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Porous Fe, Co, and N-co-doped carbon nanofibers as high-efficiency oxygen reduction catalysts

  • Ke Yu
  • Peng-Hui Shi
  • Jin-Chen FanEmail author
  • Yu-Lin Min
  • Qun-Jie XuEmail author
Research Paper
  • 52 Downloads

Abstract

Oxygen reduction reaction (ORR) is an important reaction in fuel cells. Designing electrocatalysts with outstanding performance is always the key to renewable-energy technologies for fuel cells. Herein, we demonstrate the Fe, Co, and N co-doped porous carbon nanofibers (FeCo/N-C CNFs) as a novel high-performance electrocatalyst for ORR. The synthesis method of this electrocatalysts material is very simple via high-temperature calcination pyrolysis of zinc, cobalt bimetallic zeolitic imidazolate framework (ZIF)-coated electrospun polyacrylonitrile fibers. In alkaline media, the FeCo/N-C CNFs shows a Pt-like ORR performance. The FeCo/N-C CNFs catalysts exhibit excellent performance with an onset potential of 0.99 V and a half-wave potential of 0.83 V in 0.1 M KOH solution, which is similar to those of 20 wt% Pt/C catalysts. Meanwhile, regarding long-term durability and methanol tolerance, the as-synthesized FeCo/N-C CNF catalysts also outperform commercial Pt/C. The unusual catalytic activity mainly from the improvement of electron transfer channels and catalytic sites arise from Fe, Co, and N doping in the porous structure carbon nanofibers.

Graphical abstract

The preparation process of FeCo/N-C CNFs ORR catalysts

Keywords

Electrospinning Nanostructures Oxygen reduction reaction Zeolitic imidazolate framework Electrocatalysts 

Notes

Acknowledgments

We thank Mr. Jing-Ze Zhang for his contribution to the characterization of samples and analysis of results.

Funding information

This work was sponsored by Shanghai Rising-Star Program (19QA1404100). This research was also supported by the National Natural Science Foundation of China (nos. 21671133 and 91745112). This work was funded by the Shanghai Municipal Education Commission (nos. 15ZZ088 and 15SG49), the Science and Technology Commission of Shanghai Municipality (18020500800).

Compliance with ethical standards

Conflict of Interest

The authors declare that they have no conflict of interest.

Supplementary material

11051_2019_4678_MOESM1_ESM.docx (403 kb)
ESM 1 (DOCX 402 kb)

