The development of non-precious metal catalysts with high efficiency and superior reaction durability for oxygen reduction reaction (ORR) is of great importance for construction of next-generation fuel cells. Herein, we report the preparation of in-situ nitrogen-doped carbon nanotube electrocatalysts (PPy-NCNTs) which were prepared by the pyrolysis of one-dimensional nanotube-like polypyrrole conjugated polymers precursor (PPy-Tubes) synthesized by oxidative polymerization and self-assembly method. The as-prepared PPy-NCNTs show good ORR performance, e.g., its half-wave potential reaches 0.826 V. In order to further improve the ORR performance of PPy-NCNTs, we prepared the Co-N co-doped carbon nanotube materials (Co-N-PPy-NCNTs) with different Co contents by adding cobalt nitrate into the polymerization solution during synthesis of PPy nanotube followed by a pyrolysis treatment. Comparatively, the Co-N-PPy-NCNTs have better ORR performance than that of PPy-NCNTs with a half-wave potential of 0.830 V, a biased 4e− reaction pathway, and better stability and methanol tolerance (high than Pt/C catalysts in the methanol tolerance test and the durability test). Taking advantages of its simple and cost-efficient preparation, high ORR performance and superior stability and methanol tolerance, the Co-N-PPy-NCNTs should be a kind of ideal candidate as an alternative to the precious metal platinum-based catalysts for fuel cells.
This is a preview of subscription content, access via your institution.
Buy single article
Instant access to the full article PDF.
Tax calculation will be finalised during checkout.
Subscribe to journal
Immediate online access to all issues from 2019. Subscription will auto renew annually.
Tax calculation will be finalised during checkout.
Banham D, Ye S (2017) Current status and future development of catalyst materials and catalyst layers for proton exchange membrane fuel cells: an industrial perspective. ACS Energy Lett 2(3):629–638
Andújar JM, Segura F (2009) Fuel cells history and updating. A walk along two centuries. Renew Sust Energ Rev 13(9):2309–2322
Dresselhaus MS, Thomas IL (2001) Alternative energy technologies. Nature 414(6861):332–337
Marković N, Schmidt T, Stamenkovic V, Ross P (2001) Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells 1(2):105–116
Wang Z, Yao X, Kang Y, Miao L, Xia D, Gan L (2019) Structurally ordered low-Pt intermetallic electrocatalysts toward durably high oxygen reduction reaction activity. Adv Funct Mater 29(35):1902987
Nørskov JK, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin JR, Bligaard T, Jónsson H (2004) Origin of the overpotential for oxygen reduction at a fuel-cell cathode. J Phys Chem B 108(46):17886–17892
Gottesfeld S, Dekel DR, Page M, Bae C, Yan Y, Zelenay P, Kim YS (2018) Anion exchange membrane fuel cells: current status and remaining challenges. J Power Sources 375:170–184
Wang X, Li Z, Qu Y, Yuan T, Wang W, Wu Y, Li Y (2019) Review of metal catalysts for oxygen reduction reaction: from nanoscale engineering to atomic design. Chem 5(6):1486–1511
Samad S, Loh KS, Wong WY, Lee TK, Sunarso J, Chong ST, Daud WRW (2018) Carbon and non-carbon support materials for platinum-based catalysts in fuel cells. Int J Hydrog Energy 43(16):7823–7854
Stephens IEL, Bondarenko AS, Grønbjerg U, Rossmeisl J, Chorkendorff I (2012) Understanding the electrocatalysis of oxygen reduction on platinum and its alloys. Energy Environ Sci 5(5):6744–6762
Greeley J, Stephens IE, Bondarenko AS, Johansson TP, Hansen HA, Jaramillo TF, Rossmeisl J, Chorkendorff I, Norskov JK (2009) Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nat chem 1(7):552–556
