Efficient Synthesis of Nitrogen- and Sulfur-co-Doped Ketjenblack with a Single-Source Precursor for Enhancing Oxygen Reduction Reaction Activity.

Promoting the oxygen reduction reaction (ORR) catalytic activities of cost-effective catalysts is of great significance for the development of various energy conversion and storage systems. Herein, we describe the preparation of a highly active N- and S-co-doped ketjenblack (Kb) by facile pyrolysis of a mixture of thiourea and Kb in the presence of FeCl3 ⋅6 H2 O followed by an acid-leaching process. This novel synthetic approach was rationally designed with the consideration that thiourea could easily introduce both N and S heteroatoms into the carbon matrix by a heat-treatment method by releasing plentiful reactive N- and S-containing gases, which could simultaneously optimize the porous structure of the resultant catalyst. Physical characterization revealed that N and S were homogeneously incorporated into the nanostructure of Kb and formed a hierarchical porous structure with a high specific surface area. The N/S-Kb catalyst showed impressive ORR activity, with an onset potential of 0.08 V at 0.1 mA cm-2 , which is 20 mV more positive than that of commercial 20 wt. % Pt/C catalyst. This was coupled with long-term durability and superior methanol tolerance in alkaline media. The improved ORR performance can be mainly ascribed to synergistic contributions of highly efficient active sites arising from high contents of thiophene S and pyridinic N along with the high specific surface area and the favorable mass-transport properties arising from the hierarchical porous structure. The remarkable ORR performance and facile preparation method make the N/S-Kb catalyst a promising substitute for Pt in electrochemical energy devices.

N/S/B-doped graphitized carbon encased Fe species as a highly active and durable catalyst towards oxygen reduction reaction.

Exploring cost-effective, high-performance and durable non-precious metal catalysts is of great significance for the acceleration of sluggish oxygen reduction reaction (ORR). Here, we report an intriguing heteroatom-doped graphitized carbon encased Fe species composite by introducing N, S and B sequentially. The experimental approach was designed ingeniously for that the FeCl3·6H2O could catalyze thiourea to synthesize N, S co-doped carbon materials which would further react with H3BO3 and NH3 (emerged at the heat-treatment process) to prepare N, S and B co-doped carbon materials (Fe-N/S/B-C). The Fe-N/S/B-C exhibits an impressive ORR activity for its half-wave potential of -0.1 V, which is 36 mV or 19 mV higher than that of the corresponding single or dual doped counterparts (Fe-N-C or Fe-N/S-C) and 31 mV positive than that of Pt/C catalyst, respectively. Further chronoamperometric measurement and accelerated aging test confirm the excellent electrochemical durability of Fe-N/S/B-C with the stable core-shell structure. The remarkable ORR performance and facile preparation method enable Fe-N/S/B-C as a potential candidate in electrochemical energy devices.