Abstract
Under operating conditions relevant to polymer electrolyte membrane fuel cell (PEMFC), NixPt1−x is known to exhibit oscillations in Pt compositions with the layer position, which is crucial to the catalytic activity of the alloy material. For example, the outermost and third layers of NiPt3 are Pt-rich, whereas as the subsurface layer is Ni-rich. Using Monte Carlo simulations, we investigate the surface segregation behavior in the presence of solvent. An inversion in the segregation behavior can be observed as Ni content is increased, such that the surface becomes Ni-rich when x ≥ 0.6 compared to the bulk layer composition. A thermodynamic framework based on distribution coefficients is employed to elucidate this effect. The distribution coefficients have a value less than 1, which indicates Pt-enrichment at the surface for small x, increases to a value beyond 1 when x is large causing Ni atoms to populate the surface layer.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
A. Ruban, H. Skriver, J. Nørskov, Surface segregation energies in transition-metal alloys. Phys. Rev. B (1999)
F. Gautier, F. Ducastelle, J. Giner, Ordering and segregation processes in transition metal alloys in relation to their electronic structures. Phil. Mag. 31, 1373–1390 (1975). https://doi.org/10.1080/00318087508228689
J.C. Hamilton, Prediction of surface segregation in binary alloys using bulk alloy variables. Phys. Rev. Lett. 42, 989–992 (1979). https://doi.org/10.1103/PhysRevLett.42.989
J.R. Kitchin, K. Reuter, M. Scheffler, Alloy surface segregation in reactive environments: First-principles atomistic thermodynamics study of Ag3 Pd(111) in oxygen atmospheres. Phys. Rev. B: Condens. Matter Mater Phys. 77, 1–12 (2008). https://doi.org/10.1103/PhysRevB.77.075437
R. Mu, Q. Fu, H. Liu et al., Reversible surface structural changes in Pt-based bimetallic nanoparticles during oxidation and reduction cycles. Appl. Surf. Sci. 255, 7296–7301 (2009). https://doi.org/10.1016/j.apsusc.2009.03.086
N.V. Semagina, A.V. Bykov, E.M. Sulman et al., Selective dehydrolinalool hydrogenation with poly(ethylene oxide)-block-poly-2-vinylpyridine micelles filled with Pd nanoparticles. J. Mol. Catal. A: Chem. 208, 273–284 (2004). https://doi.org/10.1016/S1381-1169(03)00541-7
S. Vivek, R. Murthi, C. Urian, S. Mukerjee, Oxygen reduction kinetics in low and medium temperature acid environment: Correlation of water activation and surface properties in supported Pt and Pt alloy electrocatalysts (2004). https://doi.org/10.1021/jp048985k
B.C. Han, A. Van der Ven, G. Ceder, B.-J. Hwang, Surface segregation and ordering of alloy surfaces in the presence of adsorbates. Phys. Rev. B 72, 205409 (2005). https://doi.org/10.1103/PhysRevB.72.205409
J. Snyder, I. Mccue, K. Livi, J. Erlebacher, Structure/processing/properties relationships in nanoporous nanoparticles as applied to catalysis of the cathodic oxygen reduction reaction. https://doi.org/10.1021/ja3019498
G. Tréglia, B. Legrand, Surface-sandwich segregation in Pt-Ni and Ag-Ni alloys: two different physical origins for the same phenomenon. Phys. Rev. B 35, 4338–4344 (1987). https://doi.org/10.1103/PhysRevB.35.4338
Y. Gauthier, W. Hoffmann, M. Wuttig, Structure and composition of Pt10Ni90(100): a low energy electron diffraction study. Surf. Sci. 233, 239–247 (1990). https://doi.org/10.1016/0039-6028(90)90635-L
J. Eymery, J. Joud, Surface segregation in binary Cu-Ni and Pt-Ni alloys using Monte Carlo simulation. Surf. Sci. 231, 419–426 (1990). https://doi.org/10.1016/0039-6028(90)90211-P
S. Divi, A. Chatterjee, Understanding segregation behavior in AuPt, NiPt, and AgAu bimetallic nanoparticles using distribution coefficients. J. Phys. Chem. C 120, 27296–27306 (2016). https://doi.org/10.1021/acs.jpcc.6b08325
Y. Gauthier, Y. Joly, R. Baudoing, J. Rundgren, Surface-sandwich segregation on nondilute bimetallic alloys: Pt50 Ni50 and Pt78 Ni22 probed by low-energy electron diffraction. Phys. Rev. B 31, 6216–6218 (1985). https://doi.org/10.1103/PhysRevB.31.6216
Acknowledgements
AC acknowledges support from Science and Engineering Research Board, Department of Science and Technology Grant No. SB/S3/CE/022/2014 and Indian National Science Academy Grant No. SP/YSP/120/2015/307.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2020 Springer Nature Singapore Pte Ltd.
About this paper
Cite this paper
Agrahari, G., Sarkar, A., Chatterjee, A. (2020). Effect of Solvent on Segregation Behavior in Pt-Ni Bimetallic Alloy. In: Singh, S., Ramadesigan, V. (eds) Advances in Energy Research, Vol. 1. Springer Proceedings in Energy. Springer, Singapore. https://doi.org/10.1007/978-981-15-2666-4_24
Download citation
DOI: https://doi.org/10.1007/978-981-15-2666-4_24
Published:
Publisher Name: Springer, Singapore
Print ISBN: 978-981-15-2665-7
Online ISBN: 978-981-15-2666-4
eBook Packages: EnergyEnergy (R0)