Nanoscale colloidal metals and alloys stabilized by solvents and surfactants Preparation and use as catalyst precursors

Solvent-stabilized organosols of the early transition metal series, e.g. Ti, Zr, Nb, and Mn, may be prepared by the reduction of the THF adducts or thioether solutions of the corresponding metal halides with K[BEt3H]. Mono- and bimetallic organosols of Group 6–11 metals stabilized by tetraalkylammonium halides may be formed either by the reduction of the metal salts using NR4 hydrotriorganoborates or conventional agents, e.g. H2 or HCO2H, after the pretreatment of the metal salts with NR4X. The chemical reduction of transition metal salts in the presence of hydrophilic surfactants provides straightforward access to nanostructured mono- and bimetallic hydrosols. This synthesis can be performed even in water. Mono- and bimetallic nanoparticles stabilized by lipophilic or hydrophilic surfactants of the cationic, anionic or nonionic type serve as precursors for heterogeneous metal colloid catalysts effective for the hydrogenation and oxidation of organic substrates. Bimetallic precursors, e.g. PtRh, have a synergic effect on the catalytic activity. A comparison of catalytic results and CO chemisorption experiments has revealed that the protecting surfactants still cover the nanoparticle surface after adsorption on supports, which markedly improves the lifetime of the catalysts. Chiral protecting agents may induce enantioselectivity in metal colloid catalysts.

[1]  H. Bönnemann,et al.  Herstellung feinverteilter Metall‐ und Legierungspulver , 1990 .

[2]  Peter P. Edwards,et al.  Strukturelle Charakterisierung von kolloidalem Platin durch hochauflösende Elektronenmikroskopie und EXAFS‐Analyse , 1989 .

[3]  G. Schmid Metal clusters and cluster metals , 1988 .

[4]  G. Schmid Clusters and Colloids , 1994 .

[5]  Manfred T. Reetz,et al.  Size-Selective Synthesis of Nanostructured Transition Metal Clusters , 1994 .

[6]  L. Lewis Chemical catalysis by colloids and clusters , 1993 .

[7]  C. Larpent,et al.  Catalytic Hydrogenations in Biphasic Liquid-Liquid Systems: Part 2: Utilization of Sulfonated Tripod Ligands for the Stabilization of Colloidal Rhodium Dispersions , 1988 .

[8]  M. Graetzel,et al.  Projection, size factors, and reaction dynamics of colloidal redox catalysts mediating light induced hydrogen evolution from water , 1979 .

[9]  M. Baerns,et al.  Infrared Spectroscopic Studies of CO Adsorption on Rhodium Supported by SiO2, Al2O3, and TiO2 , 1994 .

[10]  K. Klabunde,et al.  Clustering of metal atoms in organic media: V. Production of tailored selectivity in nickel catalysts: Comparisons with Raney nickel , 1978 .

[11]  Y. Yonezawa,et al.  Photochemical formation of silver metal films from silver salt of natural high molecular carboxylic acid , 1990 .

[12]  K. Klabunde,et al.  The building of a Catal.ytic metal particle one atom at a time: solvated metal atom dispersed Catalysts , 1983 .

[13]  K. Torigoe,et al.  Preparation of bimetallic silver-palladium colloids from silver(I) bis(oxalato)palladate(II) , 1993 .

[14]  I. Moiseev Synthesis and catalytic activity of carbonyl palladium clusters , 1989 .

[15]  K. Klabunde,et al.  Solvated nickel atoms and their free cluster formation in organic media , 1976 .

[16]  K. Torigoe,et al.  Preparation of organo gold particles by reduction of extracted chlorauric acid with some reductants , 1988 .

[17]  D. Ostgard,et al.  The Mechanism of Hydrogenolysis and Isomerization of Oxacycloalkanes on Metals, Part X. Nature of the Active Sites in the Regioselective Hydrogenation of Oxiranes , 1991 .

[18]  I. Moiseev,et al.  Mechanism of the formation of palladium complexes serving as catalysts in hydrogenation reactions : I. Reactions of complexes with molecular hydrogen , 1982 .

[19]  Y. Yonezawa,et al.  Photochemical formation of silver-gold (Ag-Au) composite colloids in solutions containing sodium alginate , 1991 .

[20]  Bruno Chaudret,et al.  Surface Chemistry on Colloidal Metals. Reversible Adsorbate-Induced Surface Composition Changes in Colloidal Palladium-Copper Alloys , 1995 .

[21]  G. Schmid Clusters and colloids: bridges between molecular and condensed material , 1990 .

[22]  N. Toshima Polymer-Protected Bimetallic Clusters. Preparation and Application to Catalysis , 1990 .

[23]  N. Toshima,et al.  Selective Hydrogenation of Cyclooctadienes Using Colloidal Palladium in Poly(N-vinyl-2-pyrrolidone) , 1985 .

[24]  B. Hayden,et al.  Rhodium geminal dicarbonyl on TiO2(110) , 1992 .

[25]  N. Lewis,et al.  Metal colloid morphology and catalytic activity: Further proof of the intermediacy of colloids in the platinum-catalyzed hydrosilylation reaction , 1991 .

[26]  A. Baiker,et al.  Enantioselective hydrogenation of α-ketoesters : preparation and catalytic behavior of different alumina-supported platinum catalysts modified with cinchonidine , 1990 .

[27]  B. C. Gates,et al.  Organometallchemie an Oberflächen – Reaktivität von Carbonylmetall‐Verbindungen auf Metalloxiden , 1988 .

[28]  G. Schmid Tetraedrische Carbonylcobalt‐Cluster , 1978 .

