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N, P-dual doped carbon with trace Co and rich edge sites as highly efficient electrocatalyst for oxygen reduction reaction

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  • ReceivedOct 23, 2017
  • AcceptedNov 30, 2017
  • PublishedDec 29, 2017

Abstract

Oxygen reduction reaction (ORR) is key to fuel cells and metal-air batteries which are considered as the alternative clean energy. Various carbon materials have been widely researched as ORR electrocatalysts. It has been accepted that heteroatom doping and exposure of the edge sites can effectively improve the activity of carbon materials. In this work, we used a simple method to prepare a novel N, P-dual doped carbon-based catalyst with many holes on the surface. In addition, trace level Co doping in the carbon material forming Co–N–C active species can further enhance the ORR performance. On one hand, the doping can adjust the electronic structure of carbon atoms, which would induce more active sites for ORR. And on the other hand, the holes formed on the surface of carbon nanosheets would expose more edge sites and can improve the intrinsic activity of carbon. Due to the heteroatom doping and the exposed edge sites, the prepared carbon materials showed highly excellent ORR performance, close to that of commercial Pt/C.


Funded by

the National Natural Science Foundation of China(21701043,21573066,51402100)

the Provincial Natural Science Foundation of Hunan(2016JJ1006,2016TP1009)

the Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province and Shenzhen Science and Technology Program(JCYJ20170306141659388)


Acknowledgment

This work was supported by the National Natural Science Foundation of China (21701043, 21573066, and 51402100), the Provincial Natural Science Foundation of Hunan (2016JJ1006 and 2016TP1009), the Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province and Shenzhen Science and Technology Program (JCYJ20170306141659388).


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Yan D and Guo L designed and engineered the samples; Yan D, Guo L, Xie C, Wang Y, Li Y, Li H performed the experiment and the characterizations. Yan D and Guo L wrote the paper with support from Wang S. All authors contributed to the general discussion.


Author information

Dafeng Yan received his BSc degree in 2014 from the Department of Chemistry, Hunan University, China. He is currently pursuing his PhD degree under the supervision of Prof. Shuangyin Wang. His current interests include the synthesis and characterization of nanomaterials with various defects and the relationship between the defects and the electrocatalytic performance of renewable energy-related reactions.


Shuangyin Wang received his BSc degree in 2006 from Zhejiang University and PhD in 2010 from Nanyang Technological University, Singapore. He was a postdoctoral fellow working with Prof. Liming Dai (2010–2011) and Prof. A. Manthiram (2011–2012). He is currently a Professor of Hunan University. His research interests are in novel carbon catalysts, defects in various crystals and their application on electrocatalysis and batteries.


Supplement

Supplementary information

Supporting data are available in the online version of the paper.


References

[1] Dai L, Xue Y, Qu L, et al. Metal-free catalysts for oxygen reduction reaction. Chem Rev, 2015, 115: 4823-4892 CrossRef PubMed Google Scholar

[2] Gong K, Du F, Xia Z, et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009, 323: 760-764 CrossRef PubMed ADS Google Scholar

[3] Jasinski R. A new fuel cell cathode catalyst. Nature, 1964, 201: 1212-1213 CrossRef Google Scholar

[4] Wang S, Jiang SP. Prospects of fuel cell technologies. Nat Sci Rev, 2017, 4: 163-166 CrossRef Google Scholar

[5] Shao M, Chang Q, Dodelet JP, et al. Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev, 2016, 116: 3594-3657 CrossRef PubMed Google Scholar

[6] Wang S, Zhang L, Xia Z, et al. BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angew Chem Int Ed, 2012, 51: 4209-4212 CrossRef PubMed Google Scholar

[7] Zhao C, Yu C, Liu S, et al. 3D porous N-doped graphene frameworks made of interconnected nanocages for ultrahigh-rate and long-life Li-O2 batteries. Adv Funct Mater, 2015, 25: 6913-6920 CrossRef Google Scholar

[8] Zhou T, Du Y, Yin S, et al. Nitrogen-doped cobalt phosphate@ nanocarbon hybrids for efficient electrocatalytic oxygen reduction. Energy Environ Sci, 2016, 9: 2563-2570 CrossRef Google Scholar

[9] Yang L, Jiang S, Zhao Y, et al. Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem Int Ed, 2011, 50: 7132-7135 CrossRef PubMed Google Scholar

