1-Naphthylamine functionalized Pt nanoparticles: electrochemical activity and redox chemistry occurring on one surfaceElectronic supplementary information (ESI) available. See DOI: 10.1039/c4nj02040e

We present the preparation and electrochemical application of Pt nanoparticles (Pt NPs) functionalized with 1-naphthylamine. Under electrochemical conditions, Pt surface bound 1-naphthylamine (NA) can be reversibly switched (oxidized and reduced), while simultaneously electrocatalytic reactions ( e.g. CO oxidation) can proceed on the Pt surface. While the redox activity of the ligand is established immediately after functionalization, the functionalized NPs have to be stored as a colloidal dispersion in tetrahydrofuran (THF) prior to deposition onto the support material in order to induce their catalytic activity. We interpret this catalytic activation due to partial desorption of ligands from the particle surface induced by storing the particles in THF. However, the experimental results do not indicate a loss of ligands from the ligand shell, but evidence that the ligands form oligomers when kept as colloids in THF. As a result the catalytic surface becomes partially available while the redox activity of the ligands is maintained. Platinum nanoparticles functionalized with oligomerized 1-naphthylamine form a material where the organic ligand exhibits electrochemical activity and the metal surface catalytic activity.