Skip to main content
SpringerLink
Log in

Developments in Electrocatalysts for Oxygen Reduction and Ethanol Oxidation

  • Chapter
  • First Online:
Nanoenergy

  • 1071 Accesses

Abstract

In this chapter, we review the development of electrocatalysts for electrochemical reactions that take place in low-temperature fuel cells. It is focused on the oxygen reduction reaction (ORR), and on the ethanol oxidation reaction (EOR) for proton exchange membrane fuel cells. In the case of the ORR, which is the bottleneck in the development of fuel cells, the major problem is the low platinum mass activity and its low long-term stability. For the ORR, it is reviewed the research activities of two new classes of electrocatalysts: (i) composed by platinum sub-monolayer deposited on metal nanoparticles, for which it is presented the activity—Pt d-band center correlations, and stability tests and; (ii) composed by nitrogen-coordinated iron–carbon nanostructures. In the second case, it is presented the last steps toward the understanding of the factors that govern their electrocatalytic activity and stability and, so, allowing the development of low-cost materials. For the ethanol electrochemical oxidation, it is showed the important parameters that permit high faradaic efficiency for CO2, formation on Pt-based electrocatalysts, which will serve as a guide for the next steps in the development of ethanol-powered 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 129.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 169.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 169.99
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. Yeager E (1984) Electrocatalysts for O2 reduction. Electrochim Acta 29(11):1527–1537

    Article  Google Scholar 

  2. Kinoshita K (1992) Electrochemical oxygen technology. Wiley-Interscience, New York, p 431

    Google Scholar 

  3. Adzic R (1998) Recent advances in the kinetics of oxygen reduction. In: Lipkowski J, Ross PN (eds) Electrocatalysis, vol 197. Wiley-VCH, New York

    Google Scholar 

  4. Zhang J, Vukmirovic MB, Xu Y, Mavrikakis M, Adzic RR (2005) Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. Angew Chem Int Ed 44:2132–2135

    Article  Google Scholar 

  5. Lima F, Zhang J, Shao M, Sasaki K, Vukmirovic M, Ticianelli E, Adzic R (2007) Catalytic activity-d-band center correlation for the O2 reduction reaction on platinum in alkaline solutions. J Phys Chem C 111(1):404–410

    Article  Google Scholar 

  6. Hammer B, Nørskov JK (2000) Theoretical surface science and catalysis–calculations and concepts. Adv Catal 45:71–129

    Google Scholar 

  7. Greeley J, Nørskov JK, Mavrikakis M (2002) Electronic structure and catalysis on metal surfaces. Annu Rev Phys Chem 53(1):319–348

    Article  Google Scholar 

  8. Mukerjee S, Srinivasan S, Soriaga MP, McBreen J (1995) Effect of preparation conditions of Pt alloys on their electronic, structural, and electrocatalytic activities for oxygen reduction-XRD, XAS, and electrochemical studies. J Phys Chem 99(13):4577–4589

    Article  Google Scholar 

  9. Lima FHB, Ticianelli EA (2004) Oxygen electrocatalysis on ultra-thin porous coating rotating ring/disk platinum and platinum-cobalt electrodes in alkaline media. Electrochim Acta 49(24):4091–4099

    Article  Google Scholar 

  10. Brankovic S, Wang J, Adzic R (2001) Pt submonolayers on Ru nanoparticles: a novel low Pt loading, high CO tolerance fuel cell electrocatalyst. Electrochem Solid-State Lett 4:A217

    Article  Google Scholar 

  11. Adzic RR, Zhang J, Sasaki K, Vukmirovic MB, Shao M, Wang J, Nilekar AU, Mavrikakis M, Valerio J, Uribe F (2007) Platinum monolayer fuel cell electrocatalysts. Top Catal 46(3):249–262

    Article  Google Scholar 

  12. Zhang J, Mo Y, Vukmirovic M, Klie R, Sasaki K, Adzic R (2004) Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd (111) and on carbon-supported Pd nanoparticles. J Phys Chem B 108(30):10955–10964

