Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold–copper nanoparticles

The oxidation of 5-hydroxymethyl-2-furfural was studied under mild reaction conditions using TiO2-supported Au and Au–Cu catalysts synthesized from pre-formed nanoparticles. Bimetallic gold-copper catalysts display superior activity as compared to monometallic gold. Moreover, after reaction, the bimetallic Au–Cu catalysts can be recovered by filtration and reused without significant loss of activity and selectivity whereas gold materials are not stable. STEM-HAADF imagining and XEDS spectra obtained from bimetallic materials show that particles are homogeneous AuCu alloys. No AuCu ordering or segregation effects were noted from these analyses, and the Au:Cu ratio was quite consistent from particle-to-particle irrespective of its absolute size, proving the efficiency of the original method of synthesis utilized. Isolation effects of gold by copper in the alloy nanoparticles is imagined to play a pivotal role in the reaction. The effect of oxygen pressure, metal loading, reaction time, amount of base and temperature were studied in detail and a 99% yield of furandicarboxylic acid was achieved under optimized reaction conditions.

[1]  A. Gandini.  The irruption of polymers from renewable resources on the scene of macromolecular science and technology , 2011 .

[2]  C. Afonso,et al.  5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications , 2011 .

[3]  A. Corma,et al.  Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts , 2011 .

[4]  Robert J. Davis,et al.  Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts , 2011 .

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

[6]  A. Corma,et al.  Biomass into chemicals: aerobic oxidation of 5-hydroxymethyl-2-furfural into 2,5-furandicarboxylic acid with gold nanoparticle catalysts. , 2009, ChemSusChem.

[7]  T. Akita,et al.  Au@ZIF-8: CO oxidation over gold nanoparticles deposited to metal-organic framework. , 2009, Journal of the American Chemical Society.

[8]  G. Hutchings,et al.  Application of copper-gold alloys in catalysis: current status and future perspectives. , 2009, Chemical Society reviews.

[9]  John M Woodley,et al.  Gold-catalyzed aerobic oxidation of 5-hydroxymethylfurfural in water at ambient temperature. , 2009, ChemSusChem.

[10]  A. Corma,et al.  Biomass into chemicals: One pot-base free oxidative esterification of 5-hydroxymethyl-2-furfural into 2,5-dimethylfuroate with gold on nanoparticulated ceria , 2009 .

[11]  G. Hutchings,et al.  Oxidation of glycerol using gold-palladium alloy-supported nanocrystals. , 2009, Physical chemistry chemical physics : PCCP.

[12]  Onofre Casanova Navarro,et al.  Chemicals from Biomass: Aerobic Oxidation of 5-Hydroxymethyl-2-Furaldehyde into Diformylfurane Catalyzed by Immobilized Vanadyl-Pyridine Complexes on Polymeric and Organofunctionalized Mesoporous Supports , 2009 .

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

[14]  G. Hutchings,et al.  Palladium and gold-palladium catalysts for the direct synthesis of hydrogen peroxide. , 2008, Angewandte Chemie.

[15]  H. Matsumoto,et al.  Nanocolloidal Pd-Au as catalyst for the direct synthesis of hydrogen peroxide from H2 and O2. , 2008, ChemSusChem.

[16]  C. Christensen,et al.  Chemicals from renewables: aerobic oxidation of furfural and hydroxymethylfurfural over gold catalysts. , 2008, ChemSusChem.

[17]  L. Prati,et al.  Microgel-stabilized gold nanoclusters: Powerful “quasi-homogeneous” catalysts for the aerobic oxidation of alcohols in water , 2007 .

[18]  G. Huber,et al.  Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. , 2007, Angewandte Chemie.

[19]  G. Hutchings,et al.  Solvent free liquid phase oxidation of benzyl alcohol using Au supported catalysts prepared using a sol immobilization technique , 2007 .

[20]  Jie Fu,et al.  A simple and green method for the synthesis of Au, Ag, and Au-Ag alloy nanoparticles , 2006 .

[21]  Claudia L. Bianchi,et al.  Gold on titania: Effect of preparation method in the liquid phase oxidation , 2006 .

[22]  A. Villa,et al.  Effect of Particle Size on Monometallic and Bimetallic (Au,Pd)/C on the Liquid Phase Oxidation of Glycerol , 2006 .

[23]  Juncheng Liu,et al.  Facile "green" synthesis, characterization, and catalytic function of beta-D-glucose-stabilized Au nanocrystals. , 2006, Chemistry.

[24]  Charlotte K. Williams,et al.  The Path Forward for Biofuels and Biomaterials , 2006, Science.

[25]  G. Hutchings,et al.  Tunable gold catalysts for selective hydrocarbon oxidation under mild conditions , 2005, Nature.

[26]  M. Haruta,et al.  Simulation of pathways for CO oxidation over Au nano-clusters by paired interacting orbitals (PIO) analysis , 2005 .

[27]  G. Huber,et al.  Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates , 2005, Science.

[28]  J. Rostrup-Nielsen.  Making Fuels from Biomass , 2005, Science.

[29]  G. Bond,et al.  Gold on titania catalysts for the oxidation of carbon monoxide: control of pH during preparation with various gold contents , 2005 .

[30]  A. Corma,et al.  Nanocrystalline CeO2 increases the activity of Au for CO oxidation by two orders of magnitude. , 2004, Angewandte Chemie.

[31]  B. Gates,et al.  Catalysis by supported gold: correlation between catalytic activity for CO oxidation and oxidation states of gold. , 2004, Journal of the American Chemical Society.

[32]  Alessandro Gandini,et al.  Recent Catalytic Advances in the Chemistry of Substituted Furans from Carbohydrates and in the Ensuing Polymers , 2004 .

[33]  Ulf Schuchardt,et al.  Cooperative effect of cobalt acetylacetonate and silica in the catalytic cyclization and oxidation of fructose to 2,5-furandicarboxylic acid , 2003 .

[34]  Klaus-Dieter Vorlop,et al.  A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose , 2000 .

[35]  J. Grunwaldt,et al.  Preparation of Supported Gold Catalysts for Low-Temperature CO Oxidation via “Size-Controlled” Gold Colloids , 1999 .

[36]  Antoine Gaset,et al.  Oxydation catalytique du HMF en acide 2,5-furane dicarboxylique , 1993 .

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

[38]  G. Hutchings.  Vapor phase hydrochlorination of acetylene: Correlation of catalytic activity of supported metal chloride catalysts , 1985 .

[39]  G. Bond,et al.  Hydrogenation of alkenes over supported gold , 1979 .

[40]  M. Dondi,et al.  Microwave-assisted synthesis of Au, Ag and Au-Ag nanoparticles and their catalytic activities for the reduction of nitrophenol , 2010 .