Abstract
Ethanol, with its high energy density, likely production from renewable sources and ease of storage and transportation, is almost the ideal combustible for fuel cells wherein its chemical energy can be converted directly into electrical energy. However, commercialization of direct ethanol fuel cells has been impeded by ethanol’s slow, inefficient oxidation even at the best electrocatalysts1,2. We synthesized a ternary PtRhSnO2/C electrocatalyst by depositing platinum and rhodium atoms on carbon-supported tin dioxide nanoparticles that is capable of oxidizing ethanol with high efficiency and holds great promise for resolving the impediments to developing practical direct ethanol fuel cells. This electrocatalyst effectively splits the C–C bond in ethanol at room temperature in acid solutions, facilitating its oxidation at low potentials to CO2, which has not been achieved with existing catalysts. Our experiments and density functional theory calculations indicate that the electrocatalyst’s activity is due to the specific property of each of its constituents, induced by their interactions. These findings help explain the high activity of Pt–Ru for methanol oxidation and the lack of it for ethanol oxidation, and point to the way to accomplishing the C–C bond splitting in other catalytic processes.
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Change history
29 January 2009
In the version of this Letter originally published online, reference 19 was incorrect, it has now been corrected in the HTML and PDF versions, and will appear correctly in print.
References
Lamy, C., Rousseau, S., Belgsir, E. M., Coutanceau, C. & Leger, J.-M. Recent progress in the direct ethanol fuel cell: Development of new platinum-tin electrocatalysts. Electrochim. Acta 49, 3901–3908 (2004).
Antolini, E. Catalysts for direct ethanol fuel cells. J. Power Sources 170, 1–12 (2007).
Mann, J., Yao, N. & Bocarsly, A. B. Characterization and analysis of new catalysts for a direct ethanol fuel cell. Langmuir 22, 10432–10436 (2006).
Lai, S. C. S. & Koper, M. T. M. Electro-oxidation of ethanol and acetaldehyde on platinum single-crystal electrodes. Faraday Discuss. 140, 399–416 (2008).
Tarnowski, D. J. & Korzeniewski, C. Effects of surface step density on the electrochemical oxidation of ethanol to acetic acid. J. Phys. Chem. B 101, 253–258 (1997).
Colmati, F. et al. Surface structure effect on the electrochemical oxidation of ethanol on platinum single crystal electrodes. Faraday Discuss. 140, 379–397 (2008).
Wang, J. T., Wasmus, S. & Savinell, R. F. Evaluation of ethanol, 1-propanol, and 2-propanol on a direct oxidation polymer-electrolyte fuel cell. A real-time mass spectrometry study. J. Electrochem. Soc. 142, 4218–4224 (1995).
Xia, X. H., Liess, H. D. & Iwasita, T. Early stages in the oxidation of ethanol at low index single crystal platinum electrodes. J. Electroannal. Chem. 437, 233–240 (1997).
Wang, Q. et al. 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, 2686–2696 (2007).
Wang, H., Jusys, Z. & Behm, R. J. Ethanol electro-oxidation on carbon-supported Pt, PtRu and Pt3Sn/C catalysts: A quantitative study. J. Power Sources 154, 351–359 (2006).
Adzic, R. et al. US Patent Application No. 20070264189 (2007).
Zhang, J. L. et al. Mixed-metal Pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. J. Am. Chem. Soc. 127, 12480–12481 (2005).
Batzill, M. & Diebold, U. The surface and materials science of tin oxide. Prog. Surf. Sci. 79, 47–154 (2005).
Lindan, P. J. D. Water chemistry at the SnO2(111) surface: The role of inter-molecular interactions and surface geometry. Chem. Phys. Lett. 328, 325–329 (2000).
Trasatti, S. in Interfacial Electrochemistry—Theory, Experiment, and Applications (ed. Wieckowski, A.) 769–788 (Dekker, 1999).
Frenkel, A. Solving the 3D structure of metal nanoparticles. Z. Kristallogr. 222, 605–611 (2007).
Nashner, M. S., Frenkel, A. I., Adler, D. L., Sharpeley, J. R. & Nuzzo, D. Structural characterization of carbon-supported platinum-ruthenium nanoparticles from the molecular cluster precursor PtRu5C(CO)16 . J. Am. Chem. Soc. 119, 7760–7771 (1997).
Willsau, J. & Heitbaum, J. Elementary steps of ethanol oxidation on Pt in sulfuric-acid as evidenced by isotope labeling. J. Electroannal. Chem. 194, 27–35 (1985).
Shao, M. & Adzic, R. R. Electrooxidation of ethanol on a Pt electrode in acid solutions: In situ ATR-SEIRAS study. Electrochim. Acta 50, 2415–2422 (2005).
Wieckowski, A., Sobkowski, J., Zelenay, P. & Franaszczuk, K. Adsorption of acetic acid on platinum, gold and rhodium electrodes. Electrochim. Acta 26, 1111–1119 (1981).
Mavrikakis, M. & Barteau, M. A. Oxygenate reaction pathways on transition metal surfaces. J. Mol. Catal. A 131, 135–147 (1998).
Idriss, H. Ethanol reaction over the surfaces of noble metal/cerium oxide catalysts. Platinum Metals Rev. 48, 105–115 (2004).
Scott-Jones, G., Mavrikakis, M., Barteau, M. A. & Vohs, J. M. First synthesis, experimental and theoretical vibrational spectra of an oxametallacycle on a metal surface. J. Am. Chem. Soc. 120, 3196–3204 (1998).
Batista, E. A. M., Motheo, G. R. P. & Iwasita, A. J. New mechanistic aspects of methanol oxidation. J. Electroanal. Chem. 571, 273–282 (2004).
Wang, J. X., Marinković, N. S., Zajonz, H., Ocko, B. M. & Adzic, R. R. In situ X-ray reflectivity and voltammetry study of Ru(0001) surface oxidation in electrolyte solutions. J. Phys. Chem. 105, 2809–2814 (2001).
Jiang, L. et al. Size-controllable synthesis of monodispersed SnO2 nanoparticles and application in electrocatalysts. J. Phys. Chem. B 109, 8774 (2005).
Bradely, D. An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92, 508 (1990).
Acknowledgements
This work was carried out at Brookhaven National Laboratory under Contract No. DE-AC02-98CH10886 with the US Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences and Biosciences and its Division of Materials Sciences and Engineering, within the Office of Basic Energy Sciences. Part of the calculations were performed using the supercomputing facility at Center for Functional Nanomaterials of Brookhaven National Laboratory. A.I.F. acknowledges financial support by the DOE BES grant No. DE-FG02-03ER15476. Work at the NSLS was supported by the DOE BES grant DE-FG02-03ER15688.
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Kowal, A., Li, M., Shao, M. et al. Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2. Nature Mater 8, 325–330 (2009). https://doi.org/10.1038/nmat2359
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DOI: https://doi.org/10.1038/nmat2359
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