Skip to main content
Log in

New insight into effect of potential on degradation of Fe-N-C catalyst for ORR

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

Abstract

In recent years, Fe-N-C catalyst is particularly attractive due to its high oxygen reduction reaction (ORR) activity and low cost for proton exchange membrane fuel cells (PEMFCs). However, the durability problems still pose challenge to the application of Fe-N-C catalyst. Although considerable work has been done to investigate the degradation mechanisms of Fe-N-C catalyst, most of them are simply focused on the active-site decay, the carbon oxidation, and the demetalation problems. In fact, the 2e pathway in the ORR process of Fe-N-C catalyst would result in the formation of H2O2, which is proved to be a key degradation source. In this paper, a new insight into the effect of potential on degradation of Fe-N-C catalyst was provided by quantifying the H2O2 intermediate. In this case, stability tests were conducted by the potential-static method in O2 saturated 0.1 mol/L HClO4. During the tests, H2O2 was quantified by rotating ring disk electrode (RRDE). The results show that compared with the loading voltage of 0.4 V, 0.8 V, and 1.0 V, the catalysts being kept at 0.6 V exhibit a highest H2O2 yield. It is found that it is the combined effect of electrochemical oxidation and chemical oxidation (by aggressive radicals like H2O2/radicals) that triggered the highest H2O2 release rate, with the latter as the major cause.

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.

Similar content being viewed by others

References

  1. Martinez U, Komini Babu S, Holby E F, et al. Progress in the development of Fe-based PGM-free electrocatalysts for the oxygen reduction reaction. Advanced Materials, 2019, 31(31): 1806545

    Article  Google Scholar 

  2. Konnerth H, Matsagar B M, Chen S S, et al. Metal-organic framework (MOF)-derived catalysts for fine chemical production. Coordination Chemistry Reviews, 2020, 416: 213319

    Article  Google Scholar 

  3. Yang L J, Shui J L, Du L, et al. Carbon-based metal-free ORR electrocatalysts for fuel cells: past, present, and future. Advanced Materials, 2019, 31(13): 1804799

    Article  Google Scholar 

  4. Banham D, Ye S Y. Current status and future development of catalyst materials and catalyst layers for proton exchange membrane fuel cells: an industrial perspective. ACS Energy Letters, 2017, 2(3): 629–638

    Article  Google Scholar 

  5. Zhang L, Si R, Liu H, et al. Atomic layer deposited Pt-Ru dual-metal dimers and identifying their active sites for hydrogen evolution reaction. Nature Communications, 2019, 10(1): 4936

    Article  Google Scholar 

  6. Liu M L, Zhao Z P, Duan X F, et al. Nanoscale structure design for high-performance Pt-based ORR catalysts. Advanced Materials, 2019, 31(6): 1802234

    Article  Google Scholar 

  7. Chang Q W, Xu Y, Zhu S Q, et al. Pt-Ni nanourchins as electrocatalysts for oxygen reduction reaction. Frontiers in Energy, 2017, 11(3): 254–259

    Article  Google Scholar 

  8. Guo Y, Tang J, Henzie J, et al. 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 

  9. Tan H, Li Y, Kim J, et al. 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 

  10. Tan H, Tang J, Henzie J, et al. 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 

  11. Cai J J, Zhou Q Y, Liu B, et al. A sponge-templated sandwich-like cobalt-embedded nitrogen-doped carbon polyhedron/graphene composite as a highly efficient catalyst for Zn-air batteries. Nanoscale, 2020, 12(2): 973–982

    Article  Google Scholar 

  12. Zhang X, Chen A, Zhong M, et al. Metal-organic frameworks (MOFs) and MOF-derived materials for energy storage and conversion. Electrochemical Energy Reviews, 2019, 2(1): 29–104

    Article  Google Scholar 

  13. Chueh C C, Chen C I, Su Y A, et al. Harnessing MOF materials in photovoltaic devices: recent advances, challenges, and perspectives. Journal of Materials Chemistry A, Materials for Energy and Sustainability, 2019, 7(29): 17079–17095

