Abstract
This paper presents a periodic density functional theory study on the adsorption of H, CO, and OH on Pt2Ru3 alloy surfaces containing different conformations of Pt and Ru atoms. The results show that for separate adsorption, H is preferentially adsorbed at Pt sites, whereas CO and OH are preferentially adsorbed at Ru sites. The adsorption strengths of H, CO, and OH are affected by ratio of the alloying atoms in top surface, the nature of the neighboring atom nearest to the adsorption site, and the conformation of alloying atoms in subsurface. We also investigated the coadsorption of CO with OH and the coadsorption of CO with H and found that the Pt–CO bond strength weakens. We also uncovered some information about the competitive adsorption behavior of adsorbates (CO, OH) with the aim of designing CO-tolerant Pt–Ru alloy catalysts.
Similar content being viewed by others
References
G. Hoogers and D. Thompsett: Catalysis in proton exchange membrane fuel cell technology. Cattech 3, 106 (2000).
H.A. Gasteiger, N. Markovic, P.N. Ross, and E.J. Cairns: Co electrooxidation on well-characterized Pt–Ru alloys. J. Phys. Chem. 98, 617 (1994).
M. Watanabe, H. Igarashi, and T. Fujino: Design of CO tolerant anode catalysts for polymer electrolyte fuel cell. Electrochemistry 67, 1194 (1999).
G. Avgouropoulos and T. Ioannides: CO tolerance of Pt and Rh catalysts: Effect of CO in the gas-phase oxidation of H2 over Pt and Rh supported catalysts. Appl. Catal., B 56, 77 (2005).
K. Wang, H.A. Gasteiger, N.M. Markovic, and P.N. Ross: On the reaction pathway for methanol and carbon monoxide electrooxidation on Pt–Sn alloy versus Pt–Ru alloy surfaces. Electrochim. Acta 41, 2587 (1996).
L. Carrette, K.A. Friedrich, and U. Stimming: Fuel cells-fundamentals and applications. Fuel Cells 1, 5 (2001).
R. Ferrando, J. Jellinek, and R.L. Johnston: Nanoalloys: From theory to applications of alloy clusters and nanoparticles. Chem. Rev. 108 (3), 845 (2008).
T. Yajima, H. Uchida, and M. Watanabe: In situ ATR-FTIR spectroscopic study of electro-oxidation of methanol and adsorbed co at Pt−Ru alloy. J. Phys. Chem. B 108, 2654 (2004).
W.F. Lin, M.S. Zei, M. Eiswirth, G. Ertl, T. Iwasita, and W. Vielstich: Electro-catalytic activity of Ru-modified Pt(111) electrodes toward co oxidation. J. Phys. Chem. B 103, 6968 (1999).
K-W. Park and Y-E. Sung: Catalytic activity of platinum on ruthenium electrodes with modified (electro) chemical states. J. Phys. Chem. B 109, 13585 (2005).
C. Lu, C. Rice, R.I. Masel, P.K. Babu, P. Waszczuk, H.S. Kim, E. Oldfield, and A. Wieckowski: UHV, electrochemical NMR, and electrochemical studies of platinum/ruthenium fuel cell catalysts. J. Phys. Chem. B 106, 9581 (2002).
F.B. de Mongeot, M. Scherer, B. Gleich, E. Kopatzki, and R.J. Behm: CO adsorption and oxidation on bimetallic Pt/Ru(0001) surfaces—A combined STM and TPD/TPR study. Surf. Sci. 411, 249 (1998).
Q. Ge, S. Desai, M. Neurock, and K. Kourtakis: Co adsorption on Pt–Ru surface alloys and on the surface of Pt–Ru bulk alloy. J. Phys. Chem. 105, 9533 (2001).
C. Pistonesi, E. Pronsato, and A. Juan: A DFT study of H adsorption on Pt(111) and Pt–Ru(111) surfaces. Appl. Surf. Sci. 254, 5827 (2008).
H. Orita, N. Itoh, and Y. Inada: All electron scalar relativistic calculations on adsorption of co on Pt(111) with full-geometry optimization: A correct estimation for co site-preference. Chem. Phys. Lett. 384, 271 (2004).
M.T.M. Koper, T.E. Shubina, and R.A. van Santen: Periodic density functional study of co and OH adsorption on Pt−Ru alloy surfaces: Implications for co tolerant fuel cell catalysts. J. Phys. Chem. B 106, 686 (2002).
Y. Shimodaira, T. Tanaka, T. Miura, A. Kudo, and H. Kobayashi: Density functional theory study of anode reactions on Pt-based alloy electrodes. J. Phys. Chem. C 111, 272 (2007).
