Influence of cluster–support interactions on reactivity of size-selected NbxOy clusters

Size-selected niobium oxide nanoclusters (Nb3O5, Nb3O7, Nb4O7, and Nb4O10) were deposited at room temperature onto a Cu(111) surface and a thin film of Cu2O on Cu(111), and their interfacial electronic interactions and reactivity toward water dissociation were examined. These clusters were specifically chosen to elucidate the effects of the oxidation state of the metal centers; Nb3O5 and Nb4O7 are the reduced counterparts of Nb3O7 and Nb4O10, respectively. From two-photon photoemission spectroscopy (2PPE) measurements, we found that the work function increases upon cluster adsorption in all cases, indicating a negative interfacial dipole moment with the positive end pointing into the surface. The amount of increase was greater for the clusters with more metal centers and higher oxidation state. Further analysis with DFT calculations of the clusters on Cu(111) indicated that the reduced clusters donate electrons to the substrate, indicating that the intrinsic cluster dipole moment makes a larger contributi...

[1]  B. D. Kay,et al.  Oxidation, reduction, and condensation of alcohols over (MO3)3 (M = Mo, W) nanoclusters , 2014 .

[2]  Ping Liu,et al.  Surface Dipoles and Electron Transfer at the Metal Oxide–Metal Interface: A 2PPE Study of Size-Selected Metal Oxide Clusters Supported on Cu(111) , 2014 .

[3]  Ping Liu,et al.  Density functional study of water-gas shift reaction on M3O(3x)/Cu(111). , 2012, Physical chemistry chemical physics : PCCP.

[4]  M. K. Hota,et al.  Studies on switching mechanisms in Pd-nanodot embedded Nb2O5 memristors using scanning tunneling microscopy , 2012 .

[5]  L. Giordano,et al.  Tuning the Charge State of (WO3)3 Nanoclusters Deposited on MgO/Ag(001) Films , 2012 .

[6]  Jia Zhou,et al.  Electronic charging of non-metallic clusters: size-selected Mo(x)S(y) clusters supported on an ultrathin alumina film on NiAl(110). , 2012, Physical chemistry chemical physics : PCCP.

[7]  F. Netzer,et al.  Structure and Bonding of Tungsten Oxide Clusters on Nanostructured Cu-O Surfaces , 2011 .

[8]  Lai‐Sheng Wang,et al.  Stoichiometric and oxygen-rich M2O(n)- and M2O(n) (M = Nb, Ta; n = 5-7) clusters: molecular models for oxygen radicals, diradicals, and superoxides. , 2011, Journal of the American Chemical Society.

[9]  Ping Liu.  Water-gas shift reaction on oxide∕Cu(111): Rational catalyst screening from density functional theory. , 2010, The Journal of chemical physics.

[10]  Ping Liu,et al.  Autocatalytic reduction of a Cu2O/Cu (111) surface by CO: STM, XPS, and DFT studies , 2010 .

[11]  Ping Liu,et al.  Electronic Structure of the Thiophene/Au(111) Interface Probed by Two-Photon Photoemission , 2010 .

[12]  J. Hrbek,et al.  Inverse oxide/metal catalysts: A versatile approach for activity tests and mechanistic studies , 2010 .

[13]  L. Giordano,et al.  X-ray Photoemission Study of the Charge State of Au Nanoparticles on Thin MgO/Fe(001) Films , 2009 .

[14]  Manuel Pérez,et al.  Water-gas shift reaction on a highly active inverse CeOx/Cu111 catalyst: unique role of ceria nanoparticles. , 2009, Angewandte Chemie.

[15]  A. Corma,et al.  Water Resistant, Catalytically Active Nb and Ta Isolated Lewis Acid Sites, Homogeneously Distributed by Direct Synthesis in a Beta Zeolite , 2009 .

[16]  J. Hanson,et al.  Water-gas shift activity of Cu surfaces and Cu nanoparticles supported on metal oxides , 2009 .

[17]  G. Pacchioni,et al.  Work function changes induced by deposition of ultrathin dielectric films on metals: A theoretical analysis , 2008 .

[18]  K. Jordan,et al.  Hydroxyl chain formation on the Cu(110) surface: Watching water dissociation , 2008 .

[19]  T. Mallouk,et al.  Niobium Oxide Nanoscrolls as Building Blocks for Dye-Sensitized Hydrogen Production from Water under Visible Light Irradiation , 2008 .

[20]  Gianfranco Pacchioni,et al.  Oxide ultra-thin films on metals: new materials for the design of supported metal catalysts. , 2008, Chemical Society reviews.

[21]  E. Shalaeva,et al.  Photoelectron spectroscopy and diffraction of NbOx/Nb(110) surface , 2008 .

[22]  B. D. Kay,et al.  Catalytic dehydration of 2-propanol on (WO3)3 clusters on TiO2(110). , 2008, Journal of the American Chemical Society.