    Article  Google Scholar 

  14. Banham D, Choi J Y, Kishimoto T, et al. Integrating PGM-free catalysts into catalyst layers and proton exchange membrane fuel cell devices. Advanced Materials, 2019, 31(31): 1804846

    Article  Google Scholar 

  15. Doustkhah E, Lin J, Rostamnia S, et al. Development of sulfonic-acid-functionalized mesoporous materials: synthesis and catalytic applications. Chemistry (Weinheim an der Bergstrasse, Germany), 2019, 25(7): 1614–1635

    Google Scholar 

  16. Liao Y T, Nguyen V C, Ishiguro N, et al. Engineering a homogeneous alloy-oxide interface derived from metal-organic frameworks for selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid. Applied Catalysis B: Environmental, 2020, 270: 118805

    Article  Google Scholar 

  17. Xia W, Tang J, Li J, et al. Defect-rich graphene nanomesh 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 

  18. Jasinski R. New fuel cell cathode catalyst. Nature, 1964, 201(4925): 1212–1213

    Article  Google Scholar 

  19. Jahnke H, Schönborn M, Zimmermann G. Organic dyestuffs as catalysts for fuel cells. In: Schäfer F P, eds. Physical and Chemical Applications of Dyestuffs. Berlin, Heidelberg: Springer, 1976, 61

    Google Scholar 

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

    Article  Google Scholar 

  21. Yarlagadda V, Carpenter M K, Moylan T E, et al. Boosting fuel cell performance with accessible carbon mesopores. ACS Energy Letters, 2018, 3(3): 618–621

    Article  Google Scholar 

  22. Cheng N, Zhang L, Doyle-Davis K, et al. Single-atom catalysts: from design to application. Electrochemical Energy Reviews, 2019, 2: 539–573

    Article  Google Scholar 

  23. Shao Y Y, Dodelet J P, Wu G, et al. PGM-free cathode catalysts for PEM fuel cells: a mini-review on stability challenges. Advanced Materials, 2019, 31(31): 1807615

    Article  Google Scholar 

  24. Lefevre M, Dodelet J P. Fe-based catalysts for the reduction of oxygen in polymer electrolyte membrane fuel cell conditions: determination of the amount of peroxide released during electroreduction and its influence on the stability of the catalysts. Electrochimica Acta, 2003, 48: 2749–2760

    Article  Google Scholar 

  25. Artyushkova K, Serov A, Rojas-Carbonell S, et al. Chemistry of multitudinous active sites for oxygen reduction reaction in transition metal-nitrogen-carbon electrocatalysts. Journal of Physical Chemistry C, 2015, 119(46): 25917–25928

    Article  Google Scholar 

  26. Muthukrishnan A, Nabae Y, Okajima T, et al. Kinetic approach to investigate the mechanistic pathways of oxygen reduction reaction on Fe-containing N-doped carbon catalysts. ACS Catalysis, 2015, 5 (9): 5194–5202

    Article  Google Scholar 

  27. Zheng W, Wang L, Deng F, et al. Durable and self-hydrating tungsten carbide-based composite polymer electrolyte membrane fuel cells. Nature Communications, 2017, 8(1): 418

    Article  Google Scholar 

  28. Choi C H, Lim H K, Chung M W, et al. The Achilles’ heel of iron-based catalysts during oxygen reduction in an acidic medium. Energy & Environmental Science, 2018, 11(11): 3176–3182

    Article  Google Scholar 

  29. Goellner V, Armel V, Zitolo A, et al. Degradation by hydrogen peroxide of metal-nitrogen-carbon catalysts for oxygen reduction. Journal of the Electrochemical Society, 2015, 162(6): H403–H414

    Article  Google Scholar 

  30. Kumar K, Dubau L, Mermoux M, et al. On the influence of oxygen on the degradation of Fe-N-C catalysts. Angewandte Chemie International Edition, 2020, 59(8): 3235–3243

