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The development of highly active and stable acidic water oxidation electrocatalysts is of great significant for promoting the industrial application of proton exchange membrane electrolyzers. Ru-based catalysts have broad application prospects in acidic water oxidation, but their limitations in stability and activity hinder their further application. Herein, a nitrogen-doped carbon (NC) coated porous Ru/RuO2 heterojunctional hollow sphere (Ru/RuO2/NC) is designed as high-active and stable bifunctional electrocatalyst for acidic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). In synthesis, the key is to use mesoporous polydopamine spheres as a template for forming hollow spheres, a source of NC coating and a reducing agent for forming Ru/RuO2 heterojunction. The Ru/RuO2 heterojunction adjusts the electronic structure of Ru active sites, optimizing the adsorption of intermediate species. Furthermore, the NC coating and the interaction between NC and Ru/RuO2 effectively prevent Ru from over-oxidation and dissolution. The porous hollow structure provides more exposed active sites and promotes mass transfer. Impressively, Ru/RuO2/NC exhibits outstanding OER and HER performance with low overpotentials of 211 and 32 mV at 10 mA·cm−2, respectively, and shows excellent stability. The acid water splitting electrolyzer, based on the bifunctional Ru/RuO2/NC, requires low cell voltages of 1.46 and 1.76 V at 10 and 100 mA·cm−2, respectively, with good stability for over 100 h operation, surpassing Pt/C||RuO2 and most of the reported catalysts.
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