Factors influencing the catalytic oxidation of benzyl alcohol using supported phosphine-capped gold nanoparticles

Two phosphine-stabilised gold clusters, Au101(PPh3)21Cl5 and Au9(PPh3)8(NO3)3, were deposited and activated on anatase TiO2 and fumed SiO2. These catalysts showed an almost complete oxidation of benzyl alcohol (>90%) within 3 hours at 80 °C and 3 bar O2 in methanol with a high substrate-to-metal molar ratio of 5800 and turn-over frequency of 0.65 s−1. Factors influencing catalytic activity were investigated, including metal–support interaction, effects of heat treatments, chemical composition of gold clusters, the size of gold nanoparticles and catalytic conditions. It was found that the anions present in gold clusters play a role in determining the catalytic activity in this reaction, with NO3− diminishing the catalytic activity. High catalytic activity was attributed to the formation of large gold nanoparticles (>2 nm) that coincides with partial removal of ligands which occurs during heat treatment and catalysis. Selectivity towards the formation of methyl benzoate can be tuned by selection of the reaction temperature. The catalysts were characterised using transmission electron microscopy, UV-vis diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy.

[1]  R. Jin,et al.  Thermally robust Au99(SPh)42 nanoclusters for chemoselective hydrogenation of nitrobenzaldehyde derivatives in water. , 2014, Journal of the American Chemical Society.

[2]  B. E. Williamson,et al.  Tuning the selectivity of a supported gold catalyst in solvent- and radical initiator-free aerobic oxidation of cyclohexene , 2014 .

[3]  M. Haruta.  Chance and necessity: my encounter with gold catalysts. , 2014, Angewandte Chemie.

[4]  V. Golovko,et al.  Establishing a Au Nanoparticle Size Effect in the Oxidation of Cyclohexene Using Gradually Changing Au Catalysts , 2013 .

[5]  Rong Zhang,et al.  Stabilizer substitution and its effect on the hydrogenation catalysis by Au nanoparticles from colloidal synthesis , 2013 .

[6]  Di Wang,et al.  Sol immobilization technique: a delicate balance between activity, selectivity and stability of gold catalysts , 2013 .

[7]  Xiaopeng Zhao,et al.  Surface plasmon induced photoluminescence enhancement in the Au–ZnS nanocomposite , 2013 .

[8]  S. Stahl,et al.  Aerobic oxidation of diverse primary alcohols to methyl esters with a readily accessible heterogeneous Pd/Bi/Te catalyst. , 2013, Organic letters.

[9]  M. Jia,et al.  Selective oxidative esterification of alcohols on Au/ZrO2 catalyst under ambient conditions , 2013, Reaction Kinetics, Mechanisms and Catalysis.

[10]  Huifeng Qian,et al.  CeO2-supported Au38(SR)24 nanocluster catalysts for CO oxidation: a comparison of ligand-on and -off catalysts. , 2013, Nanoscale.

[11]  Nikolaos Dimitratos,et al.  Selective catalytic oxidation using supported gold-platinum and palladium-platinum nanoalloys prepared by sol-immobilisation. , 2013, Physical chemistry chemical physics : PCCP.

[12]  Yuhan Sun,et al.  Atomically precise Au25 superatoms immobilized on CeO2 nanorods for styrene oxidation. , 2013, Nanoscale.

[13]  Robert J. Davis,et al.  Selective oxidation of alcohols and aldehydes over supported metal nanoparticles , 2013 .

[14]  G. Andersson,et al.  Chemically synthesised atomically precise gold clusters deposited and activated on titania. Part II. , 2013, Physical chemistry chemical physics : PCCP.

[15]  S. Mandal,et al.  Sm-CeO2 supported gold nanoparticle catalyst for benzyl alcohol oxidation using molecular O2 , 2013 .

[16]  J. Bokhoven,et al.  Particle size and support effects in hydrogenation over supported gold catalysts , 2013 .

[17]  R. Jin,et al.  Au25 nanocluster-catalyzed Ullmann-type homocoupling reaction of aryl iodides. , 2012, Chemical communications.

[18]  R. Jin,et al.  Gold nanocluster-catalyzed selective oxidation of sulfide to sulfoxide. , 2012, Nanoscale.

[19]  K. Rademann,et al.  Size dependent catalysis with CTAB-stabilized gold nanoparticles. , 2012, Physical chemistry chemical physics : PCCP.

[20]  Manolis Stratakis,et al.  Catalysis by supported gold nanoparticles: beyond aerobic oxidative processes. , 2012, Chemical reviews.

[21]  A. Baiker,et al.  Potential of gold nanoparticles for oxidation in fine chemical synthesis. , 2012, Annual review of chemical and biomolecular engineering.

[22]  C. Prestipino,et al.  Following the Creation of Active Gold Nanocatalysts from Phosphine-Stabilized Molecular Clusters , 2012 .

[23]  G. Hutchings,et al.  Selective liquid phase oxidation with supported metal nanoparticles , 2012 .

