Skip to main content
SpringerLink
Log in

Metal-Free Electrocatalysts for Oxygen Reduction

  • Chapter
  • First Online:
Electrocatalysis in Fuel Cells

Part of the book series: Lecture Notes in Energy ((LNEN,volume 9))

Abstract

Polymer electrolyte membrane (PEM) fuel cells are attracting much attention as promising clean alternative power sources to conventional power sources, including internal combustion engines and secondary batteries. Electrocatalysts for the oxygen reduction reaction (ORR) are a key component of PEM fuel cells, which convert chemical energy directly into electricity by coupling the ORR with the oxidation of fuel molecules at the other electrode via the diffusion of ions through the membrane. Although Pt-based ORR catalysts are given high priority in formulating electrodes for PEM fuel cells, they still suffer from multiple competitive disadvantages, including their high cost, susceptibility to CO gas poisoning, and fuel crossover effect. Due to their unique electrical and thermal properties, wide availability, environmental acceptability, corrosion resistance, and large surface area, certain carbon nanomaterials have recently been studied as metal-free ORR electrocatalysts to circumvent those issues associated with the Pt catalyst. Much effort has been devoted to developing metal-free ORR catalysts for fuel cells, which led to great advances in both fundamental and applied research. In this chapter, we present an overview on recent progresses in the development of metal-free ORR electrocatalysts for fuel cells.

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

Access this chapter

Log in via an institution
Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 169.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 219.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 219.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Borup R, Meyers J, Pivovar B, Kim YS, Mukundan R, Garland N, Myers D, Wilson M, Garzon F, Wood D, Zelenay P, More K, Stroh K, Zawodzinski T, Boncella J, McGrath JE, Inaba M, Miyatake K, Hori M, Ota K, Ogumi Z, Miyata S, Nishikata A, Siroma Z, Uchimoto Y, Yasuda K, Kimijima KI, Iwashita N (2007) Scientific aspects of polymer electrolyte fuel cell durability and degradation. Chem Rev 107(10):3904–3951

    Article  Google Scholar 

  2. Zhang S, Shao YY, Yin GP, Lin YH (2010) Electrostatic self-assembly of a Pt-around-Au nanocomposite with high activity towards formic acid oxidation. Angew Chem Int Ed 49(12): 2211–2214

    Article  Google Scholar 

  3. Wu G, More KL, Johnston CM, Zelenay P (2011) High-performance electrocatalysts for oxygen reduction derived from polyaniline, iron, and cobalt. Science 332(6028):443–447

    Article  Google Scholar 

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

    Article  Google Scholar 

  5. 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(5915):760–764

    Article  Google Scholar 

  6. Yu D, Nagelli E, Du F, Dai L (2010) Metal-free carbon nanomaterials become more active than metal catalysts and last longer. J Phys Chem Lett 1(14):2165–2173

    Article  Google Scholar 

  7. Dai L, Chang DW, Baek J-B, Lu W (2012) Carbon nanomaterials for advanced energy conversion and storage. Small 8(8):1130–1166

    Article  Google Scholar 

  8. Zhang S, Shao YY, Yin GP, Lin YH (2009) Stabilization of platinum nanoparticle electrocatalysts for oxygen reduction using poly(diallyldimethylammonium chloride). J Mater Chem 19(42):7995–8001

    Article  Google Scholar 

  9. Stamenkovic VR, Fowler B, Mun BS, Wang GF, Ross PN, Lucas CA, Markovic NM (2007) Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315(5811):493–497

    Article  Google Scholar 

  10. Chen Z, Higgins D, Yu A, Zhang L, Zhang J (2011) A review on non-precious metal electrocatalysts for PEM fuel cells. Energy Environ Sci 4(9):3167–3192

    Article  Google Scholar 

  11. Zhang S, Shao YY, Yin GP, Lin YH (2010) Carbon nanotubes decorated with Pt nanoparticles via electrostatic self-assembly: a highly active oxygen reduction electrocatalyst. J Mater Chem 20(14):2826–2830

    Article  Google Scholar 

  12. 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(10):780–786

    Article  Google Scholar 

  13. Zhang S, Shao Y, Yin G, Lin Y (2011) Self-assembly of Pt nanoparticles on highly graphitized carbon nanotubes as an excellent oxygen-reduction catalyst. Appl Catal B Environ 102(3–4): 372–377

