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Electrochemical Reactions, Chemical Ordering Effects, and Calculated Electronic Structure, for Pt100-xMx (M = V, Zr) Thin-Film Surfaces in Acid Electrolytes

Published online by Cambridge University Press:  16 January 2017

Charles C. Hays  and
Uichiro Mizutani
Charles C. Hays*
Affiliation:
Department of Physics & Astronomy, Texas A&M University, College Station, TX77843, U.S.A.
Uichiro Mizutani
Affiliation:
Nagoya Industrial Science Research Institute, Chikusa-ku, Nagoya, Aichi Ken, Japan Crystalline Materials Science, Nagoya University, Nagoya, Aichi Ken, Japan.
*
*(Email: [email protected])
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Abstract

Microstructural, chemical, and electrochemical property measurements results, for (111) crystallographically oriented Pt100-xMx (M = V, Zr; 3 < xv < 14; and 4 < xZr < 35, At.%) sputtered thin films are presented, with electronic structure calculations. These Pt-based alloys were prepared to investigate early transition metal (ETM), late-transition-metal (LTM) alloys as potential electrode materials in hydrogen-air polymer-electrolyte-membrane fuel cells (PEMFCs). The Pt100-xMx oxygen-reduction-reaction (ORR) currents peak for 8 < x < 10 atomic percent, so local chemical-short-range-order, may exist; as the peak in ORR activity is commensurate with the strong ordering in Pt8M (M = Ti, V, Zr). The hydrogen under potential deposition (Hupd) at Pt active area, and ORR reaction kinetics, on the alloyed surfaces are composition dependent, suggesting three possible effects: 1) charge transfer from V-(3d)3 [or Zr- (4d)2] states, to the hole in the top of the Pt-(5d)9 band alters the electronic structure at the Fermi energy; 2) alloying Pt with the ETM elements introduces a bi-functional character to the electrode surface, and 3) or the presence of short range chemical order induces a Fermi energy shift. To confirm the 1st and 3rd hypotheses, the electronic structure of Pt8Ti, Pt8V, and Pt8Zr, were calculated using the WIEN2k program package. The electronic structure calculations for ordered Pt8M give strong confirmation of the hypotheses, as they reveal that the Pt8M Fermi energy lies within the Pt-5d anti-bonding band, and also falls into a pseudogap in between the Md bonding and anti-bonding bands. In addition, the Pt8M DOS calculations confirm the presence of a deep pseudogap formed across the Fermi energy for both the Pt-sp and M-sp electrons. These experimental and theoretical results motivate additional studies of the novel Pt8M phases.

Keywords

catalyticPtsputtering
Type
Articles
Information
MRS Advances , Volume 2 , Issue 8: Electrochemistry , 2017 , pp. 459 - 464
Copyright
Copyright © Materials Research Society 2017 

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References

REFERENCES

U.S. Department of Energy’s (DOE’s) 2016 Annual Merit Review (AMR) for the Hydrogen and Fuel Cells Program, held on June 6–10, 2016, in Washington, D.C.Google Scholar
Watanabe, M., Tsurumi, K., Mizukami, T., Nakamura, T., and Stonehart, Paul, J. Electrochem. Soc. 141, No. 10, 2659 (1994).CrossRefGoogle Scholar
Toda, T., Igarashi, H., and Watanabe, M., J. Electrochem. Soc.., 145, No.12, 4155 (1998).Google Scholar
Stamenkovic, V. R., Mun, B. S., Arenz, M., Mayrhofer, K. J. J., Lucas, C. A., Wang, G., Ross, P. N., and Markovic, N. M., Nat. Mater. 6, 241 (2007).CrossRefGoogle Scholar
Ding, E., More, K. L., He, T., J. of Power Sources 175, 794 (2008).CrossRefGoogle Scholar
Cui, Z., Chen, H., Zhao, M., Marshall, D., Yu, Y., Abruña, H., and DiSalvo, F. J, J. Am. Chem. Soc. 136, 10206−10209 (2014).Google Scholar
Stephens, I. L., Bondarenko, A. S., Bech, L., Chorkendorff, Ib, ChemCatChem 4, 341 (2012).Google Scholar
Waterstrat, R. M., Metall. Trans., 4(6) 1585–1592 (1973).CrossRefGoogle Scholar
Stalick, J. K. and Waterstrat, R. M., J. Alloy Compd. 430 (1-2), 123–131 (2007).Google Scholar
Fairbank, G. B., Intermetallics 8, 1091–1100 (2000).Google Scholar
Pietrokowsky, P., Ph.D. Dissertation, California Inst. of Tech., Pasadena, CA, (1959); and Pietrokowsky, P., Nature, 206, 291(1965).Google Scholar
Schryvers, D., Van Landuyt, J., and Amelinckx, S., Mat. Res. Bull. 18, 375 (1983).Google Scholar
Mabunda, K. P. and Lang, C. I., J. Alloy Compd. 613, 375 (2014).Google Scholar
Whitacre, J.F., Valdez, T.I., Narayanan, S.R., Electrochimica Acta 53, 3680–3689 (2008); and Hays, C. C., Kulleck, J. G., Haines, B. E., and Narayan, S.R., ECS Trans, 25 (1) 619(2009).Google Scholar
Straumanis, M. E., James, W. J., and Custead, W. C., J. Electrochem. Soc. 107, 502 (1960).Google Scholar
Manoharan, R. and Goodenough, J. B. Chem. of Mat. 1 (No. 4), 391 (1989); and Hays, C. C., Manoharan, R., and Goodenough, J. B., J. Power Sources 45, 291(1993).Google Scholar