As of today, Pt-based catalysts are the predominant ORR catalysts that meet the desired activity requirements of ORR in fuel cells. However, their broader applications are still challenging due to highly sluggish ORR kinetics, limited stability and higher cost of Pt. In order to develop novel electrocatalyst materials, herein we report surface tuning of binary PtCo alloy through transition metal doping, which reveals superior ORR activity achieving a mass activity of 2.07 A mg_Pt^-1 at 0.9 V vs. reversible hydrogen electrode (RHE) and excellent durability with minor degradation after 30000 cycles. The ternary PtCoMn@NGNS alloy prepared through facile molten salt pyrolysis reveals a strong metal-support interaction via metal-nitrogen-graphene coordination.

Furthermore, Mn dopants alter the electronic structure of Pt alloy, which improves the oxygen-intermediate binding energy on the interface and suppress the Co dissolution through unique configuration, resulting in enhanced activity and durability of the catalyst. According to the DFT calculations, the surface Mn extensively adsorbs an OH, resulting in increased surface Co stability and overall ORR catalytic performance. Therefore, it is understandable that the development of ternary Pt alloy results in considerable changes in the structural and electrical characteristics of metal overlayer, which varies dramatically from monometallic surfaces.

Our experimental results corroborated by theoretical calculations show that electronic perturbation of PtCo by Mn doping stabilizes the Co and causes significant strain in the Pt(111), which accounts for the increased ORR performance. The strained lattice of Pt caused by Co alloying and surface segregation of Mn both play important roles in the increased ORR activity. Similarly, the Pt₃CoMn-OH configuration diminishes Co dissolution and improves overall stability. It is anticipated that such a facile preparation of high-performance electrocatalysts will advance the practical applications of ORR catalysts.

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