Defects-rich porous carbon microspheres as green electrocatalysts for efficient and stable oxygen-reduction reaction over a wide range of pH values

Carbon materials are promising alternatives to noble metal catalysts for oxygen reduction reactions (ORR) in energy conversion devices. Here we report hierarchically porous carbon microspheres with a trace amount of encapsulated cobalt as highly active and stable electrocatalysts for the ORR under wide pH values ranged from high alkaline to high acidic conditions. We use renewable natural date pulp as the carbon precursor and a facile hydrothermal carbonization method with in situ formed recyclable cobalt as a template for the synthesis. These catalysts yield competitive catalytic activity (a small Tafel slope of 53 mV dec^-1) as well as superb durability and methanol tolerance compared to the benchmark Pt/C catalyst in alkaline electrolyte. Even under harsh acidic conditions, the catalysts deliver a satisfactory catalytic performance and good stability, indicating their extensive applicability. This performance is mainly attributed to the rich surface defects and the hierarchically porous structure that provide abundant active sites for the ORR. In situ formed cobalt nanoparticles are critical to the creation of the abundant mesopores, high specific surface area, and catalytically active defect sites over the carbon material. The encapsulated cobalt residual further enhances the ORR activity of the catalysts, while having a negligible effect on the cost due to its trace level (0.2 at.%).