Skip to main content

Thin Oxide Films as Model Systems for Heterogeneous Catalysts

  • Chapter
Springer Handbook of Surface Science

Abstract

This chapter summarizes efforts to use thin oxide films as model supports for heterogeneous catalysts. We demonstrate that the oxide film route provides a useful platform to study oxide surfaces, per se its interaction with species from the gas phase, supported metal and oxide nanoparticles using the entire tool box of surfaces science under ultrahigh vacuum conditions. The extension to use thin oxide films as template also under ambient conditions or under water, is discussed and the potential to use oxide films as genuine two-dimensional materials is exemplified with vitreous and crystalline silica films.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Chapter
USD 29.95
Price excludes VAT (USA)
  • Available as PDF
  • Read on any device
  • Instant download
  • Own it forever
eBook
USD 309.00
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  • H.-J. Freund: The surface science of catalysis and more, using ultrathin oxide films as templates: A perspective, J. Am. Chem. Soc. 138, 8985–8996 (2016)

    Google Scholar 

  • G. Ertl: Reactions at surfaces: From atoms to complexity (Nobel lecture), Angew. Chem. Int. Ed. 47, 3524–3535 (2008)

    Google Scholar 

  • P.A. Cox: Transition Metal Oxides. An Introduction to Their Electronic Structure and Properties (Clarendon, Oxford 1992)

    Google Scholar 

  • V.E. Henrich, P.A. Cox: The Surface Science of Metal Oxides (Cambridge Univ. Press, Cambridge 1994)

    Google Scholar 

  • C. Noguera: Physics and Chemistry at Oxide Surfaces (Cambridge Univ. Press, Cambridge 1996)

    Google Scholar 

  • U. Diebold: The surface science of titanium dioxide, Surf. Sci. Rep. 48, 53–229 (2003)

    ADS  Google Scholar 

  • C.L. Pang, R. Lindsay, G. Thornton: Structure of clean and adsorbate-covered single-crystal rutile TiO2 surfaces, Chem. Rev. 113, 3887–3948 (2013)

    Google Scholar 

  • H.J. Freund, H. Kuhlenbeck, V. Staemmler: Oxide surfaces, Rep. Prog. Phys. 59, 283–347 (1996)

    ADS  Google Scholar 

  • M. Bäumer, H.-J. Freund: Metal deposits on well-ordered oxide films, Prog. Surf. Sci. 61, 127–198 (1999)

    ADS  Google Scholar 

  • C.R. Henry: Surface studies of supported model catalysts, Surf. Sci. Rep. 31, 231–326 (1998)

    ADS  Google Scholar 

  • C.T. Campbell: Ultrathin metal films and particles on oxide surfaces: Structural, electronic and chemisorption properties, Surf. Sci. Rep. 27, 1–111 (1997)

    ADS  Google Scholar 

  • D.W. Goodman: Model catalysts: From extended single crystals to supported particles, Surf. Rev. Lett. 2, 9–24 (1995)

    ADS  Google Scholar 

  • J. Libuda, H.-J. Freund: Reaction kinetics on complex model catalysts under single scattering conditions, J. Phys. Chem. B106, 4901–4915 (2002)

    Google Scholar 

  • H. Kuhlenbeck, S. Shaikhutdinov, H.-J. Freund: Well-ordered transition metal oxide layers in model catalysis: A series of case studies, Chem. Rev. 113, 3986–4034 (2013)

    Google Scholar 

  • G. Pacchioni, H.-J. Freund: Electron transfer at oxide surfaces. The MgO paradigm: From defects to ultrathin films, Chem. Rev. 113, 4035–4072 (2013)

    Google Scholar 

  • H.-J. Freund, G. Pacchioni: Oxide ultra-thin films on metals: New materials for the design of supported metal catalysts, Chem. Soc. Rev. 37, 2224–2242 (2008)

    Google Scholar 

  • H.J. Freund, N. Nilius, T. Risse, S. Schauermann: A fresh look at an old nano-technology: Catalysis, Phys. Chem. Chem. Phys. 16, 8148–8167 (2014)

    Google Scholar 

  • H.-J. Freund: Oxide films as catalytic materials and models of real catalysts. In: Oxide Ultrathin Films: Science and Technology, ed. by G. Pacchioni, S. Valeri (Wiley-VCH, Weinheim 2012) pp. 145–179

    Google Scholar 

  • F.P. Netzer, A. Fortunelli: Oxide Materials at the Two-Dimensional Limit, Springer Series in Materials Science (Springer, Cham 2016)

    Google Scholar 

  • D. Löffler, J.J. Uhlrich, M. Baron, B. Yang, X. Yu, L. Lichtenstein, L. Heinke, C. Büchner, M. Heyde, S. Shaikhutdinov, H.-J. Freund, R. Włodarczyk, M. Sierka, J. Sauer: Growth and structure of crystalline silica sheet on Ru(0001), Phys. Rev. Lett. 105, 146104 (2010)

    ADS  Google Scholar 

  • L. Lichtenstein, M. Heyde, H.-J. Freund: Atomic arrangement in two-dimensional silica: From crystalline to vitreous structures, J. Phys. Chem. C 116, 20426–20432 (2012)

    Google Scholar 

  • L. Lichtenstein, C. Büchner, B. Yang, S. Shaikhutdinov, M. Heyde, M. Sierka, R. Włodarczyk, J. Sauer, H.-J. Freund: The atomic structure of a metal-supported vitreous thin silica film, Angew. Chem. Int. Ed. 51, 404–407 (2012)

    Google Scholar 

  • J.A. Boscoboinik, X. Yu, B. Yang, F.D. Fischer, R. Włodarczyk, M. Sierka, S. Shaikhutdinov, J. Sauer, H.-J. Freund: Modeling zeolites with metal-supported two-dimensional aluminosilicate films, Angew. Chem. Int. Ed. 51, 6005–6008 (2012)

    Google Scholar 

  • S. Foerster, K. Meinel, R. Hammer, M. Trautmann, W. Widdra: Quasicrystalline structure formation in a classical crystalline thin-film system, Nature 502, 215–218 (2013)

    ADS  Google Scholar 

  • G. Pacchioni, L. Giordano, M. Baistrocchi: Charging of metal atoms on ultrathin MgO/Mo(100) films, Phys. Rev. Lett. 94, 226104 (2005)

    ADS  Google Scholar 

  • D. Ricci, A. Bongiorno, G. Pacchioni, U. Landman: Bonding trends and dimensionality crossover of gold nanoclusters on metal-supported MgO thin films, Phys. Rev. Lett. 97, 036106 (2006)

    ADS  Google Scholar 

  • M. Sterrer, T. Risse, M. Heyde, H.-P. Rust, H.-J. Freund: Crossover from three-dimensional to two-dimensional geometries of Au nanostructures on thin MgO(001) films: A confirmation of theoretical predictions, Phys. Rev. Lett. 98, 206103 (2007)

    ADS  Google Scholar 

  • Y. Martynova, B.H. Liu, M.E. McBriarty, I.M.N. Groot, M.J. Bedzyk, S. Shaikhutdinov, H.J. Freund: CO oxidation over ZnO films on Pt(111) at near-atmospheric pressures, J. Catal. 301, 227–232 (2013)

    Google Scholar 

  • I.X. Green, W.J. Tang, M. Neurock, J.T. Yates: Spectroscopic observation of dual catalytic sites during oxidation of CO on a Au/TiO2 catalyst, Science 333, 736–739 (2011)

    ADS  Google Scholar 

  • J.A. Rodriguez, S. Ma, P. Liu, J. Hrbek, J. Evans, M. Pérez: Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water-gas shift reaction, Science 318, 1757–1760 (2007)

    ADS  Google Scholar 

  • K. Hayek, M. Fuchs, B. Klötzer, W. Reichl, G. Rupprechter: Studies of metal–support interactions with “real” and “inverted” model systems: Reactions of CO and small hydrocarbons with hydrogen on noble metals in contact with oxides, Top. Catal. 13, 55–66 (2000)

    Google Scholar 

  • M. Bowker, P. Stone, P. Morrall, R. Smith, R. Bennett, N. Perkins, R. Kvon, C. Pang, E. Fourre, M. Hall: Model catalyst studies of the strong metal–support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110), J. Catal. 234, 172–181 (2005)

    Google Scholar 

  • Z.H. Qin, M. Lewandowski, Y.N. Sun, S. Shaikhutdinov, H.J. Freund: Encapsulation of Pt nanoparticles as a result of strong metal-support interaction with Fe3O4(111), J. Phys. Chem. C 112, 10209–10213 (2008)

