Nitrogen and Sulfur Co‐Doping Modulates the Interface Interaction Between Pt Nanoparticles and Hollow Carbon Nanospheres for Boosted Methanol Oxidation Performance

ABSTRACT The synergistic regulation mechanism involving heteroatom doping and strong metal‐support interaction (SMSI) is of great significance for boosting the performance of supported electrocatalysts. Herein, Pt nanoparticles were anchored onto nitrogen and sulfur co‐doped hollow carbon nanospheres (Pt@N,S‐HCN) through the template‐assisted method combined with wet chemical reduction, thereby constructing a highly active interface for effective methanol oxidation reaction (MOR). This approach effectively addressed the challenges associated with platinum‐based catalysts, including high cost, low activity, and facile aggregation. N/S co‐doping not only synergistically modulates the electronic arrangement of the carbon framework, but also enhances the overall electron affinity of the carbon support, thereby facilitating more efficient charge transfer between metal atoms and the carbon support. This co‐doping of N and S significantly strengthens the metal‐support interaction, thereby promoting the rearrangement of platinum electron structures (Pt°→Pt x + ) and increasing the density of Pt active sites. There‐doping of S atoms further fine‐tunes the electronic configuration of Pt, to enhance the adsorption affinity of Pt active centers for OH intermediates. Consequently, this reduces the binding strength of CO and accelerates its further oxidation, ultimately achieving superior methanol oxidation activity and CO tolerance. Electrochemical results demonstrated that under both acidic and basic conditions, Pt@N,S‐HCN exhibited boosted mass activity and specific activity compared to commercial Pt/C. Additionally, chronocurrent tests reveal significantly enhanced stability relative to single‐doped systems, which is facilitated to the confinement effect of hollow carbon nanospheres and the optimization of CO oxidation kinetics by sulfur doping. This strategy of adjusting metal‐support interface interactions through heteroatom doping offers new opportunities for designing highly efficient supported catalysts.