CO adsorption on a Au/CeO2 (111) model catalyst

We prepared a Au/CeO2 (111) model catalyst by depositing a thin cerium oxide film on a Ru(0001) surface and subsequently depositing gold. This model system was investigated using high-resolution photoemission spectroscopy. Gold forms metallic nanoparticles on CeO2 with an average particle size that depends on the Au dose. At 80 K adsorption of CO was observed on the supported Au particles, which induces a chemical shift of +0.9 eV in the An 4f level of the An atoms directly involved in the Au-CO bond. CO adsorption also induces an additional, particle-size-dependent shift, which affects all Au atoms in the particle; i.e., the whole Au particle is affected by CO adsorption. The fraction of surface atoms involved in CO bonding decreases with increasing gold particle size, from similar to 60-70% for small particles to 15-20% for large particles. It is concluded that CO only adsorbs on defects (low-coordinated Au atoms). The CO desorption temperature decreases with increasing particle size. This is explained as follows: on small particles the most abundant defects are corner atoms and kinks (6-coordinated), which interact strongly with CO. On large particles the most abundant defects are edges between two planes (7-coordinated), which interact less strongly with CO. (Less)

[1]  R. Behm,et al.  Au/TiO2/Ru(0001) model catalysts and their interaction with CO , 2006 .

[2]  Junling Lu,et al.  Morphology and defect structure of the CeO2(111) films grown on Ru(0001) as studied by scanning tunneling microscopy , 2006 .

[3]  G. Briggs,et al.  Defect formation on CeO2(111) surfaces after annealing studied by STM , 1999 .

[4]  Robert J. Davis,et al.  Understanding Au-Catalyzed Low-Temperature CO Oxidation , 2007 .

[5]  Sungsik Lee,et al.  Agglomeration, support effects, and CO adsorption on Au/TiO2(110) prepared by ion beam deposition , 2005 .

[6]  R. Caudano,et al.  Electron spectroscopic characterization of oxygen adsorption on gold surfaces: II. Production of gold oxide in oxygen DC reactive sputtering , 1984 .

[7]  Ling Zhou,et al.  Electron Localization Determines Defect Formation on Ceria Substrates , 2005, Science.

[8]  Shawn D. Lin,et al.  The beneficial effect of the addition of base metal oxides to gold catalysts on reactions relevant to air pollution abatement , 2004 .

[9]  D. King,et al.  Origin and activity of oxidized gold in water-gas-shift catalysis. , 2005, Physical review letters.

[10]  Bjørk Hammer,et al.  Some recent theoretical advances in the understanding of the catalytic activity of Au , 2005 .

[11]  P. Pianetta,et al.  Photoemission of gold in the energy range 30-300 eV using synchrotron radiation , 1976 .

[12]  M. Flytzani-Stephanopoulos,et al.  Nanostructured Au–CeO2 Catalysts for Low-Temperature Water–Gas Shift , 2001 .

[13]  J. Hrbek,et al.  Activity of CeOx and TiOx Nanoparticles Grown on Au(111) in the Water-Gas Shift Reaction , 2007, Science.

[14]  Hiroshi Sano,et al.  Novel Gold Catalysts for the Oxidation of Carbon Monoxide at a Temperature far Below 0 °C , 1987 .

[15]  L. Martinu,et al.  Substrate and morphology effects on photoemission from core-levels in gold clusters , 2001 .

[16]  Avelino Corma,et al.  Spectroscopic evidence for the supply of reactive oxygen during CO oxidation catalyzed by gold supported on nanocrystalline CeO2. , 2005, Journal of the American Chemical Society.

[17]  K. Wandelt,et al.  Properties of noble metal and binary alloy monolayer films on Ru(001) , 1991 .

[18]  S. Overbury,et al.  Electron spectroscopy of single crystal and polycrystalline cerium oxide surfaces , 1998 .

[19]  T. Akita,et al.  TEM observation of gold nanoparticles deposited on cerium oxide , 2005 .

[20]  S. Ito,et al.  HELIX-COIL TRANSITION OF POLY-α,L-GLUTAMIC ACID IN AQUEOUS SOLUTION STUDIED BY THE DISSOCIATION FIELD EFFECT RELAXATION METHOD , 1973 .

[21]  S. Overbury,et al.  Ordered cerium oxide thin films grown on Ru(0001) and Ni(111) , 1999 .

[22]  J. Niemantsverdriet,et al.  Thermal desorption of strained monoatomic Ag and Au layers from Ru(001) , 1987 .

[23]  D. Goodman,et al.  Onset of catalytic activity of gold clusters on titania with the appearance of nonmetallic properties , 1998, Science.

[24]  Hongjun Gao,et al.  Gold supported on well-ordered ceria films: nucleation, growth and morphology in CO oxidation reaction , 2007 .

[25]  H. Freund,et al.  CO adsorption on oxide supported gold: from small clusters to monolayer islands and three-dimensional nanoparticles , 2004 .

[26]  A. Corma,et al.  CO oxidation catalyzed by supported gold: cooperation between gold and nanocrystalline rare-earth supports forms reactive surface superoxide and peroxide species. , 2005, Angewandte Chemie.

[27]  M. Flytzani-Stephanopoulos,et al.  Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts , 2003, Science.

[28]  Matsumoto,et al.  Resonant photoemission study of CeO2. , 1994, Physical review. B, Condensed matter.

[29]  Wertheim Gk,et al.  Cluster growth and core-electron binding energies in supported metal clusters. , 1988 .

[30]  M. Bäumer,et al.  Universal Phenomena of CO Adsorption on Gold Surfaces with Low-Coordinated Sites , 2007 .

[31]  J. Hanson,et al.  Gold nanoparticles on ceria: importance of O vacancies in the activation of gold , 2007 .

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

[33]  R. Egdell,et al.  Initial and final state effects in photoemission from Au nanoclusters on TiO2(110) , 2002 .

[34]  Tsuyoshi Nakajima,et al.  Studies of mixed-valence states in three-dimensional halogen-bridged gold compounds, Cs2AuIAuIIIX6, (X = Cl, Br or I). Part 2. X-Ray photoelectron spectroscopic study , 1991 .

[35]  G. Briggs,et al.  Defect Structure of Nonstoichiometric CeO{sub 2}(111) Surfaces Studied by Scanning Tunneling Microscopy , 1997 .

[36]  J. H. Weaver,et al.  Quantitative analysis of synchrotron radiation photoemission core level data , 1989 .

[37]  F. Netzer,et al.  Growth and thermal properties of ultrathin cerium oxide layers on Rh( 1 1 1 ) , 2002 .