    Google Scholar 

  • Y.-N. Sun, Z.-H. Qin, M. Lewandowski, S. Kaya, S. Shaikhutdinov, H.-J. Freund: When an encapsulating oxide layer promotes reaction on noble metals: Dewetting and in situ formation of an “inverted” FeOx/Pt catalyst, Catal. Lett. 126, 31–35 (2008)

    Google Scholar 

  • Y.N. Sun, Z.H. Qin, M. Lewandowski, E. Carrasco, M. Sterrer, S. Shaikhutdinov, H.J. Freund: Monolayer iron oxide film on platinum promotes low temperature CO oxidation, J. Catal. 266, 359–368 (2009)

    Google Scholar 

  • Y. Lei, M. Lewandowski, Y.-N. Sun, Y. Fujimori, Y. Martynova, I.M.N. Groot, R.J. Meyer, L. Giordano, G. Pacchioni, J. Goniakowski, C. Noguera, S. Shaikhutdinov, H.-J. Freund: CO+NO versus CO+O2 reaction on monolayer FeO(111) films on Pt(111), ChemCatChem 3, 671–674 (2011)

    Google Scholar 

  • L. Giordano, M. Lewandowski, I.M.N. Groot, Y.N. Sun, J. Goniakowski, C. Noguera, S. Shaikhutdinov, G. Pacchioni, H.J. Freund: Oxygen-induced transformations of an FeO(111) film on Pt(111): A combined DFT and STM study, J. Phys. Chem. C 114, 21504–21509 (2010)

    Google Scholar 

  • M. Lewandowski, Y.N. Sun, Z.H. Qin, S. Shaikhutdinov, H.J. Freund: Promotional effect of metal encapsulation on reactivity of iron oxide supported Pt catalysts, Appl. Catal. A 391, 407–410 (2011)

    Google Scholar 

  • Y.N. Sun, L. Giordano, J. Goniakowski, M. Lewandowski, Z.H. Qin, C. Noguera, S. Shaikhutdinov, G. Pacchioni, H.J. Freund: The interplay between structure and CO oxidation catalysis on metal-supported ultrathin oxide films, Angew. Chem. Int. Ed. 49, 4418–4421 (2010)

    Google Scholar 

  • M.G. Willinger, W. Zhang, O. Bondarchuk, S. Shaikhutdinov, H.-J. Freund, R. Schlögl: A case of strong metal–support interactions: Combining advanced microscopy and model systems to elucidate the atomic structure of interfaces, Angew. Chem. Int. Ed. 53, 5998–6001 (2014)

    Google Scholar 

  • O. Dulub, W. Hebenstreit, U. Diebold: Imaging cluster surfaces with atomic resolution: The strong metal-support interaction state of Pt supported on TiO2(110), Phys. Rev. Lett. 84, 3646–3649 (2000)

    ADS  Google Scholar 

  • Y. Cui, X. Shao, S. Prada, L. Giordano, G. Pacchioni, H.-J. Freund, N. Nilius: Surface defects and their impact on the electronic structure of Mo-doped CaO films: An STM and DFT study, Phys. Chem. Chem. Phys. 16, 12764–12772 (2014)

    Google Scholar 

  • Y. Cui, X. Shao, M. Baldofski, J. Sauer, N. Nilius, H.-J. Freund: Adsorption, activation, and dissociation of oxygen on doped oxides, Angew. Chem. Int. Ed. 52, 11385–11387 (2013)

    Google Scholar 

  • F. Stavale, X. Shao, N. Nilius, H.-J. Freund, S. Prada, L. Giordano, G. Pacchioni: Donor characteristics of transition-metal-doped oxides: Cr-doped MgO versus Mo-doped CaO, J. Am. Chem. Soc. 134, 11380–11383 (2012)

    Google Scholar 

  • X. Shao, N. Nilius, H.-J. Freund: Crossover from two- to three-dimensional gold particle shapes on CaO films of different thicknesses, Phys. Rev. B 85, 115444 (2012)

    ADS  Google Scholar 

  • X. Shao, N. Nilius, H.-J. Freund: Li/Mo codoping of CaO films: A means to tailor the equilibrium shape of Au deposits, J. Am. Chem. Soc. 134, 2532–2534 (2012)

    Google Scholar 

  • X. Shao, S. Prada, L. Giordano, G. Pacchioni, N. Nilius, H.-J. Freund: Tailoring the shape of metal ad-particles by doping the oxide support, Angew. Chem. Int. Ed. 50, 11525–11527 (2011)

    Google Scholar 

  • R.A. Bennett, P. Stone, M. Bowker: Scanning tunnelling microscopy studies of the reactivity of the TiO2(110) surface: Re-oxidation and the thermal treatment of metal nanoparticles, Faraday Discuss. 114, 267–277 (1999)

    ADS  Google Scholar 

  • W. Mönch: Electronic Properties of Semiconductor Interfaces (Springer, Berlin, Heidelberg 2004)

    Google Scholar 

  • S. Schäfer, S.A. Wyrzgol, R. Caterino, A. Jentys, S.J. Schoell, M. Hävecker, A. Knop-Gericke, J.A. Lercher, I.D. Sharp, M. Stutzmann: Platinum nanoparticles on gallium nitride surfaces: Effect of semiconductor doping on nanoparticle reactivity, J. Am. Chem. Soc. 134, 12528–12535 (2012)

    Google Scholar 

  • X. Song, E. Primorac, H. Kuhlenbeck, H.-J. Freund: Decoupling a thin well-ordered TiO2(110) layer from a TiO2(110) substrate with a Ti+Ta mixed oxide interlayer, J. Phys. Chem. C 120, 8185–8190 (2016)

    Google Scholar 

  • O. Karsliouglu, X. Song, H. Kuhlenbeck, H.-J. Freund: Mo+TiO2(110) mixed oxide layer: Structure and reactivity, Top. Catal. 56, 1389–1403 (2013)

    Google Scholar 

  • X. Song, H. Kuhlenbeck, H.-J. Freund: Effect of vanadium admixing on the surface structure of TiO2(110) under non-oxidizing conditions, Surf. Sci. 653, 181–186 (2016)

    ADS  Google Scholar 

  • H.P. Boehm, A. Clauss, G.O. Fischer, U. Hofmann: Das Adsorptionsverhalten sehr dünner Kohlenstoff-Folien, Z. Anorg. Allg. Chem. 316, 119–127 (1962)

    Google Scholar 

  • H.P. Boehm, R. Setton, E. Stumpp: Nomenclature and terminology of graphite intercalation compounds (IUPAC recommendations 1994), Pure Appl. Chem. 66, 1893–1901 (1994)

    Google Scholar 

  • K.S. Novoselov, A.K. Geim, S.V. Morozov, D. Jiang, Y. Zhang, S.V. Dubonos, I.V. Grigorieva, A.A. Firsov: Electric field effect in atomically thin carbon films, Science 306, 666–669 (2004)

    ADS  Google Scholar 

  • C. Büchner, Z.-J. Wang, K.M. Burson, M.-G. Willinger, M. Heyde, R. Schlögl, H.-J. Freund: A large-area transferable wide band gap 2D silicon dioxide layer, ACS Nano 10, 7982–7989 (2016)

    Google Scholar 

  • H.-J. Freund, M. Heyde, C. Büchner: Transferable Silica Bilayer Film, EP3217423A1 (EPO, Munich 2016)

    Google Scholar 

  • P. Zhao, S. Desai, M. Tosun, T. Roy, H. Fang, A. Sachid, M. Amani, C. Hu, A. Javey: 2D layered materials: From materials properties to device applications. In: IEEE Int. Electron Devices Meet. (IEDM) (2015) pp. 27.23.21–27.23.24

    Google Scholar 

  • M. Sterrer, N. Nilius, S. Shaikhutdinov, M. Heyde, T. Schmidt, H. Freund: Interaction of water with oxide thin film model systems, J. Mater. Res. 34(3), 360–378 (2019)

    ADS  Google Scholar 

  • N. Nilius: Properties of oxide thin films and their adsorption behavior studied by scanning tunneling microscopy and conductance spectroscopy, Surf. Sci. Rep. 64, 595–659 (2009)

    ADS  Google Scholar 

  • S. Surnev, M.G. Ramsey, F.P. Netzer: Vanadium oxide surface studies, Prog. Surf. Sci. 73, 117–165 (2003)

    ADS  Google Scholar 

  • G. Kresse, M. Schmid, E. Napetschnig, M. Shishkin, L. Köhler, P. Varga: Structure of the ultrathin aluminum oxide film on NiAl(110), Science 308, 1440–1442 (2005)

    ADS  Google Scholar 

  • S. Schintke, S. Messerli, M. Pivetta, F. Patthey, L. Libioulle, M. Stengel, A. De Vita, W.-D. Schneider: Insulator at the ultrathin limit: MgO on Ag(001), Phys. Rev. Lett. 87, 2768011–2768014 (2001)

