Carbon nanotubes supported core–shell catalysts Pt-Ru/Ni, Pt-Ru/Pb and Pt-Ru/Ni for methanol oxidation reaction in fuel cell

The core-shell type catalysts were obtained by spontaneous surface substitution of electrodeposited Pb, Ni and Cu by platinum metals Pt-Ru. The surface layer of obtained catalysts was tested by EDAX; the amount of platinum was determined by ICP-AES. The catalytic activity of obtained catalysts was examined in methanol oxidation reaction. The stationary state currents were referred to EAS, determined from hydrogen adsorption. For all investigated systems the catalytic effect was registered thus confirming the activity of core–shell catalyst.


1. Brankovic S. R., Wang J. X., Adzic R. R. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces. Surface Science. 2001, vol. 474, pp. L173-L179.
2. Sasaki K., Mo Y., Wang J. X., Balasubramanian M., Uribe F., McBreen J., Adzic R. R. Pt submonolayers on metal nanoparticles–novel electrocatalysts for H2 oxidation and O2 reduction. Electrochimica Acta. 2003, vol. 48, pp. 3841–3849.
3. Zang J., Mo Y., Vukmirovic M. B., Klie R., Sasaki K., Adzic R. R. Platinum Monolayer Electrocatalysts for O2 Reduction: Pt Monolayer on Pd(111) and on Carbon-Supported Pd Nanoparticles. J. Phys. Chem. B. 2004, vol. 108, pp. 10955–10964.
4. Vukmirovic M. B., Zhang J., Sasaki K., Nilekar A. U., Uribe F., Mavrikakis M., Adzic R. R. Platinum monolayer electrocatalysts for oxygen reduction. Electrochimica Acta. 2007, vol. 52, pp. 2257–2263.
5. Sasaki K., Wang J. X., Naohara H., Marinkovic N., More K., Inada H., Adzic R. R. Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores. Eleсtrochim. Acta. 2010, vol. 55, pp. 2645–2652.
6. Mayorova N. A., Zigalina O. M., Zigalina V. M., Khazova O. A. Pt/Pd/C catalysts with ultra low platinum content for oxygen reduction reaction. Russian Journal of Electrochemistry, 2014, vol. 40, no. 3, pp. 223–230.
7. Mavrikakis M., Hammer B., Norskov J. K. Effect of Strain on the Reactivity of Metal Surfaces. Physical Review Letters. 1998, vol. 81, pp. 2819–2822.
8. Ruban A., Hammer B., Stoltze P., Skriver H. L., Norskov J. K. Surface electronic structure and reactivity of transition and noble metals. J. Mol. Catal. A: Chem. 1997, vol. 115, pp. 421–429.
9. Kitchin J. R., Norskov J. K., Barteau M. A., Chen J. G. J.Chem. Phys. 2004, vol. 120 (21), pp. 10240–10246.
10. Norskov J. K., Rossmeisi J., Logadottir A., Lindqvist L., Kitchin J. R., Bligaard T., Jonsson H. Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode. J. Phys. Chem. B. 2004, vol. 108, pp. 17886–17892.
11. Hammer B., Norskov J. K. Theoretical surface science and catalysis–calculations and concepts. Adv. Catal. 2000, vol. 45, pp. 71–129.
12. Christoffersen E., Liu P., Ruban A., Skiver H. L., Norskov J. K. Anode Materials for Low-Temperature Fuel Cells: A Density Functional Theory Study. J. Catal. 2001, vol. 199, pp. 123–131.
13. Van Brussel M., Kokkinidis G., Vandendael I., Buess-Herman C. High performance gold-supported platinum electrocatalyst for oxygen reduction. Electrochem. Commun. 2002, vol. 4, pp. 808–813.
14. Van Brussel M., Kokkinidis G., Hubin A., Buess-Herman C. Oxygen reduction at platinum modified gold electrodes. Electrochim. Acta. 2003, vol. 48, pp. 3909–3919.
15. Tegou A., Papadimitriou S., Armyanov S., Valova E., Kokkinidis G., Sotiropoulos S. Oxygen reduction at platinum- and gold-coated iron, cobalt, nickel and lead deposits on glassy carbon substrates. J. Electroanal. Chem. 2008, vol. 623, pp. 187–196.
16. Papadimitriou S., Tegou A., Pavlidou E., Kokkinidis G., Sotiropoulos S. Methanol oxidation at platinized lead coatings prepared by a two-step electrodeposition–electroless deposition process on glassy carbon and platinum substrates. Electrochim. Acta. 2007, vol. 52, pp. 6254–6260.
17. Podlovchenko B. I., Gladysheva T. D.,Filatov A. Yu., Yashina L. V. The use of galvanic displacement in synthesizing Pt(Cu) catalysts with the core-shell structure. Russian Journal of Electrochemistry, 2010, vol. 46. no. 10, pp. 11189–1197.
18. Podlovchenko B. I., Zhutaev U. E., Maksimov Yu.M. Galvanic displacement of copper adatoms on platinum in PtCl42- solutions. J. Electroanal. Chem. 2011, vol. 651, pp. 30–37.
19. Podlovchenko B. I., Gladysheva T. D.,Filatov A.Yu., Yashina L. V. Peculiarities of the Pt(Cu)/C catalyst formation by galvanic displacement of copper in H2PtCl4 solutions. Russian Journal of Electrochemistry, 2012, vol. 48, no. 2. pp. 173–180.
20. Mayorova N. A., Tusseeva E. K., Sosenkin V. E., Rychagov A.Yu., Volfkovich Yu.M., Krestinin A. V., Zvereva G. I., Zigalina O. M., Khazova O. A.. Effect of the functionalizing of carbon nanotubes on the electrodeposited catalysts' structure and catalytic properties. Russian Journal of Electrochemistry, 2009, vol. 45, pp. 1089–1097.