Recent advances in cathode electrocatalysts for PEM fuel cells

Abstract

Great progress has been made in the past two decades in the development of the electrocatalysts for proton exchange membrane fuel cells (PEMFCs). This review article is focused on recent advances made in the kinetic-activity improvement on platinum- (Pt-) based cathode electrocatalysts for the oxygen reduction reaction (ORR). The origin of the limited ORR activity of Pt catalysts is discussed, followed by a review on the development of Pt alloy catalysts, Pt monolayer catalysts, and shape- and facet-controlled Pt-alloy nanocrystal catalysts. Mechanistic understanding is reviewed as well on the factors contributing to the enhanced ORR activity of these catalysts. Finally, future directions for PEMFC catalyst research are proposed.

Key words： proton exchange membrane fuel cells (PEMFCs); cathode electrocatalysts; platinum; oxygen reduction reaction (ORR)

Acknowledgments

The author is grateful to Dr. Frederick T. Wagner for his helpful discussions.

References

1 Conway B E, Tilak B V. Interfacial processes involving electrocatalytic evolution and oxidation of H₂, and the role of chemisorbed H. Electrochimica Acta, 2002, 47(22–23): 3571–3594

2 Gasteiger H A, Markovic N M, Ross P N. H₂ and CO Electrooxidation on well-characterized Pt, Ru, and Pt-Ru. 2. Rotating disk electrode studies of CO/H₂ mixtures at 62°C. Journal of Physical Chemistry, 1995, 99(45): 16757–16767

3 Mukerjee S, McBreen J. Hydrogen electrocatalysis by carbon supported Pt and Pt alloys. Journal of the Electrochemical Society, 1996, 143(7): 2285–2294

4 Neyerlin K C, Gu W B, Jorne J, Gasteiger H A. Study of the exchange current density for the hydrogen oxidation and evolution reactions. Journal of the Electrochemical Society, 2007, 154(7): B631–B635

5 Tarasevich M R, Sadkowski A, Yeager E. Oxygen Electrochemistry. In: Conway B E, Bockris J O, Yeager E, Khan S U M, White R E. Eds. Comprehensive Treatise in Electrochemistry, New York: Plenum Press, 1983, 301

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

7 Kinoshita K. Electrochemical Oxygen Technology. New York: Wiley, 1992

8 Markovic N M, Gasteiger H A, Ross P N. Oxygen reduction on platinum low-index single-crystal surfaces in sulfuric acid solution: Rotating ring-Pt(hkl) disk studies. Journal of Physical Chemistry, 1995, 99(11): 3411–3415

9 Gasteiger H A, Panels J E, Yan S G. Dependence of PEM fuel cell performance on catalyst loading. Journal of Power Sources, 2004, 127(1–2): 162–171

10 Damjanovic A, Brusic V. Electrode kinetics of oxygen reduction on oxide-free platinum electrodes. Electrochimica Acta, 1967, 12(6): 615–628

11 Wang J X, Markovic N M, Adzic R R. Kinetic analysis of oxygen reduction on Pt(111) in acid solutions: Intrinsic kinetic parameters and anion adsorption effects. Journal of Physical Chemistry B, 2004, 108(13): 4127–4133

12 Markovic N M, Gasteiger H A, Grgur B N, Ross P N. Oxygen reduction reaction on Pt(111): Effects of bromide. Journal of Electroanalytical Chemistry, 1999, 467(1): 157–163

13 Adzic R R. Surface morphology effects in oxygen electrochemistry. In: Scherson D D, Tryk D, Xing X, eds. Proceedings of the Workshop on Structural Effects in Electrocatalysis and Oxygen Electrochemistry, Pennington: The Electrochem. Soc., 1992, 419

14 Uribe F A, Wilson M S, Springer T E, Gottesfeld S. Oxygen reduction (ORR) at the Pt/recast ionomer interface and some general comments on the ORR at Pt/aqueous electrolyte interfaces. In: Scherson D D, Tryk D, Xing X, eds. Proceedings of the Workshop on Structural Effects in Electrocatalysis and Oxygen Electrochemistry, Pennington: The Electrochem. Soc., 1992, 494

15 Norskov J K, Rossmeisl J, Logadottir A, Lindqvist L, Kitchin J R, Bligaard T, Jonsson H. Origin of the overpotential for oxygen reduction at a fuel-cell cathode. Journal of Physical Chemistry B, 2004, 108(46): 17886–17892

16 Wang J X, Zhang J L, Adzic R R. Double-trap kinetic equation for the oxygen reduction reaction on Pt(111) in acidic media. Journal of Physical Chemistry A, 2007, 111(49): 12702–12710