    Google Scholar 

  • M. Klaua, D. Ullmann, J. Barthel, W. Wulfhekel, J. Kirschner, R. Urban, T.L. Monchesky, A. Enders, J.F. Cochran, B. Heinrich: Growth, structure, electronic, and magnetic properties of MgO/Fe(001) bilayers and Fe/MgO/Fe(001) trilayers, Phys. Rev. B 64, 134411 (2001)

    ADS  Google Scholar 

  • M.C. Wu, J.S. Corneille, C.A. Estrada, J.W. He, D.W. Goodman: Synthesis and characterization of ultra-thin MgO films on Mo(100), Chem. Phys. Lett. 182, 472–478 (1991)

    ADS  Google Scholar 

  • S. Benedetti, H.M. Benia, N. Nilius, S. Valeri, H.J. Freund: Morphology and optical properties of MgO thin films on Mo(001), Chem. Phys. Lett. 430, 330–335 (2006)

    ADS  Google Scholar 

  • X. Shao, P. Myrach, N. Nilius, H.J. Freund: Growth and morphology of calcium-oxide films grown on Mo(001), J. Phys. Chem. C 115, 8784–8789 (2011)

    Google Scholar 

  • N. Nilius, S. Benedetti, Y. Pan, P. Myrach, C. Noguera, L. Giordano, J. Goniakowski: Electronic and electrostatic properties of polar oxide nanostructures: MgO(111) islands on Au(111), Phys. Rev. B 86, 205410 (2012)

    ADS  Google Scholar 

  • J. Goniakowski, C. Finocchi, C. Noguera: Polarity of oxide surfaces and nanostructures, Rep. Prog. Phys. 71, 016501–016555 (2008)

    ADS  Google Scholar 

  • F. Finocchi, A. Barbier, J. Jupille, C. Noguera: Stability of rocksalt (111) polar surfaces: Beyond the octopole, Phys. Rev. Lett. 92, 136101 (2004)

    ADS  Google Scholar 

  • J. Pal, M. Smerieri, E. Celasco, L. Savio, L. Vattuone, M. Rocca: Morphology of monolayer MgO films on Ag(100): Switching from corrugated islands to extended flat terraces, Phys. Rev. Lett. 112, 126102 (2014)

    ADS  Google Scholar 

  • J. Pal, M. Smerieri, E. Celasco, L. Savio, L. Vattuone, R. Ferrando, S. Tosoni, L. Giordano, G. Pacchioni, M. Rocca: How growing conditions and interfacial oxygen affect the final morphology of MgO/Ag(100) films, J. Phys. Chem. C 118, 26091–26102 (2014)

    Google Scholar 

  • K.P. McKenna, A.L. Shluger: Electron-trapping polycrystalline materials with negative electron affinity, Nat. Mater. 7, 859–862 (2008)

    ADS  Google Scholar 

  • S. Benedetti, P. Torelli, S. Valeri, H.M. Benia, N. Nilius, G. Renaud: Structure and morphology of thin MgO films on Mo(001), Phys. Rev. B 78, 195411–195418 (2008)

    ADS  Google Scholar 

  • S. Benedetti, F. Stavale, S. Valeri, C. Noguera, H.J. Freund, J. Goniakowski, N. Nilius: Steering the growth of metal ad-particles via interface interactions between a MgO thin film and a Mo support, Adv. Funct. Mater. 23, 75–80 (2013)

    Google Scholar 

  • L. Giordano, F. Cinquini, G. Pacchioni: Tuning the surface metal work function by deposition of ultrathin oxide films: Density functional calculations, Phys. Rev. B 73, 045414 (2006)

    ADS  Google Scholar 

  • H.M. Benia, P. Myrach, N. Nilius, H.J. Freund: Structural and electronic characterization of the MgO/Mo(001) interface using STM, Surf. Sci. 604, 435–441 (2010)

    ADS  Google Scholar 

  • M. Sterrer, E. Fischbach, T. Risse, H.-J. Freund: Geometric characterization of a singly charged oxygen vacancy on a single-crystalline MgO(001) film by electron paramagnetic resonance spectroscopy, Phys. Rev. Lett. 94, 186101 (2005)

    ADS  Google Scholar 

  • M. Sterrer, E. Fischbach, M. Heyde, N. Nilius, H.P. Rust, T. Risse, H.J. Freund: Electron paramagnetic resonance and scanning tunneling microscopy investigations on the formation of F+ and F0 color centers on the surface of thin MgO(001) films, J. Phys. Chem. B 110, 8665–8669 (2006)

    Google Scholar 

  • M. Sterrer, M. Heyde, M. Novicki, N. Nilius, T. Risse, H.P. Rust, G. Pacchioni, H.J. Freund: Identification of color centers on MgO(001) thin films with scanning tunneling microscopy, J. Phys. Chem. B 110, 46–49 (2006)

    Google Scholar 

  • T. König, G.H. Simon, H.P. Rust, G. Pacchioni, M. Heyde, H.J. Freund: Measuring the charge state of point defects on MgO/Ag(001), J. Am. Chem. Soc. 131, 17544–17545 (2009)

    Google Scholar 

  • H.M. Benia, P. Myrach, A. Gonchar, T. Risse, M. Nilius, H.J. Freund: Electron trapping in misfit dislocations of MgO thin films, Phys. Rev. B 81, 241415 (2010)

    ADS  Google Scholar 

  • K.P. McKenna, A.L. Shluger: First-principles calculations of defects near a grain boundary in MgO, Phys. Rev. B 79, 224116 (2009)

    ADS  Google Scholar 

  • H.M. Benia, P. Myrach, N. Nilius: Photon emission spectroscopy of thin MgO films with the STM: From a tip-mediated to an intrinsic emission characteristic, New J. Phys. 10, 013010 (2008)

    ADS  Google Scholar 

  • E.D.L. Rienks, N. Nilius, H.P. Rust, H.J. Freund: Surface potential of a polar oxide film: FeO on Pt(111), Phys. Rev. B 71, 2414041–2414044 (2005)

    Google Scholar 

  • M. Sterrer, T. Risse, H.J. Freund: CO adsorption on the surface of MgO(001) thin films, Appl. Catal. A 307, 58–61 (2006)

    Google Scholar 

  • L.M. Molina, B. Hammer: Some recent theoretical advances in the understanding of the catalytic activity of Au, Appl. Catal. A 291, 21–31 (2005)

    Google Scholar 

  • B. Yoon, H. Häkkinen, U. Landman, A.S. Wörz, J.M. Antonietti, S. Abbet, K. Judai, U. Heiz: Charging effects on bonding and catalyzed oxidation of CO on Au-8 clusters on MgO, Science 307, 403–407 (2005)

    ADS  Google Scholar 

  • S. Sastry, P.G. Debenedetti, F.H. Stillinger: Signatures of distinct dynamical regimes in the energy landscape of a glass-forming liquid, Nature 393, 554–557 (1998)

    ADS  Google Scholar 

  • R. Zallen: The Physics of Amorphous Solids (Wiley-VCH, Weinheim 2004)

    Google Scholar 

  • L. Berthier, G. Biroli: Theoretical perspective on the glass transition and amorphous materials, Rev. Mod. Phys. 83, 587–645 (2011)

    ADS  Google Scholar 

  • J.C. Mauro, E.D. Zanotto: Two centuries of glass research: Historical trends, current status, and grand challenges for the future, Int. J. Appl. Glass Sci. 5, 313–327 (2014)

    Google Scholar 

  • W.H. Zachariasen: The atomic arrangement in glass, J. Am. Chem. Soc. 54, 3841–3851 (1932)

    Google Scholar 

  • L. Lichtenstein, M. Heyde, H.-J. Freund: Crystalline-vitreous interface in two dimensional silica, Phys. Rev. Lett. 109, 106101 (2012)

    ADS  Google Scholar 

  • X. Yu, B. Yang, J.A. Boscoboinik, S. Shaikhutdinov, H.-J. Freund: Support effects on the atomic structure of ultrathin silica films on metals, Appl. Phys. Lett. 100, 151608 (2012)

    ADS  Google Scholar 

  • P.Y. Huang, S. Kurasch, A. Srivastava, V. Skakalova, J. Kotakoski, A.V. Krasheninnikov, R. Hovden, Q. Mao, J.C. Meyer, J. Smet, D.A. Muller, U. Kaiser: Direct imaging of a two-dimensional silica glass on graphene, Nano Lett. 12, 1081–1086 (2012)