[23]  H. Ogasawara,et al.  Autocatalytic water dissociation on Cu(110) at near ambient conditions. , 2008, Journal of the American Chemical Society.

[24]  M. Mavrikakis,et al.  On the mechanism of low-temperature water gas shift reaction on copper. , 2008, Journal of the American Chemical Society.

[25]  Lai‐Sheng Wang,et al.  Probing the electronic structure of early transition-metal oxide clusters: polyhedral cages of (V2O5)n(-) (n = 2-4) and (M2O5(2)(-) (M = Nb, Ta). , 2007, Journal of the American Chemical Society.

[26]  Jianyi Shen,et al.  Dehydration of methanol to dimethyl ether over Nb2O5 and NbOPO4 catalysts: Microcalorimetric and FT-IR studies , 2007 .

[27]  Israel E. Wachs,et al.  In Situ Spectroscopic Investigation of the Molecular and Electronic Structures of SiO2 Supported Surface Metal Oxides , 2007 .

[28]  D. Nandi,et al.  Reversible switching of tetra-tert-butyl-azobenzene on a Au(1 1 1) surface induced by light and thermal activation , 2007 .

[29]  L. Giordano,et al.  Control of the charge state of metal atoms on thin MgO films. , 2007, Physical review letters.

[30]  J. Rocca,et al.  Formation and distribution of neutral vanadium, niobium, and tantalum oxide clusters: single photon ionization at 26.5 eV. , 2006, The Journal of chemical physics.

[31]  G. Henkelman,et al.  A fast and robust algorithm for Bader decomposition of charge density , 2006 .

[32]  M. Daturi,et al.  WGS and reforming properties of NbMCM-41 materials , 2006 .

[33]  F. Zhang,et al.  Improved Performance of Au/Fe2O3 Catalysts Promoted with ZrO2 and Nb2O5 in the WGS Reaction under Hydrogen-rich Conditions , 2006 .

[34]  B. Delley,et al.  Oxygen adsorption and stability of surface oxides on Cu(111) : A first-principles investigation , 2006 .

[35]  M. G. White,et al.  Gas-phase reactivity of the Ti8C12+ met-car with triatomic sulfur-containing molecules: CS2, SCO, and SO2. , 2006, The journal of physical chemistry. A.

[36]  K. Domen,et al.  Exfoliated HNb3O8 Nanosheets as a Strong Protonic Solid Acid. , 2005 .

[37]  V. Atuchin,et al.  Nb 3d and O 1s core levels and chemical bonding in niobates , 2005 .

[38]  Wei Wei,et al.  Two-photon photoemission spectroscopy: atomic oxygen on Cu(111) and styrene on oxygen covered Cu(111) , 2004, SPIE Optics + Photonics.

[39]  J. Hanson,et al.  Nanostructured oxides in chemistry: characterization and properties. , 2004, Chemical reviews.

[40]  Harvey G. Stenger,et al.  Water gas shift reaction kinetics and reactor modeling for fuel cell grade hydrogen , 2003 .

[41]  Gao Qing Lu,et al.  Recent advances in catalysts for methanol synthesis via hydrogenation of CO and CO2 , 2003 .

[42]  M. Ziolek.  Niobium-Containing Catalysts: State of the Art , 2003 .

[43]  Robert J. Farrauto,et al.  A new generation of water gas shift catalysts for fuel cell applications , 2003 .

[44]  G. Meijer,et al.  Infrared spectroscopy of niobium oxide cluster cations in a molecular beam: identifying the cluster structures. , 2003, Journal of the American Chemical Society.

[45]  K. Tanabe.  Catalytic Application of Niobium Compounds , 2003 .

[46]  A. Castleman,et al.  Studies of Metal Oxide Clusters: Elucidating Reactive Sites Responsible for the Activity of Transition Metal Oxide Catalysts , 2002 .

[47]  Michael A. Henderson,et al.  The Interaction of Water with Solid Surfaces: Fundamental Aspects Revisited , 2002 .

[48]  B. Delley,et al.  Surface distribution of Cu adatoms deduced from work function measurements , 2002 .

[49]  A. Castleman,et al.  Reactions of Niobium and Tantalum Oxide Cluster Cations and Anions with n-Butane , 2001 .

[50]  K. Domen,et al.  Scanning tunneling microscopy studies of oxygen adsorption on Cu(111) , 2001 .

[51]  K. Fisher,et al.  The catalytic activation of primary alcohols on niobium oxide surfaces unraveled: the gas phase reactions of NbxOy− clusters with methanol and ethanol , 2000 .

[52]  G. Henkelman,et al.  A climbing image nudged elastic band method for finding saddle points and minimum energy paths , 2000 .

[53]  Hanfu Wang,et al.  Electronic Structure at Organic/Metal Interfaces: Naphthalene/Cu(111) , 2000 .

[54]  T. Ushikubo.  Recent topics of research and development of catalysis by niobium and tantalum oxides , 2000 .

