Carbon-supported cobalt (III) complex for direct reduction of oxygen in alkaline medium

Transition metal-nitrogen-carbon catalysts obtained from pyrolysis of simple sources of metal and nitrogen or metal-organic frameworks are envisioned as promising replacement of Pt-based catalysts for oxygen reduction reaction (ORR) in fuel cells and metal-air batteries. However, the lack of clarity on the active site structure is a fundamental problem in developing efficient catalysts for the complete reduction of oxygen with maximum active site density. In this study, we have synthesized a simple metal-organic complex, [ Co ( bpy ) 2 CO 3 ] NO 3 ⋅ 5 H 2 O , 1 (bpy = 2, 2′-bipyridine) and studied its ORR activity in 0.1 M KOH supporting on Ketjenblack EC-600JD, 1/C. The crystal structure of 1 was unambiguously determined using single-crystal X-ray diffraction. The onset potential of ORR, Tafel slopes, kinetic current density, the fraction of oxygens reduced to peroxyl ion ( χ HO 2 − ) and the electron transfer number (n) were compared with relevant literature and commercial 20 wt % Pt/C. Primarily, 1/C reduces O2 through the direct 4-electron pathway. ‘n’ and χ HO 2 − on 1/C were found to be 3.87 and 7% at 0.7 ViR-free vs. RHE, respectively. The turn-over frequencies for the 4- and 2-electron process were found to be 0.124 and 0.001 electrons [Co]−1 s−1 at 0.7 ViR-free vs. RHE, respectively. Density-functional theory analysis reveals that the preferential activation of the side-on mode of adsorption on 1 is responsible for high selectivity in the direct 4-electron pathway.