    ADS  Google Scholar 

  • E.I. Altman, U.D. Schwarz: Structural and electronic heterogeniety of two dimensional amorphous silica layers, Adv. Mater. Interfaces 1, 1400108 (2014)

    Google Scholar 

  • R.M. Cornell, U. Schwertmann: The Iron Oxides (Wiley-VCH, Weinheim 2004)

    Google Scholar 

  • G. Ertl, H. Knözinger, F. Schueth, J. Weitkamp: Handbook of Heterogeneous Catalysis (VCH, Weinheim 2008)

    Google Scholar 

  • R. Zboril, M. Mashlan, D. Petridis: Iron(III) oxides from thermal processessynthesis, structural and magnetic properties, Mössbauer spectroscopy characterization, and applications, Chem. Mater. 14, 969–982 (2002)

    Google Scholar 

  • W. Weiss, W. Ranke: Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers, Prog. Surf. Sci. 70, 1–151 (2002)

    ADS  Google Scholar 

  • N.G. Condon, F.M. Leibsle, T. Parker, A.R. Lennie, D.J. Vaughan, G. Thornton: Biphase ordering on Fe3O4(111), Phys. Rev. B 55, 15885–15894 (1997)

    ADS  Google Scholar 

  • A. Barbieri, W. Weiss, M.A.V. Hove, G.A. Somorjai: Magnetite Fe3O4(111): Surface structure by LEED crystallography and energetics, Surf. Sci. 302, 259–279 (1994)

    ADS  Google Scholar 

  • G.S. Parkinson: Iron oxide surfaces, Surf. Sci. Rep. 71, 272–365 (2016)

    ADS  Google Scholar 

  • A. Sala, H. Marchetto, Z.H. Qin, S. Shaikhutdinov, T. Schmidt, H.-J. Freund: Defects and inhomogeneities in Fe3O4(111) thin film growth on Pt(111), Phys. Rev. B 86, 155430 (2012)

    ADS  Google Scholar 

  • N. Nilius, E.D.L. Rienks, H.-P. Rust, H.-J. Freund: Self-organization of gold atoms on a polar FeO(111) surface, Phys. Rev. Lett. 95, 066101 (2005)

    ADS  Google Scholar 

  • M. Melzer, J. Urban, H. Sack-Kongehl, K. Weiss, H.-J. Freund, R. Schlögl: Preparation of vanadium and vanadium oxide clusters by means of inert gas aggregation, Catal. Lett. 81, 219–221 (2002)

    Google Scholar 

  • W. Weiss, M. Ritter: Metal oxide heteroepitaxy: Stranski–Krastanov growth of iron oxides on Pt(111), Phys. Rev. B 59, 5201–5213 (1999)

    ADS  Google Scholar 

  • D.T. Margulies, F.T. Parker, M.L. Rudee, F.E. Spada, J.N. Chapman, P.R. Aitchison, A.E. Berkowitz: Origin of the anomalous magnetic behavior in single crystal Fe3O4 films, Phys. Rev. Lett. 79, 5201–5165 (1997)

    Google Scholar 

  • M. Ritter, W. Weiss: Fe3O4(111) surface structure determined by LEED crystallography, Surf. Sci. 432, 81–94 (1999)

    ADS  Google Scholar 

  • F. Genuzio, A. Sala, T. Schmidt, D. Menzel, H.-J. Freund: Interconversion of α-Fe2O3 and Fe3O4 thin films: Mechanisms, morphology, and evidence for unexpected substrate participation, J. Phys. Chem. C 118, 29068–29076 (2014)

    Google Scholar 

  • F. Genuzio, A. Sala, T. Schmidt, D. Menzel, H.-J. Freund: Phase transformations in thin iron oxide films: Spectromicroscopic study of velocity and shape of the reactions fronts, Surf. Sci. 648, 177–187 (2016)

    ADS  Google Scholar 

  • C. Schlueter, M. Lubbe, A.M. Gigler, W. Moritz: Growth of iron oxides on Ag(111)—Reversible Fe2O3/Fe3O4 transformation, Surf. Sci. 605, 1986–1993 (2011)

    ADS  Google Scholar 

  • B. Grzybowska-Swierkosz, F. Trifiro, J.C. Vedrine: Vanadia catalysts for selective oxidation of hydrocarbons and their derivatives, Appl. Catal. A 157(1–2), 1–425 (1997)

    Google Scholar 

  • A. Chieregato, J.M.L. Nieto, F. Cavani: Mixed-oxide catalysts with vanadium as the key element for gas-phase reactions, Coord. Chem. Rev. 301, 3–23 (2015)

    Google Scholar 

  • B.B. Jiang, S.L. Yuan, N. Chen, H.B. Wang, J.D. Wang, Z.L. Huang: Reaction kinetics of n-butane oxidation on VPO catalyst, Prog. Chem. 27, 1679–1688 (2015)

    Google Scholar 

  • M. Sutradhar, L. Martins, M. da Silva, A.J.L. Pombeiro: Vanadium complexes: Recent progress in oxidation catalysis, Coord. Chem. Rev. 301, 200–239 (2015)

    Google Scholar 

  • L. Artiglia, S. Agnoli, G. Granozzi: Vanadium oxide nanostructures on another oxide: The viewpoint from model catalysts studies, Coord. Chem. Rev. 301, 106–122 (2015)

    Google Scholar 

  • C.A. Carrero, R. Schloegl, I.E. Wachs, R. Schomaecker: Critical literature review of the kinetics for the oxidative dehydrogenation of propane over well-defined supported vanadium oxide catalysts, ACS Catalysis 4, 3357–3380 (2014)

    Google Scholar 

  • S. Guimond, D. Göbke, Y. Romanyshyn, J.M. Sturm, M. Naschitzki, H. Kuhlenbeck, H.-J. Freund: Growth and characterization of ultrathin V2Oy(y ≈ 5) films on Au(111), J. Phys. Chem. C 112, 12363–12373 (2008)

    Google Scholar 

  • S. Guimond, J.M. Sturm, D. Göbke, Y. Romanyshyn, M. Naschitzki, H. Kuhlenbeck, H.J. Freund: Well-ordered V2O5(001) thin films on Au(111): Growth and thermal stability, J. Phys. Chem. C 112, 11835–11846 (2008)

    Google Scholar 

  • F.E. Feiten, H. Kuhlenbeck, H.J. Freund: Surface structure of V2O3(0001): A combined I/V-LEED and STM study, J. Phys. Chem. C 119, 22961–22969 (2015)

    Google Scholar 

  • F.E. Feiten, J. Seifert, J. Paier, H. Kuhlenbeck, H. Winter, J. Sauer, H.J. Freund: Surface structure of V2O3(0001) revisited, Phys. Rev. Lett. 114, 216101 (2015)

    ADS  Google Scholar 

  • A.C. Dupuis, M. Abu Haija, B. Richter, H. Kuhlenbeck, H.J. Freund: V2O3(0001) on Au(111) and W(110): Growth, termination and electronic structure, Surf. Sci. 539, 99–112 (2003)

    ADS  Google Scholar 

  • J. Schoiswohl, M. Sock, S. Surnev, M.G. Ramsey, F.P. Netzer, G. Kresse, J.N. Andersen: V2O3(0001) surface terminations: From oxygen- to vanadium-rich, Surf. Sci. 555, 101 (2004)

    ADS  Google Scholar 

  • A.J. Window, A. Hentz, D.C. Sheppard, G.S. Parkinson, H. Niehus, D. Ahlbehrendt, T.C.Q. Noakes, P. Bailey, D.P. Woodruff: V2O3(0001) surface termination: Phase equilibrium, Phys. Rev. Lett. 107, 016105 (2011)

    ADS  Google Scholar 

  • H. Niehus, R.P. Blum, D. Ahlbehrendt: Structure of vanadium oxide (V2O3) grown on Cu3Au(100), Surf. Rev. Lett. 10, 353–359 (2003)

    ADS  Google Scholar 

  • B. Tepper, B. Richter, A.C. Dupuis, H. Kuhlenbeck, C. Hucho, P. Schilbe, M.A. bin Yarmo, H.J. Freund: Adsorption of molecular and atomic hydrogen on vacuum-cleaved V2O5(001), Surf. Sci. 496, 64–72 (2002)

    ADS  Google Scholar 

  • A. Atrei, U. Bardi, C. Tarducci, G. Rovida: Growth, composition, and structure of ultrathin vanadium films deposited on the SnO2(110) surface, J. Phys. Chem. B 104, 3121–3129 (2000)

    Google Scholar 

  • A. Atrei, U. Bardib, B. Cortigiani, G. Rovida: XPD study of vanadium oxide films grown on the SnO2(110) surface, Surf. Rev. Lett. 6, 1187–1193 (1999)