P. Liu, A. Logadottir, and J.K. Nørskov: Modeling the electro-oxidation of co and H2/CO on Pt, Ru, PtRu and Pt3Sn. Electrochim. Acta 48, 3731 (2003).
Z. Ji and J.Q. Li: Density functional study of CO oxidation on Pt and PtMo. Chem. Phys. Lett. 424, 111 (2006).
Z. Ji, A.F. Jalbout, and J.Q. Li: Adsorption and diffusion of OH on Mo modified Pt(111) surface: First-principles theory. Solid State Commun. 142, 148 (2007).
M.T.M. Koper and R.A. van Santen: Interaction of H, O and OH with metal surfaces. J. Electroanal. Chem. 472, 126 (1999).
B.C. Han and G. Ceder: Effect of coadsorption and Ru alloying on the adsorption of CO on Pt. Phys. Rev. B 74, 205418 (2006).
T. Sato, K. Kunimatsu, K. Okaya, H. Yano, M. Watanabe, and H. Uchida: In situ ATR-FTIR analysis of the co-tolerance mechanism on Pt2Ru3/C catalysts prepared by the nanocapsule method. Energy Environ. Sci. 4, 433 (2011).
T. Sato, K. Okaya, K. Kunimatsu, H. Yano, M. Watanabe, and H. Uchida: Effect of particle size and composition on co-tolerance at Pt–Ru/C catalysts analyzed by in situ attenuated total reflection FTIR spectroscopy. ACS Catal. 2, 450 (2012).
T. Takeguchi, T. Yamanaka, K. Asakura, E.N. Muhamad, K. Uosaki, and W. Ueda: Evidence of nonelectrochemical shift reaction on a CO-tolerant high-entropy state Pt–Ru anode catalyst for reliable and efficient residential fuel cell systems. J. Am. Chem. Soc. 134, 14508 (2012).
Y. Ishikawa, M-S. Liao, and C.R. Cabrera: Energetics of H2O dissociation and COads + OHads reaction on a series of Pt–M mixed metal clusters: A relativistic density-functional study. Surf. Sci. 513, 98 (2002).
T.E. Shubina and M.T.M. Koper: Quantum-chemical calculations of CO and OH interacting with bimetallic surfaces. Electrochim. Acta 47, 3621 (2002).
B. Delley: An all-electron numerical method for solving the local density functional for polyatomic molecules. J. Chem. Phys. 92, 508 (1990).
B. Delley: Fast calculation of electrostatics in crystals and large molecules. J. Phys. Chem. 100, 6107 (1996).
B. Delley: From molecules to solids with the DMol3 approach. J. Chem. Phys. 113, 7756 (2000).
J.P. Perdew, K. Burke, and M. Ernzerhof: Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).
Y. Ishikawa, J.J. Mateo, D.A. Tryk, and C.R. Cabrera: Direct molecular dynamics and density functional theoretical study of the electrochemical hydrogen oxidation reaction and underpotential deposition of H on Pt(111). J. Electroanal. Chem. 607, 37 (2007).
G.E. Gdowski, J.A. Fair, and R.J. Madix: Reactive scattering of small molecules from platinum crystal surfaces: D2CO, CH3OH, HCOOH, and the nonanomalous kinetics of hydrogen atom recombination. Surf. Sci. 127, 541 (1983).
M.K. Alam and H. Takaba: Density functional theory study of OH and CO adsorption on the Pt2Ru3 surface. ECS Trans. 64 (3), 689 (2014).
S. Volkening, K. Bedurftig, K. Jacobi, J. Wintterlin, and G. Ertl: Dual-path mechanism for catalytic oxidation of hydrogen on platinum surfaces. Phys. Rev. Lett. 83, 2672 (1999).
G.B. Fisher and B.A. Sexton: Identification of an adsorbed hydroxyl species on the Pt(111) Surface. Phys. Rev. Lett. 44, 683 (1980).
M.K. Alam and H. Takaba: Stability of Pt–Ru alloy for anode catalyst in PEFC fuel cell: A density functional theory study. ECS Trans. 61 (13), 1 (2014).
A.V. Ruban, H.L. Skriver, and J.K. Nørskov: Surface segregation energies in transition-metal alloys. Phys. Rev. B 59, 15990 (1999).
ACKNOWLEDGMENTS
We are grateful to the New Energy and Industrial Technology Development Organization (NEDO) for providing financial support.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Alam, M.K., Saito, S. & Takaba, H. Density functional theory study on the adsorption of H, OH, and CO and coadsorption of CO with H/OH on the Pt2Ru3 surfaces. Journal of Materials Research 31, 2617–2626 (2016). https://doi.org/10.1557/jmr.2016.286
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/jmr.2016.286