[10] Xia BY, Yan Y, Li N, et al. A metal–organic framework-derived bifunctional oxygen electrocatalyst. Nat Energy, 2016, 1: 15006 CrossRef ADS Google Scholar

[11] Wang S, Yu D, Dai L. Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J Am Chem Soc, 2011, 133: 5182-5185 CrossRef PubMed Google Scholar

[12] Guo D, Shibuya R, Akiba C, et al. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351: 361-365 CrossRef PubMed ADS Google Scholar

[13] Liang HW, Wei W, Wu ZS, et al. Mesoporous metal–nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. J Am Chem Soc, 2013, 135: 16002-16005 CrossRef PubMed Google Scholar

[14] Zhang G, Jin X, Li H, et al. N-doped crumpled graphene: bottom-up synthesis and its superior oxygen reduction performance. Sci China Mater, 2016, 59: 337-347 CrossRef Google Scholar

[15] Wu S, Zhu Y, Huo Y, et al. Bimetallic organic frameworks derived CuNi/carbon nanocomposites as efficient electrocatalysts for oxygen reduction reaction. Sci China Mater, 2017, 60: 654-663 CrossRef Google Scholar

[16] Wang L, Jia W, Liu X, et al. Sulphur-doped ordered mesoporous carbon with enhanced electrocatalytic activity for the oxygen reduction reaction. J Energy Chem, 2016, 25: 566-570 CrossRef Google Scholar

[17] Seredych M, László K, Rodríguez-Castellón E, et al. S-doped carbon aerogels/GO composites as oxygen reduction catalysts. J Energy Chem, 2016, 25: 236-245 CrossRef Google Scholar

[18] Preuss K, Kannuchamy VK, Marinovic A, et al. Bio-inspired carbon electro-catalysts for the oxygen reduction reaction. J Energy Chem, 2016, 25: 228-235 CrossRef Google Scholar

[19] Zhang J, Dai L. Heteroatom-doped graphitic carbon catalysts for efficient electrocatalysis of oxygen reduction reaction. ACS Catal, 2015, 5: 7244-7253 CrossRef Google Scholar

[20] Zhang L, Xia Z. Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C, 2011, 115: 11170-11176 CrossRef Google Scholar

[21] Xiao Z, Wang Y, Huang YC, et al. Filling the oxygen vacancies in Co3O4 with phosphorus: an ultra-efficient electrocatalyst for overall water splitting. Energy Environ Sci, 2017, 44 CrossRef Google Scholar

[22] Dou S, Dong CL, Hu Z, et al. Atomic-scale CoOx species in metal-organic frameworks for oxygen evolution reaction. Adv Funct Mater, 2017, 27: 1702546 CrossRef Google Scholar

[23] Zhang J, Qu L, Shi G, et al. N,P-codoped carbon networks as efficient metal-free bifunctional catalysts for oxygen reduction and hydrogen evolution reactions. Angew Chem Int Ed, 2016, 55: 2230-2234 CrossRef PubMed Google Scholar

[24] Chang Y, Hong F, He C, et al. Nitrogen and sulfur dual-doped non-noble catalyst using fluidic acrylonitrile telomer as precursor for efficient oxygen reduction. Adv Mater, 2013, 25: 4794-4799 CrossRef PubMed Google Scholar

[25] Wang X, Wang J, Wang D, et al. One-pot synthesis of nitrogen and sulfur co-doped graphene as efficient metal-free electrocatalysts for the oxygen reduction reaction. Chem Commun, 2014, 50: 4839-4842 CrossRef PubMed Google Scholar

[26] Shen A, Zou Y, Wang Q, et al. Oxygen reduction reaction in a droplet on graphite: direct evidence that the edge is more active than the basal plane. Angew Chem Int Ed, 2014, 53: 10804-10808 CrossRef PubMed Google Scholar

[27] Tang C, Wang HF, Chen X, et al. Topological defects in metal-free nanocarbon for oxygen electrocatalysis. Adv Mater, 2016, 28: 6845-6851 CrossRef PubMed Google Scholar

[28] Yan D, Li Y, Huo J, et al. Defect chemistry of nonprecious-metal electrocatalysts for oxygen reactions. Adv Mater, 2017, 414: 1606459 CrossRef PubMed Google Scholar