    Article  Google Scholar 

  13. Kitchin JR, Nørskov JK, Barteau MA, Chen J (2004) Role of strain and ligand effects in the modification of the electronic and chemical properties of bimetallic surfaces. Phys Rev Lett 93(15):156801

    Article  Google Scholar 

  14. Stamenkovic V, Mun BS, Mayrhofer KJJ, Ross PN, Markovic NM, Rossmeisl J, Greeley J, Nørskov JK (2006) Changing the activity of electrocatalysts for oxygen reduction by tuning the surface electronic structure. Angew Chem 118(18):2963–2967

    Article  Google Scholar 

  15. Ruban A, Skriver HL, Nørskov JK (1999) Surface segregation energies in transition-metal alloys. Phys Rev B 59(24):15990

    Article  Google Scholar 

  16. Bardi U, Atrei A, Zanazzi E, Rovida G, Ross P (1990) Study of the reconstructed (001) surface of the Pt80Co20 alloy. Vacuum 41(1–3):437–440

    Article  Google Scholar 

  17. Mun BS, Watanabe M, Rossi M, Stamenkovic V, Markovic NM, Ross PN Jr (2005) A study of electronic structures of Pt3M (M = Ti,V,Cr,Fe,Co,Ni) polycrystalline alloys with valence-band photoemission spectroscopy. J Chem Phys 123:204717

    Google Scholar 

  18. Markovic N, Gasteiger H, Grgur B, Ross P (1999) Oxygen reduction reaction on Pt (111): effects of bromide. J Electroanal Chem 467(1–2):157–163

    Article  Google Scholar 

  19. Somorjai GA, Li Y (2010) Introduction to surface chemistry and catalysis. Wiley, New York

    Google Scholar 

  20. Chorkendorff I, Niemantsverdriet JW, Wiley J (2003) Concepts of modern catalysis and kinetics, vol 138. Wiley Online Library, Weinheim

    Google Scholar 

  21. Nørskov JK, Bligaard T, Logadottir A, Bahn S, Hansen LB, Bollinger M, Bengaard H, Hammer B, Sljivancanin Z, Mavrikakis M (2002) Universality in heterogeneous catalysis. J Catal 209(2):275–278

    Article  Google Scholar 

  22. Clouser S, Huang J, Yeager E (1993) Temperature dependence of the Tafel slope for oxygen reduction on platinum in concentrated phosphoric acid. J Appl Electrochem 23(6):597–605

    Article  Google Scholar 

  23. Yeager E, Gervasio D, Razaq M, Razaq A, Tryk D (1993) Dioxygen reduction in various acid electrolytes. Serb J Chem Soc 57:819

    Google Scholar 

  24. Sidik RA, Anderson AB (2002) Density functional theory study of O2 electroreduction when bonded to a Pt dual site. J Electroanal Chem 528(1–2):69–76

    Article  Google Scholar 

  25. Sasaki K, Wang J, Balasubramanian M, McBreen J, Uribe F, Adzic R (2004) Ultra-low platinum content fuel cell anode electrocatalyst with a long-term performance stability. Electrochim Acta 49(22–23):3873–3877

    Article  Google Scholar 

  26. Gong K, Su D, Adzic RR (2010) Platinum-monolayer shell on AuNi0.5Fe nanoparticle core electrocatalyst with high activity and stability for the oxygen reduction reaction. J Am Chem Soc 845–910

    Google Scholar 

  27. Lima FHB, Zhang J, Shao M, Sasaki K, Vukmirovic M, Ticianelli E, Adzic R (2008) Pt monolayer electrocatalysts for O2 reduction: PdCo/C substrate-induced activity in alkaline media. J Solid State Electrochem 12(4):399–407

    Article  Google Scholar 

  28. Lima F, De Castro J, Santos L, Ticianelli E (2009) Electrocatalysis of oxygen reduction on carbon-supported Pt-Co nanoparticles with low Pt content. J Power Sources 190(2):293–300

    Article  Google Scholar 

  29. Obradovic M, Grgur B, Vracar LM (2003) Adsorption of oxygen containing species and their effect on oxygen reduction on Pt3Co electrode. J Electroanal Chem 548:69–78

