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 (Pt_NP–Mn_SA/C) as in situ constructed Pt_NP–Mn_SA 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 Mn_SA 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, Mn_SA also serves as a “stabilizer” to endow Pt_NP–Mn_SA/C with excellent structural stability and low Fenton-like reactivity, resisting the fast demetalation of metal sites. As a result, Pt_NPs–Mn_SA/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/mg_Pt 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, Pt_NPs–Mn_SA/C reaches a power density of 1214 mW/cm² at 2.87 A/cm² in an H₂–O₂ fuel cell.