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Electrochemical alcohol oxidation: a comparative study of the behavior of methanol, ethanol, propanol, and butanol on carbon-supported PtSn, PtCu, and Pt nanoparticles

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Abstract

Carbon-supported PtCu and PtSn (both with an atomic ratio of 3:1) nanoparticles were prepared by reducing Pt, Sn, and Cu precursors via refluxing in ethanol. They were characterized using energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and transmission electron microscopy (TEM). X-ray diffraction indicated that the lattice parameter of Pt increases with the addition of Sn and decreases with the addition of Cu, indicating that both PtCu and PtSn are solid solutions. EDX analysis revealed that the compositions of these materials are close to their nominal compositions, while TEM showed that both materials presented a homogeneous particle distribution on the carbon support and low particle agglomeration. Electrochemical experiments indicated that all of the materials are electrochemically active with respect to methanol, ethanol, propanol, and butanol oxidation in H2SO4 solution. The electrochemical measurements also showed that PtSn is more active in ethanol oxidation, whereas PtCu is more active in methanol oxidation. Both materials showed similar electrooxidative activities towards propanol and butanol, and they presented higher electrochemical acidities than pure platinum for alcohol oxidation.

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Acknowledgments

The authors would like to thank the Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Proc. 554569/2010-8 and Proc. 475609/2008-5) for financial support as well as the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) for granting our scholarship. We would also like to thank Tatiane Oliveira dos Santos from the Microscopy Laboratory (LABMIC) of the Federal University of Goiás, Goiânia, Brazil, for permitting the use of the microscope (a JEM-2010 HRTEM microscope, JEOL, Tokyo, Japan).

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Authors and Affiliations

  1. Instituto de Química, Universidade Federal de Goiás, Avenida Esperança, s/n, Goiânia, Goiás, Brazil, CEP 74690-900

    Renan G. C. S. dos Reis & Flavio Colmati

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  1. Renan G. C. S. dos Reis
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  2. Flavio Colmati
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Correspondence to Flavio Colmati.

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Appendix

Appendix

As illustrated in Fig. 8, the alcohol oxidation current was relatively stable at 1800 s, except for isopropanol. This behavior can be attributed to differences in the adsorption of the alcohols on the electrode surface. Some studies have found that small and linear alcohols such as methanol and ethanol are adsorbed at a platinum electrode in an acidic medium via the α-carbon in the alcohol molecule. Propanol and butanol are also adsorbed in this manner, but the α-carbon is shielded by methyl groups in isopropanol, so only weak adsorption occurs on the Pt surface and the oxidation current does not stabilize within 1800 s. At this section, the scale of the y-axis of the graphics was not similar for all figures to emphasize the behavior of the curves with time once the current values are very different.

Fig. 8a–d
figure 8

Chronoamperometric curves (obtained at 0.3 V vs Ag / AgCl/Cl− sat) for a methanol, b ethanol, c propanol, and d butanol on Pt3Sn/C, Pt3Cu/C, and Pt/C electrodes in 0.5 mol L−1H2SO4

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dos Reis, R.G.C.S., Colmati, F. Electrochemical alcohol oxidation: a comparative study of the behavior of methanol, ethanol, propanol, and butanol on carbon-supported PtSn, PtCu, and Pt nanoparticles. J Solid State Electrochem 20, 2559–2567 (2016). https://doi.org/10.1007/s10008-016-3323-3

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  • DOI: https://doi.org/10.1007/s10008-016-3323-3

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