Acetic acid decarboxylation by amorphous alloys with low loading of platinum

The aim of this work focuses on studying the metallic amorphous alloys of composition Ni₅₉Nb₄₀Pt_1-xY_x (Y = Cu, Ru, x = 0.4% at.), obtained by mechanical alloying (MA), in the ethanol oxidation. The addition of copper or ruthenium as co-catalysts, modifies the electronic properties of platinum, demonstrating better performance in ethanol and CO electro-oxidation reactions. Ni₅₉Nb₄₀Pt _0.6Cu_0.4 alloy provides higher current densities towards ethanol electro-oxidation than Ni₅₉Nb₄₀Pt _0.6Ru_0.4 alloy but the possible formation of copper oxides limits its performance. The voltammograms for CO stripping clearly show that alloy with ruthenium possesses a better CO tolerance, decreasing the onset potential 109 mV with regard to Ni₅₉Nb₄₀Pt _0.6Cu_0.4 alloy. The presence of ruthenium is able to provide oxygenated adsorbed species coming from the cleavage of the water molecule, according to Langmmuir-Hinshelwood mechanism that it allows the CO oxidation to CO₂. The homolytic cleavage C-C bond is critical step in the ethanol electro-oxidation to CO₂. The formation of acetic acid (AA) as final product is known, limiting the electric efficiency in Direct Ethanol Fuel Cells (DEFCs). The oxidation process was investigated by in situ Fourier Transformed Infrared Reflectance (FTIR) spectroscopy. The experimental results showed that both amorphous alloys can oxidize AA to CO₂.