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Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2

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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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Figure 1: Current–potential and current–time polarization curves comparing the activity of PtRhSnO2/C with several other catalysts for ethanol oxidation.
Figure 2: In situ XANES and EXAFS spectra for determining the structural and electronic properties of PtRhSnO2.
Figure 3: In situ IRRAS spectra for identifying the intermediates and products of ethanol oxidation on several electrocatalysts.
Figure 4: DFT investigations of ethanol oxidation on a RhPt/SnO2(110) surface.

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  • 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.

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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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Correspondence to A. Kowal, M. Shao, J. Zhang or R. R. Adzic.

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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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