Abstract
Fuel cells powered by hydrogen from secure and renewable sources are the ideal solution for non-polluting vehicles, and extensive research and development on all aspects of this technology over the past fifteen years has delivered prototype cars with impressive performances. But taking the step towards successful commercialization requires oxygen reduction electrocatalysts—crucial components at the heart of fuel cells—that meet exacting performance targets. In addition, these catalyst systems will need to be highly durable, fault-tolerant and amenable to high-volume production with high yields and exceptional quality. Not all the catalyst approaches currently being pursued will meet those demands.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 51 print issues and online access
$199.00 per year
only $3.90 per issue
Buy this article
- Purchase on SpringerLink
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
The. US Department of Energy (DOE). Energy Efficiency and Renewable Energyhttp://www.eere.energy.gov/hydrogenandfuelcells/mypp/pdfs/fuel_cells.pdf and the US DRIVE Fuel Cell Technical Team Technology Roadmap (revised 25 January 2012) http://www.uscar.org/guest/teams/17/Fuel-Cell-Tech-Team.These websites define the most critical performance, durability and cost targets for the PEM fuel-cell MEA and each of its components, as well as stack and system requirements.
Wagner, F. T., Lakshmanan, B. & Mathias, M. F. Electrochemistry and the future of the automobile. J. Phys. Chem. Lett. 1, 2204–2219 (2010)
Gasteiger, H., Kocha, S., Sompalli, B. & Wagner, F. Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs. Appl. Catal. B 56, 9–35 (2005)This paper first defined and explained the ORR activity targets and requirements for the PEM fuel-cell cathodes, particularly for fuel-cell vehicles.
Markovic, N., Schmidt, T., Stamenkovic, V. & Ross, P. Oxygen reduction reaction on Pt and Pt bimetallic surfaces: a selective review. Fuel Cells 1, 105–116 (2001)
Nørskov, J. K., Bligaard, T., Rossmeisl, J. & Christensen, C. H. Towards the computational design of solid catalysts. Nature Chem. 1, 37–46 (2009)
Greeley, J. et al. Alloys of platinum and early transition metals as oxygen reduction electrocatalysts. Nature Chem. 1, 552–556 (2009)
Wipke, K. et al. Controlled Hydrogen Fleet and Infrastructure Analysis: 2011 DOE Hydrogen Program Annual Merit Review and Peer Evaluation Meetinghttp://www.hydrogen.energy.gov/pdfs/review11/tv001_wipke_2011_o.pdf (National Renewable Energy Laboratory, 2011)
Reiser, C. A. et al. A reverse-current decay mechanism for fuel cells. Electrochem. Solid-State Lett. 8, A273 (2005)This explains the basic mechanism by which fuel starvation or start-up and shut-down events in a PEM fuel cell can cause carbon corrosion on the cathode.
Atanasoska, L. L., Vernstrom, G. D., Haugen, G. M. & Atanasoski, R. T. Catalyst durability for fuel cells under start-up and shutdown conditions: evaluation of Ru and Ir sputter-deposited films on platinum in PEM environment. ECS Trans. 41, 785–795 (2011)
Halalay, I. C. et al. Anode materials for mitigating hydrogen starvation effects in PEM fuel cells. J. Electrochem. Soc. 158, B313–B321 (2011)
Sepa, D. B., Vojnovic, M. V. & Damjanovic, A. Reaction intermediates as a controlling factor in the kinetics and mechanism of oxygen reduction at platinum electrodes. Electrochim. Acta 26, 781–793 (1981)
Markovic, N. M. & Ross, P. N. Surface science studies of model fuel cell electrocatalysts. Surf. Sci. Rep. 45, 117–229 (2002)
Debe, M. K. Effect of electrode surface area distribution on high current density performance of PEM fuel cells. J. Electrochem. Soc. 159, B54–B67 (2012)
Mayrhofer, K. J. J. et al. Measurement of oxygen reduction activities via the rotating disc electrode method: from Pt model surfaces to carbon-supported high surface area catalysts. Electrochim. Acta 53, 3181–3188 (2008)
Garsany, Y., Barurina, O. A., Swider-Lyons, K. E. & Kocha, S. S. Experimental methods for quantifying the activity of platinum electrocatalysts for the oxygen reduction reaction. Anal. Chem. 82, 6321–6328 (2010)
Stamenkovic, V. R. et al. Improved oxygen reduction activity on Pt3Ni(111) via increased surface site availability. Science 315, 493–497 (2007)This paper showed that the fundamental kinetic activity for oxygen reduction on bulk Pt–Ni alloy surfaces could be nearly two orders of magnitude higher than the standard dispersed Pt on carbon.
