The unique core–shell structure drives the richness and high utilization of Ru species to stimulate the HER performance exceeding Pt.

• A capture & ions exchange strategy is used to construct Ru@HMCS/Ru-CoP with rich Ru form. • Ru nanoparticles and Ru dopants synergistically optimize the alkaline HER kinetics. • The unique core–shell structure enhances the conductivity and structural stability. • The η 10 value of Ru@HMCS/Ru-CoP is 2.9 mV, which is 48.8 mV lower than Pt/C. It is challenging to synchronously introduce Ru nanoparticles with strong H* adsorption ability and Ru dopants with excellent electronic regulation to improve hydrogen evolution reaction (HER) performance. With these in mind, this work creatively adopts the capture&ions exchange strategy to construct the Ru@HMCS/Ru-CoP catalyst with the Ru nanoparticles-coated hollow mesoporous carbon spheres (HMCS) shell and the Ru-doped CoP core. Notably, Ru nanoparticles and Ru dopants synergistically promote the optimization of HER kinetics. Moreover, the unique core–shell structure effectively increases the active area, conductivity, and structural stability of Ru@HMCS/Ru-CoP. As expected, the η 10 value of Ru@HMCS/Ru-CoP catalyst (2.9 mV) is 48.8 mV lower than that of Pt/C (51.7 mV). In summary, this work greatly improves the utilization of noble metal atoms and points out the direction for the development of electrocatalysts with low-load noble metal content. [ABSTRACT FROM AUTHOR]