Co, N co-doped porous carbons as high-performance oxygen reduction electrocatalysts

Although the Co and N co-doped carbon catalyst (Co-NC) has attracted much attention because of its low cost and the natural abundance of the dopants, it has a low oxygen reduction reaction (ORR) activity and a high selectivity for the two-electron (2e-) reduction of oxygen to H2O2, which affects its use in fuel cells. Co-NC catalysts were prepared by the pyrolysis of a mixture of cobalt chloride and chitosan pretreated with zinc chloride at 650, 750 and 850 oC, followed by washing with nitric acid and annealing at 900 oC. The results indicate that zinc chloride helps the complexing of chitosan with Co2+, which is also a chemical activator that generates pores, and annealing caused the evaporation of the spherical Zn metal nanoparticles formed by the carbothermal reduction of Zn ions, leading to a unique porous structure of the catalysts with spherical pores filled with spherical carbon nanoparticles formed by the growth of nitrogen-doped carbon as a result of the Co catalyst. The degree of graphitization is also improved by the Co catalyst. The Co-NC catalyst obtained at a pyrolysis temperature of 750 oCshows the same four-electron (4e-) reduction of oxygen as a commercial Pt/C catalyst, and a significantly higher ORR catalytic activity, longer-term stability and better methanol tolerance than a commercial Pt/C catalyst. These are due to its large specific surface area, high contents of pyridinic nitrogen and graphitic nitrogen that disperse the Co species and its excellent electrical conductivity.