    Article  Google Scholar 

  14. Shao YY, Yin GP, Wang HH, Gao YZ, Shi PF (2006) Multi-walled carbon nanotubes based Pt electrodes prepared with in situ ion exchange method for oxygen reduction. J Power Sources 161(1):47–53

    Article  Google Scholar 

  15. Wang C, Waje M, Wang X, Tang JM, Haddon RC, Yan YS (2004) Proton exchange membrane fuel cells with carbon nanotube based electrodes. Nano Lett 4(2):345–348

    Article  Google Scholar 

  16. Zhang S, Shao YY, Li XH, Nie ZM, Wang Y, Liu J, Yin GP, Lin YH (2010) Low-cost and durable catalyst support for fuel cells: graphite submicronparticles. J Power Sources 195(2): 457–460

    Article  Google Scholar 

  17. Geng D, Liu H, Chen Y, Li R, Sun X, Ye S, Knights S (2011) Non-noble metal oxygen reduction electrocatalysts based on carbon nanotubes with controlled nitrogen contents. J Power Sources 196(4):1795–1801

    Article  Google Scholar 

  18. Wang Z, Jia R, Zheng J, Zhao J, Li L, Song J, Zhu Z (2011) Nitrogen-promoted self-assembly of N-doped carbon nanotubes and their intrinsic catalysis for oxygen reduction in fuel cells. ACS Nano 5(3):1677–1684

    Article  Google Scholar 

  19. Xu X, Jiang S, Hu Z, Liu S (2010) Nitrogen-doped carbon nanotubes: high electrocatalytic activity toward the oxidation of hydrogen peroxide and its application for biosensing. ACS Nano 4(7):4292–4298

    Article  MathSciNet  Google Scholar 

  20. Shao Y, Sui J, Yin G, Gao Y (2008) Nitrogen-doped carbon nanostructures and their composites as catalytic materials for proton exchange membrane fuel cell. Appl Catal B Environ 79(1):89–99

    Article  Google Scholar 

  21. Jin C, Nagaiah TC, Xia W, Spliethoff B, Wang S, Bron M, Schuhmann W, Muhler M (2010) Metal-free and electrocatalytically active nitrogen-doped carbon nanotubes synthesized by coating with polyaniline. Nanoscale 2(6):981–987

    Article  Google Scholar 

  22. Maldonado S, Stevenson KJ (2005) Influence of nitrogen doping on oxygen reduction electrocatalysis at carbon nanofiber electrodes. J Phys Chem B 109(10):4707–4716

    Article  Google Scholar 

  23. Yang J, Liu D-J, Kariuki NN, Chen LX (2008) Aligned carbon nanotubes with built-in FeN4 active sites for electrocatalytic reduction of oxygen. Chem Commun 3:329–331

    Article  Google Scholar 

  24. Tang Y, Allen BL, Kauffman DR, Star A (2009) Electrocatalytic activity of nitrogen-doped carbon nanotube cups. J Am Chem Soc 131(37):13200–13201

    Article  Google Scholar 

  25. Yu D, Zhang Q, Dai L (2010) Highly efficient metal-free growth of nitrogen-doped single-walled carbon nanotubes on plasma-etched substrates for oxygen reduction. J Am Chem Soc 132(43):15127–15129

    Article  Google Scholar 

  26. Liu RL, Wu DQ, Feng XL, Mullen K (2010) Nitrogen-doped ordered mesoporous graphitic arrays with high electrocatalytic activity for oxygen reduction. Angew Chem Int Ed 49(14): 2565–2569

    Article  Google Scholar 

  27. Wang X, Lee JS, Zhu Q, Liu J, Wang Y, Dai S (2010) Ammonia-treated ordered mesoporous carbons as catalytic materials for oxygen reduction reaction. Chem Mater 22(7):2178–2180

    Article  Google Scholar 

  28. Chen Z, Higgins D, Tao H, Hsu RS, Chen Z (2009) Highly active nitrogen-doped carbon nanotubes for oxygen reduction reaction in fuel cell applications. J Phys Chem C 113(49):21008–21013

