Journal of Solid State Electrochemistry

, Volume 22, Issue 5, pp 1525–1537 | Cite as

Activity, mechanism, and short-term stability evaluation of PtSn-rare earth/C electrocatalysts for the ethanol oxidation reaction

  • Patricia Gon Corradini
  • Joelma Perez
Original Paper


Rare earths (RE) have been studied in the literature as additives in Pt and PtSn catalysts for the ethanol oxidation reaction (EOR), but their stability and influence on the mechanism of the EOR have not been reported. In this work, PtSnRE/C (RE: La, Ce, and Pr) catalysts were obtained by the polyol method, characterized, and their stability toward the EOR evaluated by cycling at two different potential ranges. The accelerated aging tests indicated that despite the changes in the CO stripping profiles, the ternary catalysts exhibit higher current densities after aging than Pt/C and PtSn/C catalysts. Even after dissolution of the rare-earth metals, as observed by energy-dispersive X-ray spectroscopy (EDS) before and after aging, the EOR activity after short-term stability tests was found to be higher than the initial one. The addition of these metals facilitates the retention of tin in the material, contributing to the overall stability of the bimetallic catalyst. The oxidation products of the ternary catalysts were evaluated by in situ Fourier transform infrared spectroscopy (FTIR) spectroscopy and high-performance liquid chromatography (HPLC), where the major products were found to be acetaldehyde and acetic acid, with only small concentrations of CO2. The improvement in the ethanol oxidation efficiency by PtSnRE/C catalysts can be explained by a bifunctional mechanism in which the rare-earth oxides are able to provide oxygenated species at low potentials.


Rare earths Platinum Tin Ethanol oxidation reaction Short-term stability 



The authors thank the São Paulo Research Foundation (FAPESP) for the resources (2013/16930-7) and for the fellowships granted (2012/12189-8; 2015/13218-0).

Funding information

FAPESP grant #2013/16930-7, #2012/12189-8; and #2015/13218-0.

Supplementary material

10008_2017_3793_MOESM1_ESM.docx (141 kb)
ESM 1 (DOCX 140 kb)


