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Russian Journal of Electrochemistry

, Volume 54, Issue 11, pp 902–911 | Cite as

Quantum-Chemical Study of the Adsorption of Pb2+ on Au(111)

  • N. A. RogozhnikovEmail author
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Abstract

The interaction between the Pb2+ ion and gold is studied using the cluster metal surface model and the density functional method. The geometric and energy characteristics of the interaction between this ion and the gold surface are estimated. The form in which the Pb2+ ion exists on the surface is more ad-ionic than ad-atomic. The electron structure of the Au–Pbads2+ system is analyzed. The participation of the adsorbed lead ion and its neighboring gold atoms in the formation of molecular orbitals in this system is estimated. It is established that the contribution to their formation is predominantly provided by the lead s-orbitals and the gold d-orbitals. The interaction with a solvent decreases the transfer of a charge from an adsorbed lead ion to gold. It is demonstrated that the hydrolyzability of a lead ion decreases upon its transition from the electrolyte phase to the surface.

Keywords

quantum chemistry surface adsorption gold lead 
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References

  1. 1.
    Haissinsky, M., Mécanisme des dépots électrolytiques et expériences avec les radioéléments, J. Chim. Phys. Phys.-Chim. Biol., 1946. vol. 43, pp. 21–29.Google Scholar
  2. 2.
    Kolb, D.M., Przasnyski, M., and Gerischer, H., Underpotential deposition of metals and work function differences, J. Electroanal. Chem. Interfacial Electrochem., 1974, vol. 54, no. 1, pp. 25–38.Google Scholar
  3. 3.
    Kolb, D.M., Leutloff, D., and Przasnyski, M., Optical properties of gold electrode surfaces covered with metal monolayers, Surf. Sci., 1975, vol. 47, no. 2, pp. 622–634.Google Scholar
  4. 4.
    Takamura, T., Watanabe, F., and Takamura, K., Electro-optical studies of submonolayers of lead formed on gold electrodes by faradaic adsorption in 1M HClO4, Electrochim. Acta, 1974, vol. 19, no. 12, pp. 933–939.Google Scholar
  5. 5.
    Adžić, R.R. and Despić, A.R., Catalytic effect of metal adatoms deposited at underpotential, J. Chem. Phys., 1974, vol. 61, no. 8, pp. 3482–3483.Google Scholar
  6. 6.
    Petrii, O.A. and Lapa, A.S., Electrochemistry of adatomic layers, in Itogi Nauki Tekh., Ser.: Elektrokhim., Polukarov, Yu.M., Ed, Moscow: VINITI, 1987, vol. 24, pp. 96–153.Google Scholar
  7. 7.
    Rodes, A., Feliu, J.M., Aldaz, A., and Clavilier, J. The influence of polyoriented gold electrodes modified by reversibly and irreversibly adsorbed ad-atoms on the redox behaviour of the Cr(III)/Cr(II), J. Electroanal. Chem. Interfacial Electrochem.,1989, vol. 271, nos. 1–2, pp. 127–139.Google Scholar
  8. 8.
    Paliteiro, C. and Martins, N., Electroreduction of oxygen on a (100)-like polycrystalline gold surface in an alkaline solution containing Pb(II), Electrochim. Acta, 1998, vol. 44, nos. 8–9, p. 1359–1368.Google Scholar
  9. 9.
    Oh, I., Gewirth, A.A., and Kwak, J., Electrocatalytic dioxygen reduction on underpotentially deposited Pb on Au(111) studied by an active site blocking strategy, J. Catal., 2003, vol. 213, no. 1, pp. 17–22.Google Scholar
  10. 10.
    Hsieh, S.-J. and Gewirth, A.A., Poisoning the catalytic reduction of peroxide on Pb underpotential deposition modified Au surfaces with iodine, Surf. Sci., 2002, vol. 498, nos. 1–2, pp. 147–160.Google Scholar
  11. 11.
    McJntyre, J.D.E. and Peck, W.F., Electrodeposition of gold: depolarization effects induced by heavy metal ions, J. Electrochem. Soc., 1976, vol. 123, no. 12, pp. 1800–1813.Google Scholar
  12. 12.
