Skip to main content
Log in

Fe–N–C catalyst derived from solid-state coordination complex as durable oxygen reduction electrocatalyst in alkaline electrolyte

  • Original Paper
  • Published:
Ionics Aims and scope Submit manuscript

    We’re sorry, something doesn't seem to be working properly.

    Please try refreshing the page. If that doesn't work, please contact support so we can address the problem.

Abstract

Nitrogen-doped Fe-based carbon electrocatalyst (Fe–N–C) is developed by a one-pot pyrolysis method, using a solid-state Fe-EDTA coordination complex. The synthesized catalyst was analytically evaluated by various physical and electrochemical measurements. The effect of various synthetic parameters such as sucrose and EDTA and the effect of metal contents were systematically evaluated. The synthesized Fe–N–C shows significant oxygen reduction activity with half-wave potential of 0.81 V, closer to the commercial Pt/C catalyst, with a nearly 3.9 e transferred per oxygen molecule. The developed catalyst also shows admirable stability under repeated potential cycling conditions, when compared to the Pt/C catalyst. In a single-cell fuel cell performance analysis, the Fe–N–C catalyst exhibited a peak power density of 118 mW cm−2. Moreover, the Fe–N–C showed remarkable durability during the accelerated stress test (AST) at highly corrosive conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Shao M, Chang Q, Dodelet JP, Chenitz R (2016) Recent advances in electrocatalysts for oxygen reduction reaction. Chem Rev 116:3594–3657

    CAS  PubMed  Google Scholar 

  2. Borup R, Meyers J, Pivovar B, Kim YS, Mukundan R, Garland N, Myers D, Wilson M, Garzon F, Wood D (2007) Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev 107:3904–3951

    CAS  PubMed  Google Scholar 

  3. Hickner MA (2010) Ion-containing polymers: new energy & clean water. Mater Today 13:34–41

    CAS  Google Scholar 

  4. Zhang H, Shen PK (2012) Recent development of polymer electrolyte membranes for fuel cells. Chem Rev 112:2780–2832

    CAS  PubMed  Google Scholar 

  5. Brocq ML, Job N, Eskenazi D, Pireaux JJ (2014) Pt/C catalyst for PEM fuel cells: control of Pt nanoparticles characteristics through a novel plasma deposition method. Appl Catal B 147:453–463

    Google Scholar 

  6. Peera SG, Lee TG, Sahu AK (2019) Pt-rare earth metal alloy/metal oxide catalysts for oxygen reduction and alcohol oxidation reactions: an overview. Sustain. Energy Fuel 3:1866–1891

    CAS  Google Scholar 

  7. Shi J, Zhou X, Xu P, Qiao J, Chen Z, Liu Y (2014) Nitrogen and sulfur co-doped mesoporous carbon materials as highly efficient electrocatalysts for oxygen reduction reaction. Electrochim Acta 145:259–269

    CAS  Google Scholar 

  8. Wang DW, Su D (2014) Heterogeneous nanocarbon materials for oxygen reduction reaction. Energy Environ Sci 7:576–591

    Google Scholar 

  9. Lee S, Choun M, Ye Y, Lee J, Mun Y, Kang E, Hwang J, Lee YH, Shin CH, Moon SH, Kim SK, Lee E, Lee J (2015) Designing a highly active metal-free oxygen reduction catalyst in membrane electrode assemblies for alkaline fuel cells: effects of pore size and doping-site position. Angew Chem Int Ed 54:9230–9234

    CAS  Google Scholar 

  10. Yi M, Hua Y, Wang K, Wang Y, Song S, Tsiakaras P (2018) Enhancement of oxygen reduction reaction performance: the characteristic role of FeN coordinations. Electrochim Acta 260:264–273

    CAS  Google Scholar 

  11. Ferrero GA, Diez N, Sevilla M, Fuertes AB (2019) Iron/nitrogen co-doped mesoporous carbon synthesized by an endo-templating approach as an efficient electrocatalyst for the oxygen reduction reaction. Microporous Mesoporous Mater 278:280–288

