Abstract
In this study, the density functional theory (DFT) and Monte Carlo (MC) simulations were conducted to determine the equilibrium conformation of Pt2Ru3 nanoparticles with diameters 1.0–3.5 nm at finite temperature. DFT calculations were carried out to estimate the binding energy using slab configurations and energy could be correlated with some structural descriptors and multilinear regression equations to calculate the binding energy from descriptors related to the number of a specific bond to neighboring atoms. MC simulations were carried out to obtain the equilibrium conformation of atoms in Pt2Ru3 at 150–363 K. MC simulations’ result shows that atoms of the same element tend to segregate each other, and Pt/Ru ratio on the surface increases with increasing particle size; also, most of the Pt are located on the surface whereas most of the Ru are located on the subsurface or at the core sites. It is qualitatively exhibited that the Pt/Ru ratio on the surface decreases with increasing temperature.
Similar content being viewed by others
References
H.A. Gasteiger, N.M. Markovic, and P.N. Ross: H2 and CO electrooxidation on well-characterized Pt, Ru, and Pt–Ru. 1. Rotating disk electrode studies of the pure gases including temperature effects. J. Phys. Chem. 99, 8290 (1995).
E.P.M. Leiva, E. Santos, and T.J. Iwasita: The effect of adsorbed carbon monoxide on hydrogen adsorption and hydrogen evolution on platinum. J. Electroanal. Chem. Interfacial Electrochem. 215, 357 (1986).
O.A. Petrii and G.A. Tsirlina: Electrocatalytic activity prediction for hydrogen electrode reaction: Intuition, art, science. Electrochim. Acta 39, 1739 (1994).
V. Ponce and G.C. Bond: Catalysis by Metals and Alloys; Studies in Surface Science and Catalysis 95 (Elsevier, Amsterdam, 1995).
M. Krausa and W. Vielstich: Study of the electrocatalytic influence of Pt/Ru and Ru on the oxidation of residues of small organic molecules. J. Electroanal. Chem. 379, 307 (1994).
T. Frelink, W. Visscher, and J.A.R. Vanveen: On the role of Ru and Sn as promotors of methanol electro-oxidation over Pt. Surf. Sci. 335, 353 (1995).
Y.Y. Tong, H.S. Kim, P.K. Babu, P. Waszczuk, A. Wieckowski, and E. Oldfield: An NMR investigation of CO tolerance in a Pt/Ru fuel cell catalyst. J. Am. Chem. Soc. 124, 468 (2002).
M. Watanabe and S. Motoo: Electrocatalysis by ad-atoms: Part II. Enhancement of the oxidation of methanol on platinum by ruthenium ad-atoms. J. Electroanal. Chem. Interfacial Electrochem. 60, 267 (1975).
T. Yajima, N. Wakabayashi, H. Uchida, and M. Watanabe: Adsorbed water for the electro-oxidation of methanol at Pt–Ru alloy. Chem. Commun. 7, 828 (2003).
M. Watanabe and S. Motoo: Electrocatalysis by ad-atoms: Part III. Enhancement of the oxidation of carbon monoxide on platinum by ruthenium ad-atoms. J. Electroanal. Chem. 60, 275 (1975).
B.C. Hanand and G. Ceder: Effect of coadsorption and Ru alloying on the adsorption of CO on Pt. Phys. Rev. B: Condens. Matter Mater. Phys. 74, 205418 (2006).
P.K. Babu, H.S. Kim, E. Oldfield, and A. Wieckowski: Electronic alterations caused by ruthenium in Pt–Ru alloy nanoparticles as revealed by electrochemical NMR. J. Phys. Chem. B 107, 7595 (2003).
P.K. Babu, H.S. Kim, S.T. Kuk, J.H. Chung, E. Oldfield, E.S. Smotkin, and A. Wieckowski: Activation of nanoparticle PtRu fuel cell catalysts by heat treatment: A 195 Pt NMR and electrochemical study. J. Phys. Chem. B 109, 17192 (2005).
T. Takeguchi, T. Yamanaka, K. Asakura, E.N. Muhamad, K. Uosaki, and W. Ueda: Evidence of non electrochemical 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).
K.M. Bratlie, H. Lee, K. Komvopoulos, P.D. Yang, and G.A. Somorjai: Pt nanoparticle shape effects on benzene hydrogenation selectivity. Nano Lett. 7, 3097 (2007).
Y.J. Xiong, J.M. McLellan, J.Y. Chen, Y.D. Yin, Z.Y. Li, and Y.N. Xia: Kinetically controlled synthesis of triangular and hexagonal nanoplates of palladium and their SPR/SERS properties. J. Am. Chem. Soc. 127, 17118 (2005).
K.H. Park, K. Jang, H.J. Kim, and S.U. Son: Near-mono disperse tetrahedral rhodium nanoparticles on charcoal the shape-dependent catalytic hydrogenation of arenes. Angew. Chem., Int. Ed. 46, 1152 (2007).
