Enhanced Ageing Performance of Sulfonic Acid-Grafted Pt/C Catalysts.

Chemical functionalization of carbon support for Pt catalysts is a promising way to enhance the performance of catalysts. In this study, Pt/C catalysts grafted with various amounts of phenylsulfonic acid groups were prepared under mild conditions. The influence of sulfonic acid groups on the physiochemical characteristics and electrochemical activities of the modified catalysts were studied using X-ray diffraction, X-ray photoelectron spectroscopy, a transmission electron microscope, and cyclic voltammetry (CV). The presence of the chemical groups enhanced the hydrogen adsorption onto/desorption off the Pt surface during the CV cycling. In contrast, the hydrogen peaks of the grafted catalysts increased after 500 CV cycles, especially for Pt (111) facets. The highest electrochemical surface area (ECSA) after the aging test was obtained for the catalyst with 18.0 wt.% graft, which was ca. 87.3% higher than that of the non-functionalized Pt catalyst. In the density functional theory (DFT) calculation, it was proven that SO3H adsorption on the crystalline was beneficial for Pt stability. The adsorption energy and bond distance of the adsorbed SO3H on Pt (110), (100), and (111) surfaces were calculated. All the stable configurations were obtained when O from S-O single bond or S was bound to the Pt surface, with the adsorption energy following the trend of (111)F > (100)H > (110)H. This result was consistent with the ECSA experiment, which explained the high electrochemical stability of the sulfonic acid groups-grafted Pt/C catalyst.