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Doped Mesoporous Carbon as Efficient Non-precious Electrocatalyst for Oxygen Reduction Reaction both in Alkaline and Acidic Electrolytes
Last modified: 2014-10-08
Abstract
Oxygen reduction reaction (ORR), i.e., 2H2O + O2 + 4e−→ 4OH− (in alkaline solution) or 4H + + O2 + 4e−→2H2O (in acidic solution), significantly affects the electrochemical performance of fuel cells and metal-air batteries. Although a large thermodynamic driving force(E=1.2V RHE) is available, the ORR is kinetically slow in the absence of electrocatalysts. “Metal-free” catalysts exhibit better stability than transition metal N-containing complexes because there are no issues related to metal dissolution and poisoning as observed from those metal-containing catalysts [1]. In particular, doping carbon with heteroatoms with electronegativity different from of C (c =2.55) may create a net positive charge on adjacent carbon atoms. This effect makes such doped carbon material catalysts readily facilitate the side-on O2 surface adsorption, thus effectively weakening the O−O bonding [2] and leading to a high ORR catalytic activity. However, their insufficient catalytic ORR activity when compared with Pt-based catalysts still remains a great challenge. More importantly, the resulting catalysts yield ORR activity in base but poor ORR activity in acidic solutions [3,4]. On the basis of these observations, we here report the remarkable observation that N,Cl- and N, S-dual doped mesoporous carbons are highly efficient for oxygen reduction reaction both in alkaline and acidic electrolytes due to the dual active sites mechanism originated from the synergy of N and Cl, and N and S elements.
References
[1] L. Qu, Y. Liu, J.B. Baek, L.M. Dai, Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells, ACS Nano 4(3) (2010) 1321.[2] H. Wang, X. Bo, Y. Zhang, L. Guo, Sulfur-doped ordered mesoporous carbon with high electrocatalytic activity for oxygen reduction, Electrochim. Acta 108 (2013) 404. [3] K.P. Gong, F. Du, Z.H. Xia, M. Durstock, L.M. Dai, Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction, Science 323 (2009) 760.[4] L. P. Zhang, J.B. Niu, L.M. Dai, Z.H. Xia, Effect of microstructure of nitrogen-doped graphene on oxygen reduction activity in fuel cells, Langmuir 28 (2012) 7542.[5] J. J. Shi, M. Y. Fang, J. L. Qiao, Y. Y. Liu, Nitrogen and Chlorine Dual-doped Mesoporous Carbon as Efficient Non-precious Electrocatalyst for Oxygen Reduction Reaction both in Alkaline and Acidic Electrolytes, Chem. Lett. 2014, Advance Publication, 10.1246/cl.140589
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