Platinum alloys with other transition metals are widely used as catalysts as a promising strategy to improve the activity. However, the vulnerability of transition metals to the liquid electrolyte and fuel gases present during the device operation results in degradation of the catalytic activity. Highly stable catalyst is achieved by encapsulating the carbon-supported PtCo intermetallic core nanoparticles in a robust Pt shell. The hydride from Hantzsch ester reduces the residual Cl on the surface of the Pt skeleton and slowly forms negatively charged defect sites without damaging the core structure. Then, a secondary Pt reduction reaction via the hydride is employed to cover the activated surfaces of the Pt skeleton to optimize the shell thickness without the formation of isolated Pt nanoparticles. The PtCo@Pt with the unique Pt shell shows higher catalytic activity and durability than commercial Pt/C for oxygen reduction reaction electrocatalysts in proton exchange membrane fuel cells. (C) 2019 Elsevier Inc. All rights reserved.