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. J. Am. Chem. Soc. 128, 8813–8819 (2006)This paper demonstrates the sensitivity and specificity of ORR activity to the fundamental surface structure and composition of the top few layers of Pt transition metal alloys.
Stamenkovic, V. R. et al. Trends in electrocatalysis on extended and nanoscale Pt-bimetallic alloy surfaces. Nature Mater. 6, 241–247 (2007)
Paulus, U. A. et al. Oxygen reduction on high surface area Pt-based alloy catalysts in comparison to well defined smooth bulk alloy electrodes. Electrochim. Acta 47, 3787–3798 (2002)
Stamenković, 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. J. Phys. Chem. B 106, 11970–11979 (2002)
Debe, M. K. in Handbook of Fuel Cells—Fundamentals, Technology and Applications (eds Vielstich, W., Lamm, A. & Gasteiger, H. A. ) Ch. 45 (John Wiley & Sons, 2003)
Debe, M. K., Atanasoski, R. T. & Steinbach, A. J. Nanostructured thin film electrocatalysts—current status and future potential. ECS Trans. 41, 937–954 (2011)
Debe, M. K. 2009–2011 Annual Merit Reviews DOE Hydrogen and Fuel Cells and Vehicle Technologies Programs: Advanced Cathode Catalysts and Supports for PEM Fuel Cells http://www.hydrogen.energy.gov/pdfs/review11/fc001_debe_2011_o.pdf (DOE, 2011)
Debe, M. K. Nanostructured thin film electrocatalysts for PEM fuel cells—a tutorial on the fundamental characteristics and practical properties of NSTF catalysts. ECS Trans. 45 (2). 47–68 (2012)This paper defines all the catalyst and MEA measured properties and published papers so far for the NSTF type catalyst electrodes.
Gancs, L., Kobayashi, T., Debe, M. K., Atanasoski, R. & Wieckowski, A. Crystallographic characteristics of nanostructured thin film fuel cell electrocatalysts—a HRTEM study. Chem. Mater. 20, 2444–2454 (2008)
van. der Vliet, D. et al. Platinum-alloy nanostructured thin film catalysts for the oxygen reduction reaction. Electrochim. Acta 56, 8695–8699 (2011)
Debe, M. K., Schmoeckel, A. K., Vernstrom, G. D. & Atanasoski, R. High voltage stability of nanostructured thin film catalysts for PEM fuel cells. J. Power Sources 161, 1002–1011 (2006)
Debe, M. K., Steinbach, A. J. & Noda, K. Stop-start and high-current durability testing of nanostructured thin film catalysts for PEM fuel cells. ECS Trans. 3, 835–853 (2006)
Debe, M. K. et al. Durability aspects of nanostructured thin film catalysts for PEM fuel cells. ECS Trans. 1, 51–56 (2006)
Debe, M. K. et al. in Proc. 50th Annual Technical Conference of the Society of Vacuum Coaters 175–185 (The Society of Vacuum Coaters, 2006)
Haugen, G., Barta, S., Emery, M., Hamrock, S. & Yandrasits, M. in Fuel Cell Chemistry and Operation (eds Herring, A. M., Zawodzinski Jr., T. A. & Hamrock, S. J. ) 137 (ACS Symposium Series 1040, 2010)
Steinbach, A. et al. Influence of anode GDL on PEMFC ultra-thin electrode water management at low temperatures. ECS Trans. 41, 449–457 (2011)
Debe, M. K. et al. Extraordinary oxygen reduction activity of Pt3Ni. J. Electrochem. Soc. 158, B910–B918 (2011)
Park, S. et al. Polarization losses under accelerated stress test using multiwalled carbon nanotube supported Pt catalyst in PEM fuel cells. J. Electrochem. Soc. 158, B297–B302 (2011)
