Catalysis Letters

, Volume 149, Issue 2, pp 390–398 | Cite as

CO Oxidation Promoted by a Pt4/TiO2 Catalyst: Role of Lattice Oxygen at the Metal/Oxide Interface

  • Ho Viet ThangEmail author
  • Gianfranco Pacchioni


CO oxidation promoted by a subnano Pt4 cluster deposited on the anatase a-TiO2(101) surface has been investigated by means of DFT + U calculations. The focus of the study is on the role of supported Pt4 in favoring the formation of an oxygen vacancy at interface sites between Pt4 and the TiO2 surface, a key step in CO oxidation reactions according to a Mars–van Krevelen mechanism. The motivation is to compare this reaction mechanism with other processes described in the literature for Pt clusters on anatase TiO2 where the reaction involves O2 dissociation at the surface of the metal particle or its activation at the metal/oxide interface. A significant decrease in the energetic cost to remove a lattice oxygen is observed at the interface sites between Pt4 and TiO2, compared to regular sites. This favors the CO oxidation processes by a direct interaction of the CO molecule with a lattice oxygen, with formation of CO2 and an oxygen vacancy. The processes is slightly endothermic, and occurs with barriers comparable, or even lower, than found for the case of Au nanoparticles supported on the same a-TiO2 (101) surface. The next step consists in the re-oxidation of the support. The calculations show that the O2 molecule adsorbs strongly on the reduced catalyst, dissociates with one O atom that recreates the stoichiometric surface, and the other that remains adsorbed on the surface, ready to react with a second CO molecule.

Graphical Abstract


CO oxidation TiO2 anatase Density functional theory Pt/TiO2 Oxygen vacancy Mars–van Krevelen mechanism Heterogeneous catalysts 



The work is supported by the Italian MIUR through the PRIN Project 2015K7FZLH SMARTNESS “Solar driven chemistry: new materials for photo– and electro–catalysis”. We acknowledge the CINECA facility for the availability of high-performance computing resources.


