Active Site Structures in Nitrogen-Doped Carbon-Supported Cobalt Catalysts for the Oxygen Reduction Reaction
Qian, YD (Qian, Yingdan)[ 1 ] ; Liu, Z (Liu, Zheng)[ 1 ] ; Zhang, H (Zhang, Hui)[ 1 ] ; Wu, P (Wu, Ping)[ 1 ]*（吴萍）; Cai, CX (Cai, Chenxin)[ 1 ]*（蔡称心）
[ 1 ] Nanjing Normal Univ, Jiangsu Collaborat Innovat Ctr Biomed Funct Mat, Natl & Local Joint Engn Res Ctr Biomed Funct Mat, Coll Chem & Mat Sci,Jiangsu Key Lab New Power Bat, Nanjing 210097, Jiangsu, Peoples R China
ACS APPLIED MATERIALS & INTERFACES, Dec.2016, 8(48) 32875-32886
The catalytic mechanism and the nature of active sites are revealed for the oxygen reduction reaction (ORR) with new non-noble-metal nitrogen-doped carbon-supported transition-metal catalysts (metal-N-C catalyst). Specifically, new nitrogen-doped carbon-supported cobalt catalysts (Co-N-C catalysts) are made by pyrolyzing various ratios of the nitrogen atom rich heterocycle compound, 1-ethyl-3-methyl imidazolium dicyanamide (EMIM-dca) and cobalt salt (Co(NO3)(2)). The ORR activity (J(K) at 0.8 V vs RHE, in 0.1 M KOH solution) of a typical catalyst in this family, Co-15-N-C800, is 8.25 mA/mg, which is much higher than the ORR. activity values of N-C catalysts (0.41 mA/mg). The active site in the catalyst is found to be the Co-N species, which is most likely in the form of Co2N. Metallic cobalt (Co) particles, Co3C species, and N-C species are not catalytically active sites, nor do these moieties interact with the Co-N active sites during the catalysis of the ORR Increasing the Co salt content during the synthesis favors the formation of Co-N active sites in the final catalyst. Higher pyrolysis temperatures (e.g., a temperature higher than 800 degrees C) do not favor the formation of the Co-N active sites, but cause the formed Co-N active sites to decompose, which, therefore, leads to a lower catalytic activity. This reveals that the control of the parameters that affect the final structure is critical to catalyst performance and, therefore, the effective development of high-performance heteroatom-doped non-noble-metal ORR catalysts.