Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper–nickel/graphite bimetallic nanocomposite catalyst

A novel graphite supported Cu–Ni bimetallic nanocomposite catalyst for direct synthesis of dimethyl carbonate (DMC) from CH3OH and CO2 has been synthesized and investigated. The support and the synthesized catalysts were fully characterized using BET surface area, TG–DSC, Raman spectra, FTIR, SEM–EDX, TEM, XRD, TPR and XPS techniques. The catalytic activities were investigated by performing micro-reactions. It has been found that the nitrogen adsorption isotherm of graphite oxide support showed a typical Type II features. The layered structure of graphite was well maintained in the synthesized catalysts. Metal particles with an average size of 15.8 nm were uniformly dispersed on the support surface. Metal phase and alloy phase of Cu and Ni in the catalyst were partially formed during the reduction and activation step. The Cu–Ni/graphite nanocomposite catalyst exhibited remarkably high activity, selectivity and stability for the direct synthesis of DMC. The highest DMC yield was higher than 9.0% at 378 K and 1.2 MPa and the selectivity of DMC was higher than 88.0%. The high catalytic activity of Cu–Ni/graphite nanocomposite catalyst in DMC synthesis could be attributed to the synergetic effects of metal Cu, Ni and Cu–Ni alloy in the activation of CH3OH and CO2, the unique structure of graphite and the interaction between the metal particles and the supports.

[1]  J. Kizlink.  Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol in the Presence of Organotin Compounds , 1993 .

[2]  Yoshiki Ikeda,et al.  A novel method of direct synthesis of dimethyl carbonate from methanol and carbon dioxide catalyzed by zirconia , 1999 .

[3]  Michel Mermoux,et al.  FTIR and 13C NMR study of graphite oxide , 1991 .

[4]  J. D. Lopez-Gonzalez,et al.  Kinetics of the formation of graphite oxide , 1975 .

[5]  G. Wedler,et al.  Interaction of carbon dioxide with Fe(110), stepped Fe(100) and Fe(111) , 1986 .

[6]  P. Jessop,et al.  Homogeneous catalysis in supercritical fluids. , 1999, Science.

[7]  M. Xiao,et al.  Direct synthesis of poly(arylenedisulfide)/carbon nanosheet composites via the oxidation with graphite oxide , 2005 .

[8]  R. Baker,et al.  CATALYTIC BEHAVIOR OF GRAPHITE NANOFIBER SUPPORTED NICKEL PARTICLES. 3. THE EFFECT OF CHEMICAL BLOCKING ON THE PERFORMANCE OF THE SYSTEM , 1999 .

[9]  M. Aresta,et al.  Carbon Dioxide: A Substitute for Phosgene , 1997 .

[10]  C. Hwang,et al.  Preparation and characteristics of ferrite catalysts for reduction of CO2 , 2004 .

[11]  K. Tominaga,et al.  Ruthenium-catalyzed one-pot hydroformylation of alkenes using carbon dioxide as a reactant , 2004 .

[12]  D. Manos,et al.  Synthesis of carbon nanosheets by inductively coupled radio-frequency plasma enhanced chemical vapor deposition , 2004 .

[13]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate (DMC) using Cu-Ni/VSO as catalyst , 2006 .

[14]  Dimitrios Gournis,et al.  Graphite Oxide: Chemical Reduction to Graphite and Surface Modification with Primary Aliphatic Amines and Amino Acids , 2003 .

[15]  M. Aresta,et al.  Carbon dioxide coordination chemistry. 3. Vibrational, NMR, theoretical studies of (carbon dioxide)bis(tricyclohexylphosphine)nickel , 1993 .

[16]  Ultrathin supported graphite oxide and carbon films , 1998 .

[17]  Jacek Klinowski,et al.  Structure of Graphite Oxide Revisited , 1998 .

[18]  K. Fujimoto,et al.  Direct synthesis of dimethyl carbonate from carbon dioxide and methanol catalyzed by base , 1996 .