[29] Tang C, Wang B, Wang HF, et al. Defect engineering toward atomic Co-Nx-C in hierarchical graphene for rechargeable flexible solid Zn-air batteries. Adv Mater, 2017, 29: 1703185 CrossRef PubMed Google Scholar

[30] Liu Z, Zhao Z, Wang Y, et al. In situ exfoliated, edge-rich, oxygen-functionalized graphene from carbon fibers for oxygen electrocatalysis. Adv Mater, 2017, 29: 1606207 CrossRef PubMed Google Scholar

[31] Wu G, More KL, Johnston CM, et al. High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science, 2011, 332: 443-447 CrossRef PubMed ADS Google Scholar

[32] Chen Y, Gokhale R, Serov A, et al. Novel highly active and selective Fe-N-C oxygen reduction electrocatalysts derived from in-situ polymerization pyrolysis. Nano Energy, 2017, 38: 201-209 CrossRef Google Scholar

[33] Hu K, Xiao Z, Cheng Y, et al. Iron phosphide/N, P-doped carbon nanosheets as highly efficient electrocatalysts for oxygen reduction reaction over the whole pH range. Electrochim Acta, 2017, 254: 280-286 CrossRef Google Scholar

[34] Jiang Y, Yang L, Sun T, et al. Significant contribution of intrinsic carbon defects to oxygen reduction activity. ACS Catal, 2015, 5: 6707-6712 CrossRef Google Scholar

[35] Tao L, Wang Q, Dou S, et al. Edge-rich and dopant-free graphene as a highly efficient metal-free electrocatalyst for the oxygen reduction reaction. Chem Commun, 2016, 52: 2764-2767 CrossRef PubMed Google Scholar

[36] Yan D, Dou S, Tao L, et al. Electropolymerized supermolecule derived N, P co-doped carbon nanofiber networks as a highly efficient metal-free electrocatalyst for the hydrogen evolution reaction. J Mater Chem A, 2016, 4: 13726-13730 CrossRef Google Scholar

[37] Sun M, Zhang G, Liu H, et al. α- and γ-Fe2O3 nanoparticle/nitrogen doped carbon nanotube catalysts for high-performance oxygen reduction reaction. Sci China Mater, 2015, 58: 683-692 CrossRef Google Scholar

[38] Zhang J, Zhao Z, Xia Z, et al. A metal-free bifunctional electrocatalyst for oxygen reduction and oxygen evolution reactions. Nat Nanotechnol, 2015, 10: 444-452 CrossRef PubMed ADS Google Scholar

  • Figure 1

    (a, b) SEM images of MPSA-Co-900 and (c, d) SEM images of MPSA-Co-900-Acid.

  • Scheme 1

    The preparation process of MPSA-Co-900-Acid via cooperative assembly, pyrolysis and acid washing.

  • Figure 2

    (a, b) TEM images of MPSA-Co-900-Acid.

  • Figure 3

    (a) XPS survey spectra of MPSA-Co-900-Acid, (b–d) are the spectra of C 1s, N 1s and P 2p respectively. In C 1s spectrum, the peak at about 284.6 eV was assigned to the graphitic sp2 carbon while the additional component centred at 286.4 eV was attributable to C–N. The N 1s spectrum is deconvoluted into four N species: pyridinic N (398.6 eV), pyrrolic N (399.9 eV), graphitic N (401.1 eV), and oxidized N (403.4 eV), respectively. P 2p spectrum had two typical peaks: P–C (132.7 eV) and P–O (133.6 eV)[38].

  • Figure 4

    (a) Rotating disk electrode (RDE) voltammograms of MPSA-Co-900, MPSA-Co-900-Acid and Pt/C in an O2-saturated 0.1 mol L−1 KOH solution with a scan rate of 10 mV s−1. (b) RDE of MPSA-Co-900-Acid at different rotation rates from 400 to 1600 rpm. (c) RRDE measurements for MPSA-Co-900-Acid electrode in O2-saturated 0.1 mol L−1 KOH and (d) percentage of peroxide in the total oxygen reduction products together with the number of electron transfer.

  • Figure 5

    (a) Chronoamperometric responses for MPSA-Co-900-Acid and Pt/C electrodes on addition of 1.0 mol L−1 methanol after about 150 s and (b) electrochemical durability tests of MPSA-Co-900-Acid and Pt/C electrodes.

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