Metallated porphyrin based porous organic polymers as efficient electrocatalysts.
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.
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.
Guolong
G
Lu
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA. Wei.Zhang@colorado.edu.
Youlong
Y
Zhu
Key Laboratory of Bionic Enginneering (Ministry of Education), Jilin University, Changchun 130022, P. R. China. Liu_zhenning@jlu.edu.cn.
Kongliang
K
Xu
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA. Wei.Zhang@colorado.edu.
Yinghua
Y
Jin
Department of Civil, Environmental, and Architectural Engineering, University of Colorado, Boulder, CO 80309, USA.
Zhiyong Jason
ZJ
Ren
Key Laboratory of Bionic Enginneering (Ministry of Education), Jilin University, Changchun 130022, P. R. China. Liu_zhenning@jlu.edu.cn.
Zhenning
Z
Liu
Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309, USA. Wei.Zhang@colorado.edu.
Wei
W
Zhang