    ADS  Google Scholar 

  • Y. Romanyshyn, S. Guimond, D. Göbke, J.M. Sturm, H. Kuhlenbeck, J. Döbler, M.V. Ganduglia-Pirovano, J. Sauer, H.J. Freund: Methanol adsorption on V2O3(0001), Top. Catal. 54, 669–684 (2011)

    Google Scholar 

  • P.W. Tasker: Stability of ionic-crystal surfaces, J. Phys. C 12, 4977–4984 (1979)

    ADS  Google Scholar 

  • A.J. Window, A. Hentz, D.C. Sheppard, G.S. Parkinson, D.P. Woodruff, W. Unterberger, T.C.Q. Noakes, P. Bailey, M.V. Ganduglia-Pirovano, J. Sauer: The structure of epitaxial V2O3 films and their surfaces: A medium energy ion scattering study, Surf. Sci. 606, 1716–1727 (2012)

    ADS  Google Scholar 

  • J. Seifert, E. Meyer, H. Winter, H. Kuhlenbeck: Surface termination of an ultrathin V2O3-film on Au(111) studied via ion beam triangulation, Surf. Sci. 606, L41–L44 (2012)

    ADS  Google Scholar 

  • F. Sedona, G.A. Rizzi, S. Agnoli, F. Xamena, A. Papageorgiou, D. Ostermann, M. Sambi, P. Finetti, K. Schierbaum, G. Granozzi: Ultrathin TiOx films on Pt(111): A LEED, XPS, and STM investigation, J. Phys. Chem. B 109, 24411–24426 (2005)

    Google Scholar 

  • C.M. Yim, C.L. Pang, G. Thornton: Oxygen vacancy origin of the surface band-gap state of TiO2(110), Phys. Rev. Lett. 104, 036806 (2010)

    ADS  Google Scholar 

  • S. Wendt, P.T. Sprunger, E. Lira, G.K.H. Madsen, Z. Li, J.Ø. Hansen, J. Matthiesen, A. Blekinge-Rasmussen, E. Lægsgaard, B. Hammer, F. Besenbacher: The role of interstitial sites in the Ti3d defect state in the band gap of titania, Science 320, 1755–1759 (2008)

    ADS  Google Scholar 

  • C. Di Valentin, G. Pacchioni, A. Selloni: Reduced and n-type doped TiO2: Nature of Ti3+ species, J. Phys. Chem. C 113, 20543–20552 (2009)

    Google Scholar 

  • S. Wendt, R. Schaub, J. Matthiesen, E.K. Vestergaard, E. Wahlstrom, M.D. Rasmussen, P. Thostrup, L.M. Molina, E. Laegsgaard, I. Stensgaard, B. Hammer, F. Besenbacher: Oxygen vacancies on TiO2(110) and their interaction with H2O and O2: A combined high-resolution STM and DFT study, Surf. Sci. 598, 226–245 (2005)

    ADS  Google Scholar 

  • M. Li, W. Hebenstreit, U. Diebold, A.M. Tyryshkin, M.K. Bowman, G.G. Dunham, M.A. Henderson: The influence of the bulk reduction state on the surface structure and morphology of rutile TiO2(110) single crystals, J. Phys. Chem. B 104, 4944–4950 (2000)

    Google Scholar 

  • M. Yulikov, M. Sterrer, M. Heyde, H.P. Rust, T. Risse, H.-J. Freund, G. Pacchioni, A. Scagnelli: Binding of single gold atoms on thin MgO(001) films, Phys. Rev. Lett. 96, 146804 (2006)

    ADS  Google Scholar 

  • M. Sterrer, M. Yulikov, T. Risse, H.-J. Freund, J. Carrasco, F. Illas, C. Di Valentin, L. Giordano, G. Pacchioni: When the reporter induces the effect: Unusual IR spectra of CO on Au1/MgO(001)/Mo(001), Angew. Chem. Int. Ed. 45, 2633–2635 (2006)

    Google Scholar 

  • L. Giordano, G. Pacchioni: Charge transfers at metal/oxide interfaces: A DFT study of formation of K+ and Au species on MgO/Ag(100) ultra-thin films from deposition of neutral atoms, Phys. Chem. Chem. Phys. 8, 3335–3341 (2006)

    Google Scholar 

  • P. Frondelius, A. Hellman, K. Honkala, H. Häkkinen, H. Grönbeck: Charging of atoms, clusters, and molecules on metal-supported oxides: A general and long-ranged phenomenon, Phys. Rev. B 78, 085426–085427 (2008)

    ADS  Google Scholar 

  • J. Goniakowski, C. Noguera: Electronic states and schottky barrier height at metal/MgO(100) interfaces, Interface Sci. 12, 93–103 (2004)

    Google Scholar 

  • H. Grönbeck: Mechanism for NO2 charging on metal supported MgO, J. Phys. Chem. B 110, 11977–11981 (2006)

    Google Scholar 

  • A. Gonchar, T. Risse, H.-J. Freund, L. Giordano, C. Di Valentin, G. Pacchioni: Activation of oxygen on MgO: O2 radical ion formation on thin, metal-supported MgO(001) films, Angew. Chem. Int. Ed. 50, 2635–2638 (2011)

    Google Scholar 

  • J. Tersoff, D.R. Hamann: Theory of the scanning tunneling microscope, Phys. Rev. B 31, 805 (1985)

    ADS  Google Scholar 

  • M. Sterrer, T. Risse, U. Martinez Pozzoni, L. Giordano, M. Heyde, H.-P. Rust, G. Pacchioni, H.-J. Freund: Control of the charge state of metal atoms on thin MgO films, Phys. Rev. Lett. 98, 096107 (2007)

    ADS  Google Scholar 

  • J. Repp, G. Meyer, F.E. Olsson, M. Persson: Controlling the charge state of individual gold adatoms, Science 305, 493–495 (2004)

    ADS  Google Scholar 

  • K. Honkala, H. Häkkinen: Au adsorption on regular and defected thin MgO(100) films supported by Mo, J. Phys. Chem. C 111, 4319–4327 (2007)

    Google Scholar 

  • A. Hellman, S. Klacar, H. Grönbeck: Low temperature CO oxidation over supported ultrathin MgO films, J. Am. Chem. Soc. 131, 16636–16637 (2009)

    Google Scholar 

  • P. Frondelius, H. Häkkinen, K. Honkala: Adsorption and activation of O2 at Au chains on MgO/Mo thin films, Phys. Chem. Chem. Phys. 12, 1483–1492 (2010)

    Google Scholar 

  • H. Schlienz, M. Beckendorf, U.J. Katter, T. Risse, H.-J. Freund: Electron-spin-resonance investigations of the molecular-motion of NO2 on Al2O3(111) under ultrahigh-vacuum conditions, Phys. Rev. Lett. 74, 761–764 (1995)

    ADS  Google Scholar 

  • M. Chiesa, E. Giamello, M.C. Paganini, Z. Sojka, D.M. Murphy: Continuous wave electron paramagnetic resonance investigation of the hyperfine structure of 17O2 adsorbed on the MgO surface, J. Chem. Phys. 116, 4266–4274 (2002)

    ADS  Google Scholar 

  • G. Pacchioni, A.M. Ferrari, E. Giamello: Cluster model of O2 adsorption on regular and defect sites and Fs centers of the MgO(100) surface, Chem. Phys. Lett. 255, 58–64 (1996)

    ADS  Google Scholar 

  • M. Sterrer, O. Diwald, E. Knözinger: Vacancies and electron deficient surface anions on the surface of MgO nanoparticles, J. Phys. Chem. B 104, 3601–3607 (2000)

    Google Scholar 

  • X. Lin, N. Nilius, H.J. Freund, M. Walter, P. Frondelius, K. Honkala, H. Häkkinen: Quantum well states in two-dimensional gold clusters on MgO thin films, Phys. Rev. Lett. 102, 206801 (2009)

    ADS  Google Scholar 

  • N. Nilius, M.V. Ganduglia-Pirovano, V. Brazdova, M. Kulawik, J. Sauer, H.J. Freund: Counting electrons transferred through a thin alumina film into Au chains, Phys. Rev. Lett. 100, 096802 (2008)

    ADS  Google Scholar 

  • X. Lin, N. Nilius, M. Sterrer, P. Koskinen, H. Häkkinen, H.-J. Freund: Characterizing low-coordinated atoms at the periphery of MgO-supported Au islands using scanning tunneling microscopy and electronic structure calculations, Phys. Rev. B 81, 153406 (2010)

    ADS  Google Scholar 

  • M. Walter, P. Frondelius, K. Honkala, H. Häkkinen: Electronic structure of MgO-supported Au clusters: Quantum dots probed by scanning tunneling microscopy, Phys. Rev. Lett. 99, 096102 (2007)