    CAS  Google Scholar 

  12. Yan Z, Dai C, Zhang M, Lv X, Zhao X, Xie J (2019) Nitrogen doped porous carbon with iron promotion for oxygen reduction reaction in alkaline and acidic media. Int J Hydrog Energy 44:4090–4101

    CAS  Google Scholar 

  13. Liu Y, Fan YS, Liu ZM (2019) Pyrolysis of iron phthalocyanine on activated carbon as highly efficient non-noble metal oxygen reduction catalyst in microbial fuel cells. Chem Eng 361:416–427

    CAS  Google Scholar 

  14. Peera SG, Hyuk-Jun K, Tae GL, Mohammed HA (2020) Heteroatom- and metalloid-doped carbon catalysts for oxygen reduction reaction: a mini-review. Ionics 26:1563–1589

    Google Scholar 

  15. Peers SG, Hyuk-Jun K, Lee TG (2020) Highly efficient Co@NCS nanosheet electrocatalyst for oxygen reduction reaction: an environment-friendly, low-cost and sustainable electrocatalyst. Mater Res Bull 128:110873–110885

    Google Scholar 

  16. Zhang P, Chen C, Zhang X, Jiang Z, Huang J, Chen J (2019) Fe and S co-doped N-enriched hierarchical porous carbon polyhedron as efficient non-noble-metal electrocatalyst toward oxygen reduction reaction in both alkaline and acidic medium. Electrochim Acta 298:570–579

    CAS  Google Scholar 

  17. Li T, Deng H, Liu J, Jin C, Song Y, Wang F (2019) First-row transition metals and nitrogen co-doped carbon nanotubes: the exact origin of the enhanced activity for oxygen reduction reaction. Carbon 143:859–868

    CAS  Google Scholar 

  18. Li Y, Li Z, Wu Y, Wu H, Zhang H, Wu T, Yuan C, Xu Y, Zeng B, Dai L (2019) Carbon particles co-doped with N, B and Fe from metal-organic supramolecular polymers for boosted oxygen reduction performance. J Power Sources 412:623–630

    CAS  Google Scholar 

  19. Lu Y, Jiang Y, Chen W (2013) PtPd porous nanorods with enhanced electrocatalytic activity and durability for oxygen reduction reaction. Nano Energy 2:836–844

    CAS  Google Scholar 

  20. Liu Z, Lin X, Lee J, Zhang W, Han M, Gan L (2002) Preparation and characterization of platinum-based electrocatalysts on multiwalled carbon nanotubes for proton exchange membrane fuel cells. Langmuir 18:4054–4060

    CAS  Google Scholar 

  21. Sun M, Davenport D, Liu H, Qu J, Elimelech M, Li J (2018) Highly efficient and sustainable non-precious-metal Fe-N-C electrocatalysts for the oxygen reduction reaction. J Mater Chem A 6:2527–2539

    CAS  Google Scholar 

  22. Brock SL, Duan N, Tian ZR, Giraldo O, Zhou H, Suib SL (1998) A review of porous manganese oxide materials. Chem Mater 10:2619–2628

    CAS  Google Scholar 

  23. Jiang WJ, Gu L, Li L, Zhang Y, Zhang X, Zhang LJ, Wang JQ, Hu JS, Wei Z, Wan LJ (2016) Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx. J Am Chem Soc 138:3570–3578

    CAS  PubMed  Google Scholar 

  24. Jia Q, Ramaswamy N, Hafiz H, Tylus U, Strickland K, Wu G, Barbiellini B, Bansil A, Holby EF, Zelenay P, Mukerjee S (2015) Experimental observation of redox-induced Fe-N switching behavior as a determinant role for oxygen reduction activity. ACS Nano 9:12496–12505

