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

N. A. Rogozhnikov N. A. Rogozhnikov
Российский электрохимический журнал
Abstract / Full Text

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.

Author information
  • Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch, Russian Academy of Sciences, Novosibirsk, 630128, Russia

    N. A. Rogozhnikov

  • Novosibirsk State Technical University, Novosibirsk, 630073, Russia

    N. A. Rogozhnikov

  1. Haissinsky, M., Mécanisme des dépots électrolytiques et expériences avec les radioéléments, J. Chim. Phys. Phys.-Chim. Biol., 1946. vol. 43, pp. 21–29.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  28. Koch, W. and Holthausen, M.C., A Chemist’s Guide to Density Functional Theory, Weinheim: Wiley-VCH, 2001.
  29. Becke, A.D., Density-functional thermochemistry. III. The role of exact exchange, J. Chem. Phys., 1993, vol. 98, no. 7, pp. 5648–5652.
  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.
  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.
  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.
  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.
  34. Leach, A.R., Molecular Modeling: Principles and Applications, Harlow: Pearson Education, 2001.
  35. Löwdin, P.-O., On the nonorthogonality problem, Adv. Quantum Chem., 1970, vol. 5, pp. 185–199.
  36. Dean, J.A., Lange’s Handbook of Chemistry, New York: McGraw-Hill, 1999.
  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.
  38. Greenwood, N.N. and Earnshow, A., Chemistry of Elements, Oxford: Butterworth-Heinemann, 1998.
  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.
  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.
  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.
  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.
  43. Jensen, F., Introduction to Computational Chemistry, Chichester: Wiley, 2007.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  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.
  60. Robinson, R.A. and Stokes, R.H., Electrolyte solutions, London: Butterworths, 1959.
  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.
  62. Bondi, A., Van der Waals volumes and radii, J. Phys. Chem., 1964, vol. 68, no. 3, pp. 441–451.
  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.