    Bek, R.Yu. and Shuraeva, L.I., Effect of lead ions on the kinetics of gold deposition from cyanide electrolytes, Russ. J. Electrochem., 2004. vol. 40, no. 7, pp. 704–710.Google Scholar
  13. 13.
    Nicol, M.J., The anodic behaviour of gold. Part II—Oxidation in alkaline solutions, Gold Bull., 1980, vol. 13, no. 3, pp. 105–111.Google Scholar
  14. 14.
    Bek, R.Yu., Comparison of catalytic activity of thallium and lead adatoms at the gold electrodeposition and dissolution in cyanide solutions, Russ. J. Electrochem., 2008, vol. 44, no. 9, pp. 1078–1082.Google Scholar
  15. 15.
    Hamelin, A. and Lipkowski, J., Underpotential deposition of lead on gold single crystal faces. Part II. General discussion, J. Electroanal. Chem. Interfacial Electrochem., 1984, vol. 171, nos. 1–2, pp. 317–330.Google Scholar
  16. 16.
    Schmidt, U., Vinzelberg, S., and Staikov, G., Pb UPD on Ag(100) and Au(100)—2D phase formation studied by in situ STM, Surf. Sci., 1996, vol. 348, no. 3, pp. 261–279.Google Scholar
  17. 17.
    Horkans, J., Cahan, B.D., and Yeager, E., An ellipsometric investigation of the underpotential deposition of lead on gold, J. Electrochem. Soc., 1975, vol. 122, no. 12, pp. 1585–1589.Google Scholar
  18. 18.
    Leung, L.-W.H. and Weaver, M.J., Extending the metal interface generality of surface-enhanced Raman spectroscopy: Underpotential deposited layers of mercury, thallium, and lead on gold electrodes, J. Electroanal. Chem. Interfacial Electrochem., 1987, vol. 217, no. 2, pp. 367–384.Google Scholar
  19. 19.
    Motheo, A.J., Gonzalez, E.R, Tremilliosi-Filho, G., Racotondrainibe, A., Léger, J.-M., Beden, B., and Lamy, C., A study of the underpotential deposition of lead on gold by UV-visible differential reflectance spectroscopy, J. Braz. Chem. Soc., 1998, vol. 9, no. 1, pp. 31–38.Google Scholar
  20. 20.
    Adžić, R., Yeager, E., and Cahan, B.D., Optical and electrochemical studies of underpotential deposition of lead on gold evaporated and single-crystal electrodes, J. Electrochem. Soc., 1974, vol. 121, no. 4, pp. 474–484.Google Scholar
  21. 21.
    Swathirajan, S., Mizota, H., and Bruckenstein, S., Thermodynamic properties of monolayers of silver and lead deposited on polycrystalline gold in the underpotential region, J. Phys. Chem., 1982, vol. 86, no. 13, pp. 2480–2485.Google Scholar
  22. 22.
    Sudha, V., and Sangaranarayanan, M.V., Underpotential deposition of metals–Progress and prospects in modeling, J. Chem. Sci., 2005, vol. 117, no. 3, pp. 207–218.Google Scholar
  23. 23.
    Rojas, M.I., Dassie, S.A., and Leiva, E.P.M., Theoretical study about the adsorption of lead on (111), (100), (110) monocrystalline surfaces of gold, Z. Phys. Chem., 1994, vol. 185, no. 1, pp. 33–50.Google Scholar
  24. 24.
    Pershina, V., Anton, J., and Fricke, B., Intermetallic compounds of the heaviest elements and their homologs: The electronic structure and bonding of MM', where M = Ge, Sn, Pb, and element 114, and M' = Ni, Pd, Pt, Cu, Ag, Au, Sn, Pb, and element 114, J. Chem. Phys., 2007, vol. 127, no. 13, p. 134310.Google Scholar
  25. 25.
    Pershina, V., Anton, J., and Jacob, T., Theoretical predictions of adsorption behavior of elements 112 and 114 and their homologs Hg and Pb, J. Chem. Phys., 2009, vol. 131, no. 8, p. 084713.Google Scholar
  26. 26.
    Zaitsevskii, A., van Wüllen, C., Rykova, E.A., and Titov, A.V., Two-component relativistic density functional theory modeling of the adsorption of element 114(eka-lead) on gold, Phys. Chem. Chem. Phys., 2010, vol. 12, no. 16, pp. 4152–4156.Google Scholar
  27. 27.
    Schmidt, M.W., Baldridge, K.K., Boatz, J.A., Elbert, S.T., Gordon, M.S., Jensen, J.H., Koseki, S., Matsunaga, N., Nguyen, K.A., Su, S.J., Windus, T.L., Dupuis, M., and Montgomery, J.A., General atomic and molecular electronic structure system, J. Comput. Chem., 1993, vol. 14, no. 11, pp. 1347–1363.Google Scholar
