Pt Nanoparticle–Mn Single-Atom Pairs for Enhanced Oxygen Reduction

The intrinsic roadblocks for designing promising Pt-based oxygen reduction reaction (ORR) catalysts emanate from the strong scaling relationship and activity–stability–cost trade-offs. Here, a carbon-supported Pt nanoparticle and a Mn single atom (PtNP–MnSA/C) as in situ constructed PtNP–MnSA pairs are demonstrated to be an efficient catalyst to circumvent the above seesaws with only ∼4 wt % Pt loadings. Experimental and theoretical investigations suggest that MnSA functions not only as the "assist" for Pt sites to cooperatively facilitate the dissociation of O2 due to the strong electronic polarization, affording the dissociative pathway with reduced H2O2 production, but also as an electronic structure "modulator" to downshift the d-band center of Pt sites, alleviating the overbinding of oxygen-containing intermediates. More importantly, MnSA also serves as a "stabilizer" to endow PtNP–MnSA/C with excellent structural stability and low Fenton-like reactivity, resisting the fast demetalation of metal sites. As a result, PtNPs–MnSA/C shows promising ORR performance with a half-wave potential of 0.93 V vs reversible hydrogen electrode and a high mass activity of 1.77 A/mgPt at 0.9 V in acid media, which is 19 times higher than that of commercial Pt/C and only declines by 5% after 80,000 potential cycles. Specifically, PtNPs–MnSA/C reaches a power density of 1214 mW/cm2 at 2.87 A/cm2 in an H2–O2 fuel cell.