[19]  Yoshio Ono,et al.  Catalysis in the Production and Reactions of Dimethyl Carbonate, an Environmentally Benign Building-Block , 1997 .

[20]  Jacek Klinowski,et al.  A new structural model for graphite oxide , 1998 .

[21]  S. Jackson.  Isotopic exchange of carbon dioxide and its interaction with carbon monoxide over copper catalysts , 1989 .

[22]  Tsuyoshi Nakajima,et al.  Formation process and structure of graphite oxide , 1994 .

[23]  Imre Dékány,et al.  Evolution of surface functional groups in a series of progressively oxidized graphite oxides , 2006 .

[24]  Takuya Gotou,et al.  Thin-film particles of graphite oxide. 2: Preliminary studies for internal micro fabrication of single particle and carbonaceous electronic circuits , 2005 .

[25]  Brian C. Holloway,et al.  Free-standing subnanometer graphite sheets , 2004 .

[26]  T. Etsell,et al.  XRD and XPS Study of Cu−Ni Interactions on Reduced Copper−Nickel−Aluminum Oxide Solid Solution Catalysts , 2006 .

[27]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate on H3PO4 modified V2O5 , 2005 .

[28]  Andre K. Geim,et al.  Electric Field Effect in Atomically Thin Carbon Films , 2004, Science.

[29]  Robin K. Harris,et al.  Electrochemically oxidised graphite.: Characterisation and some ion exchange properties , 2000 .

[30]  J. D. Lopez-Gonzalez,et al.  Products of oxidation at 0°C of mineralogical and artificial graphite—I. Chemical composition, structure and theoretical interlaminar surface area , 1969 .

[31]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate from carbon dioxide and methanol using supported copper (Ni, V, O) catalyst with photo-assistance , 2007 .

[32]  J. D. Lopez-Gonzalez,et al.  Study of oxygen-containing groups in a series of graphite oxides: Physical and chemical characterization , 1995 .

[33]  M. Xiao,et al.  Novel synthesis of conductive poly(arylene disulfide)/graphite nanocomposite , 2004 .

[34]  A. Geim,et al.  Two-dimensional gas of massless Dirac fermions in graphene , 2005, Nature.

[35]  Juraj Kizlink,et al.  Preparation of Dimethyl Carbonate from Methanol and Carbon Dioxide in the Presence of Sn(IV) and Ti(IV) Alkoxides and Metal Acetates , 1995 .

[36]  P. Kim,et al.  Experimental observation of the quantum Hall effect and Berry's phase in graphene , 2005, Nature.

[37]  M. Steigerwald,et al.  Crystalline graphite from an organometallic solution-phase reaction. , 2006, Journal of the American Chemical Society.

[38]  F. Trotta,et al.  Gas-liquid phase-transfer catalysis: a new continuous-flow method in organic synthesis , 1989 .

[39]  A. Trotman‐Dickenson,et al.  ‘Comprehensive’ Inorganic Chemistry , 1958, Nature.

[40]  S. Stankovich,et al.  Graphene-based composite materials , 2006, Nature.

[41]  A. Hamwi,et al.  Some chemical and electrochemical properties of graphite oxide , 1996 .

[42]  Changwen Hu,et al.  Synthesis of dimethyl carbonate from methanol and carbon dioxide in the presence of polyoxometalates under mild conditions , 2003 .

[43]  R. Madix,et al.  The selective oxidation of CH3OH to H2CO on a copper(110) catalyst , 1978 .

[44]  G. Webb,et al.  The influence of the substrate on the behavior of graphite-supported palladium catalysts , 1969 .

[45]  A. Bell,et al.  Effects of Catalyst Phase Structure on the Elementary Processes Involved in the Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Zirconia , 2002 .

[46]  Min Xiao,et al.  Preparation and characterization of poly(vinyl acetate)-intercalated graphite oxide nanocomposite , 2000 .