Polymer-derived Co/Ni–SiOC(N) ceramic electrocatalysts for oxygen reduction reaction in fuel cells

Abstract

Cobalt/nickel-containing SiOC-based porous ceramic electrocatalysts were prepared by pyrolysis of poly(methyl silsesquioxane) and poly(methyl phenyl silsesquioxane) as preceramic precursors combined with graphite and Co/Ni metal salts at 1000 °C in an atmosphere of nitrogen. Subsequently, the Co/Ni–SiOC materials were N-doped using dicyandiamide (DCDA) as a nitrogen source and pyrolysed at 800 °C in an inert atmosphere. The structural properties and composition of the catalysts were characterised by scanning electron microscopy (SEM), X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and N₂ adsorption analysis. The evaluation of the polymer-derived SiOC(N) ceramic electrocatalysts as a new class of catalysts for the oxygen reaction reduction (ORR) was carried out by the rotating disk electrode (RDE) method under acidic, neutral and alkaline conditions. The O₂ reduction studies revealed that the N-doped materials exhibited enhanced ORR performance, confirming the positive influence of the nitrogen functionalities introduced into the catalysts. The Co-containing N-doped SiOC catalyst exhibited significantly higher ORR activity compared with the studied materials along with the highest electron transfer number in all the studied solutions. Long-term ORR performance testing indicated that the durability of this catalyst was superior as compared to that of commercial Pt/C. These observations suggest that the Co-containing N-doped SiOC catalyst is a promising cathode material for fuel cells (FCs) and microbial FC devices.