  1. 1.
    Badwal SPS, Giddey S, Kulkarni A, Goel J, Basu S (2015) Direct ethanol fuel cells for transport and stationary applications—a comprehensive review. Appl Energ 145:80–103CrossRefGoogle Scholar
  2. 2.
    Abdullah S, Kamarudin SK, Hasran UA, Masdar MS, Daud WRW (2014) Modeling and simulation of a direct ethanol fuel cell: an overview. J Power Sources 262:401–406CrossRefGoogle Scholar
  3. 3.
    Zhang SS, Yuan XZ, Hin JNC, Wang HJ, Friedrich KA, Schulze M (2009) A review of platinum-based catalyst layer degradation in proton exchange membrane fuel cells. J Power Sources 194(2):588–600CrossRefGoogle Scholar
  4. 4.
    Speder J, Zana A, Spanos I, Kirkensgaard JJK, Mortensen K, Hanzlik M, Arenz M (2014) Comparative degradation study of carbon supported proton exchange membrane fuel cell electrocatalysts—the influence of the platinum to carbon ratio on the degradation rate. J Power Sources 261:14–22CrossRefGoogle Scholar
  5. 5.
    Li YS, Zhao TS (2012) Understanding the performance degradation of anion-exchange membrane direct ethanol fuel cells. Int J Hydrogen Energ 37(5):4413–4421CrossRefGoogle Scholar
  6. 6.
    Linse N, Scherer GG, Wokaun A, Gubler L (2012) Quantitative analysis of carbon corrosion during fuel cell start-up and shut-down by anode purging. J Power Sources 219:240–248CrossRefGoogle Scholar
  7. 7.
    Park YC, Kakinuma K, Uchida M, Tryk DA, Kamino T, Uchida H, Watanabe M (2013) Investigation of the corrosion of carbon supports in polymer electrolyte fuel cells using simulated start-up/shutdown cycling. Electrochim Acta 91:195–207CrossRefGoogle Scholar
  8. 8.
    Nikkuni FR, Vion-Dury B, Dubau L, Maillard F, Ticianelli EA, Chatenet M (2014) The role of water in the degradation of Pt3Co/C nanoparticles: an identical location transmission electron microscopy study in polymer electrolyte environment. Appl Catal B-Environ 156:301–306CrossRefGoogle Scholar
  9. 9.
    Cherevko S, Kulyk N, Mayrhofer KJJ (2016) Durability of platinum-based fuel cell electrocatalysts: dissolution of bulk and nanoscale platinum. Nano Energy 29:275–298CrossRefGoogle Scholar
  10. 10.
    Jung DH, Bae SJ, Kim SJ, Nahm KS, Kim P (2011) Effect of the Pt precursor On the morphology and catalytic performance of Pt-impregnated on Pd/C for the oxygen reduction reaction in polymer electrolyte fuel cells. Int J Hydrogen Energ 36(15):9115–9122CrossRefGoogle Scholar
  11. 11.
    Zignani SC, Baglio V, Linares JJ, Monforte G, Gonzalez ER, Aricò AS (2013) Endurance study of a solid polymer electrolyte direct ethanol fuel cell based on a Pt–Sn anode catalyst. Int J Hydrogen Energ 38(26):11576–11582CrossRefGoogle Scholar
  12. 12.
    Hsieh CT, Liu YY, Chen WY, Hsieh YH (2011) Electrochemical activity and durability of Pt-Sn alloys on carbon-based electrodes prepared by microwave-assisted synthesis. Int J Hydrogen Energ 36(24):15766–15774CrossRefGoogle Scholar
  13. 13.
    Tang ZC, GX L (2006) High performance rare earth oxides LnO(x) (Ln = Sc, Y, La, Ce, Pr and Nd) modified Pt/C electrocatalysts for methanol electrooxidation. J Power Sources 162(2):1067–1072CrossRefGoogle Scholar
  14. 14.
    Oliveira Neto A, Watanabe AY, Rodrigues RMD, Linardi M, Forbicini CALGO, Spinace EV (2008) Electrooxidation of ethanol using Pt rare earth-C electrocatalysts prepared by an alcohol reduction process. Ionics 14(6):577–581CrossRefGoogle Scholar
  15. 15.
    Corradini PG, Santos NA, Silva GC, Perez J (2016) Pt-rare earth catalysts for ethanol electrooxidation: modification of polyol synthesis. J Solid State Electr 20(9):2581–2587CrossRefGoogle Scholar
  16. 16.
    Wang F, Zheng Y, Guo Y (2010) The promoting effect of europium on PtSn/C catalyst for ethanol oxidation. Fuel Cell 10(6):1100–1107CrossRefGoogle Scholar
  17. 17.
    Jacob JM, Corradini PG, Antolini E, Santos NA, Perez J (2015) Electro-oxidation of ethanol on ternary Pt-Sn-Ce/C catalysts. Applied Catalysis B 165:176–184CrossRefGoogle Scholar
  18. 18.
    Corradini PG, Antolini E, Perez J (2015) Electro-oxidation of ethanol on ternary non-alloyed Pt-Sn-Pr/C catalysts. J Power Sources 275:377–383CrossRefGoogle Scholar
  19. 19.
    Antolini E, Colmati F, Gonzalez ER (2009) Ethanol oxidation on carbon supported (PtSn)alloy/SnO2 and (PtSnPd)alloy/SnO2 catalysts with a fixed Pt/SnO2 atomic ratio: effect of the alloy phase characteristics. J Power Sources 193(2):555–561CrossRefGoogle Scholar
  20. 20.
    Malheiro AR, Perez J, Villullas HM (2010) Surface structure and electronic properties of Pt–Fe/C nanocatalysts and their relation with catalytic activity for oxygen reduction. J Power Sources 195(10):3111–3118CrossRefGoogle Scholar
  21. 21.
    Paganin VA, Ticianelli EA, Gonzalez ER (1996) Development and electrochemical studies of gas diffusion electrodes for polymer electrolyte fuel cells. J Appl Electrochem 26(3):297–304CrossRefGoogle Scholar