References

  1. Alegre C, Busacca C, Di Blasi O, Antonucci V, Aricò AS, Di Blasi A, Baglio V (2017) A combination of CoO and Co nanoparticles supported on electrospun carbon nanofibers as highly stable air electrodes. J Power Sources 364:101–109.  https://doi.org/10.1016/j.jpowsour.2017.08.007 CrossRefGoogle Scholar
  2. An L, Jiang N, Li B, Hua S, Fu Y, Liu J, Hao W, Xia D, Sun Z (2018) A highly active and durable iron/cobalt Alloy catalyst encapsulated in N-doped graphitic carbon nanotubes for oxygen reduction reaction by a nanofibrous dicyandiamide template. J Mater Chem A 6:5962–5970.  https://doi.org/10.1039/C8TA01247D CrossRefGoogle Scholar
  3. Chen YZ, Wang C, Wu ZY, Xiong Y, Xu Q, Yu SH, Jiang HL (2015) From bimetallic metal-organic framework to porous carbon: high surface area and multicomponent active dopants for excellent electrocatalysis. Adv Mater 27:5010–5016.  https://doi.org/10.1002/adma.201502315 CrossRefGoogle Scholar
  4. Chen Y, Li X, Park K, Lu W, Wang C, Xue W, Yang F, Zhou J, Suo L, Lin T, Huang H, Li J, Goodenough JB (2017) Nitrogen-doped carbon for sodium-ion battery anode by self-etching and graphitization of bimetallic MOF-based composite. Chem 3:152–163.  https://doi.org/10.1016/j.chempr.2017.05.021 CrossRefGoogle Scholar
  5. Chai L, Zhang L, Wang X, Xu L, Han C, Li TT, Hu Y, Qian J, Huang S (2019) Bottom-up synthesis of MOF-derived hollow N-doped carbon materials for enhanced ORR performance. Carbon 146:248–256.  https://doi.org/10.1016/j.carbon.2019.02.006 CrossRefGoogle Scholar
  6. Deng H, Zhang C, Xie Y, Tumlin T, Giri L, Karna SP, Lin J (2016) Laser induced MoS2/carbon hybrids for hydrogen evolution reaction catalysts. J Mater Chem A 4(18):6824–6830.  https://doi.org/10.1039/C5TA09322H CrossRefGoogle Scholar
  7. Deng J, Yu L, Deng D, Chen X, Yang F, Bao X (2013) Highly active reduction of oxygen on A FeCo alloy catalyst encapsulated in pod-like carbon nanotubes with fewer walls. J Mater Chem A 1:14868.  https://doi.org/10.1039/C3TA13759G CrossRefGoogle Scholar
  8. Dresselhaus MS, Thomas IL (2001) Alternative energy technologies. Nature 414:332–337.  https://doi.org/10.1038/35104599 CrossRefGoogle Scholar
  9. Gao S, Fan B, Feng R, Ye C, Wei X, Liu J, Bu X (2017) N-doped-carbon-coated Fe3O4 from metal-organic framework as efficient electrocatalyst for ORR. Nano Energy 40:462–470.  https://doi.org/10.1016/j.nanoen.2017.08.044 CrossRefGoogle Scholar
  10. Gong K, Du F, Xia Z, Durstock M, Dai L (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764.  https://doi.org/10.1126/science.1168049 CrossRefGoogle Scholar
  11. Guan BY, Lu Y, Wang Y, Wu M, Lou XWD (2018) Porous iron-cobalt alloy/nitrogen-doped carbon cages synthesized via pyrolysis of complex metal-organic framework hybrids for oxygen reduction. Adv Funct Mater 28:1706738.  https://doi.org/10.1002/adfm.201706738 CrossRefGoogle Scholar
  12. Guo Y, Yuan P, Zhang J, Hu Y, Amiinu IS, Wang X, Zhou J, Xia H, Song Z, Xu Q, Mu S (2018) Carbon nanosheets containing discrete Co-Nx-By-C active sites for efficient oxygen electrocatalysis and rechargeable Zn-air batteries. ACS Nano 12:1894–1901.  https://doi.org/10.1021/acsnano.7b08721 CrossRefGoogle Scholar
  13. Guruvammal D, Selvaraj S, Meenakshi Sundar S (2016) Effect of Ni-doping on the structural, optical and magnetic properties of ZnO nanoparticles by solvothermal method. J Alloys Compd 682:850–855.  https://doi.org/10.1016/j.jallcom.2016.05.038 CrossRefGoogle Scholar