S.H. Zhou, B. Varughese, B. Eichhorn, G. Jackson, and K. McIlwrath: Pt–Cu core–shell and alloy nanoparticles for heterogeneous NOx reduction: Anomalous stability and reactivity of a core–shell nanostructure. Angew. Chem., Int. Ed. 117, 4515 (2005).
S. Alayoglu, A.U. Nilekar, M. Mavrikakis, and B. Eichhorn: Ru–Pt core–shell nanoparticles for preferential oxidation of carbon monoxide in hydrogen. Nat. Mater. 7, 333 (2008).
J.I. Park, M.G. Kim, Y.W. Jun, J.S. Lee, and W.R. Lee: Characterization of super paramagnetic “core–shell” nanoparticles and monitoring their anisotropic phase transition to ferromagnetic “solid solution” nanoalloys. J. Am. Chem. Soc. 126, 9072 (2004).
C.W. Hills, M.S. Nashner, A.I. Frenkel, J.R. Shapley, and R.G. Nuzzo: Carbon support effects on bimetallic Pt–Ru nanoparticles formed from molecular precursors. Langmuir 15, 690 (1999).
M.S. Nashner, A.I. Frenkel, D.L. Adler, J.R. Shapley, and R.G. Nuzzo: Structural characterization of carbon-supported platinum–ruthenium nanoparticles from the molecular cluster precursor PtRu5C(CO)16. J. Am. Chem. Soc. 119, 7760 (1997).
J.W. Long, R.M. Stroud, K.E. Swider-Lyons, and D.R. Rolison: How to make electrocatalysts more active for direct methanol oxidation avoid PtRu bimetallic alloys. J. Phys. Chem. B 104, 9772 (2000).
K. Yuge: Segregation of Pt28Rh27 bimetallic nanoparticles: A first-principles study. J. Phys.: Condens. Matter 22, 245401 (2010).
S. Alayoglu, P. Zavalij, B. Eichhorn, O. Wang, A.I. Frenkel, and P. Chupas: Structural and architectural evaluation of bimetallic nanoparticles: A case study of Pt–Ru core-shell and alloy nanoparticles. ACS Nano 3, 3127 (2009).
M.T.M. Koper, A.P.J. Jansen, R.A. van Santen, J.J. Lukkien, and P.A.J. Hilbers: Monte Carlo simulations of a simple model for the electrocatalytic CO oxidation on platinum. J. Chem. Phys. 109, 6051 (1998).
B. Andreaus and M. Eikerling: Active site model for CO adlayer electrooxidation on nanoparticle catalysts. J. Electroanal. Chem. 607, 121 (2007).
C. Saravanan, N.M. Markovic, M. Head-Gordon, and P.N. Ross: Stripping and bulk CO electro-oxidation at the Pt–electrode interface: Dynamic Monte Carlo simulations. J. Chem. Phys. 114, 6404 (2001).
F. Maillard, G.-Q. Lu, A. Wieckowski, and U. Stimming: Ru-decorated Pt surfaces as model fuel cell electrocatalysts for CO electrooxidation. J. Phys. Chem. B 109, 16230 (2005).
B. Andreaus, F. Maillard, J. Kocylo, E.R. Savinova, and M. Eikerling: Kinetic modeling of CO ad monolayer oxidation on carbon-supported platinum nanoparticles. J. Phys. Chem. B 110, 21028 (2006).
V. Petukhov: Effect of molecular mobility on kinetics of an electrochemical Langmuir–Hinshelwood reaction. Chem. Phys. Lett. 277, 539 (1997).
C. Saravanan, M.T.M. Koper, N.M. Markovic, M. Head-Gordon, and P.N. Ross: Modeling base voltammetry and CO electrooxidation at the Pt(111)-electrolyte interface: Monte Carlo simulations including anion adsorption. Phys. Chem. Chem. Phys. 4, 2660 (2002).
P.A. Dowben and A. Miller, eds.: Surface Segregation Phenomena (CRC Press, Boca Raton, Florida, 1990).
J.A. Rodriguez: Physical and chemical properties of bimetallic surfaces. Surf. Sci. Rep. 24, 223 (1996).
M. Polak and L. Rubinovich: The interplay of surface segregation and atomic order in alloys. Surf. Sci. Rep. 38, 127 (2000).
B. Shan, L. Wang, S. Yang, J. Hyun, N. Kapur, Y. Zhao, J. Nicholas, and K. Cho: First-principles-based embedded atom method for PdAu nanoparticles. Phys. Rev. B: Condens. Matter Mater. Phys. 80, 035404 (2009).
G. Wang, M.A. Van Hove, and P.N. Ross: Monte Carlo simulations of segregation in Pt–Ni catalyst nanoparticles. J. Chem. Phys. 122, 024706 (2005).
