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.
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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)
G. Ertl: Reactions at surfaces: From atoms to complexity (Nobel lecture), Angew. Chem. Int. Ed. 47, 3524–3535 (2008)
P.A. Cox: Transition Metal Oxides. An Introduction to Their Electronic Structure and Properties (Clarendon, Oxford 1992)
V.E. Henrich, P.A. Cox: The Surface Science of Metal Oxides (Cambridge Univ. Press, Cambridge 1994)
C. Noguera: Physics and Chemistry at Oxide Surfaces (Cambridge Univ. Press, Cambridge 1996)
U. Diebold: The surface science of titanium dioxide, Surf. Sci. Rep. 48, 53–229 (2003)
C.L. Pang, R. Lindsay, G. Thornton: Structure of clean and adsorbate-covered single-crystal rutile TiO2 surfaces, Chem. Rev. 113, 3887–3948 (2013)
H.J. Freund, H. Kuhlenbeck, V. Staemmler: Oxide surfaces, Rep. Prog. Phys. 59, 283–347 (1996)
M. Bäumer, H.-J. Freund: Metal deposits on well-ordered oxide films, Prog. Surf. Sci. 61, 127–198 (1999)
C.R. Henry: Surface studies of supported model catalysts, Surf. Sci. Rep. 31, 231–326 (1998)
C.T. Campbell: Ultrathin metal films and particles on oxide surfaces: Structural, electronic and chemisorption properties, Surf. Sci. Rep. 27, 1–111 (1997)
D.W. Goodman: Model catalysts: From extended single crystals to supported particles, Surf. Rev. Lett. 2, 9–24 (1995)
J. Libuda, H.-J. Freund: Reaction kinetics on complex model catalysts under single scattering conditions, J. Phys. Chem. B106, 4901–4915 (2002)
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)
G. Pacchioni, H.-J. Freund: Electron transfer at oxide surfaces. The MgO paradigm: From defects to ultrathin films, Chem. Rev. 113, 4035–4072 (2013)
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)
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)
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
F.P. Netzer, A. Fortunelli: Oxide Materials at the Two-Dimensional Limit, Springer Series in Materials Science (Springer, Cham 2016)
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)
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)
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)
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)
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)
G. Pacchioni, L. Giordano, M. Baistrocchi: Charging of metal atoms on ultrathin MgO/Mo(100) films, Phys. Rev. Lett. 94, 226104 (2005)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
W. Mönch: Electronic Properties of Semiconductor Interfaces (Springer, Berlin, Heidelberg 2004)
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)
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)
O. Karsliouglu, X. Song, H. Kuhlenbeck, H.-J. Freund: Mo+TiO2(110) mixed oxide layer: Structure and reactivity, Top. Catal. 56, 1389–1403 (2013)
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)
H.P. Boehm, A. Clauss, G.O. Fischer, U. Hofmann: Das Adsorptionsverhalten sehr dünner Kohlenstoff-Folien, Z. Anorg. Allg. Chem. 316, 119–127 (1962)
H.P. Boehm, R. Setton, E. Stumpp: Nomenclature and terminology of graphite intercalation compounds (IUPAC recommendations 1994), Pure Appl. Chem. 66, 1893–1901 (1994)
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)
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)
H.-J. Freund, M. Heyde, C. Büchner: Transferable Silica Bilayer Film, EP3217423A1 (EPO, Munich 2016)
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
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)
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)
S. Surnev, M.G. Ramsey, F.P. Netzer: Vanadium oxide surface studies, Prog. Surf. Sci. 73, 117–165 (2003)
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)
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)
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)
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)
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)
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)
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)
J. Goniakowski, C. Finocchi, C. Noguera: Polarity of oxide surfaces and nanostructures, Rep. Prog. Phys. 71, 016501–016555 (2008)
F. Finocchi, A. Barbier, J. Jupille, C. Noguera: Stability of rocksalt (111) polar surfaces: Beyond the octopole, Phys. Rev. Lett. 92, 136101 (2004)
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)
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)
K.P. McKenna, A.L. Shluger: Electron-trapping polycrystalline materials with negative electron affinity, Nat. Mater. 7, 859–862 (2008)
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)
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)
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)
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)
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)
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)
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)
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)
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)
K.P. McKenna, A.L. Shluger: First-principles calculations of defects near a grain boundary in MgO, Phys. Rev. B 79, 224116 (2009)
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)
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)
M. Sterrer, T. Risse, H.J. Freund: CO adsorption on the surface of MgO(001) thin films, Appl. Catal. A 307, 58–61 (2006)
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)
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)
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)
R. Zallen: The Physics of Amorphous Solids (Wiley-VCH, Weinheim 2004)
L. Berthier, G. Biroli: Theoretical perspective on the glass transition and amorphous materials, Rev. Mod. Phys. 83, 587–645 (2011)
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)
W.H. Zachariasen: The atomic arrangement in glass, J. Am. Chem. Soc. 54, 3841–3851 (1932)
L. Lichtenstein, M. Heyde, H.-J. Freund: Crystalline-vitreous interface in two dimensional silica, Phys. Rev. Lett. 109, 106101 (2012)
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)
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)
E.I. Altman, U.D. Schwarz: Structural and electronic heterogeniety of two dimensional amorphous silica layers, Adv. Mater. Interfaces 1, 1400108 (2014)
R.M. Cornell, U. Schwertmann: The Iron Oxides (Wiley-VCH, Weinheim 2004)
G. Ertl, H. Knözinger, F. Schueth, J. Weitkamp: Handbook of Heterogeneous Catalysis (VCH, Weinheim 2008)
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)
W. Weiss, W. Ranke: Surface chemistry and catalysis on well-defined epitaxial iron-oxide layers, Prog. Surf. Sci. 70, 1–151 (2002)
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)
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)
G.S. Parkinson: Iron oxide surfaces, Surf. Sci. Rep. 71, 272–365 (2016)
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)
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)
