Oxygen reduction reaction and peroxide generation on shape-controlled and polycrystalline platinum nanoparticles in acidic and alkaline electrolytes.

Shape-controlled Pt nanoparticles (cubic, tetrahedral, and cuboctahedral) are synthesized using stabilizers and capping agents. The nanoparticles are cleaned thoroughly and electrochemically characterized in acidic (0.5 M H2SO4 and 0.1 M HClO4) and alkaline (0.1 M NaOH) electrolytes, and their features are compared to that of polycrystalline Pt. Even with less than 100% shape-selectivity and with the truncation at the edges and corners as shown by the ex-situ TEM analysis, the voltammetric features of the shape-controlled nanoparticles correlate very well with that of the respective single-crystal surfaces, particularly the voltammograms of shape-controlled nanoparticles of relatively larger size. Shape-controlled nanoparticles of smaller size show somewhat higher contributions from the other orientations as well because of the unavoidable contribution from the truncation at the edges and corners. The Cu stripping voltammograms qualitatively correlate with the TEM analysis and the voltammograms. The fractions of low-index crystallographic orientations are estimated through the irreversible adsorption of Ge and Bi. Pt-nanocubes with dominant {100} facets are the most active toward oxygen reduction reaction (ORR) in strongly adsorbing H2SO4 electrolytes, while Pt-tetrahedral with dominant {111} facets is the most active in 0.1 M HClO4 and 0.1 M NaOH electrolytes. The difference in ORR activity is attributed to both the structure-sensitivity of the catalyst and the inhibiting effect of the anions present in the electrolytes. Moreover, the percentage of peroxide generation is 1.5-5% in weakly adsorbing (0.1 M HClO4) electrolytes and 5-12% in strongly adsorbing (0.5 M H2SO4 and 0.1 M NaOH) electrolytes.