    CAS  PubMed  Google Scholar 

  25. Zitolo A, Goellner V, Armel V, Sougrati MT, Mineva T, Stievano L, Fonda E, Jaouen F (2015) Identification of catalytic sites for oxygen reduction in iron-and nitrogen-doped graphene materials. Nat Mater 14:937–942

    CAS  PubMed  Google Scholar 

  26. Wu G, More K, Johnston C, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron and cobalt. Science 332:443–447

    CAS  PubMed  Google Scholar 

  27. Tian Y, Xu L, Qian J, Bao J, Yan C, Li H, Li H, Zhang S (2019) Fe3C/Fe2O3 heterostructure embedded in N-doped graphene as a bifunctional catalyst for quasi-solid-state zinc-air batteries. Carbon 146:763–771

    CAS  Google Scholar 

  28. Peera SG, Arunchander A, Sahu AK (2016) Cumulative effect of transition metals on nitrogen and fluorine co-doped graphite nanofibers: an efficient and highly durable non-precious metal catalyst for the oxygen reduction reaction. Nanoscale 8:14650–14664

    CAS  PubMed  Google Scholar 

  29. Zhang X, Huang Y, Chen X, Gao Q, Zhang W (2018) Nitrogen-doped carbon nanotubes based on melamine-formaldehyde resin as highly efficient catalyst for oxygen reduction reaction. J Colloid Interface Sci 509:1–9

    CAS  PubMed  Google Scholar 

  30. Xu J, Wu C, Yu Q, Zhao Y, Li X, Guan L (2018) Antioil Ag3PO4 nanoparticle/polydopamine/Al2O3 sandwich structure for complex wastewater treatment: dynamic catalysis under natural light. ACS Sustain Chem Eng 6:551–560

    CAS  Google Scholar 

  31. Niu W, Li L, Liu X, Wang N, Liu J, Zhou W, Tang Z, Chen S (2015) Mesoporous N-doped carbons prepared with thermally removable nanoparticle templates: an efficient electrocatalyst for oxygen reduction reaction. J Am Chem Soc 137:5555–5562

    CAS  PubMed  Google Scholar 

  32. Bashyam R, Zelenay P (2010) A class of non-precious metal composite catalysts for fuel cells. Nature 443:63–66

    Google Scholar 

  33. Öztürk A, Yurtcan AB (2018) Synthesis of polypyrrole (PPy) based porous N-doped carbon nanotubes (N-CNTs) as catalyst support for PEM fuel cells. Int J Hydrog Energy 43:18559–18571

    Google Scholar 

  34. Han SW, Bang J, Ko SH, Ryoo R (2019) Variation of nitrogen species in zeolite-templated carbon by low-temperature carbonization of pyrrole and the effect on oxygen reduction activity. J Mater Chem A 7:8353–8360

    CAS  Google Scholar 

  35. Cao S, Han N, Han J, Hu Y, Fan L, Zhou C, Guo R (2016) Mesoporous hybrid shells of carbonized polyaniline/Mn2O3 as non-precious efficient oxygen reduction reaction catalyst. ACS Appl Mater Interfaces 8:6040–6050

    CAS  PubMed  Google Scholar 

  36. Ratso S, Kruusenberg I, Vikkisk M, Joost U, Shulga E, Kink I, Kallio T, Tammeveski K (2014) Highly active nitrogen-doped few-layer graphene/carbon nanotube composite electrocatalyst for oxygen reduction reaction in alkaline media. Carbon 73:361–370

    CAS  Google Scholar 

  37. Hossen MM, Artyushkova K, Atanassov P, Serov A (2018) Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in alkaline exchange membrane fuel cells. J Power Sources 375:214–222

    CAS  Google Scholar 

  38. Guo Z, Zhang Z, Li Z, Dou M, Wang F (2019) Well-defined gradient Fe/Zn bimetal organic framework cylinders derived highly efficient iron- and nitrogen-codoped hierarchically porous carbon electrocatalysts towards oxygen reduction. Nano Energy 57:108–117