  1. 1.
    Spronsen MAV, Frenken JWM, Groot IMN (2017) Surface science under reaction conditions: CO oxidation on Pt and Pd model catalysts. Chem Soc Rev 46:4347–4374Google Scholar
  2. 2.
    Freund H, Meijer G, Scheffler M, Schlogl R, Wolf M (2011) CO oxidation as a prototypical reaction for heterogeneous processes. Angew Chem Int Ed 50:10064–10094Google Scholar
  3. 3.
    Tosoni S, Pacchioni G (2018) Oxide-supported gold clusters and nanoparticles in catalysis: a computational chemistry perspective. ChemCatChem. Google Scholar
  4. 4.
    Haruta M, Tsubota S, Kobayashi T, Kageyama H, Genet MJ, Delmon B (1993) Low-temperature oxidation of CO over gold supported on TiO2, α-FeO3, and Co3O4. J Catal 144:175–192Google Scholar
  5. 5.
    Haruta M (1997) Size- and support-dependency in the catalysis of gold. Catal Today 36:153–166Google Scholar
  6. 6.
    Widmann D, Behm RJ (2014) Activation of molecular oxygen and the nature of the active oxygen species for CO oxidation on oxide supported Au catalysts. ACC Chem Res 47:740–749Google Scholar
  7. 7.
    Wang Y, Widmann D, Juergen B (2017) Influence of TiO2 bulk defects on CO oxidation on Au/TiO2: electronic metal-support interactions (EMSIs) in supported Au catalysts. ACS Catal 7:2339–2345Google Scholar
  8. 8.
    Widmann D, Behm RJ (2011) Active oxygen on a Au/TiO2 Catalyst: Formation, stability, and CO oxidation activity. Angew Chem Int Ed 50:10241–10245Google Scholar
  9. 9.
    Kim HY, Henkelman G (2013) CO oxidation at the interface of Au nanoclusters and the stepped-CeO2(111) surface by the Mars-van Krevelen mechanism. J Phys Chem Lett 4:216–221Google Scholar
  10. 10.
    Comotti M, Li WC, Spliethoff B, Schüth F (2006) Support effect in high activity gold catalysts for CO oxidation. J Am Chem Soc 128:917–924Google Scholar
  11. 11.
    Duan Z, Henkelman G (2015) CO oxidation at the Au/TiO2 boundary: the role of the Au/Ti5c site. ACS Catal 5:1589–1595Google Scholar
  12. 12.
    Duan Z, Henkelman G (2018) Calculations of CO oxidation over a Au/TiO2 catalyst: a study of active sites, catalyst deactivation, and moisture effects. ACS Catal 8:1376–1383Google Scholar
  13. 13.
    Schlexer P, Widmann D, Behm RJ, Pacchioni G (2018) CO oxidation on a Au/TiO2 nanoparticle catalyst via the Au-Assisted Mars–van Krevelen mechanism. ACS Catal 8:6513–6525Google Scholar
  14. 14.
    Ghosh P, Camellone MF, Fabris S (2013) Fluxionality of Au clusters at Ceria surfaces during CO oxidation: relationships among reactivity, size, cohesion, and surface defects from DFT simulations. J Phys Chem Lett 4:2256–2263Google Scholar
  15. 15.
    Camellone MF, Fabris S (2009) Reaction mechanisms for the CO oxidation on Au/CeO2 catalysts: activity of substitutional Au3+/Au+ cations and deactivation of supported Au+ adatoms. J Am Chem Soc 131:10473–10483Google Scholar
  16. 16.
    Zhang S, Li XS, Chen B, Zhu X, Shi C, Zhu AM (2014) CO oxidation activity at room temperature over Au/CeO2 catalysts: disclosure of induction period and humidity effect. ACS Catal 4:3481–3489Google Scholar
  17. 17.
    Puigdollers AR, Pacchioni G (2017) CO oxidation on Au nanoparticles supported on ZrO2: role of metal/oxide interface and oxide reducibility. ChemCatChem 9:1119–1127Google Scholar
  18. 18.
    Zhang X, Wang H, Xu BQ (2005) Remarkable nanosize effect of zirconia in Au/ZrO2 catalyst for CO oxidation. J Phys Chem B 109:9678–9683Google Scholar
  19. 19.
    Linsebigler AL, Lu G, Yates JT (1995) Photocatalysis on TiO2 surfaces: principles, mechanisms, and selected results. Chem Rev 95:735–758Google Scholar
  20. 20.
    Luttrell T, Halpegamage S, Tao J, Kramer A, Sutter E, Batzill M (2014) Why is anatase a better photocatalyst than rutile?—model studies on epitaxial TiO2 films. Sci Rep 4:4043Google Scholar
  21. 21.
    Gong XQ, Selloni A, Dulub O, Jacobson P, Diebold U (2008) Small Au and Pt clusters at the anatase TiO2(101) surface: behavior at terraces, steps, and surface oxygen vacancies. J Am Chem Soc 130:370–381Google Scholar
