Transition metal oxides (TMOs) and their heterostructure hybrids have emerged as promising candidates for hydrogen evolution reaction (HER) electrocatalysts based on the recent technological breakthroughs and significant advances. Herein, Ru-Co oxides/Co O double-shelled hollow polyhedrons (RCO/Co O -350 DSHPs) with Ru-Co oxides as an outer shell and Co O as an inner shell by pyrolysis of core-shelled structured RuCo(OH) @zeolitic-imidazolate-framework-67 derivate at 350 °C are constructed. The unique double-shelled hollow structure provides the large active surface area with rich exposure spaces for the penetration/diffusion of active species and the heterogeneous interface in Ru-Co oxides benefits the electron transfer, simultaneously accelerating the surface electrochemical reactions during HER process. The theory computation further indicates that the existence of heterointerface in RCO/Co O -350 DSHPs optimize the electronic configuration and further weaken the energy barrier in the HER process, promoting the catalytic activity. As a result, the obtained RCO/Co O -350 DSHPs exhibit outstanding HER performance with a low overpotential of 21 mV at 10 mA cm , small Tafel slope of 67 mV dec , and robust stability in 1.0 m KOH. This strategy opens new avenues for designing TMOs with the special structure in electrochemical applications.
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