    CAS  Google Scholar 

  39. Peera SG, Balamurugan J, Kim NH, Lee JH (2018) Sustainable synthesis of CO@NC core shell nanostructures from metal organic frameworks via mechanochemical coordination self-assembly: an efficient electrocatalyst for oxygen reduction reaction. Small 14:1800441–1800456

    Google Scholar 

  40. Wang K, Wang Y, Tong Y, Pan Z, Song S (2016) A robust versatile hybrid electrocatalyst for the oxygen reduction reaction. ACS Appl Mater Interfaces 8:29356–29364

    CAS  PubMed  Google Scholar 

  41. Hua Y, Jiang T, Wang K, Wu M, Song S, Wang Y, Tsiakaras P (2016) Efficient Pt-free electrocatalyst for oxygen reduction reaction: highly ordered mesoporous N and S co-doped carbon with saccharin as single-source molecular precursor. Appl Catal B Environ 194:202–208

    CAS  Google Scholar 

  42. Wang C, Yang F, Qiu T, Cao Y, Zhong H, Yu C, Li R, Mao L, Li Y (2018) Preparation of an efficient Fe/N/C electrocatalyst and its application for oxygen reduction reaction in alkaline media. J Electroanal Chem 810:62–68

    CAS  Google Scholar 

  43. Sarkar IJR, Peera SG, Chetty R (2018) Manganese oxide nanoparticles supported nitrogen-doped graphene: a durable alkaline oxygen reduction electrocatalyst. J Appl Electrochem 48:849–865

    CAS  Google Scholar 

  44. Liu J, Wang L, Sun X, Zhu X (2010) Cerium vanadate nanorod arrays from ionic chelator-mediated self-assembly. Angew Chem Int Ed 49:3492–3495

    CAS  Google Scholar 

  45. Kramm UI, Lefèvre M, Larouche N, Schmeisser D, Dodelet JP (2014) Correlations between mass activity and physicochemical properties of Fe/N/C catalysts for the ORR in PEM fuel cell via 57Fe Mössbauer spectroscopy and other techniques. J Am Chem Soc 136:978–985

    CAS  PubMed  Google Scholar 

  46. Chen J, Gao J, Wang X (2006) Thermal decomposition of ethylenediaminetetraacetic acid in the presence of 1,2-phenylenediamine and hydrochloric acid. J Braz Chem Soc 17:880–885

    CAS  Google Scholar 

  47. Venezky DL, Rudzinski WE (1984) Determination of ethylenediaminetetraacetic acid in boiler water by liquid chromatography. Anal Chem 56:317–319

    Google Scholar 

  48. Huang X, Schmucker A, Dyke J, Hall SM, Retrum J, Stein B, Remmes N, Baxter DV, Dragneaa B, Bronstein LM (2009) Magnetic nanoparticles with functional silanes: evolution of well-defined shells from anhydride containing silane. J Mater Chem 19:4231–4239

    CAS  PubMed  PubMed Central  Google Scholar 

  49. Guo J, Lan M, Wang S, He Y, Zhang S, Xiang G, Boi FS (2015) Enhanced saturation magnetization in buckypaper-films of thin walled carbon nanostructures filled with Fe3C, FeCo, FeNi, CoNi, Co and Ni crystals: the key role of Cl. Phys Chem Chem Phys 17:18159–18166

    CAS  PubMed  Google Scholar 

  50. Xiao M, Zhu J, Feng L, Liu C, Xing W (2015) Meso/macroporous nitrogen-doped carbon architectures with iron carbide encapsulated in graphitic layers as an efficient and robust catalyst for the oxygen reduction reaction in both acidic and alkaline solutions. Adv Mater 27:2521–2527

    CAS  PubMed  Google Scholar 

  51. Zhang LS, Liang XQ, Song WG, Wu ZY (2010) Identification of the nitrogen species on N-doped graphene layers and Pt/NG composite catalyst for direct methanol fuel cell. Phys Chem Chem Phys 12:12055–12059