  22. 22.
    Zhou Y, Doronkin DE, Chen M, Wei S, Grunwaldt JD (2016) Interplay of Pt and crystal facets of TiO2: CO oxidation activity and operando XAS/DRIFTS studies. ACS Catal 16:7799–7809Google Scholar
  23. 23.
    Li N, Chen QY, Luo LF, Huang WX, Luo MF, Hu G, Lu JQ (2013) Kinetic study and the effect of particle size on low temperature CO oxidation over Pt/TiO2 catalysts. Appl Catal B 142–143:523–532Google Scholar
  24. 24.
    Czupryn K, Kocemba I, Rynkowski J (2018) Photocatalytic CO oxidation with water over Pt/TiO2 catalysts. Reac Kinet Mech Cat 124:187–201Google Scholar
  25. 25.
    GavinChua YP, Kasun Kalhara Gunasooriya GT, Saeys M, Seebauer EG (2014) Controlling the CO oxidation rate over Pt/TiO2 catalysts by defect engineering of the TiO2 support. J Catal 311:306–313Google Scholar
  26. 26.
    Taira K, Nakao K, Suzuki K, Einaga H (2016) SOx tolerant Pt/TiO2 catalysts for CO oxidation and the effect of TiO2 supports on catalytic activity. Environ Sci Technol 50:9773–9780Google Scholar
  27. 27.
    DeRita L, Dai S, Lopz-Zepda K, Pham N, Graham GW, Pan X, Christopher P (2017) Catalyst architecture for stable single atom dispersion enables site-specific spectroscopic and reactivity measurements of CO adsorbed to Pt atoms, oxidized Pt clusters, and metallic Pt clusters on TiO2. J Am Chem Soc 139:14150–14165Google Scholar
  28. 28.
    Therien AJ, Hensley AJ, Marcinkowski MD, Zhang R, Lucci FR, Coughlin B, Schilling AC, McEwen JS, Sykes ECH (2018) An atomic-scale view of single-site Pt catalysis for low-temperature CO oxidation. Nat Catal 1:192–198Google Scholar
  29. 29.
    Jia C, Zhong W, Deng M, Jiang J (2018) CO oxidation on Ru-Pt bimetallic nanoclusters supported on TiO2(101): the effect of charge polarization. J Chem Phys 148:124701Google Scholar
  30. 30.
    Zhou H, Chen X, Wang J (2016) CO oxidation over supported Pt clusters at different CO coverage. Int J Quantum Chem 116:939–944Google Scholar
  31. 31.
    Yin C, Negreiros FR, Barcaro G, Beniya A, Sementa L, Tyo EC, Bartling S, Meiwes-Broer KH, Seifert S, Hirata H, Isomura N, Nigam S, Majumder C, Watanabe Y, Fortunelli A, Vajda S (2017) Alumina-supported sub-nanometer Pt10 clusters: amorphization and role of the support material in a highly active CO oxidation catalyst. J Mater Chem A 5:4923Google Scholar
  32. 32.
    Wang H, An T, Selloni A (2017) Effect of reducible oxide-metal cluster charge transfer on the structure and reactivity of adsorbed Au and Pt atoms and clusters on anatase TiO2. J Chem Phys 146:184703Google Scholar
  33. 33.
    An K, Alayoglu S, Musselwhite N, Plamthottam S, Melaet G, Lindeman AE, Somorjai GA (2013) Enhanced CO oxidation rates at the interface of mesoporous oxides and Pt nanoparticles. J Am Chem Soc 135:16689–16696Google Scholar
  34. 34.
    Bruix A, Migani A, Vayssilov GN, Neyman KM, Libuda J, Illas F (2011) Effects of deposited Pt particles on the reducibility of CeO2 (111). Phys Chem Chem Phys 13:11384–11392Google Scholar
  35. 35.
    Negreiros FR, Fabris S (2014) Role of cluster morphology in the dynamics and reactivity of subnanometer Pt clusters supported on Ceria surfaces. J Phys Chem C 118:21014–21020Google Scholar
  36. 36.
    Heiz U, Landman U (2007) Nanocatalysis. Springer, BerlinGoogle Scholar
  37. 37.
    Kresse G, Furthmüller J (1996) Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. J Comput Mater Sci 6:15–50Google Scholar
  38. 38.
    Kresse G, Furthmüller J (1996) Efficient iterative scheme for ab initio total energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186Google Scholar
  39. 39.
    Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868Google Scholar
  40. 40.
    Blöchl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953Google Scholar
  41. 41.
    Kresse G, Joubert J (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758Google Scholar