    ADS  Google Scholar 

  • C. Kittel: Introduction to Solid State Physics (Wiley, New York 2005)

    MATH  Google Scholar 

  • A.A. Herzing, C.J. Kiely, A.F. Carley, P. Landon, G.J. Hutchings: Identification of active gold nanoclusters on iron oxide supports for CO oxidation, Science 321, 1331–1335 (2008)

    ADS  Google Scholar 

  • E.W. McFarland, H. Metiu: Catalysis by doped oxides, Chem. Rev. 113, 4391–4427 (2013)

    Google Scholar 

  • J. Robertson, S.J. Clark: Limits to doping in oxides, Phys. Rev. B 83, 075303 (2011)

    Google Scholar 

  • H.Y. Kim, H.M. Lee, R.G.S. Pala, V. Shapovalov, H. Metiu: CO oxidation by rutile TiO2(110) doped with V, W, Cr, Mo, and Mn, J. Phys. Chem. C 112, 12398–12408 (2008)

    Google Scholar 

  • E.N. Sgourou, D. Timerkaeva, C.A. Londos, D. Aliprantis, A. Chroneos, D. Caliste, P. Pochet: Impact of isovalent doping on the trapping of vacancy and interstitial related defects in Si, J. Appl. Phys. 113, 113506 (2013)

    ADS  Google Scholar 

  • S. Prada, L. Giordano, G. Pacchioni: Charging of gold atoms on doped MgO and CaO: Identifying the key parameters by DFT calculations, J. Phys. Chem. C 117, 9943–9951 (2013)

    Google Scholar 

  • F. Stavale, N. Nilius, H.J. Freund: Cathodoluminescence of near-surface centres in Cr-doped MgO(001) thin films probed by scanning tunnelling microscopy, New J. Phys. 14, 033006 (2012)

    ADS  Google Scholar 

  • G. Pacchioni, J.M. Ricart, F. Illas: Ab-initio cluster model-calculations on the chemisorption of CO2 and SO2 probe molecules on MgO and CaO(100) surfaces—A theoretical measure of oxide basicity, J. Am. Chem. Soc. 116, 10152–10158 (1994)

    Google Scholar 

  • Z. Hu, B. Li, X. Sun, H. Metiu: Chemistry of doped oxides: The activation of surface oxygen and the chemical compensation effect, J. Phys. Chem. C 115, 3065–3074 (2011)

    Google Scholar 

  • B. Li, H. Metiu: DFT studies of oxygen vacancies on undoped and doped La2O3 surfaces, J. Phys. Chem. C 114, 12234–12244 (2010)

    Google Scholar 

  • P. Myrach, N. Nilius, S.V. Levchenko, A. Gonchar, T. Risse, K.P. Dinse, L.A. Boatner, W. Frandsen, R. Horn, H.J. Freund, R. Schlögl, M. Scheffler: Temperature-dependent morphology, magnetic and optical properties of Li-doped MgO, ChemCatChem 2, 854–862 (2010)

    Google Scholar 

  • S. Lany, J. Osorio-Guillén, A. Zunger: Origins of the doping asymmetry in oxides: Hole doping in NiO versus electron doping in ZnO, Phys. Rev. B 75, 241203(R) (2007)

    ADS  Google Scholar 

  • F. Bebensee, V. Voigts, W. Maus-Friedrichs: The adsorption of oxygen and water on Ca and CaO films studied with MIES, UPS and XPS, Surf. Sci. 602, 1622–1630 (2008)

    ADS  Google Scholar 

  • B.C. Stipe, M.A. Rezaei, W. Ho, S. Gao, M. Persson, B.I. Lundqvist: Single-molecule dissociation by tunneling electrons, Phys. Rev. Lett. 78, 4410–4413 (1997)

    ADS  Google Scholar 

  • Y. Cui, N. Nilius, H.-J. Freund, S. Prada, L. Giordano, G. Pacchioni: Controlling the charge state of single Mo dopants in a CaO film, Phys. Rev. B 88, 205421 (2013)

    ADS  Google Scholar 

  • Y. Cui, C. Stiehler, N. Nilius, H.-J. Freund: Probing the electronic properties and charge state of gold nanoparticles on ultrathin MgO versus thick doped CaO films, Phys. Rev. B 92, 075444 (2015)

    ADS  Google Scholar 

  • C. Büchner, L. Lichtenstein, S. Stuckenholz, M. Heyde, F. Ringleb, M. Sterrer, W.E. Kaden, L. Giordano, G. Pacchioni, H.-J. Freund: Adsorption of Au and Pd on ruthenium-supported bilayer silica, J. Phys. Chem. C 118, 20959–20969 (2014)

    Google Scholar 

  • W.E. Kaden, C. Büchner, L. Lichtenstein, S. Stuckenholz, F. Ringleb, M. Heyde, M. Sterrer, H.-J. Freund, L. Giordano, G. Pacchioni, C.J. Nelin, P.S. Bagus: Understanding surface core-level shifts using the Auger parameter: A study of Pd atoms adsorbed on ultrathin SiO2 films, Phys. Rev. B 89, 115436 (2014)

    ADS  Google Scholar 

  • S. Ulrich, N. Nilius, H.-J. Freund, U. Martinez, L. Giordano, G. Pacchioni: Realization of an atomic sieve: Silica on Mo(112), Surf. Sci. 603, 1145–1149 (2009)

    ADS  Google Scholar 

  • S. Ulrich, N. Nilius, H.-J. Freund, U. Martinez, L. Giordano, G. Pacchioni: Tailoring adsorption properties of inert oxide films by inserting anchor sites, Phys. Rev. Lett. 102, 016102 (2009)

    ADS  Google Scholar 

  • J.-F. Jerratsch, N. Nilius, D. Topwal, U. Martinez, L. Giordano, G. Pacchioni, H.-J. Freund: Stabilizing monomeric iron species in a porous silica/Mo(112) film, ACS Nano 4, 863–868 (2010)

    Google Scholar 

  • X. Zhao, X. Shao, Y. Fujimori, S. Bhattacharya, L.M. Ghiringhelli, H.-J. Freund, M. Sterrer, N. Nilius, S.V. Levchenko: Formation of water chains on CaO(001): What drives the 1D growth?, J. Phys. Chem. Lett. 6, 1204–1208 (2015)

    Google Scholar 

  • J. Carrasco, F. Illas, N. Lopez: Dynamic ion pairs in the adsorption of isolated water molecules on alkaline-earth oxide (001) surfaces, Phys. Rev. Lett. 100, 016101 (2008)

    ADS  Google Scholar 

  • D. Ferry, A. Glebov, V. Senz, J. Suzanne, J.P. Toennies, H. Weiss: Observation of the second ordered phase of water on the MgO(100) surface: Low energy electron diffraction and helium atom scattering studies, J. Chem. Phys. 105, 1697–1701 (1996)

    ADS  Google Scholar 

  • J. Heidberg, B. Redlich, D. Wetter: Adsorption of water vapor on the MgO(100) single-crystal surface, Ber. Bunsenges. Phys. Chem. 99, 1333–1337 (1995)

    Google Scholar 

  • Y. Fujimori, X. Zhao, X. Shao, S.V. Levchenko, N. Nilius, M. Sterrer, H.-J. Freund: Interaction of water with the CaO(001) surface, J. Phys. Chem. C 120, 5565–5576 (2016)

    Google Scholar 

  • D. Halwidl, B. Stöger, W. Mayr-Schmölzer, J. Pavelec, D. Fobes, J. Peng, Z.Q. Mao, G.S. Parkinson, M. Schmid, F. Mittendorfer, J. Redinger, U. Diebold: Adsorption of water at the SrO surface of ruthenates, Nat. Mater. 15, 450–455 (2016)

    ADS  Google Scholar 

  • R. Włodarczyk, M. Sierka, K. Kwapień, J. Sauer, E. Carrasco, A. Aumer, J.F. Gomes, M. Sterrer, H.-J. Freund: Structures of the ordered water monolayer on MgO(001), J. Phys. Chem. C 115, 6764–6774 (2011)

    Google Scholar 

  • Y.D. Kim, R.M. Lynden-Bell, A. Alavi, J. Stulz, D.W. Goodman: Evidence for partial dissociation of water on flat MgO(100) surfaces, Chem. Phys. Lett. 352, 318–322 (2002)

    ADS  Google Scholar 

  • X.L. Hu, J. Carrasco, J. Klimes, A. Michaelides: Trends in water monomer adsorption and dissociation on flat insulating surfaces, Phys. Chem. Chem. Phys. 13, 12447–12453 (2011)