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)
W. Weiss, M. Ritter: Metal oxide heteroepitaxy: Stranski–Krastanov growth of iron oxides on Pt(111), Phys. Rev. B 59, 5201–5213 (1999)
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)
M. Ritter, W. Weiss: Fe3O4(111) surface structure determined by LEED crystallography, Surf. Sci. 432, 81–94 (1999)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
H. Niehus, R.P. Blum, D. Ahlbehrendt: Structure of vanadium oxide (V2O3) grown on Cu3Au(100), Surf. Rev. Lett. 10, 353–359 (2003)
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)
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)
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)
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)
P.W. Tasker: Stability of ionic-crystal surfaces, J. Phys. C 12, 4977–4984 (1979)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
J. Goniakowski, C. Noguera: Electronic states and schottky barrier height at metal/MgO(100) interfaces, Interface Sci. 12, 93–103 (2004)
H. Grönbeck: Mechanism for NO2 charging on metal supported MgO, J. Phys. Chem. B 110, 11977–11981 (2006)
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)
J. Tersoff, D.R. Hamann: Theory of the scanning tunneling microscope, Phys. Rev. B 31, 805 (1985)
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)
J. Repp, G. Meyer, F.E. Olsson, M. Persson: Controlling the charge state of individual gold adatoms, Science 305, 493–495 (2004)
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)
A. Hellman, S. Klacar, H. Grönbeck: Low temperature CO oxidation over supported ultrathin MgO films, J. Am. Chem. Soc. 131, 16636–16637 (2009)
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)
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)
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)
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)
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)
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)
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)
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)
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)
C. Kittel: Introduction to Solid State Physics (Wiley, New York 2005)
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)
E.W. McFarland, H. Metiu: Catalysis by doped oxides, Chem. Rev. 113, 4391–4427 (2013)
J. Robertson, S.J. Clark: Limits to doping in oxides, Phys. Rev. B 83, 075303 (2011)
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)
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)
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)
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)
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)
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)
B. Li, H. Metiu: DFT studies of oxygen vacancies on undoped and doped La2O3 surfaces, J. Phys. Chem. C 114, 12234–12244 (2010)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
W.E. Kaden, S. Pomp, M. Sterrer, H.-J. Freund: Insights into silica bilayer hydroxylation and dissolution, Top. Catal. 60, 471–480 (2016)
L.T. Zhuravlev: The surface chemistry of amorphous silica. Zhuravlev model, Colloids Surf. A 173, 1–38 (2000)
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)
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)
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)
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)
P. Mars, D.W. van Krevelen: Oxidations carried out by means of vanadium oxide catalysts, Chem. Eng. Sci. 3, 41 (1954)
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)
S.J. Tauster: Strong metal-support interactions, Acc. Chem. Res. 20, 389–394 (1987)
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)
Y. Martynova, S. Shaikhutdinov, H.-J. Freund: CO oxidation on metal-supported ultrathin oxide films: What makes them active?, ChemCatChem 5, 2162–2166 (2013)
Q. Fu, F. Yang, X. Bao: Interface-confined oxide nanostructures for catalytic oxidation reactions, Acc. Chem. Res. 46, 1692–1701 (2013)
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)
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)
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)
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)
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)
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)
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)
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)
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)
S. Schauermann, N. Nilius, S. Shaikhutdinov, H.-J. Freund: Nanoparticles for heterogeneous catalysis: New mechanistic insights, Acc. Chem. Res. 46, 1673–1681 (2013)
G.C. Bond: Metal-Catalysed Reactions of Hydrocarbons (Springer, New York 2005)
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)
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)
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)
M. Wilde, K. Fukutani, M. Naschitzki, H.J. Freund: Hydrogen absorption in oxide-supported palladium nanocrystals, Phys. Rev. B 77, 113412 (2008)
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)
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)
K.M. Neymann, S. Schauermann: Hydrogen diffusion into palladium nanoparticles: Pivotal promotion by carbon, Angew. Chem. Int. Ed. 49, 4743–4746 (2010)
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)
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)
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)
D.A. Vermilyea: Dissolution of MgO and Mg(OH)2 in aqueous solutions, J. Electrochem. Soc. 116, 1179–1183 (1969)
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)
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)
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)
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)
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)
N.B. Milić, Z.D. Bugarčić: Hydrolysis of the palladium(II) ion in a sodium-chloride medium, Transit. Met. Chem. 9, 173–176 (1984)
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)
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)
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)
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)
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)
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)
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)
F.F. Abraham, I.P. Batra: Theoretical interpretation of atomic-force-microscope images of graphite, Surf. Sci. Lett. 209, L125–L132 (1989)
M. Osada, T. Sasaki: Two-dimensional dielectric nanosheets: Novel nanoelectronics from nanocrystal building blocks, Adv. Mater. 24, 210–228 (2012)
E. Gao, B. Xie, Z. Xu: Two-dimensional silica: Structural, mechanical properties, and strain-induced band gap tuning, J. Appl. Phys. 119, 014301 (2016)
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)
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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
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