17 Wang J X, Uribe F A, Springer T E, Zhang J L, Adzic R R. Intrinsic kinetic equation for oxygen reduction reaction in acidic media: The double Tafel slope and fuel cell applications. Faraday Discussions, 2008, 140: 347–362

PMID

18 Blurton K F, Greenberg P, Oswin H G, Rutt D R. The electrochemical activity of dispersed platinum. Journal of The Electrochemical Society, 1972, 119(5): 559

19 Peuckert M, Yoneda T, Betta R A D, Boudart M. Oxygen reduction on small supported platinum particles. Journal of the Electrochemical Society, 1986, 133(5): 944

20 Kinoshita K. Particle size effects for oxygen reduction on highly dispersed platinum in acid electrolytes. Journal of the Electrochemical Society, 1990, 137(3): 845

21 Gasteiger H A, Kocha S S, Sompalli B, Wagner F T. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Applied Catalysis B: Environmental, 2005, 56(1–2): 9–35

22 Landsman D A, Luczak F J. Catalyst studies and coating technologies. In: Vielstich W, Gasteiger H, Lamm A. Eds. Handbook of Fuel Cells – Fundamentals, Technology and Applications, Chichester, UK: Wiley, 2003, 811

23 Thompsett D. Pt alloys as oxygen reduction catalysts. In: Vielstich W, Gasteiger H, Lamm A. Eds. Handbook of Fuel Cells – Fundamentals, Technology and Applications, Chichester, UK: Wiley, 2003, 467

24 Hammer B, Norskov J K. Theoretical surface science and catalysis–Calculations and concepts. In: Gates B C, Knozinger H, eds. Advances in Catalysis, San Diego: Academic Press Inc, 2000, 45: 71

25 Xu Y, Mavrikakis M. Adsorption and dissociation of O₂ on gold surfaces: Effect of steps and strain. Journal of Physical Chemistry B, 2003, 107(35): 9298–9307

26 Greeley J, Rossmeisl J, Hellman A, Norskov J K.Theoretical trends in particle size effect for the oxygen reduction reaction. Z Phys Chemie-Int J Res Phys Chem Chem Phys, 2007, 221(9,10): 1209–1220

27 Mukerjee S, McBreen J. Effect of particle size on the electrocatalysis by carbon-supported Pt electrocatalysts: an in situ XAS investigation1. Journal of Electroanalytical Chemistry, 1998, 448(2): 163–171

28 Mukerjee S, Srinivasan S, Soriaga M P, McBreen J. Role of structural and electronic properties of Pt and Pt alloys on electrocatalysis of oxygen reduction. Journal of the Electrochemical Society, 1995, 142(5): 1409

29 Wakabayashi N, Takeichi M, Uchida H, Watanabe M. Temperature dependence of oxygen reduction activity at Pt Fe, Pt Co, and Pt Ni alloy electrodes. Journal of Physical Chemistry B, 2005, 109(12): 5836–5841

30 Paulus U A, Wokaun A, Scherer G G, Schmidt T J, Stamenkovic V, Markovic N M, Ross P N. Oxygen reduction on high surface area Pt-based alloy catalysts in comparison to well defined smooth bulk alloy electrodes. Electrochimica Acta, 2002, 47(22,23): 3787–3798

31 Koh S, Hahn N, Yu C F, Strasser P. Effects of composition and annealing conditions on catalytic activities of dealloyed Pt-Cu nanoparticle electrocatalysts for PEMFC. Journal of the Electrochemical Society, 2008, 155(12): B1281–B1288

32 Schulenburg H, Muller E, Khelashvili G, Roser T, Bonnemann H, Wokaun A, Scherer G G. Heat-treated PtCo₃ nanoparticles as oxygen reduction catalysts. Journal of Physical Chemistry C, 2009, 113(10): 4069–4077

33 Gottesfeld S. The ellipsometric characterization of Pt+Cr alloy surfaces in acid solutions. Journal of Electroanalytical Chemistry, 1986, 205(1,2): 163–184

34 Paffett M T, Beery J G, Gottesfeld S. Oxygen reduction at Pt_0.65Cr_0.35, Pt_0.2Cr_0.8 and roughened platinum. Journal of the Electrochemical Society, 1988, 135(6): 1431

35 Jalan V, Taylor E J. Importance of interatomic spacing in catalytic reduction of oxygen in phosphoric acid. Journal of the Electrochemical Society, 1983, 130(11): 2299–2302

36 Mukerjee S, Srinivasan S. Enhanced electrocatalysis of oxygen reduction on platinum alloys in proton exchange membrane fuel cells. Journal of Electroanalytical Chemistry, 1993, 357(1–2): 201–224

37 Toda T, Igarashi H, Watanabe M. Enhancement of the electrocatalytic O₂ reduction on Pt–Fe alloys. Journal of Electroanalytical Chemistry, 1999, 460(1,2): 258–262