Zhang L, Doyledavis K, Sun X (2019) Pt-Based electrocatalysts with high atom utilization efficiency: from nanostructures to single atoms. Energy Environ Sci 12(2):492–517
Sun M, Wang S, Li Y, Wang Q, Xu H, Chen Y (2017) Promotion of catalytic performance by adding Cu into Pt/ZSM-5 catalyst for selective catalytic oxidation of ammonia. J Taiwan Inst Chem E 78:401–408
Di N, Kubal J, Zeng Z, Greeley J, Maroun F, Allongue P (2015) Influence of controlled surface oxidation on the magnetic anisotropy of Co ultrathin films. Appl Phys Lett 106(12):122405
Gong K, Du F, Xia Z, Durstock MF, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323(5915):760–764
Tang C, Wang H, Chen X, Li B, Hou T, Zhang B, Zhang Q, Titirici M, Wei F (2016) Topological defects in metal-free nanocarbon for oxygen electrocatalysis. Adv Mater 28(32):6845–6851
Matter PH, Ozkan US (2006) Non-metal catalysts for dioxygen reduction in an acidic electrolyte. Catal Lett 109(3):115–123
Lai L, Potts JR, Zhan D, Wang L, Poh CK, Tang C, Gong H, Shen Z, Lin J, Ruoff RS (2012) Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy Environ Sci 5(7):7936–7942
Gewirth AA, Varnell JA, DiAscro AM (2018) Nonprecious metal catalysts for oxygen reduction in heterogeneous aqueous systems. Chem Rev 118(5):2313–2339
Jasinski R (1964) A new fuel cell cathode catalyst. Nature 201(4925):1212–1213
Gupta S, Tryk D, Bae I, Aldred W, Yeager E (1989) Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction. J Appl Electrochem 19(1):19–27
Shao M, Chang Q, Dodelet JP, Chenitz R (2016) Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev 116(6):3594–3657
Park J, Nabae Y, Hayakawa T, Kakimoto M-a (2014) Highly selective two-electron oxygen reduction catalyzed by mesoporous nitrogen-doped carbon. ACS Catal 4:3749–3754
Tang C, Zhang Q (2017) Nanocarbon for oxygen reduction electrocatalysis: dopants, edges, and defects. Adv Mater 29(13):1604103
Nie H, Zhang Y, Zhou W, Li J, Wu B, Liu T, Zhang H (2014) Nitrogen-containing mesoporous carbon cathode for lithium-oxygen batteries: the influence of Nitrogen on oxygen reduction reaction. Electrochimi Acta 150:205–210
Zhang C, Hao R, Liao H, Hou Y (2013) Synthesis of amino-functionalized graphene as metal-free catalyst and exploration of the roles of various nitrogen states in oxygen reduction reaction. Nano Energy 2(1):88–97
Huang B, Luo Z, Zhang J, Xie Z (2017) 2D quasi-ordered nitrogen and sulfur co-doped carbon materials from ionic liquid as metal-free electrocatalysts for ORR. RSC 7(29):17941–17949
Jiao L, Li J, Sougrati MT, Yang F (2020) A highly active iron-based orr catalyst via chemical vapor deposition. ECS Meet Abstr 01(38):1598–1598
Gao P, Sun M, Wu X, Zhou S, Deng X, Xie Z (2018) BN-Doped 3D porous graphene–CNTs synthesized by chemical vapor deposition as a bi-functional catalyst for ORR and HER. RSC Adv 8(47):26934–7
Ryota T, Toru H, Tsuyoshi T (2019) Nitrogen doping of carbon nanoballoons by radiofrequency magnetron plasma and evaluation of their oxygen reduction reaction activity. Electron Commun Jpn 102(8):3–10
Duarte A, Pu K-Y, Liu B, Bazan GC (2011) Recent advances in conjugated polyelectrolytes for emerging optoelectronic applications. Chem Mater 23(3):501–515
He J, He Y, Fan Y, Zhang B, Du Y, Wang J, Xu P (2017) Conjugated polymer-mediated synthesis of nitrogen-doped carbon nanoribbons for oxygen reduction reaction. Carbon 124:630–636
He H, Wang M, Zhang Y, Zhao J (2017) Soluble conjugated polymer enriched with pyridinic nitrogen atoms and its application as high-performance catalyst for oxygen reduction. J Solid State Electr 21(6):1639–1651
