Skip to main content
Log in

Influence of Fe on electrocatalytic activity of iron-nitrogen-doped carbon materials toward oxygen reduction reaction

  • Research Article
  • Published:
Frontiers in Energy Aims and scope Submit manuscript

Abstract

The development of highly active nitrogen-doped carbon-based transition metal (M-N-C) compounds for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) greatly helps reduce fuel cell cost, thus rapidly promoting their commercial applications. Among different M-N-C electro-catalysts, the series of Fe-N-C materials are highly favored because of their high ORR activity. However, there remains a debate on the effect of Fe, and rare investigations focus on the influence of Fe addition in the second heat treatment usually performed after acid leaching in the catalyst synthesis. It is thus very critical to explore the influences of Fe on the ORR electrocatalytic activity, which will, in turn, guide the design of Fe-N-C materials with enhanced performance. Herein, a series of Fe-N-C electrocatalysts are synthesize and the influence of Fe on the ORR activity are speculated both experimentally and theoretically. It is deduced that the active site lies in the structure of Fe-N4, accompanied with the addition of appropriate Fe, and the number of active sites increases without the occurrence of agglomeration particles. Moreover, it is speculated that Fe plays an important role in stabilizing N as well as constituting active sites in the second pyrolyzing process.

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.

Institutional subscriptions

Similar content being viewed by others

References

  1. Nørskov J K, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin J R, Bligaard T, Jonsson H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. Journal of Physical Chemistry B, 2004, 108(46): 17886–17892

    Article  Google Scholar 

  2. Zhang J, Sasaki K, Sutter E, Adzic R. Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science, 2007, 315(5809): 220–222

    Article  Google Scholar 

  3. Luo L, Zhu F, Tian R, Li L, Shen S, Yan X, Zhang J. Composition-graded PdxNi1−x nanospheres with Pt monolayer shells as highperformance electrocatalysts for oxygen reduction reaction. ACS Catalysis, 2017, 7(8): 5420–5430

    Article  Google Scholar 

  4. Cai B, Hübner R, Sasaki K, Zhang Y, Su D, Ziegler C, Vukmirovic M B, Rellinghaus B, Adzic R R, Eychmüller A. Core-shell structuring of pure metallic aerogels towards highly efficient platinum utilization for the oxygen reduction reaction. Angewandte Chemie International Edition, 2018, 57(11): 2963–2966

    Article  Google Scholar 

  5. Guo Y, Tang J, Henzie J, Jiang B, Qian H, Wang Z, Tan H, Bando Y, Yamauchi Y. Assembly of hollow mesoporous nanoarchitectures composed of ultrafine Mo2C nanoparticles on N-doped carbon nanosheets for efficient electrocatalytic reduction of oxygen. Materials Horizons, 2017, 4(6): 1171–1177

    Article  Google Scholar 

  6. Lefèvre M, Proietti E, Jaouen F, Dodelet J P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science, 2009, 324(5923): 71–74

    Article  Google Scholar 

  7. Wang J, Huang Z, Liu W, Chang C, Tang H, Li Z, Chen W, Jia C, Yao T, Wei S, Wu Y, Li Y. Design of N-coordinated dual-metal sites: a stable and active Pt-free catalyst for acidic oxygen reduction reaction. Journal of the American Chemical Society, 2017, 139(48): 17281–17284

    Article  Google Scholar 

  8. Papageorgopoulos D. Fuel cells R&D overview. 2018, available at the website of http://hydrogen.energy.gov

  9. Vesborg P C, Jaramillo T F. Addressing the terawatt challenge: scalability in the supply of chemical elements for renewable energy. RSC Advances, 2012, 2(21): 7933–7947

    Article  Google Scholar 

  10. Zhang H, Hwang S, Wang M, Feng Z, Karakalos S, Luo L, Qiao Z, Xie X, Wang C, Su D, Shao Y, Wu G. Single atomic iron catalysts for oxygen reduction in acidic media: particle size control and thermal activation. Journal of the American Chemical Society, 2017, 139(40): 14143–14149

    Article  Google Scholar 

  11. Lee J S, Park G S, Kim S T, Liu M, Cho J. A highly efficient electrocatalyst for the oxygen reduction reaction: N-doped ketjen-black incorporated into Fe/Fe3C-functionalized melamine foam. Angewandte Chemie International Edition, 2013, 125(3): 1060–1064

