Structural Evolution and Catalytic Properties of Nanostructured Cu/ZrO2 Catalysts Prepared by Oxalate Gel-Coprecipitation Technique

A series of zirconia-supported copper oxide catalysts synthesized by decomposition of the oxalate precursors formed by oxalate gel-coprecipitation in alcoholic solution were extensively investigated in relation to their performance in methanol steam reforming. The combination of different techniques (N2 adsorption, X-ray diffraction (XRD), N2O titration, H2-TPR, diffuse reflectance Fourier transform infrared, Raman, and X-ray photoelectron spectroscopy) in the characterization of Cu/ZrO2 catalysts shows that the surface and structural characteristics of the zirconia phase as well as the dispersion and nature of the copper species depend strongly on the calcination temperature. Temperature-programmed reduction patterns reveal the presence of three types of copper species on the ZrO2 support. XRD results indicate that, depending on the calcination temperature, a substantial incorporation of Cu species into the zirconia lattice leading to a strong Cu−ZrO2 metal−support interaction may occur. The N2O titratio...

[1]  Francesco Frusteri,et al.  Synthesis, characterization and activity pattern of Cu–ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol , 2007 .

[2]  Kangnian Fan,et al.  Production of hydrogen by steam reforming of methanol over Cu/ZnO catalysts prepared via a practical soft reactive grinding route based on dry oxalate-precursor synthesis , 2007 .

[3]  R. Schlögl,et al.  Steam reforming of methanol over copper-containing catalysts: Influence of support material on microkinetics , 2007 .

[4]  K. Chary,et al.  Characterization and catalytic functionalities of copper oxide catalysts supported on zirconia. , 2007, The journal of physical chemistry. B.

[5]  B. Tyagi,et al.  Synthesis of Nanocrystalline Zirconia Using Sol-Gel and Precipitation Techniques , 2006 .

[6]  J. Cerdá,et al.  Adhesion at metal–ZrO2 interfaces , 2006 .

[7]  J. Grunwaldt,et al.  Decreased CO production in methanol steam reforming over Cu/ZrO2 catalysts prepared by the microemulsion technique , 2006 .

[8]  H. Yahiro,et al.  Effect of calcination temperature on the catalytic activity of copper supported on γ-alumina for the water-gas-shift reaction , 2006 .

[9]  Kangnian Fan,et al.  Effect of preparation method on the hydrogen production from methanol steam reforming over binary Cu/ZrO2 catalysts , 2006 .

[10]  Dong Hyun Kim,et al.  Cu–ZrO2 Catalysts for Water-gas-shift Reaction at Low Temperatures , 2005 .

[11]  M. Luo,et al.  In situ XRD, raman, and TPR studies of CuO/Al2O3 catalysts for CO oxidation , 2005 .

[12]  R. Doong,et al.  Chemical-Composition-Dependent Metastability of Tetragonal ZrO2 in Sol−Gel-Derived Films under Different Calcination Conditions , 2005 .

[13]  Kangnian Fan,et al.  A unique microwave effect on the microstructural modification of Cu/ZnO/Al2O3 catalysts for steam reforming of methanol. , 2005, Chemical communications.

[14]  Kangnian Fan,et al.  A highly efficient Cu/ZnO/Al2O3 catalyst via gel-coprecipitation of oxalate precursors for low-temperature steam reforming of methanol , 2005 .

[15]  M. Rhodes,et al.  The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalysts: Part II -- Transient-Response Infrared Studies , 2005 .

[16]  Yuhan Sun,et al.  Catalytic performance of copper supported on zirconia polymorphs for CO hydrogenation , 2005 .

[17]  M. Rhodes,et al.  The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalysts: Part I -- Steady-State Studies , 2005 .

[18]  H. Wan,et al.  Effect of zirconia phase on the reduction behaviour of highly dispersed zirconia-supported copper oxide , 2004 .

[19]  U. Ozkan,et al.  Steam reforming of methanol to H2 over nonreduced Zr-containing CuO/ZnO catalysts , 2004 .

[20]  Rufino M. Navarro,et al.  Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3 , 2003 .

[21]  A. Kozłowska,et al.  Reduction kinetics of CuO in CuO/ZnO/ZrO2 systems , 2003 .

[22]  Yuhan Sun,et al.  The Nature of Cu/ZrO2 catalyst: experimental and theoretical studies , 2003 .

[23]  M. Muhler,et al.  Deactivation of Supported Copper Catalysts for Methanol Synthesis , 2003 .

[24]  D. Kulkarni,et al.  Isopropanol oxidation by pure metal oxide catalysts: number of active surface sites and turnover frequencies , 2002 .

[25]  H. Yoshida,et al.  XPS, XANES and EXAFS investigations of CuO/ZnO/Al2O3/ZrO2 mixed oxide catalysts , 2002 .

[26]  R. Caruso,et al.  Preparation and characterization of CuO–ZrO2 nanopowders , 2002 .

[27]  A. Bell,et al.  Effects of Zirconia Phase on the Synthesis of Methanol over Zirconia-Supported Copper , 2002 .

[28]  T. Ressler,et al.  Redox Behavior of Copper Oxide /Zinc Oxide Catalysts in the Steam Reforming of Methanol studied by in situ X-ray Diffraction and Absorption Spectroscopy , 2001 .

[29]  Yu Liang,et al.  Surface active structure of ultra-fine Cu/ZrO2 catalysts used for the CO2+H2 to methanol reaction , 2001 .

[30]  Q. Xin,et al.  Phase Transformation in the Surface Region of Zirconia Detected by UV Raman Spectroscopy , 2001 .

[31]  K. Hadjiivanov,et al.  FTIR Spectroscopic Study of CO Adsorption on Cu/SiO2: Formation of New Types of Copper Carbonyls , 2001 .

