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A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions

Abstract

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are traditionally carried out with noble metals (such as Pt) and metal oxides (such as RuO2 and MnO2) as catalysts, respectively. However, these metal-based catalysts often suffer from multiple disadvantages, including high cost, low selectivity, poor stability and detrimental environmental effects. Here, we describe a mesoporous carbon foam co-doped with nitrogen and phosphorus that has a large surface area of 1,663 m2 g−1 and good electrocatalytic properties for both ORR and OER. This material was fabricated using a scalable, one-step process involving the pyrolysis of a polyaniline aerogel synthesized in the presence of phytic acid. We then tested the suitability of this N,P-doped carbon foam as an air electrode for primary and rechargeable Zn–air batteries. Primary batteries demonstrated an open-circuit potential of 1.48 V, a specific capacity of 735 mAh gZn−1 (corresponding to an energy density of 835 Wh kgZn−1), a peak power density of 55 mW cm−2, and stable operation for 240 h after mechanical recharging. Two-electrode rechargeable batteries could be cycled stably for 180 cycles at 2 mA cm−2. We also examine the activity of our carbon foam for both OER and ORR independently, in a three-electrode configuration, and discuss ways in which the Zn–air battery can be further improved. Finally, our density functional theory calculations reveal that the N,P co-doping and graphene edge effects are essential for the bifunctional electrocatalytic activity of our material.

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Figure 1: Preparation of the N and P co-doped porous carbon (NPMC) electrocatalysts.
Figure 2: Brunauer–Emmett–Teller characterization and XPS composition analysis.
Figure 3: Electrocatalytic activity for ORR and OER.
Figure 4: Performance of a primary Zn–air battery.
Figure 5: Performance of rechargeable Zn–air batteries.
Figure 6: Mechanistic study of bifunctionality for ORR and OER.

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Acknowledgements

This work is supported financially by the Air Force Office of Scientific Research (AFOSR; FA-9550-12-1-0069 and FA9550-12-1-0037) and the National Science Foundation (NSF-AIR-IIP-1343270 and NSF-CMMI-1363123). The authors thank Z. Xiang, H. Pan, Y. Xue, Y. Yu and L. Zhang for discussions and help.

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J.Z. and L.D. conceived and designed the experiments. J.Z. performed sample characterization and electrochemical studies. Z.Z. and Z.X. performed the theoretical calculation. J.Z. and L.D. analysed experimental data and wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Liming Dai.

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Zhang, J., Zhao, Z., Xia, Z. et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nature Nanotech 10, 444–452 (2015). https://doi.org/10.1038/nnano.2015.48

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