    Article  Google Scholar 

  12. Hu Y, Jensen J O, Zhang W, Cleemann L N, Xing W, Bjerrum N J, Li Q. Hollow spheres of iron carbide nanoparticles encased in graphitic layers as oxygen reduction catalysts. Angewandte Chemie International Edition, 2014, 53(14): 3675–3679

    Article  Google Scholar 

  13. Xu H, Li Y, Wang R. Pore-rich iron-nitrogen-doped carbon nanofoam as an efficient catalyst towards the oxygen reduction reaction. International Journal of Hydrogen Energy, 2019, 44(48): 26285–26295

    Article  Google Scholar 

  14. Li W, Wu J, Higgins D C, Choi J Y, Chen Z. Determination of iron active sites in pyrolyzed iron-based catalysts for the oxygen reduction reaction. ACS Catalysis, 2012, 2(12): 2761–2768

    Article  Google Scholar 

  15. Jiang W, Gu L, Li L, Zhang Y, Zhang X, Zhang L, Wang J, Hu J, Wei Z, Wan L. Understanding the high activity of Fe-N-C electrocatalysts in oxygen reduction: Fe/Fe3C nanoparticles boost the activity of Fe-Nx. Journal of the American Chemical Society, 2016, 138(10): 3570–3578

    Article  Google Scholar 

  16. Kattel S, Wang G. Reaction pathway for oxygen reduction on FeN4 embedded graphene. Journal of Physical Chemistry Letters, 2014, 5 (3): 452–456

    Article  Google Scholar 

  17. Matter P H, Wang E, Millet J M M, Ozkan U S. Characterization of the iron phase in CNx-based oxygen reduction reaction catalysts. Journal of Physical Chemistry C, 2007, 111(3): 1444–1450

    Article  Google Scholar 

  18. Nallathambi V, Lee J W, Kumaraguru S P, Wu G, Popov B N. Development of high performance carbon composite catalyst for oxygen reduction reaction in PEM Proton Exchange Membrane fuel cells. Journal of Power Sources, 2008, 183(1): 34–42

    Article  Google Scholar 

  19. Matter P H, Wang E, Arias M, Biddinger E J, Ozkan U S. Oxygen reduction reaction catalysts prepared from acetonitrile pyrolysis over alumina-supported metal particles. Journal of Physical Chemistry B, 2006, 110(37): 18374–18384

    Article  Google Scholar 

  20. Matter P H, Zhang L, Ozkan U S. The role of nanostructure in nitrogen-containing carbon catalysts for the oxygen reduction reaction. Journal of Catalysis, 2006, 239(1): 83–96

    Article  Google Scholar 

  21. Hofmann S, Blume R, Wirth C T, Cantoro M, Sharma R, Ducati C, Hävecker M, Zafeiratos S, Schnoerch P, Oestereich A, Teschner D, Albrecht M, Knop-Gericke A, Schlögl R, Robertson J. State of transition metal catalysts during carbon nanotube growth. Journal of Physical Chemistry C, 2009, 113(5): 1648–1656

    Article  Google Scholar 

  22. Liu G, Li X, Ganesan P, Popov B N. Studies of oxygen reduction reaction active sites and stability of nitrogen-modified carbon composite catalysts for PEM fuel cells. Electrochimica Acta, 2010, 55(8): 2853–2858

    Article  Google Scholar 

  23. Liu G, Li X, Ganesan P, Popov B N. Development of non-precious metal oxygen-reduction catalysts for PEM fuel cells based on N-doped ordered porous carbon. Applied Catalysis B: Environmental, 2009, 93(1–2): 156–165

    Article  Google Scholar 

  24. Lai L, Potts J R, Zhan D, Wang L, Poh C K, Tang C, Gong H, Shen Z, Lin J, Ruoff R S. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction. Energy & Environmental Science, 2012, 5(7): 7936–7942

    Article  Google Scholar 

  25. Guo D, Shibuya R, Akiba C, Saji S, Kondo T, Nakamura J. Active sites of nitrogen-doped carbon materials for oxygen reduction reaction clarified using model catalysts. Science, 2016, 351(6271): 361–365