    Google Scholar 

  • P. Liu, T. Kendelewicz, G.E. Brown, G.A. Parks, P. Pianetta: Reaction of water with vacuum-cleaved CaO(100) surfaces: An x-ray photoemission spectroscopy study, Surf. Sci. 416, 326–340 (1998)

    Google Scholar 

  • P. Liu, T. Kendelewicz, G.E. Gordon, G.A. Parks: Reaction of water with MgO(100) surfaces. Part I: Synchrotron x-ray photoemission studies of low-defect surfaces, Surf. Sci. 412/413, 287–314 (1998)

    ADS  Google Scholar 

  • E. Carrasco, M.A. Brown, M. Sterrer, H.-J. Freund, K. Kwapien, M. Sierka, J. Sauer: Thickness-dependent hydroxylation of MgO(001) thin films, J. Phys. Chem. C 114, 18207–18214 (2010)

    Google Scholar 

  • L. Savio, E. Celasco, L. Vattuone, M. Rocca, P. Senet: MgO/Ag(100): Confined vibrational modes in the limit of ultrathin films, Phys. Rev. B 67, 075420 (2003)

    ADS  Google Scholar 

  • F. Ringleb, Y. Fujimori, H.F. Wang, H. Ariga, E. Carrasco, M. Sterrer, H.J. Freund, L. Giordano, G. Pacchioni, J. Goniakowski: Interaction of water with FeO(111)/Pt(111): Environmental effects and influence of oxygen, J. Phys. Chem. C 115, 19328–19335 (2011)

    Google Scholar 

  • X. Yu, E. Emmez, Q. Pan, B. Yang, S. Pomp, W.E. Kaden, M. Sterrer, S. Shaikhutdinov, H.-J. Freund, I. Goikoetxea, R. Wlodarczyk, J. Sauer: Electron stimulated hydroxylation of a metal supported silicate film, Phys. Chem. Chem. Phys. 18, 3755–3764 (2016)

    Google Scholar 

  • M.A. Brown, Y. Fujimori, F. Ringleb, X. Shao, F. Stavale, N. Nilius, M. Sterrer, H.-J. Freund: Oxidation of Au by surface OH: Nucleation and electronic structure of gold on hydrohylated MgO(001), J. Am. Chem. Soc. 133, 10668–10676 (2011)

    Google Scholar 

  • Y. Fujimori, W.E. Kaden, M.A. Brown, B. Roldan Cuenya, M. Sterrer, H.-J. Freund: Hydrogen evolution from metal–surface hydroxyl interaction, J. Phys. Chem. C 118, 17717–17723 (2014)

    Google Scholar 

  • S. Shaikhutdinov, H.J. Freund: Ultrathin silica films on metals: The long and winding road to understanding the atomic structure, Adv. Mater. 25, 49–67 (2013)

    Google Scholar 

  • B. Yang, E. Emmez, W.E. Kaden, X. Yu, J.A. Boscoboinik, M. Sterrer, S. Shaikhutdinov, H.-J. Freund: Hydroxylation of metal-supported sheet-like silica films, J. Phys. Chem. C 117, 8336–8344 (2013)

    Google Scholar 

  • W.E. Kaden, S. Pomp, M. Sterrer, H.-J. Freund: Insights into silica bilayer hydroxylation and dissolution, Top. Catal. 60, 471–480 (2016)

    Google Scholar 

  • L.T. Zhuravlev: The surface chemistry of amorphous silica. Zhuravlev model, Colloids Surf. A 173, 1–38 (2000)

    Google Scholar 

  • M.A. Brown, E. Carrasco, M. Sterrer, H.J. Freund: Enhanced stability of gold clusters supported on hydroxylated MgO(001) surfaces, J. Am. Chem. Soc. 132, 4064–4065 (2010)

    Google Scholar 

  • D. Göbke, Y. Romanyshyn, S. Guimond, J.M. Sturm, H. Kuhlenbeck, J. Döbler, U. Reinhardt, M.V. Ganduglia-Pirovano, J. Sauer, H.J. Freund: Formaldehyde formation on vanadium oxide surfaces V2O3(0001) and V2O5(001): How does the stable methoxy intermediate form?, Angew. Chem. Int. Ed. 48, 3695–3698 (2009)

    Google Scholar 

  • J.M. Sturm, D. Göbke, H. Kuhlenbeck, J. Döbler, U. Reinhardt, M.V. Ganduglia-Pirovano, J. Sauer, H.J. Freund: Partial oxidation of methanol on well-ordered V2O5(001)/Au(111) thin films, Phys. Chem. Chem. Phys. 11, 3290–3299 (2009)

    Google Scholar 

  • F.E. Feiten, H. Kuhlenbeck, H.J. Freund: Reducing the V2O3(0001) surface through electron bombardment—A quantitative structure determination with I/V-LEED, Phys. Chem. Chem. Phys. 18, 3124–3130 (2016)

    Google Scholar 

  • P. Mars, D.W. van Krevelen: Oxidations carried out by means of vanadium oxide catalysts, Chem. Eng. Sci. 3, 41 (1954)

    Google Scholar 

  • Q. Pan, X. Weng, M.S. Chen, L. Giordano, G. Pacchioni, C. Noguera, J. Goniakowski, S. Shaikhutdinov, H.-J. Freund: Enhanced CO oxidation on oxide/metal interface: From ultra-high vacuum to near-atmospheric pressures, ChemCatChem 7, 2620–2627 (2015)

    Google Scholar 

  • S.J. Tauster: Strong metal-support interactions, Acc. Chem. Res. 20, 389–394 (1987)

    Google Scholar 

  • G.H. Vurens, M. Salmeron, G.A. Somorjai: Structure, composition and chemisorption studies of thin ordered iron oxide films on platinum (111), Surf. Sci. 201, 129–144 (1988)

    ADS  Google Scholar 

  • Y. Martynova, S. Shaikhutdinov, H.-J. Freund: CO oxidation on metal-supported ultrathin oxide films: What makes them active?, ChemCatChem 5, 2162–2166 (2013)

    Google Scholar 

  • Q. Fu, F. Yang, X. Bao: Interface-confined oxide nanostructures for catalytic oxidation reactions, Acc. Chem. Res. 46, 1692–1701 (2013)

    Google Scholar 

  • D. Sun, X.-K. Gu, R. Ouyang, H.-Y. Su, Q. Fu, X. Bao, W.-X. Li: Theoretical study of the role of a metal-cation ensemble at the oxide-metal boundary on CO oxidation, J. Phys. Chem. C 116, 7491–7498 (2012)

    Google Scholar 

  • Q. Fu, Y. Yao, X. Guo, M. Wei, Y. Ning, H. Liu, F. Yang, Z. Liu, X. Bao: Reversible structural transformation of FeOx nanostructures on Pt under cycling redox conditions and its effect on oxidation catalysis, Phys. Chem. Chem. Phys. 15, 147408–114714 (2013)

    Google Scholar 

  • Q. Fu, W.-X. Li, Y. Yao, L. Hongyang, Q. Fu, H.-Y. Su, D. Ma, X.-K. Gu, L. Chen, Z. Wang, H. Zhang, B. Wang, X. Bao: Interface-confined ferrous centers for catalytic oxidation, Science 328, 1141–1144 (2010)

    ADS  Google Scholar 

  • H. Zeuthen, W. Kudernatsch, L.R. Merte, L.K. Ono, L. Lammich, F. Besenbacher, S. Wendt: Fe oxides on Ag surfaces: Structure and reactivity, ACS Nano 9, 573–583 (2015)

    Google Scholar 

  • L. Xu, Z. Wu, Y. Jin, Y. Ma, W. Huang: Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst, Phys. Chem. Chem. Phys. 15, 12068–12074 (2013)

    Google Scholar 

  • L. Giordano, G. Pacchioni, C. Noguera, J. Goniakowski: Identification of active sites in a realistic model of strong metal–support interaction catalysts: The case of platinum (1 1 1)-supported iron oxide film, ChemCatChem 6, 185–190 (2014)

    Google Scholar 

  • L. Giordano, G. Pacchioni, J. Goniakowski, N. Nilius, E.D.L. Rienks, H.-J. Freund: Interplay between structural, magnetic, and electronic properties in a FeO/Pt (111) ultrathin film, Phys. Rev. B 76, 075416 (2007)

    ADS  Google Scholar 

  • Q. Pan, B.H. Liu, M.E. McBriarty, Y. Martynova, I.M.N. Groot, S. Wang, M.J. Bedzyk, S. Shaikhutdinov, H.-J. Freund: Reactivity of ultra-thin ZnO films supported by Ag(111) and Cu(111): A comparison to ZnO/Pt(111), Catal. Lett. 144, 648–655 (2014)