  42. 42.
    Dudarev SL, Botton GA, Savrasov SY, Humphreys CJ, Sutton AP (1998) Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA + U study. Phys Rev B 57:1505–1509Google Scholar
  43. 43.
    Hu ZP, Metiu H (2011) Effect of dopants on the energy of oxygen-vacancy formation at the surface of ceria: local or global? J Phys Chem C 115:17898–17909Google Scholar
  44. 44.
    Finazzi E, Di Valentin C, Pacchioni G, Selloni A (2008) Excess electron states in reduced bulk anatase TiO2: comparison of standard GGA, GGA + U, and hybrid DFT. J Chem Phys 129:154113Google Scholar
  45. 45.
    Henkelman G, Jónsson H (2000) Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points. J Chem Phys 113:9978–9986Google Scholar
  46. 46.
    Tang W, Sanville E, Henkelman G (2009) A grid-based bader analysis algorithm without lattice bias. J Phys: Condens Matter 21:084204Google Scholar
  47. 47.
    Sanville E, Kenny SD, Smith R, Henkelman G (2007) An improved grid-based algorithm for bader charge allocation. J Comput Chem 28:899–908Google Scholar
  48. 48.
    Henkelman G, Arnaldsson A, Jónsson H (2006) A fast and robust algorithm for bader decomposition of charge density. Comput Mater Sci 36:254–360Google Scholar
  49. 49.
    Yu M, Trinkle DR (2011) Accurate and efficient algorithm for bader charge integration. J Chem Phys 134:064111Google Scholar
  50. 50.
    Chen HYT, Tosoni S, Pacchioni G (2015) Adsorption of ruthenium atoms and clusters on anatase TiO2 and tetragonal ZrO2 surfaces: a comparative DFT study. J Phys Chem C 119:10856–10868Google Scholar
  51. 51.
    Chen HYT, Tosoni S, Pacchioni G (2016) DFT study of the acid–base properties of anatase TiO2 and tetragonal ZrO2 by adsorption of CO and CO2 probe molecules. Surf Sci 652:163–171Google Scholar
  52. 52.
    Xu Y, Getman RB, Shelton WA, Schneider WF (2008) A first-principles investigation of the effect pf Pt cluster size on CO and NO oxidation intermediates and energetics. Phys Chem Chem Phys 10:6009–6018Google Scholar
  53. 53.
    Karlberg GS, Rossmeisl J, Nørskov JK (2007) Estimation of electric field effects on the oxygen reduction reaction based on the density functional theory. Phys Chem Chem Phys 9:5158–6161Google Scholar
  54. 54.
  55. 55.
    Puigdollers AR, Schlexer P, Tosoni S, Pacchioni G (2017) Increasing oxide reducibility: the role of metal/oxide interfaces in the formation of oxygen vacancies. ACS Catal 7:6493–6513Google Scholar
  56. 56.
    Ho VT, Pacchioni G, DeRita L, Christopher P (2018) Nature of stable single atom Pt catalysts dispersed on anatase TiO2. J Catal 367:104–114Google Scholar
  57. 57.
    Ho VT, Tosoni S, Pacchioni G (2018) Evidence of charge transfer to atomic and molecular adsorbates on ZnO/X(111) (X = Cu, Ag, Au) ultrathin films. Relevance for Cu/ZnO catalysts. ACS Catal 8:4110–4119Google Scholar
  58. 58.
    Bamwenda GR, Tsubota S, Nakamura T, Haruta M (1997) The influence of the preparation methods on the catalytic activity of platinum and gold supported on TiO2 for CO oxidation. Catal Lett 44:83–87Google Scholar
  59. 59.
    Yu X, Wang Y, Kim A, Kim YK (2017) Observation of temperature-dependent kinetics for catalytic CO oxidation over TiO2-supported Pt catalysts. Chem Phys Lett 685:282–287Google Scholar
  60. 60.
    Allian AD, Takanabe K, Fujdala KL, Hao X, Truex TJ, Cai J, Bada C, Neurock M, Iglesia E (2011) Chemisorption of CO and mechanism of CO oxidation on supported platinum nanoparticles. J Am Chem Soc 133:4498–4517Google Scholar
  61. 61.
    Bourane A, Bianchi D (2001) Oxidation of CO on a Pt/Al2O3 catalyst: from the surface elementary steps to light-off tests: I. Kinetic study of oxidation of the linear CO species. J Catal 202:34–44Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Departimento di Scienza dei MaterialiUniversità di Milano-BicoccaMilanoItaly

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