38 Stamenkovic V R, Mun B S, Arenz M, Mayrhofer K J J, Lucas C A, Wang G F, Ross P N, Markovic N M. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Materials, 2007, 6(3): 241–247

PMID

39 Mun B S, Watanabe M, Rossi M, Stamenkovic V, Markovic N M, Ross P N Jr. A study of electronic structures of Pt3M (M=Ti,V,Cr,Fe,Co,Ni) polycrystalline alloys with valence-band photoemission spectroscopy. Journal of Chemical Physics, 2005, 123(20): 204717

PMID

40 Greeley J, Stephens I E L, Bondarenko A S, Johansson T P, Hansen H A, Jaramillo T F, Rossmeisl J, Chorkendorff I, Nørskov J K.Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chemistry, 2009, 1(7): 552–556

PMID

41 Uribe F A, Zawodzinski T A.A study of polymer electrolyte fuel cell performance at high voltages. Dependence on cathode catalyst layer composition and on voltage conditioning. Electrochimica Acta, 2002, 47(22, 23): 3799–3806

42 Glass J T, Cahen J G L, Stoner G E, Taylor E J. The effect of metallurgical variables on the electrocatalytic properties of PtCr alloys. Journal of the Electrochemical Society, 1987, 134(1): 58–65

43 Chen S, Ferreira P J, Sheng W C, Yabuuchi N, Allard L F, Shao-Horn Y.Enhanced activity for oxygen reduction reaction on “Pt3Co” nanoparticles: direct evidence of percolated and sandwich-segregation structures. Journal of the American Chemical Society, 2008, 130(42): 13818–13819

PMID

44 Stamenkovic V, Schmidt T J, Ross P N, Markovic N M.Surface composition effects in electrocatalysis: Kinetics of oxygen reduction on well-defined Pt₃Ni and Pt₃Co alloy surfaces. Journal of Physical Chemistry B, 2002, 106(46): 11970–11979

45 Xu Y, Ruban A V, Mavrikakis M. Adsorption and dissociation of O₂ on Pt-Co and Pt-Fe alloys. Journal of the American Chemical Society, 2004, 126(14): 4717–4725

PMID

46 Chen S, Sheng W C, Yabuuchi N, Ferreira P J, Allard L F, Shao-Horn Y. Origin of oxygen reduction reaction activity on “Pt₃Co” Nanoparticles: Atomically resolved chemical compositions and structures. Journal of Physical Chemistry C, 2009, 113(3): 1109–1125

47 Stamenkovic V R, Mun B S, Mayrhofer K J J, Ross P N, Markovic N M. Effect of surface composition on electronic structure, stability, and electrocatalytic properties of Pt-transition metal alloys: Pt-skin versus Pt-skeleton surfaces. Journal of the American Chemical Society, 2006, 128(27): 8813–8819

PMID

48 Koh S, Leisch J, Toney M F, Strasser P. Structure-activity-stability relationships of Pt-Co alloy electrocatalysts in gas-diffusion electrode layers. Journal of Physical Chemistry C, 2007, 111(9): 3744–3752

49 Neyerlin K C, Srivastava R, Yu C F, Strasser P. Electrochemical activity and stability of dealloyed Pt–Cu and Pt–Cu–Co electrocatalysts for the oxygen reduction reaction (ORR). Journal of Power Sources, 2009, 186(2): 261–267

50 Wang C, van Der Vliet D, Chang K C, You H, Strmcnik D, Schlueter J A, Markovic N M, Stamenkovic V R. Monodisperse Pt₃Co nanoparticles as a catalyst for the oxygen reduction reaction: Size-dependent activity. Journal of Physical Chemistry C, 2009, 113(45): 19365–19368

51 Colon-Mercado H R, Popov B N. Stability of platinum based alloy cathode catalysts in PEM fuel cells. Journal of Power Sources, 2006, 155(2): 253–263

52 Koh S, Strasser P. Electrocatalysis on bimetallic surfaces: modifying catalytic reactivity for oxygen reduction by voltammetric surface dealloying. Journal of the American Chemical Society, 2007, 129(42): 12624–12625

PMID

53 Brankovic S R, Wang J X, Adzic R R. Pt submonolayers on Ru nanoparticles: A novel low Pt loading, nigh CO tolerance fuel cell electrocatalyst. Electrochemical and Solid-State Letters, 2001, 4(12): A217

54 Sasaki K, Mo Y, Wang J X, Balasubramanian M, Uribe F, McBreen J, Adzic R R. Pt submonolayers on metal nanoparticles–Novel electrocatalysts for H₂ oxidation and O₂ reduction. Electrochimica Acta, 2003, 48(25–26): 3841–3849