  28. 28.
    Koch, W. and Holthausen, M.C., A Chemist’s Guide to Density Functional Theory, Weinheim: Wiley-VCH, 2001.Google Scholar
  29. 29.
    Becke, A.D., Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 1993, vol. 98, no. 7, pp. 5648–5652.Google Scholar
  30. 30.
    Stephens, P.J, Devlin, F.J., Chablowski, C.F., and Frisch, M.J., Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields, J. Phys. Chem., 1994, vol. 98, no. 45, pp. 11623–11627.Google Scholar
  31. 31.
    Hay, P.J. and Wadt, W.R., Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals, J. Chem. Phys., 1985, vol, 82, no. 1, pp. 299–310.Google Scholar
  32. 32.
    McLean, A.D. and Chandler, G.S., Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z = 11–18, J. Chem. Phys., 1980, vol. 72, no. 10, pp. 5639–5648.Google Scholar
  33. 33.
    Krishnan, R., Binkley, J.S., Seeger, R., and Pople, J.A., Self-consistent molecular orbital methods. XX. A basis set for correlated wave functions, J. Chem. Phys., 1980, vol. 72, no. 1, pp. 650–654.Google Scholar
  34. 34.
    Leach, A.R., Molecular Modeling: Principles and Applications, Harlow: Pearson Education, 2001.Google Scholar
  35. 35.
    Löwdin, P.-O., On the nonorthogonality problem, Adv. Quantum Chem., 1970, vol. 5, pp. 185–199.Google Scholar
  36. 36.
    Dean, J.A., Lange’s Handbook of Chemistry, New York: McGraw-Hill, 1999.Google Scholar
  37. 37.
    Titmuss, S., Wander, A., and King, D.A., Reconstruction of clean and adsorbate-covered metal surfaces, Chem. Rev., 1996, vol. 96, no. 4, pp. 1291–1306.Google Scholar
  38. 38.
    Greenwood, N.N. and Earnshow, A., Chemistry of Elements, Oxford: Butterworth-Heinemann, 1998.Google Scholar
  39. 39.
    Barone, V., Cossi, M., and Tomasi, J., A new definition of cavities for the computation of solvation free energies by the polarizable continuum model, J. Chem. Phys., 1997, vol. 107, no. 8, pp. 3210–3221.Google Scholar
  40. 40.
    Barone, V. and Cossi, M., Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model, J. Phys. Chem. A., 1998, vol. 102, no. 11, pp. 1995–2001.Google Scholar
  41. 41.
    Cossi, M., Rega, N., Scalmani, G., and Barone, V., Energies, structures, and electronic properties of molecules in solution with the C-PCM solvation model, J. Comput. Chem., 2003, vol. 24, no. 6, pp. 669–681.Google Scholar
  42. 42.
    Boys, S.F. and Bernardi, F., The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors, Mol. Phys., 1970, vol. 19, no. 4, pp. 553–566.Google Scholar
  43. 43.
    Jensen, F., Introduction to Computational Chemistry, Chichester: Wiley, 2007.Google Scholar
  44. 44.
    Nazmutdinov, R.R., Manyurov, I.R., Zinkicheva, T.T., Jang, J., and Ulstrup, J., Cysteine adsorption on the Au(111) surface and the electron transfer in configuration of a scanning tunneling microscope: a quantumchemical approach, Russ. J. Electrochem., 2007, vol. 43, no. 3, pp. 328–341.Google Scholar
  45. 45.
    Tang, H.-R., Wang, W.-N., Li, Z.-H., Dai, W.-L., Fan, K.-N., and Deng, J.-F., Chemisorption of iodine on Ag(110): a density-functional theory approach, Surf. Sci., 2000, vol. 450, nos. 1–2, pp. 133–141.Google Scholar
  46. 46.
    Yoon, B., Koskinen, P., Huber, B., Kostko, O., von Issendorff, B., Häkkinen, H., Moseler, M., and Landman, U., Size-Dependent Structural Evolution and Chemical Reactivity of Gold Clusters, Chem. Phys. Chem., 2007, vol. 8, no. 1, pp. 157–161.Google Scholar
  47. 47.
    Strømsnes, H., Jusuf, S., Bagatur’yants, A., Gropen, O., and Wahlgren, U., Model studies of the chemisorption of hydrogen and oxygen on the Au(100) surface, Theor. Chem. Acc., 2001, vol. 106, no. 5, pp. 329–338.Google Scholar
  48. 48.