Wang, S., Jiang, S. P., White, T. J. & Wang, X. Synthesis of Pt and Pd nanosheaths on multi-walled carbon nanotubes as potential electrocatalysts of low temperature fuel cells. Electrochim. Acta 55, 7652–7658 (2010)
Yang, R., Leisch, J., Strasser, P. & Toney, M. F. Structure of dealloyed PtCu3 thin films and catalyst activity for oxygen reduction. Chem. Mater. 22, 4712–4720 (2010)
Erlebacher, J. & Snyder, J. Dealloyed nanoporous metals for PEM fuel cell catalysis. ECS Trans. 25, 603–612 (2009)
Erlebacher, J., Aziz, M., Karma, A., Dimitrov, N. & Sieradzki, K. Evolution of nanoporosity in dealloying. Nature 410, 450–453 (2001)
Moffat, T. P., Mallett, J. J. & Hwang, S.-M. Oxygen reduction kinetics on electrodeposited Pt 100-xNix, and Pt 100-xCox . J. Electrochem. Soc. 156, B238–B251 (2009)
Imbeault, R., Antonio, P., Garbarino, S. & Guay, D. Oxygen reduction kinetics on PtxNi100-x thin films prepared by pulsed laser deposition. J. Electrochem. Soc. 157, B1051–B1058 (2010)
Ralph, T. R. & Hogarth, M. P. Catalysis for low temperature fuel cells. Platin. Met. Rev. 46, 3–14 (2002)
Schulenburg, H. et al. Heat-treated PtCo nanoparticles as oxygen reduction catalysts. J. Phys. Chem. C 113, 4069–4077 (2009)
Thompsett, D. in Handbook of Fuel Cells—Fundamentals, Technology and Applications (eds Vielstich, W., Lamm, A. & Gasteiger, H. A. ) Ch. 37 (John Wiley & Sons, 2003)
Wagner, F. T. Automotive Challenges and Opportunities for Oxygen Reduction Catalysts. In First CARISMA Intl Conf. (La Grande Motte, France, 23 September 2008)
Wang, C. et al. Monodisperse Pt3Co nanoparticles as electrocatalyst: the effects of particle size and pretreatment on electrocatalytic reduction of oxygen. Phys. Chem. Chem. Phys. 12, 6933–6939 (2010)
Wu, J. B. et al. Truncated octahedral Pt3Ni ORR electrocatalysts. J. Am. Chem. Soc. 132, 4984–4985 (2010)
Zhang, J., Yang, H., Fang, J. & Zou, S. Synthesis and oxygen reduction activity of shape-controlled Pt3Ni nanopolyhedra. Nano Lett. 10, 638–644 (2010)
Lim, B. et al. Pd-Pt bimetallic nanodendrites with high activity for oxygen reduction. Science 324, 1302–1305 (2009)
Gasteiger, H. A. & Markovic, N. M. Just a dream—or future reality? Science 324, 48–49 (2009)
Wang, C. et al. Monodisperse Pt3Co nanoparticles as a catalyst for the oxygen reduction reaction: size-dependent activity. J. Phys. Chem. C 113, 19365–19368 (2009)
Wang, C. et al. Correlation between surface chemistry and electrocatalytic properties of monodispersed PtxNi1-x nanoparticles. Adv. Funct. Mater. 21, 147–152 (2011)
Markovic, N. Nanosegregated cathode catalysts with ultra-low platinum loading. In 2010 DOE Hydrogen Program Annual Merit Review FC-006, http://www.hydrogen.energy.gov/pdfs/review10/fc008_markovic_2010_o_web.pdf (2011)
Shao, M., Sasaki, K., Marinkivic, N. S., Zhang, L. & Adzic, R. R. Synthesis and characterization of platinum monolayer oxygen-reduction electrocatalysts with Co-Pd core-shell nanoparticle supports. Electrochem. Commun. 9, 2848–2853 (2007)
Bliznakov, S. T., Vukmirovic, M. B., Yang, L., Sutter, E. A. & Adzic, R. R. Pt monolayer on electrodeposited Pd nanostructures—advanced cathode catalysts for PEM fuel cells. ECS Trans. 41, 1055 (2011)