    Article  Google Scholar 

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

    Article  Google Scholar 

  31. Xing Y, Cai Y, Vukmirovic MB, Zhou WP, Karan H, Wang JX, Adzic RR (2010) Enhancing oxygen reduction reaction activity via Pd–Au alloy sublayer mediation of Pt monolayer electrocatalysts. J Phys Chem Lett 1:3238–3242

    Google Scholar 

  32. Wang C, van der Vliet D, More KL, Zaluzec NJ, Peng S, Sun S, Daimon H, Wang G, Greeley J, Pearson J Multimetallic Au/FePt3 nanoparticles as highly durable electrocatalyst. Nano Lett 4–107. doi:10.1021/nl102369k

  33. Jasinski R (1964) A new fuel cell cathode catalyst. Nature 201:1212

    Article  Google Scholar 

  34. Jahnke H, Schönborn M, Zimmermann G (1976) Organic dyestuffs as catalysts for fuel cells. In: Boschke FL (ed) 61 topics in current chemistry—physical and chemical applications of dyestuffs. Springer, Berlin, pp 133–188

    Chapter  Google Scholar 

  35. Gupta S, Tryk D, Bae I, Aldred W, Yeager E (1989) Heat-treated polyacrylonitrile-based catalysts for oxygen electroreduction. J Appl Electrochem 19:19–27

    Article  Google Scholar 

  36. Wu G, Santandreu A, Kellogg W, Gupta S, Ogoke O, Zhang H, Wang H-L, Dai L (2016) Carbon nanocomposite catalysts for oxygen reduction and evolution reactions: from nitrogen doping to transitionmetal addition. Nano Energy 29:83–110

    Article  Google Scholar 

  37. Choi CH, Baldizzone C, Grote J-P, Schuppert AK, Jaouen F, Mayrhofer KJJ (2015) Stability of Fe-N-C catalysts in acidic medium studied by operando spectroscopy. Angew Chem Int Ed 54:12753–12757

    Article  Google Scholar 

  38. Lalande G, Faubert G, Cote R, Guay D, Dodelet JP, Weng LT, Bertrand P (1996) Catalytic activity and stability of heat-treated iron phthalocyanines for the electroreduction of oxygen in polymer electrolyte fuel cells. J Power Sources 61:227

    Article  Google Scholar 

  39. Miller HA, Bellini M, Oberhauser W, Deng X, Chen H, He Q, Passaponti M, Innocenti M, Yang R, Sun F, Jiang Z, Vizza F (2016) Heat treated carbon supported iron(ii) phthalocyanine oxygen reduction catalysts: elucidation of the structure-activity relationship using X-ray absorption spectroscopy. Phys Chem Chem Phys 18:33142–33151

    Article  Google Scholar 

  40. Strickland K, Miner E, Jia Q, Tylus U, Ramaswamy N, Liang W, Sougrati M-T, Jaouen F, Mukerjee S (2015) Highly active oxygen reduction non-platinum group metal electrocatalyst without direct metalnitrogen coordination. Nat Commun 6:7343

    Article  Google Scholar 

  41. Varnell JA, Tse ECM, Schulz CE, Fister TT, Haasch RT, Timoshenko J, Frenkel AI, Gewirth AA (2016) Identification of carbon-encapsulated iron nanoparticles as active species in non-precious metal oxygen reduction catalysts. Nat Commun 7:12582

    Article  Google Scholar 

  42. Noh SH, Seo MH, Kang J, Okajima T, Han B, Ohsaka T (2016) Towards a comprehensive understanding of FeCo coated with N-doped carbon as a stable bi-functional catalyst in acidic media. NPG Asia Mater 8:e312

    Article  Google Scholar 

  43. Lamy C, Lima A, LeRhun V, Delime F, Coutanceau C, Leger JM (2002) Recent advances in the development of direct alcohol fuel cells (DAFC). J Power Sources 105(2):283–296

    Article  Google Scholar 

  44. Iwasita T, Nart F (1997) In situ infrared spectroscopy at electrochemical interfaces. Prog Surf Sci 55(4):271–340

    Article  Google Scholar 

  45. De Souza J, Queiroz S, Bergamaski K, Gonzalez E, Nart F (2002) Electro-oxidation of ethanol on Pt, Rh, and PtRh electrodes. A study using DEMS and in-situ FTIR techniques. J Phys Chem B 106(38):9825–9830