    Muther, B., Eichler, R., and Gäggeler, H. W., Thermochormatography of 212Pb and 200–202Tl on Quartz and Gold, PSI Annual Report 2007, Bern: Paul Scherrer Institut, 2008.Google Scholar
  49. 49.
    Sellers, H., Patrito, E.M., and Olivera, P.P., Thermodynamic and ab initio calculations of chemisorption energies of ions, Surf. Sci., 1996, vol. 356, nos. 1–3, pp. 222–232.Google Scholar
  50. 50.
    Markovits, A., García-Hernández, M., Ricart, J.M., and Illas, F., Theoretical study of bonding of carbon trioxide and carbonate on Pt(111): relevance to the interpretation of “in situ” vibrational spectroscopy, J. Phys. Chem. B, 1999, vol. 103, no. 3, pp. 509–518.Google Scholar
  51. 51.
    Ample, F., Clotet, A., and Ricart, J.M., Structure and bonding mechanism of cyanide adsorbed on Pt(111), Surf. Sci., 2004, vol. 558, nos. 1–3, pp. 111–121.Google Scholar
  52. 52.
    Nazmutdinov, R.R., Zinkicheva, T.T., Probst, M., Lust, K., and Lust, E., Adsorption of halide ions from aqueous solutions at a Cd(0001) electrode surface: quantum chemical modelling and experimental study, Surf. Sci., 2005, vol. 577, nos. 2–3, pp. 112–126.Google Scholar
  53. 53.
    Liu, S., Ishimoto, T., and Koyama, M., First-principles calculation of OH–/OH adsorption on gold nanoparticles, Int. J. Quantum Chem., 2015, vol. 115, no. 22, pp. 1597–1605.Google Scholar
  54. 54.
    Encyclopedia of Computational Chemistry, Schleyer, P.V.R., Allinger, N.L., Clark T., Gasteiger, J., Kollman, P.A., Schaefer, H.F., and Schreiner, P.R., Eds., Chichester: Willey, 1998, vol. 1.Google Scholar
  55. 55.
    O’Boyle, N.M., Tenderholt, A.L., and Langner, K.M., CCLIB: a library for package-independent computational chemistry algorithms, J. Comput. Chem., 2008, vol. 29, no. 5, pp. 839–845.Google Scholar
  56. 56.
    Bligaard, T., and Nørskov, J.K., Heterogeneous catalysis, in Chemical Bonding Surfaces and Interfaces, Nilsson, A., Petersson, L.G.M., and Nørskov, J.K., Eds., Amsterdam: Elsevier, 2008, ch. 4, pp. 255–322.Google Scholar
  57. 57.
    Chambers, C.C., Hawkins, G.D., Cramer, C.J., and Truhlar, D.C., Model for aqueous solvation based on class IV atomic charges and first solvation shell effects, J. Phys. Chem., 1996, vol. 100, no. 40, pp. 16385–16398.Google Scholar
  58. 58.
    Da Silva, E.F., Svendsen, H.F., and Merz, K.M., Explicitly representing the solvation shell in continuum solvent calculations, J. Phys. Chem. A, 2009, vol. 113, no. 22, pp. 6404–6409.Google Scholar
  59. 59.
    Desnoyers, J.E. and Jolicoeur, C., Hydration effects and thermodynamic properties of ions, in Modern Aspects of Electrochemistry, Bockris, J.O’M. and Conway, B.E., Eds., New York: Plenum Press, 1969, vol. 5, ch. 1, p. 26.Google Scholar
  60. 60.
    Robinson, R.A. and Stokes, R.H., Electrolyte solutions, London: Butterworths, 1959.Google Scholar
  61. 61.
    Marcus, Y., Thermodynamics of solvation of ions. Part 5–Gibbs free energy of hydration at 298.15K, J. Chem. Soc., Faraday Trans., 1991, vol. 87, no. 18, pp. 2995–2999.Google Scholar
  62. 62.
    Bondi, A., Van der Waals volumes and radii, J. Phys. Chem., 1964, vol. 68, no. 3, pp. 441–451.Google Scholar
  63. 63.
    Powell, K.J., Brown, P.L., Byrne, R.H., Gajda, T., Hefter, G., Leuz, A.-K., Sjöberg, S., and Wanner, H., Chemical speciation of environmentally significant metals with inorganic ligands. Part 3: The Pb2+ + OH–, Cl–, and systems (IUPAC Technical Report), Pure Appl. Chem., 2009, vol. 81, no. 12, pp. 2425–2476.Google Scholar

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© Pleiades Publishing, Ltd. 2018

Authors and Affiliations

  1. 1.Institute of Solid State Chemistry and Mechanochemistry, Siberian BranchRussian Academy of SciencesNovosibirskRussia
  2. 2.Novosibirsk State Technical UniversityNovosibirskRussia

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