Vukmirovic, M. B. et al. Platinum monolayer electrocatalysts for oxygen reduction. Electrochim. Acta 52, 2257–2263 (2007)
Shao, M. H., Sasaki, K., Lui, P. & Adzic, R. R. Pd3Fe and Pt monolayer Pd3Fe electrocatalysts for oxygen reduction. Z. Phys. Chem. 221, 1175–1190 (2007)
Zhang, J. et al. Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on Pd(111) and on carbon-supported Pd nanoparticles. J. Phys. Chem. B 108, 10955–10964 (2004)
Russell, A. E. et al. In situ XAS studies of core-shell PEM fuel cell catalysts: the opportunities and challenges. ECS Trans. 41, 55–67 (2011)
Haug, A. et al. Stability of a Pt-Pd core-shell catalyst: a comparative fuel cell and RDE study. 218th ECS Meeting abstr. 743 (The Electrochemical Society, 2010)
Knupp, S. L. et al. Platinum monolayer electrocatalysts for O2 reduction: Pt monolayer on carbon-supported PdIr Nanoparticles. Electrocatalysis 1, 213–223 (2010)
Xing, Y. et al. Enhancing oxygen reduction reaction activity via Pd-Au alloy sublayer mediation of Pt monolayer electrocatalysts. J. Phys. Chem. Lett. 1, 3238–3242 (2010)
Wang, J. X. et al. Oxygen reduction on well-defined core-shell nanocatalysts: particle size, facet and Pt shell thickness effects. J. Am. Chem. Soc. 131, 17298–17302 (2009)This is an exemplary paper in a long series by the Adzic group developing core–shell nanoparticle catalysts having Pt monolayer skins, controlled size and surface facets.
Gong, K., Su, D. & Adzic, R. Platinum-monolayer shell on AuNi0. 5Fe nanoparticle core electrocatalyst with high activity and stability for the oxygen reduction reaction. J. Am. Chem. Soc. 132, 14364–14366 (2010)
Ball, S. et al. Structure and activity of novel Pt core-shell catalysts for the oxygen reduction reaction. ECS Trans. 25, 1023–1036 (2009)
Korovina, A., Garsany, Y., Epshteyn, A., Swider-Lyons, K. E. & Ramaker, D. E. Insight into oxygen reduction on platinum-tantalum oxyphosphate electrocatalysts. 218th ECS Meeting abstr. 687 (The Electrochemical Society, 2010)
Park, S. et al. Polarization losses under accelerated stress test using multiwalled carbon nanotube supported Pt catalyst in PEM fuel cells. J. Electrochem. Soc. 158, B297–B302 (2011)
Wang, X., Waje, M. & Yan, Y. CNT-based electrodes with high efficiency for PEMFCs. Electrochem. Solid-State Lett. 8, A42–A44 (2005)
Chen, Z., Waje, M., Li, W. & Yan, Y. Supportless Pt and PtPd nanotubes as electrocatalysts for oxygen-reduction reactions. Angew. Chem. Int. Edn 46, 4060–4063 (2007)
van der Vliet, D. et al. Metallic nanotubes with tunable composition and structure as advanced electrocatalysts. Nature Mater. (submitted)
Zhou, H., Zhou, W.-P., Adzic, R. & Wong, S. S. Enhanced electrocatalytic performance of one-dimensional metal nanowires and arrays generated via an ambient surfactantless synthesis. J. Phys. Chem. C 113, 5460–5466 (2009)
Adzic, R. Contiguous platinum monolayer oxygen reduction electrocatalysts on high-stability-low-cost supports. In 2011 DOE Hydrogen Program Annual Merit Review FC-009, http://www.hydrogen.energy.gov/pdfs/review11/fc009_adzic_2011_o.pdf (2011)
Shao, M. Palladium-based electrocatalysts for hydrogen oxidation and oxygen reduction reactions. J. Power Sources 196, 2433–2444 (2011)
