Effects of Acid Treatment of Pt-Ni Alloy Nanoparticles@Graphene on the Kinetics of the Oxygen Reduction Reaction in Acidic and Alkaline Solutions

Acidic dissolution of transition metals from Pt based alloy catalysts for oxygen reduction reaction (ORR) is an unavoidable process during fuel cell operation. In this work we studied the effect of acid treatment of graphene-supported Pt1Nix(x = 0, 0.25, 0.5, 1, and 2) alloys on the,kinetics of the ORR in both alkaline and acidic solutions together with the generation of OH radicals in alkaline solutions. The alloy nanoparticles were synthesized through coimpregnation and chemical reduction. The electronic and structural features of the alloy were characterized by X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, and high-resolution transmission electron microscopy. The ORR performances were studied using cyclic voltammetry and rotating ring disk electrode techniques in 0.05 M H2SO4 and 0.1 M NaOH, respectively. The alloy catalysts were more active than pure Pt toward ORR, and after acid treatment the ORR activity of Pt-Ni alloy was enhanced in both acidic and alkaline media. The maximum activity of the Pt-based catalysts was found with ca. 50 atom % Ni content in the alloys (Pt1Ni1@graphene). OH radicals were generated through dissociation of hydroperoxide at the catalysts' surface and detected by fluorescence technique using terephthalic acid as capture reagent, which readily reacts with OH radical to produce highly fluorescent product, 2-hydroxyterephthalic acid. More OH radicals were found to be generated at Pt1Ni1@graphene catalyst. This work may be valuable in the design of electrocatalysts with higher ORR activity but lower efficiency of OH radical generation.