Carboxyl Group Enhanced CO Tolerant GO Supported Pt Catalysts: DFT and Electrochemical Analysis

The effect of residual oxygen species in as-prepared Pt nanoparticle on partially reduced graphene oxide (Pt/PRGO) and partially reduced carboxylated-GO (Pt/PR(GOCOOH)) supports was investigated using electrochemical CO stripping and density functional theory (DFT) analysis. Pt/PRGO and Pt/PR(GOCOOH) revealed a clear negative shift in CO-stripping onset potential compared to commercial Pt/carbon black. DFT analysis confirmed that the presence of a -COOH group provides the most resistance for CO adsorption. This CO-Pt binding energy is significantly lower than that observed in the presence of an -OH group, which is the most abundant oxygen group in carbon supports. The Pt-CO dissociation energies (on a 42-atom graphene sheet) in the presence of various oxygen groups, in descending order, were OH > C-O approximate to COC > COOH. Although single-bonded carbonoxygen groups (-OH and COC) are more abundant on the GO basal plane and play an important role in Pt nanoparticle nucleation and distribution on graphene sheets, the double-bonded carbonoxygen (C-O and COOH) groups are more abundant residual species post Pt nanoparticle growth and play a vital role in enhancing CO tolerance.