Myers, D. Non-platinum bimetallic cathode electrocatalysts. In 2008–2010 DOE Hydrogen Program Annual Merit Reviewshttp://www.hydrogen.energy.gov/pdfs/review10/fc004_myers_2010_o_web.pdf (2010)
Atanasoski, R. & Dodelet, J.-P. in Encyclopedia of Electrochemical Power Sources (eds Garche, J. et al.) Vol. 2 639–649 (Elsevier, 2009)
Lei, M., Li, P. G., Li, L. H. & Tang, W. H. A highly ordered Fe-N-C nanoarray as a non-precious oxygen-reduction catalyst for proton exchange membrane fuel cells. J. Power Sources 196, 3548–3552 (2011)
Wang, S., Yu, D. & Dai, L. Polyelectrolyte functionalized carbon nanotubes as efficient metal-free electrocatalysts for oxygen reduction. J. Am. Chem. Soc. 133, 5182–5185 (2011)
Zelenay, P. Advanced cathode catalysts. In 2010 DOE Hydrogen Program Annual Merit Review, http://www.hydrogen.energy.gov/pdfs/review10/fc005_zelenay_2010_o_web.pdf (2010)
Ishihara, A., Ohgi, Y., Matsuzawa, K., Mitsushima, S. & Ota, K. Progress in non-precious metal oxide-based cathode for polymer electrolyte fuel cells. Electrochim. Acta 55, 8005–8012 (2010)
Lefevre, M., Proietti, E., Jaouen, F. & Dodelet, J.-P. Iron-based catalysts with improved oxygen reduction activity in polymer electrolyte fuel cells. Science 324, 71–74 (2009)
Bashyam, R. & Zelenay, P. A class of non-precious metal composite catalysts for fuel cells. Nature 443, 63–66 (2006)
Proietti, E. et al. Iron-based cathode catalyst with enhanced power density in polymer electrolyte membrane fuel cells. Nature Commun. 2, 416 (2011)This paper is the latest in a long series by these authors that show an amazing rate of improvement in non-precious metal catalysts’ beginning-of-life performances under pure oxygen.
Wood, T. E., Tan, Z., Schmoeckel, A. K., O’Neill, D. & Atanasoski, R. Non-precious metal oxygen reduction catalyst for PEM fuel cells based on nitroaniline precursor. J. Power Sources 178, 510–516 (2008)
Wu, G., More, K. L., Johnston, C. M. & Zelenay, P. High-Performance electrocatalysts for oxygen reduction derived from polyaniline, iron and cobalt. Science 332, 443–447 (2011)
Global. and China Low-E Glass Industry Reporthttp://pressexposure.com/Global_and_China_Low-E_Glass_Industry_Report,_2010_-_Published_by_ResearchInChina-205310.html (ResearchInChina, 2010)
Chen, S., Gasteiger, H. A., Hayakawa, K., Tada, T. & Shao-Horn, Y. Platinum-alloy cathode catalyst degradation in proton exchange membrane fuel cells: nanometer-scale compositional and morphological changes. J. Electrochem. Soc. 157, A82–A97 (2010)
Kongkanand, A., Liu, Z., Dutta, I. & Wagner, F. T. Electrochemical and microstructural evaluation of aged nanostructured thin film fuel cell electrocatalyst. J. Electrochem. Soc. 158, B1286–B1291 (2011)
Wagner, F. T. et al. Catalyst development needs and pathways for automotive PEM fuel cells. ECS Trans. 3, 19 (2006)
Koh, S., Hahn, N., Yu, C. & Strasser, P. Effects of composition and annealing conditions on catalytic activities of dealloyed Pt-Cu nanoparticle electrocatalysts for PEMFC. J. Electrochem. Soc. 155, B1281–B1288 (2008)
Oezaslan, M., Hasche, F. & Strasser, P. Structure-activity relationship of dealloyed PtCo3 and PtCu3 nanoparticle electrocatalyst for oxygen reduction reaction in PEMFC. ECS Trans. 33, 333–341 (2010)