  14. He D, Xiong Y, Yang J, Chen X, Deng Z, Pan M, Li Y, Mu S (2017) Nanocarbon-intercalated and Fe–N-codoped graphene as a highly active noble-metal-free bifunctional electrocatalyst for oxygen reduction and evolution. J Mater Chem A 5(5):1930–1934.  https://doi.org/10.1039/C5TA09232A CrossRefGoogle Scholar
  15. Hou H, Jun Z, Weller F, Greiner A (2003) Large-scale synthesis and characterization of helically coiled carbon nanotubes by use of Fe(CO)5 as floating catalyst precursor. Chem Mater 15:3170–3175.  https://doi.org/10.1021/cm021290g CrossRefGoogle Scholar
  16. Hu E, Yu XY, Chen F, Wu Y, Hu Y, Lou XWD (2017) Graphene layers-wrapped Fe/Fe5C2 nanoparticles supported on N-doped graphene nanosheets for highly efficient oxygen reduction. Adv Energy Mater 8:1702476.  https://doi.org/10.1002/aenm.201702476 CrossRefGoogle Scholar
  17. Jaouen F, Proietti E, Lefèvre M, Chenitz R, Dodelet JP, Wu G, Chung HT, Johnston CM, Zelenay P (2011) Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuel cells. Energy Environ Sci 4:114–130.  https://doi.org/10.1039/c0ee00011f CrossRefGoogle Scholar
  18. Jiang S, Zhu C, Dong S (2013) Cobalt and nitrogen-cofunctionalized graphene as a durable non-precious metal catalyst with enhanced ORR activity. J Mater Chem A 1:3593.  https://doi.org/10.1039/C3TA01682J CrossRefGoogle Scholar
  19. Lee CJ, Park J, Yu JA (2002) Catalyst effect on carbon nanotubes synthesized by thermal chemical vapor deposition. Chem Phys Lett 360:250–255.  https://doi.org/10.1016/S0009-2614(02)00831-X CrossRefGoogle Scholar
  20. Lefevre M, Proietti E, Jaouen F, Dodelet JP (2009) Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324:71–74.  https://doi.org/10.1126/science.1170051 CrossRefGoogle Scholar
  21. Li Y, Gong M, Liang Y, Feng J, Kim JE, Wang H, Hong G, Zhang B, Dai H (2013) Advanced zinc-air batteries based on high-performance hybrid electrocatalysts. Nat Commun 4:1805.  https://doi.org/10.1038/ncomms2812 CrossRefGoogle Scholar
  22. Liang HW, Wei W, Wu ZS, Feng X, Mullen K (2013) Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction. J Am Chem Soc 135:16002–16005.  https://doi.org/10.1021/ja407552k CrossRefGoogle Scholar
  23. Liang Y, Li Y, Wang H, Zhou J, Wang J, Regier T, Dai H (2011) Co3O4 nanocrystals on graphene as a synergistic catalyst for oxygen reduction reaction. Nat Mater 10:780–786.  https://doi.org/10.1126/10.1038/nmat3087 CrossRefGoogle Scholar
  24. Lin L, Zhu Q, Xu AW (2014) Noble-metal-free Fe-N/C catalyst for highly efficient oxygen reduction reaction under both alkaline and acidic conditions. J Am Chem Soc 136:11027–11033.  https://doi.org/10.1021/ja504696r CrossRefGoogle Scholar
  25. Liu R, Wu D, Feng X, Mullen K (2010) Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem Int Ed 49:2565–2569.  https://doi.org/10.1002/ange.200907289 CrossRefGoogle Scholar
  26. Lu B, Smart TJ, Qin D, Lu JE, Wang N, Chen L, Peng Y, Ping Y, Chen S (2017) Nitrogen and iron-codoped carbon hollow nanotubules as high-performance catalysts toward oxygen reduction reaction: a combined experimental and theoretical study. Chem Mater 29:5617–5628.  https://doi.org/10.1021/acs.chemmater.7b01265 CrossRefGoogle Scholar
  27. Mahmood J, Li F, Kim C, Hj C, Gwon O, Jung SM, Seo JM, Cho SJ, Ju YW, Jeong HY, Kim G, Baek JB (2018) Fe@C2N: a highly-efficient indirect-contact oxygen reduction catalyst. Nano Energy 44:304–310.  https://doi.org/10.1016/j.nanoen.2017.11.057 CrossRefGoogle Scholar
  28. Meng F, Zhong H, Bao D, Yan J, Zhang X (2016) In situ coupling of strung Co4N and intertwined N-C fibers toward free-standing bifunctional cathode for robust, efficient, and flexible Zn-air batteries. J Am Chem Soc 138:10226–10231.  https://doi.org/10.1021/jacs.6b05046 CrossRefGoogle Scholar
