Aromatic Ring Size Effect of a Surface Modification Agent on Platinum Nanoparticle Electrocatalysts for Oxygen Reduction Reaction

Platinum nanoparticles (NPs) modified with alkylamines containing various aromatic rings (benzyl, naphtyl, anthryl, and pyrenyl) were synthesized as model cathode catalysts for fuel cells to investigate the role of aromatic surface modification agents on catalytic performance. Surface modification of Pt was confirmed by nuclear magnetic resonance spectra for NPs and thermogravimetric analysis for carbon-supported catalysts. Surface modification of Pt NPs with aromatic alkylamines improved the electrocatalytic activities for the oxygen reduction reaction, whose activity values increased by increasing the number of aromatic rings. The effect of surface modification on the electronic properties of the catalyst was evaluated by X-ray photoelectron spectroscopy. A large positive shift in the Pt 4f binding energy of surface-modified catalyst, especially for anthryl and pyrenyl modifications, was observed, indicating that one of the important factors is metal–support interaction facilitated by the aromatic groups through the π–π interactions with carbon support.