K. Yuge, A. Seko, A. Kuwabara, F. Oba, and I. Tanaka: First-principles study of bulk ordering and surface segregation in Pt–Rh binary alloys. Phys. Rev. B: Condens. Matter Mater. Phys. 74, 174202 (2006).
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. 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 nano capsule method. Energy Environ. Sci. 4, 433 (2011).
B. Delley: Fast calculation of electrostatics in crystals and large molecules. J. Chem. Phys. 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).
Md.K. Alam, S. Saito, and H. Takaba: Density functional theory study on the adsorption of H, OH, and CO and coadsorption of CO with H/OH on the Pt2Ru3 surfaces. J. Mater. Res. 31, 2617 (2016).
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).
T.E. Shubina and M.T.M. Koper: Quantum-chemical calculations of CO and OH interacting with bimetallic surfaces. Electrochim. Acta 47, 3621 (2002).
C.T. Lee, W.T. Yang, and R.G. Parr: Development of the Colle Salvetti correlation energy formula into a functional of the electron density. Phys. Rev. B: Condens. Matter Mater. Phys. 37, 785 (1988).
E.W. Hansen and M. Neurock: First-principles-based Monte Carlo simulation of ethylene hydrogenation kinetics on Pd. J. Catal. 196, 241 (2000).
K. Reuter, D. Frenkel, and M. Scheffler: The steady state of heterogeneous catalysis, studied by first-principles statistical mechanics. Phys. Rev. Lett. 93, 116104 (2004).
M.P. Allen and D.J. Tildesley: Computer Simulation of Liquids (Clarendon Press, Oxford, 1987).
L. Eriksson, E. Johansson, M. Muller, and S.J. Wold: On the selection of training set in environmental QSAR when compounds are clustered. Chemometrics 14, 599 (2000).
A. Tropsha, P. Gramatica, and V.K. Gombar: The importance of being earnest: Validation is the absolute essential for successful application and interpretation of QSPR models. QSAR Comb. Sci. 22, 69 (2003).
R. Todeschini, V. Consonni, A. Mauri, and M. Pavan: Detecting “bad” regression models: Multicriteria fitness functions in regression analysis. Anal. Chim. Acta 515, 199 (2004).
J. Topliss and P.J. Edwards: Chance factors in studies of quantitative structure-activity relationships. J. Med. Chem. 22, 1238 (1979).
V. Consonni, D. Ballabio, and R.J. Todeschini: Comments on the definition of the Q2 parameter for QSAR validation. J. Chem. Inf. Model. 49, 1669 (2009).
E. Antolini, L. Giorgi, F. Cardellini, and E. Passalacqua: Physical and morphological characteristics and electrochemical behavior in PEM fuel cells of PtRu/C catalysts. J. Solid State Electrochem. 5, 131 (2001).
T.A. Yamamoto, S. Kageyama, S. Seino, H. Nitani, T. Nakagawa, R. Horioka, Y. Honda, K. Ueno, and H. Daimon: Methanol oxidation catalysis and substructure of PtRu/C bimetallic nanoparticles synthesized by a radiolytic process. Appl. Catal., A 396, 68 (2011).
D. Cheng, S. Huang, and W. Wang: The structure of 55-atom Cu-Au bimetallic clusters: Monte Carlo study. Eur. Phys. J. D 39, 41 (2005).
D. Cheng, S. Huang, and W. Wang: Structures of small Pd–Pt bimetallic clusters by Monte Carlo simulation. Chem. Phys. 330, 423 (2006).
P.P. Roy, S.P. Paul, I. Mitra, and K. Roy: On two novel parameters for validation of predictive QSAR models. Molecules 14, 1660 (2009).
A.R. Katritzky, M. Kuanar, S. Slavov, and C. Dennis Hall: Quantitative correlation of physical and chemical properties with chemical structure: Utility for prediction. Chem. Rev. 110, 5714 (2010).
H. Nitani, T. Nakagawa, D. Daimon, Y. Kurobe, T. Ono, Y. Honda, A. Koizumi, S. Seino, and T.A. Yamamoto: Methanol oxidation catalysis and substructure of PtRu bimetallic nanoparticles. Appl. Catal., A 326, 194 (2007).
G. Wang, M.A.V. Hove, P.N. Ross, and M.I. Baskes: Quantitative prediction of surface segregation in bimetallic Pt–M alloy nanoparticles (M = Ni, Re, Mo). Surf. Sci. 79, 28 (2005).
G. Wang, M.A.V. Hove, P.N. Ross, and M.I. Baskes: Monte Carlo simulations of segregation in Pt–Ni catalyst nanoparticles. J. Chem. Phys. 122, 024706 (2005).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Alam, M.K., Saito, S. & Takaba, H. Modeling of equilibrium conformation of Pt2Ru3 nanoparticles using the density functional theory and Monte Carlo simulations. Journal of Materials Research 32, 1573–1581 (2017). https://doi.org/10.1557/jmr.2017.57
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1557/jmr.2017.57