  29. Nai J, Zhang J, Lou XW (2018) Construction of single-crystalline Prussian blue analog hollow nanostructures with tailorable topologies. Chem 4(8):1967–1982.  https://doi.org/10.1016/j.chempr.2018.07.001 CrossRefGoogle Scholar
  30. Peng H, Mo Z, Liao S, Liang H, Yang L, Luo F, Song H, Zhong Y, Zhang B (2013) High performance Fe- and N-doped carbon catalyst with graphene structure for oxygen reduction. Sci Rep 3:1765–1772.  https://doi.org/10.1038/srep01765 CrossRefGoogle Scholar
  31. Qiu Y, Yu J, Shi T, Zhou X, Bai X, Huang JY (2011) Nitrogen-doped ultrathin carbon nanofibers derived from electrospinning: large-scale production, unique structure, and application as electrocatalysts for oxygen reduction. J Power Sources 196:9862–9867.  https://doi.org/10.1016/j.jpowsour.2011.08.013 CrossRefGoogle Scholar
  32. Qu L, Liu Y, Baek JB, Dai L (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4:1321–1326.  https://doi.org/10.1021/nn901850u CrossRefGoogle Scholar
  33. Shanmugam S, Osaka T (2011) Efficient electrocatalytic oxygen reduction over metal free-nitrogen doped carbon nanocapsules. Chem Commun 47:4463–4465.  https://doi.org/10.1039/C1CC10361J CrossRefGoogle Scholar
  34. Singh KP, Bae EJ, Yu JS (2015) Fe-P: a new class of electroactive catalyst for oxygen reduction reaction. J Am Chem Soc 137:3165–3168.  https://doi.org/10.1021/ja511759u CrossRefGoogle Scholar
  35. Su CY, Cheng H, Li W, Liu ZQ, Li N, Hou Z, Bai FQ, Zhang HX, Ma TY (2017) Atomic modulation of FeCo-nitrogen-carbon bifunctional oxygen electrodes for rechargeable and flexible all-solid-state zinc-air battery. Adv Energy Mater 7:1602420.  https://doi.org/10.1002/aenm.201602420 CrossRefGoogle Scholar
  36. Tan M, He T, Liu J, Wu H, Li Q, Zheng J, Wang Y, Sun Z, Wang S, Zhang Y (2018) Supramolecular bimetallogels: a nanofiber network for bimetal/nitrogen Co-doped carbon electrocatalysts. J Mater Chem A 6:8227–8232.  https://doi.org/10.1039/C8TA01898G CrossRefGoogle Scholar
  37. Tong Y, Chen P, Zhou T, Xu K, Chu W, Wu C, Xie Y (2017) A bifunctional hybrid electrocatalyst for oxygen reduction and evolution: cobalt oxide nanoparticles strongly coupled to B,N-decorated graphene. Angew Chem Int Ed 56:7121-7125.  https://doi.org/10.1002/ange.201702430 CrossRefGoogle Scholar
  38. Wang B (2005) Recent development of non-platinum catalysts for oxygen reduction reaction. J Power Sources 152:1–15.  https://doi.org/10.1016/j.jpowsour.2005.05.098 CrossRefGoogle Scholar
  39. Wang H, Keum JK, Hiltner A, Baer E, Freeman B, Rozanski A, Galeski A (2009) Confined crystallization of polyethylene oxide in nanolayer assemblies. Science 323:757–760.  https://doi.org/10.1126/science.1164601 CrossRefGoogle Scholar
  40. Wang H, Wang W, Asif M, Yu Y, Wang Z, Wang J, Liu H, Xiao J (2017) Cobalt ion-coordinated self-assembly synthesis of nitrogen-doped ordered mesoporous carbon nanosheets for efficiently catalyzing oxygen reduction. Nanoscale 9:15534–15541.  https://doi.org/10.1039/C7NR05208A CrossRefGoogle Scholar
  41. Wu T, Fan J, Li Q, Shi P, Xu Q, Min Y (2018) Palladium nanoparticles anchored on anatase titanium dioxide-black phosphorus hybrids with heterointerfaces: highly electroactive and durable catalysts for ethanol electrooxidation. Adv Energy Mater 8:1701799.  https://doi.org/10.1002/aenm.201701799 CrossRefGoogle Scholar