    Article  Google Scholar 

  31. Kusoglu A, Weber A Z. New insights into perfluorinated sulfonic-acid ionomers. Chemical Reviews, 2017, 117(3): 987–1104

    Article  Google Scholar 

  32. Yang L M, Bai Y Z, Zhang H J, et al. Nitrogen-doped porous carbon derived from Fe-MIL nanocrystals as an electrocatalyst for efficient oxygen reduction. RSC Advances, 2017, 7(36): 22610–22618

    Article  Google Scholar 

  33. Abe H, Hirai Y, Ikeda S, et al. Fe azaphthalocyanine unimolecular layers (Fe AzULs) on carbon nanotubes for realizing highly active oxygen reduction reaction (ORR) catalytic electrodes. NPG Asia Materials, 2019, 11(1): 57

    Article  Google Scholar 

  34. Ma R, Lin G, Zhou Y, et al. A review of oxygen reduction mechanisms for metal-free carbon-based electrocatalysts. npj Computational Materials, 2019, 5: 78

    Article  Google Scholar 

  35. Wang W, Jia Q Y, Mukerjee S, et al. Recent insights into the oxygen-reduction electrocatalysis of Fe/N/C materials. ACS Catalysis, 2019, 9(11): 10126–10141

    Article  Google Scholar 

  36. Lu Z Y, Chen G X, Siahrostami S, et al. High-efficiency oxygen reduction to hydrogen peroxide catalysed by oxidized carbon materials. Nature Catalysis, 2018, 1(2): 156–162

    Article  Google Scholar 

  37. Macauley N, Papadias D D, Fairweather J, et al. Carbon corrosion in PEM fuel cells and the development of accelerated stress tests. Journal of the Electrochemical Society, 2018, 165(6): F3148–F3160

    Article  Google Scholar 

  38. Chen L N, Yu W S, Wang T, et al. Fluorescence detection of hydroxyl radical generated from oxygen reduction on Fe/N/C catalyst. Science China. Chemistry, 2020, 63(2): 198–202

    Article  Google Scholar 

  39. Choi C H, Baldizzone C, Grote J P, et al. Stability of Fe-N-C catalysts in acidic medium studied by operando Spectroscopy. Angewandte Chemie International Edition, 2015, 54(43): 12753–12757

    Article  Google Scholar 

  40. Choi C H, Choi W S, Kasian O, et al. Unraveling the nature of sites active toward hydrogen peroxide reduction in Fe-N-C catalysts. Angewandte Chemie International Edition, 2017, 56(30): 8809–8812

    Article  Google Scholar 

  41. Cai R, Abdellaoui S, Kitt J P, et al. Confocal raman microscopy for the determination of protein and quaternary ammonium ion loadings in biocatalytic membranes for electrochemical energy conversion and storage. Analytical Chemistry, 2017, 89(24): 13290–13298

    Article  Google Scholar 

  42. Li J, Zhang H, Samarakoon W, et al. Thermally driven structure and performance evolution of atomically dispersed FeN4 sites for oxygen reduction. Angewandte Chemie International Edition, 2019, 58(52): 18971–18980

    Article  Google Scholar 

  43. Ren G Y, Gao L L, Teng C, et al. Ancient chemistry ‘Pharaoh’s Snakes’ for efficient Fe-/N-doped carbon electrocatalysts. ACS Applied Materials & Interfaces, 2018, 10(13): 10778–10785

    Article  Google Scholar 

Download references

Acknowledgements

The work was supported by the Thirteenth National Key Point Research and Invention Program (No. 2016YFB0101302).

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Ming Hou or Zhigang Shao.

Electronic Supplementary Material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Gao, Y., Hou, M., Qi, M. et al. New insight into effect of potential on degradation of Fe-N-C catalyst for ORR. Front. Energy 15, 421–430 (2021). https://doi.org/10.1007/s11708-021-0727-2

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11708-021-0727-2

Keywords

Navigation