The metal-support interactions between sulfur-doped carbon supports (SMCs) and Pt nanoparticles (NPs) were investigated, aiming at verifying how sulfur functional groups can improve the electrocatalytic performance of Pt NPs towards the oxygen reduction reaction (ORR). SMCs were synthetized, tailoring the density of sulfur functional groups, and Pt NPs were deposited by thermal reduction of Pt(acac)2 . The extent of the metal-support interaction was proved by X-ray photoelectron spectroscopy (XPS) analysis, which revealed a strong electronic interaction, proportional to the density of sulfur defects, whereas XRD spectra provided evidence of higher strain in Pt NPs loaded on SMC. DFT simulations confirmed that the metal-support interaction was strongest in the presence of a high density of sulfur defects. The combination of microstrain and electronic effects resulted in a high catalytic activity of supported Pt NPs towards ORR, with linear correlations of the half-wave potential E1/2 or the kinetic current jk with the sulfur content in the support. Furthermore, a mass activity value (550 A g-1 ) well above the United States Department of Energy target of 440 A g-1 at 0.9 V (vs. reversible hydrogen electrode, RHE), was determined.
Keywords: density functional theory; nanoparticles; oxygen reduction reaction; platinum; sulfur-doped.
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