Abstract
The sluggish kinetics of ethanol oxidation on Pt-based electrodes is one of the major drawbacks to its use as a liquid fuel in direct ethanol fuel cells, and considerable efforts have been made to improve the reaction kinetics. Herein, we report an investigation on the effect of the Pt microstructure (well-dispersed versus agglomerated nanoparticles) and the catalyst support (carbon Vulcan, SnO2, and RuO2) on the rate of the electrochemical oxidation of ethanol and its major adsorbed intermediate, namely, carbon monoxide. By using several structural characterization techniques such as X-ray diffraction, X-ray absorption spectroscopy, and transmission electron microscopy, along with potentiodynamic and potentiostatic electrochemical experiments, we show that by altering both the Pt microstructure and the support, the rate of the electrochemical oxidation of ethanol can be improved up to a factor of 12 times compared to well-dispersed carbon-supported Pt nanoparticles. As a result of a combined effect, the interaction of Pt agglomerates with SnO2 yielded the highest current densities among all materials studied. The differences in the activity are discussed in terms of structural and electronic properties as well as by mass transport effects, providing valuable insights to the development of more active materials.
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Acknowledgments
The authors thank the Brazilian funding agencies FAPESP, CAPES, and CNPq for financial assistance. EGC would like to acknowledge FAPESP for the fellowships. The authors also thank the Brazilian Synchrotron Light laboratory (LNLS) for X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) beam line facilities.
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Figures of EXAFS oscillations isolated from the XAS spectra, full CO striping curves and the corresponding charges involved in the CO electrochemical oxidation reaction are provided in the Supporting Information. (DOC 714 kb)
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Ciapina, E.G., Santos, S.F. & Gonzalez, E.R. The electro-oxidation of carbon monoxide and ethanol on supported Pt nanoparticles: the influence of the support and catalyst microstructure. J Solid State Electrochem 17, 1831–1842 (2013). https://doi.org/10.1007/s10008-013-2120-5
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DOI: https://doi.org/10.1007/s10008-013-2120-5