Physicochemical and electrochemical properties of the carbon materials containing nitrogen and cobalt derived from acetonitrile and Co–Al layered double hydroxides

Abstract

Two sets of the carbon materials containing nitrogen and cobalt were prepared by simultaneous carbonization of CH3CN and decomposition of Co–Al layered double hydroxides (LDHs) (of Co/Al atomic ratios equal to 2 or 3) at 600, 700 and 800 °C followed by treatment with HCl. The physicochemical features of the samples were characterized by means of XRD, TG, EA, XPS, XRF, FT-IR, SEM, Raman spectroscopy and nitrogen sorption. All of the composites were active in oxygen reduction reaction (ORR) in alkaline medium. Their ORR behaviour was determined by the contribution of structural defects and N-doping in graphitic lattice. The beneficial effect of metallic cobalt encapsulated inside the N-CNTs on the ORR performance was also taken into consideration. The studies showed that the likelihood of the existence of Co–N–C species and their participation in ORR seemed to be suppressed by the formation of CoAl2O4. The samples prepared at 600 and 700 °C appeared to be more active in ORR than that obtained at 800 °C. The number of electrons involved in ORR (2.89, 2.82 and 2.77) decreased with increasing synthesis temperature for the samples prepared with LDHs of Co/Al = 2 as a consequence of lowering concentration of nitrogen (3.2, 2.4 and 1.5 wt%), in particular diminishing contribution of pyridinic nitrogen, and decreasing exposure of graphitic edges (ID1/IG ~ 2.6, 2.0 and 1.0). The ORR performance of the samples prepared with LDHs of Co/Al = 3 is comparable to that of the corresponding samples prepared with LDHs of Co/Al = 2.