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Abstract

High Resolution Transmission Electron Microscopy (HR TEM) is used to identify the size, shape, and interface structure of platinum nanoparticles and carbon support of a fuel cell catalyst. Using these insights, models accessible to quantum chemical methods are designed in order to rationalize the observed features. Thus, basal plane and prism face models of the carbon black material are considered, interacting with Pt clusters of sizes up to 1 nm. Particular attention is paid to the electronic structure of the carbon support, namely, the radical character of graphene zig-zag edges. The results show that a stronger interaction is found when the nanoparticle is at the zig-zag edge of a basal plane due to the combination of dispersion interaction with the support structure and covalent interaction with carbon atoms at the edge. In this case, a distortion of both the Pt nanoparticle and the carbon support is observed, which corresponds to the observations from the HR TEM investigation. Furthermore, the analysis of the charge transfer upon interaction and the influence of the potential on the charge states and structure is carried out on our model systems. In all cases, a clear charge transfer is observed from the carbon support to the Pt nanoparticle. Finally, we show that changing the potential not only can change the charge state of the system but can also affect the nature of the interaction between Pt nanoparticles and carbon supports.