[32]  A. Wokaun,et al.  Methanol synthesis reactions over a CuZr based catalyst investigated using periodic variations of reactant concentrations , 2001 .

[33]  H. Koh,et al.  Surface properties and reactivity of Cu/γ-Al2O3 catalysts for NO reduction by C3H6: Influences of calcination temperatures and additives , 2001 .

[34]  M. Bettahar,et al.  Gas phase hydrogenation of benzaldehyde over supported copper catalysts , 2000 .

[35]  A. Davydov,et al.  Dehydrogenation of Cyclohexanol on Copper-Containing Catalysts: I. The Influence of the Oxidation State of Copper on the Activity of Copper Sites , 2000 .

[36]  Kenzi Suzuki,et al.  Oxidative Steam Reforming of Methanol over CuZnAl(Zr)-Oxide Catalysts for the Selective Production of Hydrogen for Fuel Cells: Catalyst Characterization and Performance Evaluation , 2000 .

[37]  A. Bell,et al.  Water-Assisted Tetragonal-to-Monoclinic Phase Transformation of ZrO2 at Low Temperatures , 2000 .

[38]  S. Ardizzone,et al.  XPS characterization of sulphated zirconia catalysts: the role of iron , 2000 .

[39]  A. Bell,et al.  Structure and Properties of Zirconia-Supported Molybdenum Oxide Catalysts for Oxidative Dehydrogenation of Propane , 2000 .

[40]  Julian R.H. Ross,et al.  Methanol reforming for fuel-cell applications: development of zirconia-containing Cu–Zn–Al catalysts , 1999 .

[41]  Israel E. Wachs,et al.  The origin of the support effect in supported metal oxide catalysts : in situ infrared and kinetic studies during methanol oxidation , 1999 .

[42]  A. Baiker,et al.  Copper- and Silver–Zirconia Aerogels: Preparation, Structural Properties and Catalytic Behavior in Methanol Synthesis from Carbon Dioxide , 1998 .

[43]  M. Vannice,et al.  Determination of the Dispersion and Surface Oxidation States of Supported Cu Catalysts , 1998 .

[44]  M. Primet,et al.  Surface and bulk properties of Cu–ZSM-5 and Cu/Al2O3 solids during redox treatments. Correlation with the selective reduction of nitric oxide by hydrocarbons , 1998 .

[45]  J. Fierro,et al.  Partial oxidation of methanol over supported palladium catalysts , 1998 .

[46]  M. Schmal,et al.  The cyclohexanol dehydrogenation on RhCu/Al2O3 catalysts: 2. Chemisorption and reaction , 1997 .

[47]  R. Baker,et al.  Properties of Copper Chromite Catalysts in Hydrogenation Reactions , 1997 .

[48]  A. Baiker,et al.  Catalytic Reduction of Nitrogen Oxides by Olefins in the Presence of Oxygen over Copper/Alumina: Influence of Copper Loading and Formation of Byproducts , 1997 .

[49]  Sun Qi,et al.  A novel process for preparation of a Cu/ZnO/Al2O3 ultrafine catalyst for methanol synthesis from CO2 + H2: comparison of various preparation methods , 1996 .

[50]  M. Saito,et al.  Development of copper/zinc oxide-based multicomponent catalysts for methanol synthesis from carbon dioxide and hydrogen , 1996 .

[51]  M. Vrinat,et al.  Zirconia- and alumina-supported molybdenum-based catalysts: a comparative study in hydrodesulfurization and hydrogenation reactions , 1994 .

[52]  T. Yamaguchi,et al.  Acid-base bifunctional catalysis by ZrO2 and its mixed oxides , 1994 .

[53]  Tsutomu Yamaguchi.  Application of ZrO2 as a catalyst and a catalyst support , 1994 .

[54]  A. Wokaun,et al.  Copper/zirconia catalysts for the synthesis of methanol from carbon dioxide , 1992 .

[55]  N. Takezawa,et al.  Characterization of copper/zirconia catalysts prepared by an impregnation method , 1990 .

[56]  K. C. Waugh,et al.  The activity and state of the copper surface in methanol synthesis catalysts , 1986 .

[57]  J. Mathews,et al.  The activity of cobalt-zirconia and cobalt-nickel-zirconia preparations in the Fischer-Tropsch reaction , 1983 .

[58]  K. P. Jong,et al.  An infrared spectroscopic study of the adsorption of carbon monoxide on silica-supported copper particles , 1980 .

[59]  V. Kuznetsov,et al.  Hydrogenation of carbon monoxide catalysts prepared by pyrolysis of Co2(CO)8 on various oxide supports , 1980 .

[60]  A. Heuer,et al.  Microstructural Development in MgO‐Partially Stabilized Zirconia (Mg‐PSZ) , 1979 .

[61]  Ikramullah,et al.  Dehydrogenation of cyclohexanol to cyclohexanone catalysed by Y2O3/ZrO2: activation energy , 2004 .

[62]  R. Schlögl,et al.  Rational design of nanostructured copper-zinc oxide catalysts for the steam reforming of methanol. , 2004, Angewandte Chemie.

[63]  R. Schlögl,et al.  Implication of the microstructure of binary Cu/ZnO catalysts for their catalytic activity in methanol synthesis , 2001 .

[64]  T. Ohno,et al.  Infrared, laser-Raman and X-ray diffraction investigation of MoO3/ZrO2 and the oxidation of (Z)-but-2-ene , 1990 .

[65]  R. Burch,et al.  Support and morphological effects in the synthesis of methanol over Cu/ZnO, Cu/ZrO2 and Cu/SiO2 catalysts , 1988 .

[66]  K. C. Waugh,et al.  The measurement of copper surface areas by reactive frontal chromatography , 1987 .