Carbon-supported Pt–Sn electrocatalysts for the anodic oxidation of H2, CO, and H2/CO mixtures.: Part II: The structure–activity relationship

The catalytic activity of three different carbon-supported Pt–Sn catalysts for the anodic oxidation of hydrogen, carbon monoxide, and H2/CO mixtures is correlated with the bimetallic microstructure established in Part I [V. Radmilovic, T.J. Richardson, S.J. Chen, P.N. Ross, Jr., J. Catal. 232 (2005) 199–209] of this study. These catalysts differ primarily by having differing amounts of Pt, Pt3Sn, PtSn, and SnO2 phase nanoparticles distributed on the carbon support. Further surface chemical characterization of the Pt3Sn nanoparticles is provided by comparison of in situ vibrational spectra of CO adsorbed on the nanoparticles with CO adsorbed on Pt3Sn(image) surfaces [V. Stamenkovic, M. Arenz, B.B. Blizanac, K.J.J. Mayrhofer, P.N. Ross, N.M. Markovic, Surf. Sci. 576 (2005) 145–157; V.R. Stamenkovic, M. Arenz, C.A, Lucas, M.E. Gallagher, P.N. Ross, N.M. Markovic, J. Am. Chem. Soc. 125 (2003) 2736–2745]. Qualitative measures of CO oxidation activity were also obtained from the FTIR spectra for the electrode potential at which CO2 is first detected (appearance potential). Quantitative kinetic measurements using the carbon-supported catalysts were obtained with the thin-film rotating disk electrode (TF-RDE) method. The COad stripping voltammetry clearly indicated that the 500N sample exhibits the lowest degree of alloying, showing a superposition of Pt3Sn and Pt features, whereas the catalyst consisting entirely of stoichiometric Pt3Sn cubic phase (E270 sample) exhibits no features characteristic of pure Pt. None of the three carbon-supported Pt–Sn catalysts had the splitting of the Cdouble bond; length as m-dashO stretching band of characteristic of COad on Pt3Sn(111), the surface with the highest specific activity (turnover number) for CO and H2/CO oxidation. All three catalysts had very high levels of activity for H2 oxidation. The mass activity for CO and H2/CO oxidation was proportional to the amount of Pt3Sn phase in the catalyst. There is no clear evidence that either the PtSn phase or Pt/SnO2 clusters contribute any significant activity for H2/CO or CO oxidation in these catalysts.