  22. 22.
    Rousseau S, Coutanceau C, Lamy C, Leger JM (2006) Direct ethanol fuel cell (DEFC): electrical performances and reaction products distribution under operating conditions with different platinum-based anodes. J Power Sources 158(1):18–24CrossRefGoogle Scholar
  23. 23.
    Ferro R, Saccone A (2004) Thermal analysis and alloy phase diagrams. Thermochim Acta 418(1–2):23–32CrossRefGoogle Scholar
  24. 24.
    Zhu MY, Sun GQ, Xin Q (2009) Effect of alloying degree in PtSn catalyst on the catalytic behavior for ethanol electro-oxidation. Electrochim Acta 54(5):1511–1518CrossRefGoogle Scholar
  25. 25.
    Antolini E, Perez J, Paganin VA (2011) Particle size effect for ethanol electro-oxidation on Pt/C catalysts in half-cell and in a single direct ethanol fuel cell. J Electroanal Chem 654(1–2):108–115Google Scholar
  26. 26.
    Reimann S, Schaller HJ (2006) Constitution and thermodynamics of Pt–La alloys. J Alloys Compd 419(1–2):133–139CrossRefGoogle Scholar
  27. 27.
    Janghorban A, Lomello-Tafin M, Moreau JM, Galez P (2010) The phase diagram of the Ce–Pt system. Intermetallics 18(11):2208–2218CrossRefGoogle Scholar
  28. 28.
    Beyhan S, Coutanceau C, Leger JM, Napporn TW, Kadirgan F (2013) Promising anode candidates for direct ethanol fuel cell: carbon supported PtSn-based trimetallic catalysts prepared by Bonnemann method. Int J Hydrogen Energ 38(16):6830–6841CrossRefGoogle Scholar
  29. 29.
    Lopez-Cudero A, Solla-Gullon J, Herrero E, Aldaz A, Feliu JM (2010) CO electrooxidation on carbon supported platinum nanoparticles: effect of aggregation. J Electroanal Chem 644(2):117–126CrossRefGoogle Scholar
  30. 30.
    Ciapina EG, Ticianelli EA (2011) The effect of electrochemical CO annealing on platinum-cobalt nanoparticles in acid medium and their correlation to the oxygen reduction reaction. Electrochim Acta 58:172–178CrossRefGoogle Scholar
  31. 31.
    Corradini PG, Antolini E, Perez J (2014) Activity, short-term stability (poisoning tolerance) and durability of carbon supported Pt-Pr catalysts for ethanol oxidation. J Power Sources 251:402–410CrossRefGoogle Scholar
  32. 32.
    Corradini PG, Antolini E, Perez J (2013) Structural and electrochemical characterization of carbon supported Pt-Pr catalysts for direct ethanol fuel cells prepared using a modified formic acid method in a CO atmosphere. Phys Chem Chem Phys 15(28):11730–11739CrossRefGoogle Scholar
  33. 33.
    Wu K, Sun LD, Yan CH (2016) Recent progress in well-controlled synthesis of ceria-based nanocatalysts towards enhanced catalytic performance. Adv Energy Mater 6(17):1–46Google Scholar
  34. 34.
    Brookins DG (1983) Eh-pH diagrams for the rare earth elements at 25 °C and one bar pressure. Geochem J 17(5):223–229CrossRefGoogle Scholar
  35. 35.
    Shao MH, Adzic RR (2005) Electrooxidation of ethanol on a Pt electrode in acid solutions: in situ ATR-SEIRAS study. Electrochim Acta 50(12):2415–2422CrossRefGoogle Scholar
  36. 36.
    Delpeuch AB, Maillard F, Chatenet M, Soudant P, Cremers C (2016) Ethanol oxidation reaction (EOR) investigation on Pt/C, Rh/C, and Pt-based bi- and tri-metallic electrocatalysts: a DEMS and in situ FTIR study. Applied Catalysis B 181:672–680CrossRefGoogle Scholar
  37. 37.
    Kim I, Han OH, Chae SA, Paik Y, Kwon S-H, Lee K-S, Sung Y-E, Kim H (2011) Catalytic reactions in direct ethanol fuel cells. Angew Chem 123(10):2318–2322CrossRefGoogle Scholar
  38. 38.
    Kim JH, Choi SM, Nam SH, Seo MH, Choi SH, Kim WB (2008) Influence of Sn content on PtSn/C catalysts for electrooxidation of C1-C3 alcohols: synthesis, characterization, and electrocatalytic activity. Applied Catalysis B 82(1–2):89–102CrossRefGoogle Scholar
  39. 39.
    Wang Y, Zou SZ, Cai WB (2015) Recent advances on electro-oxidation of ethanol on Pt- and Pd-based catalysts: from reaction mechanisms to catalytic materials. Catalysts 5(3):1507–1534CrossRefGoogle Scholar
  40. 40.
    Zhou WJ, Zhou ZH, Song SQ, Li WZ, Sun GQ, Tsiakaras P, Xin Q (2003) Pt based anode catalysts for direct ethanol fuel cells. Applied Catalysis B 46(2):273–285CrossRefGoogle Scholar
  41. 41.
    Simoes FC, dos Anjos DM, Vigier F, Leger JM, Hahn F, Coutanceau C, Gonzalez ER, Tremiliosi G, de Andrade AR, Olivi P, Kokoh KB (2007) Electroactivity of tin modified platinum electrodes for ethanol electrooxidation. J Power Sources 167(1):1–10CrossRefGoogle Scholar
  42. 42.
    Wang Q, Sun GQ, Jiang LH, Xin Q, Sun SG, Jiang YX, Chen SP, Jusys Z, Behm RJ (2007) Adsorption and oxidation of ethanol on colloid-based Pt/C, PtRu/C and Pt3Sn/C catalysts: in situ FTIR spectroscopy and on-line DEMS studies. Phys Chem Chem Phys 9(21):2686–2696CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany 2017

Authors and Affiliations

  1. 1.São Carlos Institute of Chemistry (IQSC)University of São PauloSão CarlosBrazil

Personalised recommendations