    Article  Google Scholar 

  29. Kundu S, Nagaiah TC, Xia W, Wang Y, Dommele SV, Bitter JH, Santa M, Grundmeier G, Bron M, Schuhmann W, Muhler M (2009) Electrocatalytic activity and stability of nitrogen-containing carbon nanotubes in the oxygen reduction reaction. J Phys Chem C 113(32): 14302–14310

    Article  Google Scholar 

  30. 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 Ed 50(31):7132–7135

    Article  Google Scholar 

  31. Liu Z, Peng F, Wang H, Yu H, Tan J, Zhu L (2011) Novel phosphorus-doped multiwalled nanotubes with high electrocatalytic activity for O2 reduction in alkaline medium. Catal Commun 16(1):35–38

    Article  Google Scholar 

  32. Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically thin carbon films. Science 306(5696): 666–669

    Article  Google Scholar 

  33. Li XL, Wang XR, Zhang L, Lee SW, Dai HJ (2008) Chemically derived, ultrasmooth graphene nanoribbon semiconductors. Science 319(5867):1229–1232

    Article  Google Scholar 

  34. Zhang S, Shao Y, Liao H, Engelhard MH, Yin G, Lin Y (2011) Polyelectrolyte-induced reduction of exfoliated graphite oxide: a facile route to synthesis of soluble graphene nanosheets. ACS Nano 5(3):1785–1791

    Article  Google Scholar 

  35. Kou R, Shao YY, Wang DH, Engelhard MH, Kwak JH, Wang J, Viswanathan VV, Wang CM, Lin YH, Wang Y, Aksay IA, Liu J (2009) Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction. Electrochem Commun 11(5):954–957

    Article  Google Scholar 

  36. Zhang S, Shao Y, Liao H-G, Liu J, Aksay IA, Yin G, Lin Y (2011) Graphene decorated with PtAu alloy nanoparticles: facile synthesis and promising application for formic acid oxidation. Chem Mater 23(5):1079–1081

    Article  Google Scholar 

  37. Qu LT, Liu Y, Baek JB, Dai LM (2010) Nitrogen-doped graphene as efficient metal-free electrocatalyst for oxygen reduction in fuel cells. ACS Nano 4(3):1321–1326

    Article  Google Scholar 

  38. Shao YY, Zhang S, Engelhard MH, Li GS, Shao GC, Wang Y, Liu J, Aksay IA, Lin YH (2010) Nitrogen-doped graphene and its electrochemical applications. J Mater Chem 20:7491–7496

    Article  Google Scholar 

  39. Choi E-K, Jeon I-Y, Bae S-Y, Lee H-J, Shin HS, Dai L, Baek J-B (2010) High-yield exfoliation of three-dimensional graphite into two-dimensional graphene-like sheets. Chem Commun 46(34):6320–6322

    Article  Google Scholar 

  40. Yang Z, Yao Z, Li G, Fang G, Nie H, Liu Z, Zhou X, Chen X, Huang S (2011) Sulfur-doped graphene as an efficient metal-free cathode catalyst for oxygen reduction. ACS Nano 6(1): 205–211

    Article  Google Scholar 

  41. Zhang L, Xia Z (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C 115(22):11170–11176

    Article  Google Scholar 

  42. Yao Z, Nie H, Yang Z, Zhou X, Liu Z, Huang S (2012) Catalyst-free synthesis of iodine-doped graphene via a facile thermal annealing process and its use for electrocatalytic oxygen reduction in an alkaline medium. Chem Commun 48(7):1027–1029

    Article  Google Scholar 

  43. Liu Z-W, Peng F, Wang H-J, Yu H, Zheng W-X, Yang J (2011) Phosphorus-doped graphite layers with high electrocatalytic activity for the O2 reduction in an alkaline medium. Angew Chem Int Ed 50(14):3257–3261

    Article  Google Scholar 

  44. Lyth SM, Nabae Y, Moriya S, Kuroki S, Kakimoto M-a, Ozaki J-i, Miyata S (2009) Carbon nitride as a nonprecious catalyst for electrochemical oxygen reduction. J Phys Chem C 113(47):20148–20151