    CAS  PubMed  Google Scholar 

  52. Chambrion P, Suzuki T, Zhang ZG, Kyotani T, Tomita A (1997) XPS of nitrogen-containing functional groups formed during the C-NO reaction. Energy Fuel 11:681–685

    CAS  Google Scholar 

  53. Wu G, Zelenay P (2013) Nanostructured nonprecious metal catalysts for oxygen reduction reaction. Acc Chem Res 46:1878–1889

    CAS  PubMed  Google Scholar 

  54. Bag S, Roy K, Gopinath CS, Raj CR (2014) Facile single-step synthesis of nitrogen-doped reduced graphene oxide-mn3o4 hybrid functional material for the electrocatalytic reduction of oxygen. ACS Appl Mater Interfaces 6:2692–2699

    CAS  PubMed  Google Scholar 

  55. Chetty R, Kundu S, Xia W, Bron M, Schuhmann W, Chirila V, Brandl W, Reinecke T, Muhler M (2009) PtRu nanoparticles supported on nitrogen-doped multiwalled carbon nanotubes as catalyst for methanol electrooxidation. Electrochim Acta 54:4208–4215

    CAS  Google Scholar 

  56. Peng H, Liu F, Liu X, Liao S, You C, Tian X, Nan H, Luo F, Song H, Fu Z, Huang P (2014) Effect of transition metals on the structure and performance of the doped carbon catalysts derived from polyaniline and melamine for ORR application. ACS Catal 4:3797–3805

    CAS  Google Scholar 

  57. Yuan K, Sfaelou S, Qiu M, Lützenkirchen-Hecht D, Zhuang X, Chen Y, Yuan C, Feng X, Scherf U (2018) Synergetic contribution of boron and Fe-Nx species in porous carbons toward efficient electrocatalysts for oxygen reduction reaction. ACS Energy Lett 3:252–260

    CAS  Google Scholar 

  58. Marcus P, Grimal JM (1992) The anodic dissolution and passivation of NiCrFe alloys studied by ESCA. Corros Sci 33:805–814

    CAS  Google Scholar 

  59. Siriwardane RV, Cook JM (1985) Interactions of SO2 with sodium deposited on silica. J Colloid Interface Sci 108:414–422

    CAS  Google Scholar 

  60. Mills P, Sullivan JL (1983) A study of the core level electrons in iron and its three oxides by means of X-ray photoelectron spectroscopy. J Phys D Appl Phys 16:723–732

    CAS  Google Scholar 

  61. Li Z, Chen H, Bao H, Gao M (2004) One-pot reaction to synthesize water-soluble magnetite nanocrystals. Chem Mater 16:1391–1393

    CAS  Google Scholar 

  62. 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

    PubMed Central  Google Scholar 

  63. Eissa AA, Peera SG, Kim NH, Lee JH (2019) g-C3N4 templated synthesis of the Fe3C@NSC electrocatalyst enriched with Fe–Nx active sites for efficient oxygen reduction reaction. J Mater Chem A 7:16920–16936

    CAS  Google Scholar 

  64. Gong KP, Du F, Xia ZH, Durstock M, Dai LM (2009) Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science 323:760–764

    CAS  PubMed  Google Scholar 

  65. Ganesan S, Leonard N, Barton SC (2014) Impact of transition metal on nitrogen retention and activity of iron–nitrogen–carbon oxygen reduction catalysts. Phys Chem Chem Phys 16:4576–4585

    CAS  PubMed  Google Scholar 

  66. Tian LL, Yang J, Weng MY, Tan R, Zheng JX, Chen HB, Zhuang QC, Dai LM, Pan F (2017) Fast diffusion of O2 on nitrogen-doped graphene to enhance oxygen reduction and its application for high-rate Zn-air batteries. ACS Appl Mater Interfaces 9:7125–7130