[55]  M. Ziolek,et al.  Niobium Compounds: Preparation, Characterization, and Application in Heterogeneous Catalysis. , 1999, Chemical reviews.

[56]  G. Kresse,et al.  From ultrasoft pseudopotentials to the projector augmented-wave method , 1999 .

[57]  M. Seah,et al.  XPS: binding energy calibration of electron spectrometers 5—re‐evaluation of the reference energies , 1998 .

[58]  G. Gemme,et al.  XPS analysis of the surface composition of niobium for superconducting RF cavities , 1998 .

[59]  Y. Iwasawa,et al.  Oxygen Atoms on Cu(100) Formed at 100 K, Active for CO Oxidation and Water−Hydrogen Abstraction, Characterized by HREELS and TPD , 1997 .

[60]  Kresse,et al.  Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. , 1996, Physical review. B, Condensed matter.

[61]  H. Deng,et al.  Formation, Structures, and Reactivities of Niobium Oxide Cluster Ions , 1996 .

[62]  G. Kresse,et al.  Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set , 1996 .

[63]  Hafner,et al.  Ab initio molecular dynamics for liquid metals. , 1995, Physical review. B, Condensed matter.

[64]  Norma Amadeo,et al.  Hydrogen production from the low-temperature water-gas shift reaction: Kinetics and simulation of the industrial reactor , 1995 .

[65]  C. Rhodes,et al.  Water-gas shift reaction: finding the mechanistic boundary , 1995 .

[66]  H. Jónsson,et al.  Reversible work transition state theory: application to dissociative adsorption of hydrogen , 1994, chem-ph/9411012.

[67]  A. Bell,et al.  Raman studies of the structure of niobium oxide/titanium oxide (Nb2O5.TiO2) , 1993 .

[68]  K. Domen,et al.  An IRAS study of hydroxyl species (OD(a)) on oxygen-modified Cu(110) surface , 1993 .

[69]  Jackson,et al.  Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation. , 1992, Physical review. B, Condensed matter.

[70]  I. Stensgaard,et al.  Two new oxygen induced reconstructions on Cu(111) , 1992 .

[71]  I. Stensgaard,et al.  Oxidation of Cu(111): two new oxygen induced reconstructions , 1991 .

[72]  J. Jehng,et al.  Molecular structures of supported niobium oxide catalysts under in situ conditions , 1991 .

[73]  A. Auroux,et al.  Acidity and basicity of metal oxide surfaces. II, Determination by catalytic decomposition of isopropanol , 1991 .

[74]  J. Jehng,et al.  The molecular structures and reactivity of supported niobium oxide catalysts , 1990 .

[75]  L. Tjeng,et al.  Electronic structure of Cu2O and CuO. , 1988, Physical review. B, Condensed matter.

[76]  M. Ai.  Oxidation activity and acid-base properties of V2O5P2O5 catalysts , 1986 .

[77]  T. Madey,et al.  The surface chemistry of H2O on clean and oxygen-covered Cu(110) , 1984 .

[78]  T. Madey,et al.  The surface chemistry of H 2 O on clean and oxygen-covered Cu(110) , 1984 .

[79]  M. G. Mason.  Electronic structure of supported small metal clusters , 1983 .

[80]  M. Ai.  The Oxidation Activity and Acid-base Properties of V2O5-based Binary Catalysts , 1977 .

[81]  H. Monkhorst,et al.  SPECIAL POINTS FOR BRILLOUIN-ZONE INTEGRATIONS , 1976 .

[82]  M. Shelef,et al.  Ammonia Formation in the Catalytic Reduction of Nitric Oxide. III. The Role of Water Gas Shift, Reduction by Hydrocarbons, and Steam Reforming , 1974 .

[83]  M. Shelef,et al.  Ammonia Formation in Catalytic Reduction of Nitric Oxide by Molecular Hydrogen. II. Noble Metal Catalysts , 1972 .

[84]  R. Bader,et al.  Virial Field Relationship for Molecular Charge Distributions and the Spatial Partitioning of Molecular Properties , 1972 .

[85]  J. Topping.  On the mutual potential energy of a plane network of doublets , 1927 .

[86]  B. Caplins.  Electronic Structure of the Metal/Phthalocyanine Interface Probed by Two-Photon Photoemission , 2014 .

[87]  F. Netzer,et al.  Structure and Bonding of Tungsten Oxide Clusters on Nanostructured CuO Surfaces , 2011 .

[88]  M. Delheusy.  X-ray investigation of Nb/O interfaces , 2008 .

[89]  Srivastava,et al.  Electronic structure , 2001, Physics Subject Headings (PhySH).

[90]  Lei Xie,et al.  The preparation of and water adsorption on thin films of niobium oxide on Pt(111) , 1994 .

[91]  K. Domen,et al.  Photodecomposition of water and hydrogen evolution from aqueous methanol solution over novel niobate photocatalysts , 1986 .

[92]  J. Yates,et al.  Adsorption of molecular nitrogen by the W(110) plane , 1976 .