[24]  Eduardo A Coronado,et al.  Optical properties of metallic nanoparticles: manipulating light, heat and forces at the nanoscale. , 2011, Nanoscale.

[25]  Qinghong Zhang,et al.  Effect of size of catalytically active phases in the dehydrogenation of alcohols and the challenging selective oxidation of hydrocarbons. , 2011, Chemical communications.

[26]  Karen Wilson,et al.  Recent advances in the heterogeneously catalysed aerobic selective oxidation of alcohols , 2011 .

[27]  T. Akita,et al.  Aerobic Oxidation of Cyclohexane Catalyzed by Size-Controlled Au Clusters on Hydroxyapatite: Size Effect in the Sub-2 nm Regime , 2011 .

[28]  Joon-Hwa Lee,et al.  Effect of ligand structure on the catalytic activity of Au nanocrystals , 2010 .

[29]  L. Palmisano,et al.  Green oxidation of alcohols to carbonyl compounds by heterogeneous photocatalysis. , 2010, ChemSusChem.

[30]  Huifeng Qian,et al.  An atomic-level strategy for unraveling gold nanocatalysis from the perspective of Au(n)(SR)m nanoclusters. , 2010, Chemistry.

[31]  B. Gates,et al.  Metal clusters on supports: synthesis, structure, reactivity, and catalytic properties. , 2010, Chemical communications.

[32]  H. Miyamura,et al.  Aerobic oxidative esterification of alcohols catalyzed by polymer-incarcerated gold nanoclusters under ambient conditions , 2010 .

[33]  F. Kapteijn,et al.  Weakly bound capping agents on gold nanoparticles in catalysis: Surface poison? , 2010 .

[34]  R. Jin,et al.  Atomically precise Au25(SR)18 nanoparticles as catalysts for the selective hydrogenation of alpha,beta-unsaturated ketones and aldehydes. , 2010, Angewandte Chemie.

[35]  T. Akita,et al.  Size Effect of Silica-supported Gold Clusters in the Microwave-assisted Oxidation of Benzyl Alcohol with H2O2 , 2010 .

[36]  Jens K Nørskov,et al.  Green Gold Catalysis , 2010, Science.

[37]  T. Akita,et al.  Efficient and selective epoxidation of styrene with TBHP catalyzed by Au(25) clusters on hydroxyapatite. , 2010, Chemical communications.

[38]  D. Su,et al.  Gold Sols as Catalysts for Glycerol Oxidation: The Role of Stabilizer , 2009 .

[39]  T. Akita,et al.  Preparation of ∼1 nm Gold Clusters Confined within Mesoporous Silica and Microwave-Assisted Catalytic Application for Alcohol Oxidation , 2009 .

[40]  H. Sakurai,et al.  Effect of electronic structures of Au clusters stabilized by poly(N-vinyl-2-pyrrolidone) on aerobic oxidation catalysis. , 2009, Journal of the American Chemical Society.

[41]  R. A. Santen,et al.  Basic metal carbonate supported gold nanoparticles: enhanced performance in aerobic alcohol oxidation , 2009 .

[42]  M. Ford,et al.  Rapid and Controllable Sintering of Gold Nanoparticle Inks at Room Temperature Using a Chemical Agent , 2009 .

[43]  M. Rossi,et al.  Highly selective oxidation of benzyl alcohol to benzaldehyde catalyzed by bimetallic gold–copper catalyst , 2008 .

[44]  T. Akita,et al.  Deposition of gold clusters on porous coordination polymers by solid grinding and their catalytic activity in aerobic oxidation of alcohols. , 2008, Chemistry.

[45]  G. Hutchings,et al.  Identification of Active Gold Nanoclusters on Iron Oxide Supports for CO Oxidation , 2008, Science.

[46]  Brian F. G. Johnson,et al.  Selective oxidation with dioxygen by gold nanoparticle catalysts derived from 55-atom clusters , 2008, Nature.

[47]  J. Grunwaldt,et al.  Gold-Catalyzed Aerobic Oxidation of Benzyl Alcohol: Effect of Gold Particle Size on Activity and Selectivity in Different Solvents , 2008 .

[48]  C. Christensen,et al.  Aerobic oxidation of aldehydes under ambient conditions using supported gold nanoparticle catalysts , 2008 .

[49]  N. Zheng,et al.  Promoting gold nanocatalysts in solvent-free selective aerobic oxidation of alcohols. , 2007, Chemical communications.

[50]  Z. Pan,et al.  Low-temperature CO oxidation on Au/fumed SiO2-based catalysts prepared from Au(en)2Cl3 precursor , 2007 .

[51]  V. Choudhary,et al.  Solvent-free selective oxidation of benzyl alcohol by molecular oxygen over uranium oxide supported nano-gold catalyst for the production of chlorine-free benzaldehyde , 2007 .

[52]  Nanfeng Zheng,et al.  A general synthetic strategy for oxide-supported metal nanoparticle catalysts. , 2006, Journal of the American Chemical Society.

[53]  C. Louis,et al.  Preparation of supported gold nanoparticles by a modified incipient wetness impregnation method. , 2006, The journal of physical chemistry. B.