Wu ZS, Chen L, Liu J, Parvez K, Liang H, Shu J, Sachdev H, Graf R, Feng X, Müllen K (2014) High-performance electrocatalysts for oxygen reduction derived from cobalt porphyrin-based conjugated mesoporous polymers. Adv Mater 26(9):1450–1455
Yang X, Zhu Z, Dai T, Lu Y (2005) Facile fabrication of functional polypyrrole nanotubes via a reactive self-degraded template. Macromol Rapid Commun 26(21):1736–1740
Abdi FF, van de Krol R (2012) Nature and light dependence of bulk recombination in Co-Pi-catalyzed BiVO4 photoanodes. J Phys Chem C 116(17):9398–9404
Ahn SH, Yu X, Manthiram A (2017) “Wiring” Fe-Nx-embedded porous carbon framework onto 1D nanotubes for efficient oxygen reduction reaction in alkaline and acidic media. Adv Mater 29(26):1606534
Ahn SH, Klein MJ, Manthiram A (2017) 1D Co-and N-doped hierarchically porous carbon nanotubes derived from bimetallic metal organic framework for efficient oxygen and Tri-iodide reduction reactions. Adv Energy Mater 7(7):1601979
Morozan A, Jégou P, Campidelli S, Palacin S, Jousselme B (2012) Relationship between polypyrrole morphology and electrochemical activity towards oxygen reduction reaction. Chem Commun 48(38):4627–4629
Yang L, Jiang S, Zhao Y, Zhu L, Chen S, Wang X, Wu Q, Ma J, Ma Y, Hu Z (2011) Boron-doped carbon nanotubes as metal-free electrocatalysts for the oxygen reduction reaction. Angew Chem Int Edit 50(31):7132–7135
Zhang W, Sun H, Zhu Z (2020) N-doped hard carbon nanotubes derived from conjugated microporous polymer for electrocatalytic oxygen reduction reaction. Renew Energy 146:2270–2280
Osmieri L, Zafferoni C, Wang L, Monteverde Videla AH, Lavacchi A, Specchia S (2018) Polypyrrole-derived Fe−Co−N−C catalyst for the oxygen reduction reaction: performance in alkaline hydrogen and ethanol fuel cells. ChemElectroChem 5(14):1954–1965
Ng W, Yang Y, van der Veen K, Rothenberg G, Yan N (2018) Enhancing the performance of 3D porous N-doped carbon in oxygen reduction reaction and supercapacitor via boosting the meso-macropore interconnectivity using the “exsolved” dual-template. Carbon 129:293–300
Osmieri L, Escudero-Cid R, Armandi M, Videla AHM, Fierro JLG, Ocón P, Specchia S (2017) Fe-N/C catalysts for oxygen reduction reaction supported on different carbonaceous materials. Performance in acidic and alkaline direct alcohol fuel cells. Appl Catal B-Environ 205:637–653
Yang D-S, Bhattacharjya D, Inamdar S, Park J, Yu J-S (2012) Phosphorus-doped ordered mesoporous carbons with different lengths as efficient metal-free electrocatalysts for oxygen reduction reaction in alkaline media. J Am Chem Soc 134(39):16127–16130
The authors are grateful to the National Natural Science Foundation of China (Grants 51962018, 21975113, and 51663012), Project of Collaborative Innovation Team, Gansu Province, China (Grant 052005), Support Program for Hongliu Young Teachers of LUT, 2019 Key Talent Project of Gansu, and Innovation and Entrepreneurship Talent Project of Lanzhou (Grant 2017-RC-33).
Conflict of interest
No conflict of interest exits in the submission of this manuscript, and manuscript is approved by all authors for publication. This work described was original research which has not been published previously and not under consideration for publication elsewhere.
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Handling Editor: Dale Huber.
About this article
Cite this article
Zhu, Z., Han, J., Cui, J. et al. Nanostructured tubular carbon materials doped with cobalt as electrocatalyst for efficient oxygen reduction reaction. J Mater Sci 56, 8143–8158 (2021). https://doi.org/10.1007/s10853-021-05806-4