Strasser, P., Hahn, N. T. & Koh, S. Corrosion and ORR activity of Pt alloy electrocatalysts during voltammetric pretreatment. ECS Trans. 3, 139–149 (2006)
Mani, P., Srivastava, R. & Strasser, P. Dealloyed binary PtM3 (M = Cu, Co, Ni) and ternary PtNi3M (M = Cu, Co, Fe, Cr) electrocatalysts for the oxygen reduction reaction: performance in polymer electrolyte membrane fuel cells. J. Power Sources 196, 666–673 (2011)
Neyerlin, K. C., Srivastava, R., Yu, C. & Strasser, P. Electrochemical activity and stability of dealloyed Pt-Cu and Pt-Cu-Co electrocatalysts for the oxygen reduction reaction (ORR). J. Power Sources 186, 261–267 (2009)
Wagner, F. T. High-activity dealloyed catalysts. 2011 DOE Hydrogen Program Annual Merit Review FC-087, http://www.hydrogen.energy.gov/pdfs/review11/fc087_wagner_2011_o.pdf (2011)
Strasser, P. et al. Lattice-strain control of the activity in dealloyed core-shell fuel cell catalysts. Nature Chem. 2, 454–460 (2010)
Snyder, J., Fujita, T., Chen, M. W. & Erlebacher, J. Oxygen reduction in nanoporous metal-ionic liquid composite electrocatalysts. Nature Mater. 9, 904–907 (2010)This paper shows that porosity on the nanometre scale can be controlled in Ni/Pt alloys, describes the spontaneous formation of core/shell catalysts during de-alloying and illustrates a new concept for enhancing the activity of solid surfaces in contact with ionic liquids.
Erlebacher, J. & Seshardi, R. Hard materials with tunable porosity. MRS Bull. 34, 561–568 (2009)
Snyder, J. & Erlebacher, J. The active surface area of nanoporous metals during oxygen reduction. ECS Trans. 41, 1021–1030 (2011)
Acknowledgements
I gratefully acknowledge support by the Fuel Cell Technologies Program in the Office of Energy Efficiency and Renewable Energy at the US Department of Energy, for grant DE-FG36-07GO17007.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Competing interests
The author declares no competing financial interests.
Rights and permissions
About this article
Cite this article
Debe, M. Electrocatalyst approaches and challenges for automotive fuel cells. Nature 486, 43–51 (2012). https://doi.org/10.1038/nature11115
Published:
Issue Date:
DOI: https://doi.org/10.1038/nature11115
This article is cited by
-
Synergistic role of MoS2 in gelation-induced fabrication of graphene oxide films
Scientific Reports (2024)
-
Current Progress of Carbon Nanotubes Applied to Proton Exchange Membrane Fuel Cells: A Comprehensive Review
International Journal of Precision Engineering and Manufacturing-Green Technology (2024)
-
Carbon Nanofibre Modified Platinum Nanomaterials: Synthesis, Characterization and Their Applications toward C1 to C3 Alcohols for Direct Alcohol Fuel Cells
Topics in Catalysis (2024)
-
Ultra-small Pt3Co intermetallic compounds: for efficient electrocatalytic methanol oxidation
Reaction Kinetics, Mechanisms and Catalysis (2024)
-
Interfacial Electronic Modulation of Dual-Monodispersed Pt–Ni3S2 as Efficacious Bi-Functional Electrocatalysts for Concurrent H2 Evolution and Methanol Selective Oxidation
Nano-Micro Letters (2024)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.