Glycerol electrooxidation on self-supported Pd₁Sn_x nanoparticules

Active self-supported Pd₁Sn_x catalysts are synthesized by the sacrificial support method. Self-supported Pd₁Sn_x catalysts display porous nanostructured morphologies with surface areas ranging from 25 to 80m²g^-1 depending on tin content. The mass activity of Pd in Pd₁Sn_x materials toward glycerol oxidation is as follows: Pd₁Sn₁>Pd₁Sn₂>Pd≈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 CC 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).