55 Wang J X, Brankovic S R, Zhu Y, Hanson J C, Adzic R R. Kinetic characterization of PtRu fuel cell anode calalysts made by spontaneous Pt deposition on Ru nanoparticles. Journal of the Electrochemical Society, 2003, 150(8): A1108–A1117

56 Brankovic S R, McBreen J, Adzic R R.Spontaneous deposition of Pt on the Ru(0001) surface. Journal of Electroanalytical Chemistry, 2001, 503(1–2): 99–104

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

58 Kolb D M, Przasnyski M, Gerischer H. Underpotential deposition of metals and work function differences. Journal of Electroanalytical Chemistry, 1974, 54(1): 25–38

59 Herrero E, Buller L J, Abruña H D. Underpotential deposition at single crystal surfaces of Au, Pt, Ag and other materials. Chemical Reviews, 2001, 101(7): 1897–1930

PMID

60 Aramata A.Underpotential deposition on single-crystal metals. In: Bockris J O, White R E , Conway B E, eds. Modern Aspects of Electrochemistry. New York: Plenum Publishing, 1997, 31: 70

61 Brankovic S R, Wang J X, Adzic R R. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces. Surface Science, 2001, 474(1–3): L173–L179

62 Zhang J, Mo Y, Vukmirovic M B, Klie R, Sasaki K, Adzic R R. Platinum monolayer electrocatalysts for O ₂ reduction: Pt monolayer on Pd(111) and on carbon-supported Pd nanoparticles. Journal of Physical Chemistry B, 2004, 108(30): 10955–10964

63 Adzic R R, Zhang J, Sasaki K, Vukmirovic M B, Shao M, Wang J X, Nilekar A U, Mavrikakis M, Valerio J A, Uribe F. Platinum monolayer fuel cell electrocatalysts. Topics in Catalysis, 2007, 46(3–4): 249–262

64 Zhang J, Vukmirovic M B, Sasaki K, Uribe F, Adzic R R. Platinum monolayer electrocatalysts for oxygen reduction: Effect of substrates, and long-term stability. J Serb Chem Soc, 2005, 70(3): 513–525

65 Zhang J L, Vukmirovic M B, Xu Y, Mavrikakis M, Adzic R R. Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. Angewandte Chemie——International Edition, 2005, 44(14): 2132–2135

66 Zhang J L, Vukmirovic M B, Sasaki K, Nilekar A U, Mavrikakis M, Adzic R R. Mixed-metal Pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. Journal of the American Chemical Society, 2005, 127(36): 12480–12481

PMID

67 Zhou W P, Yang X F, Vukmirovic M B, Koel B E, Jiao J, Peng G W, Mavrikakis M, Adzic R R. Improving electrocatalysts for O₂ reduction by fine-tuning the Pt-support interaction: Pt monolayer on the surfaces of a Pd(3)Fe(111) single-crystal alloy. Journal of the American Chemical Society, 2009, 131(35): 12755–12762

PMID

68 Zhang J, Lima F H B, Shao M H, Sasaki K, Wang J X, Hanson J, Adzic R R. Platinum monolayer on nonnoble metal noble metal core shell nanoparticle electrocatalysts for O₂ reduction. Journal of Physical Chemistry B, 2005, 109(48): 22701–22704

69 Zhang J, Sasaki K, Sutter E, Adzic R R.Stabilization of platinum oxygen-reduction electrocatalysts using gold clusters. Science, 2007, 315(5809): 220–222

PMID

70 Wang J X, Inada H, Wu L J, Zhu Y M, Choi Y M, Liu P, Zhou W P, Adzic R R. Oxygen reduction on well-defined core-shell nanocatalysts: particle size, facet, and Pt shell thickness effects. Journal of the American Chemical Society, 2009, 131(47): 17298–17302

PMID

71 Sasaki K, Naohara H, Cai Y, Choi Y M, Liu P, Vukmirovic M B,Wang J X, Adzic R R. Core-protected platinum monolayer shell high-stability electrocatalysts for fuel-cell cathodes. Angewandte Chemie–International Edition, 2010, 49(46): 8602–8607

72 Stamenkovic V R, Fowler B, Mun B S, Wang G F, Ross P N, Lucas C A, Marković N M. Improved oxygen reduction activity on Pt₃Ni(111) via increased surface site availability. Science, 2007, 315(5811): 493–497

PMID

73 Wu J, Zhang J, Peng Z,Yang S, Wagner F T, Yang H. Truncated octahedral Pt₃Ni oxygen reduction reaction electrocatalysts. Journal of the American Chemical Society, 2010, 132(14): 4984–4985

PMID

74 Zhang J, Yang H, Fang J, Zou S. Synthesis and oxygen reduction activity of shape-controlled Pt₃Ni nanopolyhedra. Nano Letters, 2010, 10(2): 638–644

PMID