Hollow Ru/RuO₂ nanospheres with nanoparticulate shells for high performance electrocatalytic oxygen evolution reactions

This work shows that hollow Ru/RuO2 nanoparticles having nanoparticulate shells (HN-Ru/RuO2) can be prepared using hollow microporous organic polymers with Ru species (H-MOP-Ru) as precursors. Using silica spheres as templates, H-MOPs were prepared through the Sonogashira-Hagihara coupling of 1,3,5-triethynylbenzene with 2,3-ethoxymethylenedioxy-1,4-diiodobenzene. Acid hydrolysis of cyclic ethyl orthoformate protecting groups generated catechol moieties to form H-MOP-Cat. Then, H-MOP-Ru was obtained by incorporating Ru species into H-MOP-Cat. Heat-treatment of H-MOP-Ru under air induced the formation of HN-Ru/RuO2 with a diameter of 61 nm and shells consisting of 6-7 nm nanoparticles. Due to the hollow structure and nanoparticulate shells, HN-Ru/RuO2 showed a high surface area of 80 m(2) g(-1) and a pore volume of 0.18 cm(3) g(-1). The HN-Ru/RuO2 showed enhanced electrocatalytic performance for the oxygen evolution reaction (OER) with an overpotential of 295 mV @ 10 mA cm(-2) and a Tafel slope of 46 mV dec(-1) in alkaline electrolyte, compared with control RuO2 such as commercial Ru/RuO2 nanoparticles (A-Ru/RuO2) and home-made Ru/RuO2 nanoparticles (N-Ru/RuO2) prepared via the same synthetic procedure as HN-Ru/RuO2. While HN-Ru/RuO2 inevitably contained Pd originated from coupling catalysts, it showed superior performance to Ru/RuO2 nanoparticles with the same Pd content (N1-Ru/RuO2), indicating that the efficient electrocatalytic performance of HN-Ru/RuO2 is attributable to its hollow structure and nanoparticulate shells.