The development of non-precious metal-based electrocatalysts has attracted much research attention because of their high oxygen reduction reaction （ORR） activities, low cost, and good durability. By one-step in-situ...The development of non-precious metal-based electrocatalysts has attracted much research attention because of their high oxygen reduction reaction （ORR） activities, low cost, and good durability. By one-step in-situ ball milling of graphite, pyrrole, and cobalt salt without resorting to high-temperature annealing, we developed a general and facile strategy to synthesize bio-inspired cobalt oxide and polypyrrole coupled with a graphene nanosheet （Co3O4-PPy/GN） complex. Herein, the exfoliation of graphite and polymerization of pyrrole occurred simultaneously during the ball milling process. Meanwhile, the Co3O4 and Co-Nx ORR active sites were generated from the oxidized cobalt ion, cobalt-PPy, and the newly exfoliated graphene nanosheets via strong π-π stacking interactions. The resultant Co3O4-PPy/GN catalysts showed efficient electrocatalytic performances for ORRs in an alkaline medium with a positive onset and reduction potentials of -0.102 and -0.196 V （vs. Ag/AgCl）, as well as a high diffusion-limited current density （4.471 mA·cm^-2）, which was comparable to that of a Pt/C catalyst （4.941 mA·cm^-2）. Compared to Pt/C, Co3O4-PPy/GN catalysts displayed better long-term stability, methanol tolerance, and anti-CO-poisoning effects, which are of great significance for the design and development of advanced non-precious metal electrocatalysts.展开更多
基金Acknowledgements The work is supported by the National Natural Science Foundation of China （Nos. 51273008 and 51473008）, the National Basic Research Program of China （No. 2012CB933200）, and the National High-tech R＆D Program of China （No. 2012AA030305）. L. M. D. is grateful to the support from NSF （Nos. AIR-IIP-1343270 and CMMI-1400274）.
文摘The development of non-precious metal-based electrocatalysts has attracted much research attention because of their high oxygen reduction reaction （ORR） activities, low cost, and good durability. By one-step in-situ ball milling of graphite, pyrrole, and cobalt salt without resorting to high-temperature annealing, we developed a general and facile strategy to synthesize bio-inspired cobalt oxide and polypyrrole coupled with a graphene nanosheet （Co3O4-PPy/GN） complex. Herein, the exfoliation of graphite and polymerization of pyrrole occurred simultaneously during the ball milling process. Meanwhile, the Co3O4 and Co-Nx ORR active sites were generated from the oxidized cobalt ion, cobalt-PPy, and the newly exfoliated graphene nanosheets via strong π-π stacking interactions. The resultant Co3O4-PPy/GN catalysts showed efficient electrocatalytic performances for ORRs in an alkaline medium with a positive onset and reduction potentials of -0.102 and -0.196 V （vs. Ag/AgCl）, as well as a high diffusion-limited current density （4.471 mA·cm^-2）, which was comparable to that of a Pt/C catalyst （4.941 mA·cm^-2）. Compared to Pt/C, Co3O4-PPy/GN catalysts displayed better long-term stability, methanol tolerance, and anti-CO-poisoning effects, which are of great significance for the design and development of advanced non-precious metal electrocatalysts.
