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Nanoscale. 2015 Nov 21;7(43):18271-7. doi: 10.1039/c5nr05324b.

Metallated porphyrin based porous organic polymers as efficient electrocatalysts.

Author information

1
Key Laboratory of Bionic Enginneering (Ministry of Education), Jilin University, Changchun 130022, P. R. China. Liu_zhenning@jlu.edu.cn and Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA. Wei.Zhang@colorado.edu.
2
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA. Wei.Zhang@colorado.edu.
3
Key Laboratory of Bionic Enginneering (Ministry of Education), Jilin University, Changchun 130022, P. R. China. Liu_zhenning@jlu.edu.cn.
4
Department of Civil, Environmental, and Architectural Engineering, University of Colorado, Boulder, CO 80309, USA.

Abstract

Developing efficient, stable and low-cost catalysts for Oxygen Reduction Reaction (ORR) is of great significance to many emerging technologies including fuel cells and metal-air batteries. Herein, we report the development of a cobalt(II) porphyrin based porous organic polymer (CoPOP) and its pyrolyzed derivatives as highly active ORR catalysts. The as-synthesized CoPOP exhibits high porosity and excellent catalytic performance stability, retaining ∼100% constant ORR current over 50,000 s in both alkaline and acidic media. Pyrolysis of CoPOP at various temperatures (600 °C, 800 °C, and 1000 °C) yields the materials consisting of graphitic carbon layers and cobalt nanoparticles, which show greatly enhanced catalytic activity compared to the as-synthesized CoPOP. Among them, CoPOP-800/C pyrolyzed at 800 °C shows the highest specific surface area and ORR activity, displaying the most positive half-wave potential (0.825 V vs. RHE) and the largest limited diffusion current density (5.35 mA cm(-2)) in an alkaline medium, which are comparable to those of commercial Pt/C (20 wt%) (half-wave potential 0.829 V vs. RHE, limited diffusion current density 5.10 mA cm(-2)). RDE and RRDE experiments indicate that CoPOP-800/C directly reduces molecular oxygen to water through a 4-e(-) pathway in both alkaline and acidic media. More importantly, CoPOP-800/C exhibits excellent durability and methanol-tolerance under acidic and alkaline conditions, which surpass the Pt/C (20 wt%) system.

PMID:
26486413
DOI:
10.1039/c5nr05324b

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