  42. Wu ZS, Yang S, Sun Y, Parvez K, Feng X, Mullen K (2012) 3D nitrogen-doped graphene aerogel-supported Fe3O4 nanoparticles as efficient electrocatalysts for the oxygen reduction reaction. J Am Chem Soc 134:9082–9085.  https://doi.org/10.1021/ja3030565 CrossRefGoogle Scholar
  43. Xu S, Kim Y, Higgins D, Yusuf M, Jaramillo TF, Prinz FB (2017) Building upon the Koutecky-Levich equation for evaluation of next-generation oxygen reduction reaction catalysts. Electrochim Acta 255:99–108.  https://doi.org/10.1016/j.electacta.2017.09.145 CrossRefGoogle Scholar
  44. Yamashita T, Hayes P (2008) Analysis of XPS spectra of Fe2+ and Fe3+ ions in oxide materials. Appl Surf Sci 254:2441–2449.  https://doi.org/10.1016/j.apsusc.2007.09.063 CrossRefGoogle Scholar
  45. Yang L, Zeng X, Wang W, Cao D (2018) Recent progress in MOF-derived, heteroatom-doped porous carbons as highly efficient electrocatalysts for oxygen reduction reaction in fuel cells. Adv Funct Mater 28:1704537.  https://doi.org/10.1002/adfm.201704537 CrossRefGoogle Scholar
  46. Yang W, Liu X, Chen L, Liang L, Jia J (2017) A metal-organic framework devised Co-N doped carbon microsphere/nanofiber hybrid as a free-standing 3D oxygen catalyst. Chem Commun 53:4034-4037. https://doi.org/10.1039/C7CC01349C CrossRefGoogle Scholar
  47. Yang W, Liu X, Yue X, Jia J, Guo S (2015) Bamboo-like carbon nanotube/Fe3C nanoparticle hybrids and their highly efficient catalysis for oxygen reduction. J Am Chem Soc 137:1436–1439.  https://doi.org/10.1021/ja5129132 CrossRefGoogle Scholar
  48. Zhang C, Liu J, Ye Y, Aslam Z, Brydson R, Liang C (2018a) Fe-N-doped mesoporous carbon with dual active sites loaded on reduced graphene oxides for efficient oxygen reduction catalysts. ACS Appl Mater Interfaces 10:2423–2429.  https://doi.org/10.1021/acsami.7b14443 CrossRefGoogle Scholar
  49. Zhang G, Lu W, Cao F, Xiao Z, Zheng X (2016) N-doped graphene coupled with Co nanoparticles as an efficient electrocatalyst for oxygen reduction in alkaline media. J Power Sources 302:114–125.  https://doi.org/10.1016/j.jpowsour.2015.10.055 CrossRefGoogle Scholar
  50. Zhang Y, Lin Y, Jiang H, Wu C, Liu H, Wang C, Chen S, Duan T, Song L (2018b) Well-defined cobalt catalyst with N-doped carbon layers enwrapping: the correlation between surface atomic structure and electrocatalytic property. Small 14:1702074.  https://doi.org/10.1002/smll.201702074 CrossRefGoogle Scholar
  51. Zhao Y, Lai Q, Wang Y, Zhu J, Liang Y (2017) Interconnected hierarchically porous Fe, N-codoped carbon nanofibers as efficient oxygen reduction catalysts for Zn-air batteries. ACS Appl Mater Interfaces 9:16178–16186.  https://doi.org/10.1021/acsami.7b01712 CrossRefGoogle Scholar
  52. Zhou B, Liu L, Cai P, Zeng G, Li X, Wen Z, Chen L (2017) Ferrocene-based porous organic polymer derived high-performance electrocatalysts for oxygen reduction. J Mater Chem A 5:22163–22169.  https://doi.org/10.1039/C7TA06515A CrossRefGoogle Scholar
  53. Zhu H, Zhang S, Su D, Jiang G, Sun S (2015) Surface profile control of FeNiPt/Pt core/shell nanowires for oxygen reduction reaction. Small 11:3545–3549.  https://doi.org/10.1002/smll.201500330 CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Shanghai Key Laboratory of Materials Protection and Advanced Materials in Electric Power, College of Environmental and Chemical EngineeringShanghai University of Electric PowerShanghaiChina
  2. 2.Department of Chemical Engineering and Biointerfaces InstituteUniversity of MichiganAnn ArborUSA
  3. 3.Shanghai Institute of Pollution Control and Ecological SecurityShanghaiP.R. China

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