[54]  Ping Liu,et al.  Studies of Gold Nanoparticles as Precursors to Printed Conductive Features for Thin-Film Transistors , 2006 .

[55]  V. Choudhary,et al.  A green process for chlorine-free benzaldehyde from the solvent-free oxidation of benzyl alcohol with molecular oxygen over a supported nano-size gold catalyst , 2005 .

[56]  A. Corma,et al.  A collaborative effect between gold and a support induces the selective oxidation of alcohols. , 2005, Angewandte Chemie.

[57]  H. Sakurai,et al.  Size-specific catalytic activity of polymer-stabilized gold nanoclusters for aerobic alcohol oxidation in water. , 2005, Journal of the American Chemical Society.

[58]  R. Murray,et al.  Reaction of Au55(PPh3)12Cl6 with thiols yields thiolate monolayer protected Au75 clusters , 2005 .

[59]  Leif O. Brown,et al.  Thiol-functionalized, 1.5-nm gold nanoparticles through ligand exchange reactions: scope and mechanism of ligand exchange. , 2005, Journal of the American Chemical Society.

[60]  S. Overbury,et al.  Comparison of Au Catalysts Supported on Mesoporous Titania and Silica: Investigation of Au Particle Size Effects and Metal-Support Interactions , 2004 .

[61]  M. Haruta,et al.  Vital role of moisture in the catalytic activity of supported gold nanoparticles. , 2004, Angewandte Chemie.

[62]  Stephan Link,et al.  Optical properties and ultrafast dynamics of metallic nanocrystals. , 2003, Annual review of physical chemistry.

[63]  Masatake Haruta,et al.  When gold is not noble: catalysis by nanoparticles. , 2003, Chemical record.

[64]  Prashant V. Kamat,et al.  Photophysical, photochemical and photocatalytic aspects of metal nanoparticles , 2002 .

[65]  Masatake Haruta,et al.  Catalysis of Gold Nanoparticles Deposited on Metal Oxides , 2002 .

[66]  Masatake Haruta,et al.  Advances in the catalysis of Au nanoparticles , 2001 .

[67]  Catherine J. Murphy,et al.  Seeding Growth for Size Control of 5−40 nm Diameter Gold Nanoparticles , 2001 .

[68]  S. Reed,et al.  Improved Synthesis of Small (dCORE ≈ 1.5 nm) Phosphine-Stabilized Gold Nanoparticles , 2000 .

[69]  F. Porta,et al.  Selective liquid phase oxidation using gold catalysts , 2000 .

[70]  G. Marin,et al.  Engineering aspects of the aqueous noble metal catalysed alcohol oxidation , 2000 .

[71]  P. Gallezot,et al.  Selective oxidation of alcohols and aldehydes on metal catalysts , 2000 .

[72]  J. Grunwaldt,et al.  Gold/Titania Interfaces and Their Role in Carbon Monoxide Oxidation , 1999 .

[73]  M. Haruta,et al.  Effect of calcination temperature on the catalytic activity of Au colloids mechanically mixed with TiO2 powder for CO oxidation , 1998 .

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

[75]  L. Prati,et al.  Gold on Carbon as a New Catalyst for Selective Liquid Phase Oxidation of Diols , 1998 .

[76]  Peter W. Stephens,et al.  Structural evolution of smaller gold nanocrystals: The truncated decahedral motif , 1997 .

[77]  P. Gallezot.  Selective oxidation with air on metal catalysts , 1997 .

[78]  H. Wan,et al.  Preparation of supported gold catalysts from gold complexes and their catalytic activities for CO oxidation , 1996 .

[79]  P. Gallezot,et al.  Chemoselective catalytic oxidation of glycerol with air on platinum metals , 1995 .

[80]  A. Baiker,et al.  Oxidation of alcohols with molecular oxygen on platinum metal catalysts in aqueous solutions , 1994 .

[81]  Bernard Delmon,et al.  Low-Temperature Oxidation of CO over Gold Supported on TiO2, α-Fe2O3, and Co3O4 , 1993 .

[82]  M. Vannice,et al.  Low temperature CO oxidation over Au/TiO2 and Au/SiO2 catalysts , 1993 .

[83]  G. Hutchings,et al.  Hydrochlorination of acetylene using carbon-supported gold catalysts: A study of catalyst reactivation , 1991 .

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

[85]  P. Buffat,et al.  Size effect on the melting temperature of gold particles , 1976 .

[86]  U. Simon,et al.  Crystal Structure, Electrochemical and Optical Properties of [Au9(PPh3)8](NO3)3 , 2008 .

[87]  Kangnian Fan,et al.  Ga-Al mixed-oxide-supported gold nanoparticles with enhanced activity for aerobic alcohol oxidation. , 2008, Angewandte Chemie.

[88]  Martin Muhler,et al.  CO Oxidation over Supported Gold Catalysts—“Inert” and “Active” Support Materials and Their Role for the Oxygen Supply during Reaction , 2001 .

[89]  G. Brauer.  Handbook of Preparative Inorganic Chemistry , 1963 .