1Snx catalysts display porous nanostructured morphologies with surface areas ranging from 25 to 80 m(2) g(-1) depending on tin content. The mass activity of Pd in Pd1Snx materials toward glycerol oxidation is as follows: Pd1Sn1 > Pd1Sn2 > Pd approximate to Pd1Sn3. In situ FTIR spectroscopy highlighted the unique catalytic behavior of self-supported PdSn materials, particularly the selectivity toward the formation of carboxylate species as soon as 0.2V vs RHE. It has also been shown that the modification of palladium by tin species led to suppress the dissociative adsorption process of glycerol with C-C bond breaking and to favor the bifunctional mechanism. Due to the oxophilic nature of tin species at the electrode surface, the selectivity is completely shifted toward production of carboxylate species as soon as the beginning of the oxidation onset potential at very low potential (ca. 0.45V vs RHE). (C) 2015 Elsevier B.V. All rights reserved.