    Article  Google Scholar 

  26. Gong K, Du F, Xia Z, Durstock M, Dai L. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction. Science, 2009, 323(5915): 760–764

    Article  Google Scholar 

  27. Kundu S, Nagaiah T C, Xia W, Wang Y, Dommele S V, Bitter J H, Santa M, Grundmeier G, Bron M, Schuhmann W, Muhler M. Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction. Journal of Physical Chemistry C, 2009, 113(32): 14302–14310

    Article  Google Scholar 

  28. Delley B. From molecules to solids with the DMol3 approach. Journal of Chemical Physics, 2000, 113(18): 7756–7764

    Article  Google Scholar 

  29. Perdew J P, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Physical Review Letters, 1996, 77 (18): 3865–3868

    Article  Google Scholar 

  30. Grimme S. Semiempirical GGA-type density functional constructed with a long-range dispersion correction. Journal of Computational Chemistry, 2006, 27(15): 1787–1799

    Article  Google Scholar 

  31. Cramer C J. Essentials of Computational Chemistry: Theories and Models. Wiley, 2004

  32. Liu Q, Liu X, Zheng L, Shui J. The solid-phase synthesis of an Fe-N-C electrocatalyst for high-power proton-exchange membrane fuel cells. Angewandte Chemie International Edition, 2018, 57(5): 1204–1208

    Article  Google Scholar 

  33. Wu M, Tang Q, Dong F, Bai Z, Zhang L, Qiao J. Fe/N/S-composited hierarchically porous carbons with optimized surface functionality, composition and nanoarchitecture as electrocatalysts for oxygen reduction reaction. Journal of Catalysis, 2017, 352: 208–217

    Article  Google Scholar 

  34. Xia W, Tang J, Li J, Zhang S, Wu K, He J, Yamauchi Y. Defect-rich graphene nanomech produced by thermal exfoliation of metal-organic frameworks for the oxygen reduction reaction. Angewandte Chemie International Edition, 2019, 58(38): 13354–13359

    Article  Google Scholar 

  35. Jiang Y, Yang L, Wang X, Wu Q, Ma J, Hu Z. Doping sp2 carbon to boost the activity for oxygen reduction in an acidic medium: a theoretical exploration. RSC Advances, 2016, 6(54): 48498–48503

    Article  Google Scholar 

  36. Hammer B, Nørskov J K. Theoretical surface science and catalysis-calculations and concepts. Advances in Catalysis, 2000, 45: 71–129

    Google Scholar 

  37. Tan H, Li Y, Kim J, Takei T, Wang Z, Xu X, Wang J, Bando Y, Kang Y, Tang J, Yamauchi Y. Sub-50 nm iron-nitrogen-doped hollow carbon sphere encapsulated iron carbide nanoparticles as efficient oxygen reduction catalysts. Advancement of Science, 2018, 5(7): 1800120

    Google Scholar 

  38. Chen P, Zhou T, Xing L, Xu K, Tong Y, Xie H, Zhang L, Yan W, Chu W, Wu C, Xie Y. Atomically dispersed iron-nitrogen species as electrocatalysts for bifunctional oxygen evolution and reduction reactions. Angewandte Chemie International Edition, 2017, 56(2): 610–614

    Article  Google Scholar 

  39. Tan H, Tang J, Henzie J, Li Y, Xu X, Chen T, Wang Z, Wang J, Ide Y, Bando Y, Yamauchi Y. Assembly of hollow carbon nanospheres on graphene nanosheets and creation of iron-nitrogen-doped porous carbon for oxygen reduction. ACS Nano, 2018, 12(6): 5674–5683

    Article  Google Scholar 

Download references

Acknowledgements

This work was funded by the National Natural Science Foundation of China (Grant Nos. 21533005 and 21802095) and the National Key R&D Program of China (2016YFB0101201).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Junliang Zhang.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Li, L., Fu, C., Shen, S. et al. Influence of Fe on electrocatalytic activity of iron-nitrogen-doped carbon materials toward oxygen reduction reaction. Front. Energy 16, 812–821 (2022). https://doi.org/10.1007/s11708-020-0669-0

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11708-020-0669-0

Keywords

Navigation