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Nanostrutured Electrocatalysts for Methanol and Ethanol-Tolerant Cathodes

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Direct Alcohol Fuel Cells

Abstract

Polymer electrolyte membrane fuel cells (PEMFC) that use small organic molecules like methanol and ethanol as fuel in the anode, and oxygen in the cathode, are attracting considerable interest for application in portable electronic devices. Carbon-supported platinum has the highest catalytic activity for oxygen reduction when compared to all other pure metals, and serves as state-of-the-art cathode material in low-temperature fuel cells. Regarding the direct methanol or ethanol fuel cells (DMFC or DEFC), one of the major problems is the alcohol crossover through the polymer electrolyte. The mixed potential, which results from the oxygen reduction reaction and the alcohol oxidation occurring simultaneously, reduces the cell voltage, generates additional water and increases the required oxygen stoichiometric ratio. This problem can be, in principle, solved either by using electrolytes with lower methanol or ethanol permeability or by developing new cathode electrocatalysts with both higher alcohol tolerance and higher activity for the oxygen reduction reaction than Pt. This chapter presents an overview of recent developments of platinum and non-platinum-based catalysts as methanol and ethanol-tolerant oxygen reduction materials for direct alcohol fuel cells.

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References

  1. Vielstich W, Gasteiger HA, Lamm A (2003) Handbook of fuel cells – fundamentals, technology and applications. Wiley, Chichester

    Google Scholar 

  2. Vielstich W, Paganin VA, Lima FHB, Ticianelli EA (2001) Nonelectrochemical pathway of methanol oxidation at a platinum-catalyzed oxygen gas diffusion electrode. J Electrochem Soc 148:A502–A505

    Article  CAS  Google Scholar 

  3. Sun S, Chojak Halseid M, Heinen M, Jusys Z, Behm RJ (2009) Ethanol electrooxidation on a carbon-supported Pt catalyst at elevated temperature and pressure: a high-temperature/high-pressure DEMS study. J Power Sources 190:2–13

    Article  CAS  Google Scholar 

  4. Yeager E (1984) Electrocatalysts for O2 reduction. Electrochim Acta 29:1527–1537

    Article  CAS  Google Scholar 

  5. Kinoshita K (1992) Electrochemical oxygen technology. Wiley-Interscience, New York

    Google Scholar 

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

    Google Scholar 

  7. 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  CAS  Google Scholar 

  8. 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 111:404–410

    Article  CAS  Google Scholar 

  9. 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 118:2963–2967

    Article  Google Scholar 

  10. 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 99:4577–4589

    Article  CAS  Google Scholar 

  11. 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 49:4091–4099

    Article  CAS  Google Scholar 

  12. 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. Topics Catal 46:249–262

    Article  CAS  Google Scholar 

  13. 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 108:10955–10964

    Article  CAS  Google Scholar 

  14. 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–A220

    Article  CAS  Google Scholar 

  15. 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 93:156801–156804

    Article  CAS  Google Scholar 

  16. Ruban A, Skriver HL, Nørskov JK (1999) Surface segregation energies in transition-metal alloys. Phys Rev B 59:15990–16000

    Article  Google Scholar 

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

    Article  CAS  Google Scholar 

  18. Mun BS, Lee C, Stamenkovic V, Markovic NM, Ross PN Jr (2005) Electronic structure of Pd thin films on Re (0001) studied by high-resolution core-level and valence-band photoemission. Phys Rev B 71:115420–115426

    Article  Google Scholar 

  19. 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 49:3873–3877

    Article  CAS  Google Scholar 

  20. Batista EA, Malpass GRP, Motheo AJ, Iwasita T (2003) New insight into the pathways of methanol oxidation. Electrochem Commun 5:843–846

    Article  CAS  Google Scholar 

  21. Batista EA, Malpass GRP, Motheo AJ, Iwasita T (2004) New mechanistic aspects of methanol oxidation. J Electroanal Chem 571:273–282

    Article  CAS  Google Scholar 

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

    Article  CAS  Google Scholar 

  23. Oh J-G, Kim H (2008) Synthesis and characterization of PtNx/C as methanol-tolerant oxygen reduction electrocatalysts for a direct methanol fuel cell. J Power Sources 181:74–78

    Article  CAS  Google Scholar 

  24. Wen Z, Liu J, Li J (2008) Core/Shell Pt/C nanoparticles embedded in mesoporous carbons a methanol-tolerant cathode catalyst in direct methanol fuel cells. Adv Mater 20:743–747

    Article  CAS  Google Scholar 

  25. Dubau L, Durst J, Maillard F, Guetaz L, Chatenet M, Andre J, Rossinot E (2011) Further insights into the durability of Pt3Co/C electrocatalysts: formation of “hollow” Pt nano particles induced by the Kirkendall effect. Electrochim Acta 56:10658–10667

    Article  CAS  Google Scholar 

  26. Wang W, Huang Q, Liu J, Zou Z, Zhao M, Vogel W, Yang H (2009) Surface and structure characteristics of carbon-supported Pd3Pt1 bimetallic nanoparticles for methanol-tolerant oxygen reduction reaction. J Catal 266:156–163

    Article  CAS  Google Scholar 

  27. Selvarani G, Vinod Selvaganesh S, Krishnamurthy S, Kiruthika GVM, Sridhar S, Pitchumani S, Shukla AK (2009) Methanol-tolerant carbon-supported Pt-Au alloy cathode catalyst for direct methanol fuel cells and its evaluation by DFT. J Phys Chem C 113:7461–7468

    Article  CAS  Google Scholar 

  28. Tsivadze AY, Tarasevich MR, Kuzov AV, Romanova IA, Pripadchev DA (2008) New nanosized cathode electrocatalysts tolerant to ethanol. Doklady Phys Chem 421:166–169

    Article  CAS  Google Scholar 

  29. Li X, Huang Q, Zou Z, Xia B, Yang H (2008) Low temperature preparation of carbon-supported Pd Co alloy electrocatalysts for methanol-tolerant oxygen reduction reaction. Electrochim Acta 53:6662–6667

    Article  CAS  Google Scholar 

  30. Mathiyarasu J, Phani KLN (2007) Carbon-supported palladium-cobalt-noble metal (Au, Ag, Pt) nanocatalysts as methanol tolerant oxygen-reduction cathode materials in DMFCs. J Electrochem Soc 154:B1100–B1105

    Article  CAS  Google Scholar 

  31. Papageorgopoulos DC, Liu F, Conrad O (2007) Reprint of “A study of RhxSy/C and RuSex/C as methanol-tolerant oxygen reduction catalysts for mixed-reactant fuel cell applications”. Electrochim Acta 53:1037–1041

    Article  CAS  Google Scholar 

  32. Savadogo O, Rodríguez Varela FJ (2006) Palladium-alloy catalysts as ethanol tolerant cathodes for direct alcohol fuel cell (DEFC) applications. ECS Trans 1(6):247–254

    Article  CAS  Google Scholar 

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Acknowledgments

E. A. Ticianelli and F. H. B. Lima acknowledge support from Fundação de Amparo à Pesquisa do Estado de São Paulo – FAPESP, Brazil.

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Correspondence to Edson A. Ticianelli .

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Ticianelli, E.A., Lima, F.H.B. (2014). Nanostrutured Electrocatalysts for Methanol and Ethanol-Tolerant Cathodes. In: Corti, H., Gonzalez, E. (eds) Direct Alcohol Fuel Cells. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-7708-8_5

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