    Article  Google Scholar 

  46. Kowal A, Li M, Shao M, Sasaki K, Vukmirovic M, Zhang J, Marinkovic N, Liu P, Frenkel A, Adzic R (2009) Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nat Mater 8(4):325–330

    Article  Google Scholar 

  47. Iwasita T, Pastor E (1994) A DEMS and FTIR spectroscopic investigation of adsorbed ethanol on polycrystalline platinum. Electrochim Acta 39(4):531–537

    Article  Google Scholar 

  48. Xia X, Liess HD, Iwasita T (1997) Early stages in the oxidation of ethanol at low index single crystal platinum electrodes. J Electroanal Chem 437(1–2):233–240

    Article  Google Scholar 

  49. Souza JPI, Queiroz SL, Nart FC (2000) The use of mass spectrometry in electrochemical measurements-the DEMS technique. Quím Nova 23(3):384–391

    Article  Google Scholar 

  50. Jiang L, Colmenares L, Jusys Z, Sun G, Behm R (2007) Ethanol electro-oxidation on novel carbon supported Pt/SnOx/C catalysts with varied Pt: Sn ratio. Electrochim Acta 53(2):377–389

    Article  Google Scholar 

  51. Colmati F, Tremiliosi-Filho G, Gonzalez ER, Berná A, Herrero E, Feliu JM (2009) The role of the steps in the cleavage of the C–C bond during ethanol oxidation on platinum electrodes. Phys Chem Chem Phys 11(40):9114–9123

    Article  Google Scholar 

  52. Gao P, Chang SC, Zhou Z (1989) Electro-oxidation pathways of simple alcohols at platinum in pure nonaqueous and concentrated aqueous environments as studied by real-time FTIR spectroscopy. J Electroanal Chem 272(1–2):161–178

    Article  Google Scholar 

  53. Leung LWH, Chang SC, Weaver MJ (1989) Real-time FTIR spectroscopy as an electrochemical mechanistic probe: Electro-oxidation of ethanol and related species on well-defined Pt (111) surfaces. J Electroanal Chem 266(2):317–336

    Article  Google Scholar 

  54. Bruckenstein S, Gadde RR (1971) Use of a porous electrode for in situ mass spectrometric determination of volatile electrode reaction products. J Am Chem Soc 93:793–794

    Article  Google Scholar 

  55. Colmati F, Tremiliosi-Filho G, Gonzalez ER, Berná A, Herrero E, Feliu JM (2008) Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes. Faraday Discuss 140:379–397

    Article  Google Scholar 

  56. Cantane DA, Gonzalez E (2009) Mechanistic aspects of ethanol electro-oxidation in unsupported platinum nanoparticles. ECS Trans 25:1161–1168

    Article  Google Scholar 

  57. Giz M, Camara G (2009) The ethanol electro-oxidation reaction at Pt (1 1 1): the effect of ethanol concentration. J Electroanal Chem 625(2):117–122

    Article  Google Scholar 

  58. Camara G, Iwasita T (2005) Parallel pathways of ethanol oxidation: the effect of ethanol concentration. J Electroanal Chem 578(2):315–321

    Article  Google Scholar 

  59. Lai SCS, Koper MTM (2008) Electro-oxidation of ethanol and acetaldehyde on platinum single-crystal electrodes. Faraday Discuss 140:399–416

    Article  Google Scholar 

  60. Sun S, Halseid MC, Heinen M, Jusys Z, Behm R (2009) Ethanol electro-oxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: a high-temperature/high-pressure DEMS study. J Power Sources 190(1):2–13

    Article  Google Scholar 

  61. Adzic R, Li M, Kowal A, Sasaki K, Marinkovic N, Su D, Korach E, Liu P (2010) Ethanol oxidation on the ternary Pt–Rh–SnO2/C electrocatalysts with varied Pt: Rh: Sn ratios. Electrochim Acta 55 (BNL–93871-2010-JA)