[29]  N. Toshima,et al.  Polymerized Micelle-Protected Platinum Clusters. Preparation and Application to Catalyst for Visible Light-Induced Hydrogen Generation , 1988 .

[30]  H. Bönnemann,et al.  Formation of Colloidal Transition Metals in Organic Phases and Their Application in Catalysis , 1991 .

[31]  N. Toshima,et al.  Selective Hydrogenation of Cyclopentadiene to Cyclopentene Using Colloidal Palladium Supported on Chelate Resin , 1984 .

[32]  H. Bönnemann,et al.  Preparation and catalytic properties of NR-stabilized palladium colloids† , 1994 .

[33]  N. Toshima,et al.  Colloidal Dispersions of Platinum and Palladium Clusters Embedded in the Micelles.Preparation and Application to the Catalysis for Hydrogenation of Olefins , 1992 .

[34]  M. E. Leonowicz,et al.  Clusters, colloids and catalysis , 1987 .

[35]  N. Lewis,et al.  Platinum-catalyzed hydrosilylation - colloid formation as the essential step , 1986 .

[36]  G. Schmid Von Metallclustern und Clustermetallen , 1987 .

[37]  W. Brijoux,et al.  Highly dispersed metal clusters and colloids for the preparation of active liquid-phase hydrogenation catalysts , 1992 .

[38]  O. Aguiar,et al.  Physical properties of high-nuclearity metal cluster compounds , 1989 .

[39]  H. Bönnemann,et al.  Erzeugung von kolloiden Übergangsmetallen in organischer Phase und ihre Anwendung in der Katalyse , 1991 .

[40]  U. Stimming,et al.  Visualization of Surfactants on Nanostructured Palladium Clusters by a Combination of STM and High-Resolution TEM , 1995, Science.

[41]  G. Pacchioni,et al.  Cluster Models for Surface and Bulk Phenomena , 1992 .

[42]  A. Henglein Physicochemical properties of small metal particles in solution: "microelectrode" reactions, chemisorption, composite metal particles, and the atom-to-metal transition , 1993 .

[43]  M. Komiyama,et al.  Effects of Polymer Support on the Substrate Selectivity of Covalently Immobilized Ultrafine Rhodium Particles as a Catalyst for Olefin Hydrogenation , 1991 .

[44]  Masayoshi Okubo,et al.  Makromol Chem-Macromol Symp , 1990 .

[45]  R. Landau,et al.  Enantioselective Catalysis: Influence of Conversion and Bulk Diffusion Limitations on Selectivity in the Hydrogenation of Ethyl Pyruvate , 1995 .

[46]  K. Torigoe,et al.  Preparation of bimetallic palladium-platinum colloids in organic solvent by solvent extraction-reduction , 1991 .

[47]  Per Stenius,et al.  The preparation of monodisperse colloidal metal particles from microemulsions , 1982 .

[48]  M. T. Reetz,et al.  Eine neue Methode zur Herstellung nanostrukturierter Metallcluster , 1995 .

[49]  K. Esumi,et al.  Preparation of organopalladium sols by thermal decomposition of palladium acetate , 1989 .

[50]  N. Toshima,et al.  Colloidal Palladium Supported on Chelate Resin Containing Iminodiacetic Acid Groups as Hydrogenation Catalyst , 1986 .

[51]  C. Klein,et al.  Synthesis of monodispersed bimetallic palladium-copper nanoscale colloids , 1993 .

[52]  K. Klabunde,et al.  BIMETALLIC SOLVATED METAL ATOM DISPERSED CATALYSTS. NEW MATERIALS WITH LOW-TEMPERATURE CATALYTIC PROPERTIES , 1984 .

[53]  I. Moiseev,et al.  Palladium clusters: Stoichiometric and catalytic reactions , 1994 .

[54]  J. Fendler Membrane-mimetic approach to advanced materials , 1994 .

[55]  H. Bönnemann,et al.  Etherlösliches Ti0 und Bis(η6‐aren)titan(0)‐Komplexe durch Reduktion von TiCl4 mit Triethylhydroborat , 1992 .

[56]  T. Yonezawa,et al.  Structural analysis of polymer-protected palladium/platinum bimetallic clusters as dispersed catalysts by using extended x-ray absorption fine structure spectroscopy , 1991 .

[57]  K. Klabunde,et al.  Solvated Metal Atom Dispersed Catalysts , 1991 .

[58]  B. Heaton,et al.  The application of transmission electron microscopy to the study of high nuclearity carbonyl clusters (HNCC’s) , 1992 .

[59]  K. Esumi,et al.  The preparation of organo colloidal precious metal particles. , 1988 .

[60]  H. Bönnemann,et al.  Preparation, characterization, and application of fine metal particles and metal colloids using hydrotriorganoborates , 1994 .

[61]  U. Simon,et al.  The Application of Au55 Clusters as Quantum Dots , 1993 .

[62]  P. Légaré,et al.  Electronic structure of palladium deposits on alumina , 1992 .

[63]  N. Lewis,et al.  Preparation and structure of platinum group metal colloids: without solvent , 1989 .

[64]  P. Stenius,et al.  Monodispersed colloidal metal particles from non-aqueous solutions: Catalytic behaviour for the hydrogenation of but-1-ene of platinum particles in solution , 1986 .

[65]  F. Solymosi,et al.  An infrared study of the influence of carbon monoxide chemisorption on the topology of supported rhodium , 1985 .

[66]  H. Bönnemann,et al.  The Preparation of Finely Divided Metal and Alloy Powders , 1990 .