    Article  Google Scholar 

  45. Zheng Y, Jiao Y, Chen J, Liu J, Liang J, Du A, Zhang W, Zhu Z, Smith SC, Jaroniec M, Lu GQ, Qiao SZ (2011) Nanoporous graphitic-C3N4@carbon metal-free electrocatalysts for highly efficient oxygen reduction. J Am Chem Soc 133(50):20116–20119

    Article  Google Scholar 

  46. Yang S, Feng X, Wang X, Müllen K (2011) Graphene-based carbon nitride nanosheets as efficient metal-free electrocatalysts for oxygen reduction reactions. Angew Chem Int Ed 50(23):5339–5343

    Article  Google Scholar 

  47. Sun Y, Li C, Xu Y, Bai H, Yao Z, Shi G (2010) Chemically converted graphene as substrate for immobilizing and enhancing the activity of a polymeric catalyst. Chem Commun 46(26): 4740–4742

    Article  Google Scholar 

  48. Liang J, Zheng Y, Chen J, Liu J, Hulicova-Jurcakova D, Jaroniec M, Qiao SZ (2012) Facile oxygen reduction on a three-dimensionally ordered macroporous graphitic C3N4/carbon composite electrocatalyst. Angew Chem Int Ed 51(16):3892–3896

    Article  Google Scholar 

  49. Wang S, Iyyamperumal E, Roy A, Xue Y, Yu D, Dai L (2011) Vertically aligned BCN nanotubes as efficient metal-free electrocatalysts for the oxygen reduction reaction: a synergetic effect by Co-doping with boron and nitrogen. Angew Chem Int Ed 50(49):11756–11760

    Article  Google Scholar 

  50. Wang S, Zhang L, Xia Z, Roy A, Chang DW, Baek J-B, Dai L (2012) BCN graphene as efficient metal-free electrocatalyst for the oxygen reduction reaction. Angew Chem Int Ed 51(17):4209–4212

    Article  Google Scholar 

  51. Wang S, Yu D, Dai L (2011) Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J Am Chem Soc 133(14):5182–5185

    Article  Google Scholar 

  52. Wang S, Yu D, Dai L, Chang DW, Baek J-B (2011) Polyelectrolyte-functionalized graphene as metal-free electrocatalysts for oxygen reduction. ACS Nano 5(8):6202–6209

    Article  Google Scholar 

  53. Sidik RA, Anderson AB, Subramanian NP, Kumaraguru SP, Popov BN (2006) O2 reduction on graphite and nitrogen-doped graphite: experiment and theory. J Phys Chem B 110(4): 1787–1793

    Article  Google Scholar 

Download references

Acknowledgments

The author is grateful for the financial support from NSF, NSF-NSFC, AFOSR, DoD-MURI, DoD-Army, DOE, AFOSR-Korea NBIT, and UNIST-WCU and would also like to thank colleagues and collaborators for their work cited in this article.

Author information

Authors and Affiliations

  1. Department of Macromolecular Science and Engineering, Case School of Engineering, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH, 44106, USA

    Sheng Zhang & Liming Dai

  2. San Jose Lab, Corporate Research Institute, Samsung Cheil Industries Inc., San Jose, 95131, California, USA

    Kuanping Gong

Authors
  1. Sheng Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Kuanping Gong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Liming Dai
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Liming Dai .

Editor information

Editors and Affiliations

  1. UTC Power, Governor’s Highway 195, South Windsor, 06074, Connecticut, USA

    Minhua Shao

Rights and permissions

Reprints and permissions

Copyright information

© 2013 Springer-Verlag London

About this chapter

Cite this chapter

Zhang, S., Gong, K., Dai, L. (2013). Metal-Free Electrocatalysts for Oxygen Reduction. In: Shao, M. (eds) Electrocatalysis in Fuel Cells. Lecture Notes in Energy, vol 9. Springer, London. https://doi.org/10.1007/978-1-4471-4911-8_12

Download citation

  • DOI: https://doi.org/10.1007/978-1-4471-4911-8_12

  • Published:

  • Publisher Name: Springer, London

  • Print ISBN: 978-1-4471-4910-1

  • Online ISBN: 978-1-4471-4911-8

  • eBook Packages: EnergyEnergy (R0)

Publish with us

Policies and ethics

Search

Navigation