Rational Construction of Ruthenium-Cobalt Oxides Heterostructure in ZIFs-Derived Double-Shelled Hollow Polyhedrons for Efficient Hydrogen Evolution Reaction.

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/Co3 O4 double-shelled hollow polyhedrons (RCO/Co3 O4 -350 DSHPs) with Ru-Co oxides as an outer shell and Co3 O4 as an inner shell by pyrolysis of core-shelled structured RuCo(OH)x @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/Co3 O4 -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/Co3 O4 -350 DSHPs exhibit outstanding HER performance with a low overpotential of 21 mV at 10 mA cm-2 , small Tafel slope of 67 mV dec-1 , and robust stability in 1.0 m KOH. This strategy opens new avenues for designing TMOs with the special structure in electrochemical applications.