    Google Scholar 

  62. Lima F, Gonzalez E (2008) Ethanol electro-oxidation on carbon-supported Pt-Ru, Pt-Rh and Pt-Ru-Rh nanoparticles. Electrochim Acta 53(6):2963–2971

    Article  Google Scholar 

  63. Camara G, De Lima R, Iwasita T (2005) The influence of PtRu atomic composition on the yields of ethanol oxidation: a study by in situ FTIR spectroscopy. J Electroanal Chem 585(1):128–131

    Article  Google Scholar 

  64. Lima F, Profeti D, Lizcano-Valbuena W, Ticianelli E, Gonzalez E (2008) Carbon-dispersed Pt-Rh nanoparticles for ethanol electro-oxidation. Effect of the crystallite size and of temperature. J Electroanal Chem 617(2):121–129

    Article  Google Scholar 

  65. Houtman C, Barteau M (1991) Divergent pathways of acetaldehyde and ethanol decarbonylation on the Rh (111) surface. J Catal 130(2):528–546

    Article  Google Scholar 

  66. Sasaki K, Wang J, Balasubramanian M, McBreen J, Uribe F, Adzic R (2004) Ultra-low platinum content fuel cell anode electrocatalyst with a long-term performance stability. Electrochim Acta 49(22–23):3873–3877

    Article  Google Scholar 

  67. Kristian N, Wang X (2008) Ptshell-Aucore/C electrocatalyst with a controlled shell thickness and improved Pt utilization for fuel cell reactions. Electrochem Commun 10(1):12–15

    Article  Google Scholar 

  68. Shao M, Sasaki K, Marinkovic NS, Zhang L, Adzic RR (2007) Synthesis and characterization of platinum monolayer oxygen-reduction electrocatalysts with Co-Pd core-shell nanoparticle supports. Electrochem Commun 9(12):2848–2853

    Article  Google Scholar 

  69. Colmati F, Antolini E, Gonzalez E (2008) Effect of thermal treatment on phase composition and ethanol oxidation activity of a carbon supported Pt50Sn50 alloy catalyst. J Solid State Electrochem 12(5):591–599

    Article  Google Scholar 

  70. Lima FHB, Profeti D, Chatenet M, Riello D, Ticianelli E, Gonzalez E (2010) Electro-oxidation of ethanol on Rh/Pt and Ru/Rh/Pt sub-monolayers deposited on Au/C nanoparticles. Electrocatalysis 1(1):72–82

    Article  Google Scholar 

Download references

Acknowledgements

N.A. Galiote, F.E.E. Oliveira, D.A. Cantane, and F.H.B. Lima acknowledge financial support from Fundação de Amparo à Pesquisa do Estado de São Paulo, FAPESP, and Conselho Nacional de Desenvolvimento Científico e Tecnológico, CNPq, Brazil.

Author information

Authors and Affiliations

  1. Institute of Chemistry of Sao Carlos, University of Sao Paulo, Sao Paulo, Brazil

    Fabio H. B. Lima, F. E. R. Oliveira & Nelson A. Galiote

  2. Battery Laboratory, Itaipu Technological Park, Foz de Iguaçu, Brazil

    Daniel A. Cantane

Authors
  1. Fabio H. B. Lima
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Daniel A. Cantane
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. E. R. Oliveira
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Nelson A. Galiote
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Fabio H. B. Lima .

Editor information

Editors and Affiliations

  1. Universidade Federal do ABC /Santo André , Santo André, Brazil

    Flavio L Souza

  2. Federal Univ Sao Carlos , Sao Carlos, São Paulo, Brazil

    Edson R Leite

Rights and permissions

Reprints and permissions

Copyright information

© 2018 Springer International Publishing AG

About this chapter

Cite this chapter

Lima, F.H.B., Cantane, D.A., Oliveira, F.E.R., Galiote, N.A. (2018). Developments in Electrocatalysts for Oxygen Reduction and Ethanol Oxidation. In: Souza, F., Leite, E. (eds) Nanoenergy. Springer, Cham. https://doi.org/10.1007/978-3-319-62800-4_6

Download citation

Publish with us

Policies and ethics

Search

Navigation