PtAu catalyst with enhanced activity for formic acid oxidation

Abstract

PtAu systems are recognized as good catalysts for the oxidation of formic acid electrooxidation, which is investigated as a possible anodic reaction in low-temperature fuel cells. In this research, bimetallic PtAu nanoparticles, supported on high area carbon Vulcan XC-72R, were synthesized by water in oil microemulsion method. The precursor reduction process took place in a single microemulsion, simultaneously, in the presence of 35% of HCl in the water phase, as a capping agent. Electrochemical behavior of the PtAu/C catalyst was investigated at as prepared electrodes by cyclic voltammetry in 0.5M H2SO4 as a supporting electrolyte, and also in the oxidation of adsorbed CO. The results were compared to the Pt/C catalyst prepared by the same synthesis procedure. PtAu/C catalyst powder was also characterized by X-Ray Diffraction (XRD), High Resolution Transmission Electron Microscopy (HRTEM) and Energy Dispersive X-Ray Spectroscopy (EDS). Average particle diameter, of 2nm, was calculated from XRD data, which is close to the value of 2.82 nm obtained from TEM images. Compared to identically synthesized Pt nanoparticles, the bimetallic ones are significantly smaller. EDS maps of PtAu/C sample confirm the presence of both elements, and indicate a very fine distribution of Au in the sample. Elemental composition of about 20% Au and 80% Pt was also determined from these maps. Prepared catalyst was tested for formic acid electro-oxidation in terms of its activity and stability over the long term cycling. The voltammograms recorded indicate the change of reaction mechanism and better utilization of the catalyst surface in comparison to Pt/C.

PtAu sistemi se smatraju veoma dobrim katalizatorima za elektrooksidaciju mravlje kiseline, kao moguće anodne reakcije u niskotemperaturnim gorivnim galvanskim spregovima. U ovom radu bimetalne PtAu nanočestice sintetizovane su mikromulzionim postupkom, i u toku sinteze nanete na ugljenični nosač Vulcan XC-72R. Procesi redukcije prekursora odigravaju se simultano, unutar vodene faze iste mikroemulzije, u prisustvu 35% HCl. Elektrohemijske karakteristike katalizatora ispitivane su cikličnom voltametrijomv na 'as prepared' elektrodama u 0.5M H2SO4 kao osnovnom elektrolitu, kao i prilikom oksidacije adsorbovanog CO. Rezultati su upoređeni sa Pt/C katalizatorom sintetizovanim istim postupkom i pod istovetnim uslovima. Pripremljeni PtAu/C prah okarakterisan je takođe difrakcijom X-zraka, transmisionom elektronskom mikroskopijom i energetski disperzionom spektroskoijom. Veličina čestice određena analizom difraktograma X-zraka iznosi 2nm, što je blisko vrednosti dobijenoj analizom TEM snimaka od 2.82 nm. U poređenju sa Pt nanočesticama sintetizovanim na isti način, bimetalne nanočestice su znatno manjeg prečnika. Mape uzorka PtAu/C dobijene energetski disperzionom spektroskopijom potvrđuju prisustvo oba elementa i pokazuju veoma finu distribuciju Au u uzorku. Analizo mapa utvrđeno je i da je katalizator sastava 20% Au i 80% Pt. Konačno, ispitane su aktivnost i stabilnost bimetalnog katalizatora za oksidaciju mravlje kiseline. Snimljeni voltamogrami ukazuju na promenu reakcionog mehanizma i bolje iskorišćenje površine katalizatora u poređenju ra Pt/C katalizatorom sintetizovanim istim postupkom.