    Google Scholar 

  • A.M. Doyle, S.K. Shaikhutdinov, H.J. Freund: Alkene chemistry on the palladium surface: Nanoparticles vs single crystals, J. Catal. 223, 444–453 (2004)

    Google Scholar 

  • S. Schauermann, N. Nilius, S. Shaikhutdinov, H.-J. Freund: Nanoparticles for heterogeneous catalysis: New mechanistic insights, Acc. Chem. Res. 46, 1673–1681 (2013)

    Google Scholar 

  • G.C. Bond: Metal-Catalysed Reactions of Hydrocarbons (Springer, New York 2005)

    Google Scholar 

  • M. Wilde, K. Fukutani, W. Ludwig, B. Brandt, J.-H. Fischer, S. Schauermann, H.J. Freund: Influence of carbon deposition on the hydrogen distribution in Pd nanoparticles and their reactivity in olefin hydrogenation, Angew. Chem. Int. Ed. 47, 9289–9293 (2008)

    Google Scholar 

  • W. Ludwig, A. Savara, S. Schauermann, H.-J. Freund: Role of low-coordinated surface sites in olefin hydrogenation: A molecular beam study on Pd nanoparticles and Pd(111), ChemPhysChem 11, 2319–2322 (2010)

    Google Scholar 

  • W. Ludwig, A. Savara, K.-H. Dostert, S. Schauermann: Olefin hydrogenation on Pd model supported catalysts: New mechanistic insights, J. Catal. 284, 148–156 (2011)

    Google Scholar 

  • M. Wilde, K. Fukutani, M. Naschitzki, H.J. Freund: Hydrogen absorption in oxide-supported palladium nanocrystals, Phys. Rev. B 77, 113412 (2008)

    ADS  Google Scholar 

  • F. Viñes, C. Loschen, F. Illas, K.M. Neymann: Edge sites as a gate for subsurface carbon in palladium nanoparticles, J. Catal. 266, 59–63 (2009)

    Google Scholar 

  • A.M. Doyle, S.K. Shaikhutdinov, S.D. Jackson, H.-J. Freund: Hydrogenation on metal surfaces: Why are nanoparticles more active than single crystals?, Angew. Chem. Int. Ed. 42, 5240–5243 (2003)

    Google Scholar 

  • K.M. Neymann, S. Schauermann: Hydrogen diffusion into palladium nanoparticles: Pivotal promotion by carbon, Angew. Chem. Int. Ed. 49, 4743–4746 (2010)

    Google Scholar 

  • W. Ludwig, A. Savara, R.J. Madix, S. Schauermann, H.-J. Freund: Subsurface hydrogen diffusion into Pd nanoparticles: Role of low-coordinated surface sites and facilitation by carbon, J. Phys. Chem. C 116, 3539–3544 (2012)

    Google Scholar 

  • F. Ringleb, M. Sterrer, H.-J. Freund: Preparation of Pd–MgO model catalysts by deposition of Pd from aqueous precursor solutions onto Ag(001)-supported MgO(001) thin films, Appl. Catal. A 474, 186–193 (2014)

    Google Scholar 

  • B.R. Bickmore, J.C. Wheeler, B. Bates, K.L. Nagy, D.L. Eggett: Reaction pathways for quartz dissolution determined by statistical and graphical analysis of macroscopic experimental data, Geochim. Cosmochim. Acta 72, 4521–4536 (2008)

    ADS  Google Scholar 

  • D.A. Vermilyea: Dissolution of MgO and Mg(OH)2 in aqueous solutions, J. Electrochem. Soc. 116, 1179–1183 (1969)

    ADS  Google Scholar 

  • O.S. Pokrovsky, J. Schott: Experimental study of brucite dissolution and precipitation in aqueous solutions: Surface speciation and chemical affinity control, Geochim. Cosmochim. Acta 68, 31–45 (2004)

    ADS  Google Scholar 

  • H.F. Wang, H. Ariga, R. Dowler, M. Sterrer, H.J. Freund: Surface science approach to catalyst preparation—Pd deposition onto thin Fe3O4(111) films from PdCl2 precursor, J. Catal. 286, 1–5 (2012)

    Google Scholar 

  • H.F. Wang, W.E. Kaden, R. Dowler, M. Sterrer, H.J. Freund: Model oxide-supported metal catalysts—Comparison of ultrahigh vacuum and solution based preparation of Pd nanoparticles on a single-crystalline oxide substrate, Phys. Chem. Chem. Phys. 14, 11525–11533 (2012)

    Google Scholar 

  • S. Pomp, W.E. Kaden, M. Sterrer, H.J. Freund: Exploring Pd adsorption, diffusion, permeation, and nucleation on bilayer SiO2/Ru as a function of hydroxylation and precursor environment: From UHV to catalyst preparation, Surf. Sci. 652, 286–293 (2016)

    ADS  Google Scholar 

  • M. Sterrer, H.-J. Freund: Towards realistic surface science models of heterogeneous catalysts: Influence of support hydroxylation and catalyst preparation method, Catal. Lett. 143, 375–385 (2013)

    Google Scholar 

  • N.B. Milić, Z.D. Bugarčić: Hydrolysis of the palladium(II) ion in a sodium-chloride medium, Transit. Met. Chem. 9, 173–176 (1984)

    Google Scholar 

  • J.M. van Middlesworth, S.A. Wood: The stability of palladium(II) hydroxide and hydroxy-chloride complexes: An experimental solubility study at 25–85 °C and 1 bar, Geochim. Cosmochim. Acta 63, 1751–1765 (1999)

    ADS  Google Scholar 

  • B. Didillon, E. Merlen, T. Pages, D. Uzio: From colloidal particles to supported catalysts: A comprehensive study of palladium oxide hydrosols deposited on alumina, Stud. Surf. Sci. Catal. 118, 41–54 (1998)

    Google Scholar 

  • L. Jiao, J.R. Regalbuto: The synthesis of highly dispersed noble and base metals on silica via strong electrostatic adsorption: I. Amorphous silica, J. Catal. 260, 329–341 (2008)

    Google Scholar 

  • A.M. Shah, J.R. Regalbuto: Retardation of Pt adsorption over oxide supports at pH extremes—Oxide dissolution or high ionic-strength, Langmuir 10, 500–504 (1994)

    Google Scholar 

  • K. Wolter, O. Seiferth, H. Kuhlenbeck, M. Bäumer, H.-J. Freund: Infrared spectroscopic investigation of CO adsorbed on Pd aggregates deposited on an alumina model support, Surf. Sci. 399, 190–198 (1998)

    ADS  Google Scholar 

  • C. Büchner, L. Lichtenstein, M. Heyde, H.-J. Freund: The atomic structure of two-dimensional silica. In: Noncontact Atomic Force Microscopy, ed. by S. Morita, F.J. Giessibl, E. Meyer, R. Wiesendanger (Springer, Cham 2015)

    Google Scholar 

  • K.M. Burson, L. Gura, B. Kell, C. Büchner, A.L. Lewandowski, M. Heyde, H.-J. Freund: Resolving amorphous solid-liquid interfaces by atomic force microscopy, Appl. Phys. Lett. 108, 201602 (2016)

    ADS  Google Scholar 

  • F.F. Abraham, I.P. Batra: Theoretical interpretation of atomic-force-microscope images of graphite, Surf. Sci. Lett. 209, L125–L132 (1989)

    ADS  Google Scholar 

  • M. Osada, T. Sasaki: Two-dimensional dielectric nanosheets: Novel nanoelectronics from nanocrystal building blocks, Adv. Mater. 24, 210–228 (2012)

    Google Scholar 

  • E. Gao, B. Xie, Z. Xu: Two-dimensional silica: Structural, mechanical properties, and strain-induced band gap tuning, J. Appl. Phys. 119, 014301 (2016)

    ADS  Google Scholar 

  • L. Lichtenstein, M. Heyde, S. Ulrich, N. Nilius, H.-J. Freund: Probing the properties of metal-oxide interfaces: Silica films on Mo and Ru supports, Phys. Condens. Matter 24, 354010–354017 (2012)

    Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Hans-Joachim Freund .

Editor information

Editors and Affiliations

Rights and permissions

Reprints and permissions

Copyright information

© 2020 Springer Nature Switzerland AG

About this chapter

Cite this chapter

Freund, HJ. et al. (2020). Thin Oxide Films as Model Systems for Heterogeneous Catalysts. In: Rocca, M., Rahman, T.S., Vattuone, L. (eds) Springer Handbook of Surface Science. Springer Handbooks. Springer, Cham. https://doi.org/10.1007/978-3-030-46906-1_10

Download citation

Publish with us

Policies and ethics