    CAS  PubMed  Google Scholar 

  67. Wu J, Ma L, Yadav RM, Yang Y, Zhang X, Vajtai R, Lou J, Ajayan PM (2015) Nitrogen-doped graphene with pyridinic dominance as a highly active and stable electrocatalyst for oxygen reduction. ACS Appl Mater Interfaces 7:14763–14769

    CAS  PubMed  Google Scholar 

  68. Ratso S, Kruusenberg I, Sarapuu A, Rauwel P, Saar R, Joost U, Aruvali J, Kanninen P, Kallio T, Tammeveski K (2016) Enhanced oxygen reduction reaction activity of iron-containing nitrogen-doped carbon nanotubes for alkaline direct methanol fuel cell application. J Power Sources 332:129–138

    CAS  Google Scholar 

  69. Jin Z, Li P, Xiao D (2014) Enhanced electrocatalytic performance for oxygen reduction via active interfaces of layer-by-layered titanium nitride/titanium carbonitride structures. Sci Rep 4:6712–6719

    CAS  PubMed  PubMed Central  Google Scholar 

  70. Li X, Popov BN, Kawahara T, Yanagi H (2011) Non-precious metal catalysts synthesized from precursors of carbon, nitrogen, and transition metal for oxygen reduction in alkaline fuel cells. J Power Sources 196:1717–1722

    CAS  Google Scholar 

  71. Gasteiger HA, Kocha SS, Sompalli B, Wagner FT (2005) Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl Catal B 56:9–35

    CAS  Google Scholar 

  72. Lefèvre 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

    PubMed  Google Scholar 

  73. Sun W, Hsu A, Chen R (2011) Carbon supported tetragonal MnOOH catalysts for oxygen reduction reaction in alkaline media. J Power Sources 196:627–635

    CAS  Google Scholar 

  74. Peera SG, Arunchander A, Sahu AK (2016) Platinum nanoparticles supported on nitrogen and fluorine co-doped graphite nanofibers as an excellent and durable oxygen reduction catalyst for polymer electrolyte fuel cells. Carbon 107:667–679

    CAS  Google Scholar 

  75. Reiser CA, Bregoli L, Patterson TW, Yi JS, Yang JDL, Perry ML, Jarvi TD (2005) A reverse-current decay mechanism for fuel cells. Electrochem Solid State Lett 8:A273–A276

    CAS  Google Scholar 

  76. Knights SD, Colbow KM, St-Pierre J, Wilkinson DP (2004) Aging mechanism and lifetime of PEFC and DMFC. J Power Sources 127:127–134

    CAS  Google Scholar 

  77. Zadick A, Dubau L, Sergent N, Berthomé G, Chatenet M (2015) Huge instability of Pt/C catalysts in alkaline medium. ACS Catal 5:4819–4824

    CAS  Google Scholar 

  78. Li L, Xing YC (2006) Electrochemical durability of carbon nanotubes in non-catalyzed and catalyzed oxidations. J Electrochem Soc 153:A1823–A1828

    CAS  Google Scholar 

Download references

Acknowledgments

We would like to thank the Indian Institute of Technology (IIT) Madras for the fellowship to IJRS. We also acknowledge the DST-FIST for providing the instrumentation facility to the Department of Chemical Engineering, IIT Madras.

Funding

RC received funding through Grant No. DST/TMD/HFC/2 K18/34 from the Department of Science and Technology (DST), India.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Raghuram Chetty.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Electronic supplementary material

ESM 1

(DOC 138 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Sarkar, I.J.R., Peera, S.G. & Chetty, R. Fe–N–C catalyst derived from solid-state coordination complex as durable oxygen reduction electrocatalyst in alkaline electrolyte. Ionics 26, 5685–5696 (2020). https://doi.org/10.1007/s11581-020-03722-2

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11581-020-03722-2

Keywords

Navigation