The route to functional graphene oxide.

We report on an easy-to-use, successful, and reproducible route to synthesize functionalized graphite oxide (GO) and its conversion to graphene-like materials through chemical or thermal reduction of GO. Graphite oxide containing hydroxyl, epoxy, carbonyl, and carboxyl groups loses mainly hydroxyl and epoxy groups during reduction, whereas carboxyl species remain untouched. The interaction of functionalized graphene with fluorescent methylene blue (MB) is investigated and compared to graphite, fully oxidized GO, as well as thermally and chemically reduced GO. Optical absorption and emission spectra of the composites indicate a clear preference for MB interaction with the GO derivatives containing a large number of functional groups (GO and chemically reduced GO), whereas graphite and thermally reduced GO only incorporate a few MB molecules. These findings are consistent with thermogravimetric, X-ray photoelectron spectroscopic, and Raman data recorded at every stage of preparation. The optical data also indicate concentration-dependent aggregation of MB on the GO surface leading to stable MB dimers and trimers. The MB dimers are responsible for fluorescence quenching, which can be controlled by varying the pH value.

[1]  J. Bujdák,et al.  Structure of cationic dyes assemblies intercalated in the films of montmorillonite , 2008 .

[2]  C. T. O'konski,et al.  A SPECTROSCOPIC STUDY OF METHYLENE BLUE MONOMER, DIMER, AND COMPLEXES WITH MONTMORILLONITE , 1963 .

[3]  S. Stankovich,et al.  Synthesis and exfoliation of isocyanate-treated graphene oxide nanoplatelets , 2006 .

[4]  R. Car,et al.  Single Sheet Functionalized Graphene by Oxidation and Thermal Expansion of Graphite , 2007 .

[5]  E. Sacher,et al.  s–p Hybridization in highly oriented pyrolytic graphite and its change on surface modification, as studied by X-ray photoelectron and Raman spectroscopies , 2002 .

[6]  Lei Su,et al.  Adsorption of Methylene Blue Dye onto Carbon Nanotubes: A Route to an Electrochemically Functional Nanostructure and Its Layer-by-Layer Assembled Nanocomposite , 2005 .

[7]  M. Inagaki,et al.  Exfoliated Graphite as a New Sorbent for Removal of Engine Oils from Wastewater , 2003 .

[8]  F. Stoeckli,et al.  On the characterization of acidic and basic surface sites on carbons by various techniques , 1999 .

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

[10]  Sandip Niyogi,et al.  Solution properties of graphite and graphene. , 2006, Journal of the American Chemical Society.

[11]  P. J. Ollivier,et al.  Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations , 1999 .

[12]  J. Dentzer,et al.  Surface Characterizations of Carbon Multiwall Nanotubes: Comparison between Surface Active Sites and Raman Spectroscopy , 2004 .

[13]  G. Wallace,et al.  Processable aqueous dispersions of graphene nanosheets. , 2008, Nature nanotechnology.

[14]  Kobayash. Hiroyuki,et al.  Spontaneous formation of an ordered structure during dip-coating of methylene blue on fused quartz , 2001 .

[15]  Roberto Car,et al.  Functionalized single graphene sheets derived from splitting graphite oxide. , 2006, The journal of physical chemistry. B.

[16]  E. Braswell Evidence for trimerization in aqueous solutions of methylene blue , 1968 .

[17]  Connie B. Chang,et al.  Quantification of methylene blue aggregation on a fused silica surface and resolution of individual absorbance spectra , 2001 .

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

[19]  J. A. Menéndez,et al.  Basic surface oxides on carbon materials: A global view , 2003 .

[20]  P. Kamat,et al.  TiO2-graphene nanocomposites. UV-assisted photocatalytic reduction of graphene oxide. , 2008, ACS nano.

[21]  J. Fendler,et al.  High Density Rechargeable Lithium‐Ion Batteries Self‐Assembled from Graphite Oxide Nanoplatelets and Polyelectrolytes , 1998 .

[22]  N. Kotov,et al.  Ultrathin graphite oxide–polyelectrolyte composites prepared by self‐assembly: Transition between conductive and non‐conductive states , 1996 .

[23]  Carla C Schmitt,et al.  Time-dependent spectrophotometric study of the interaction of basic dyes with clays. I: Methylene blue and neutral red on montmorillonite and hectorite , 1994 .

[24]  K. Komvopoulos,et al.  Tetrahedral and Trigonal Carbon Atom Hybridization in Thin Amorphous Carbon Films Synthesized by Radio-Frequency Sputtering , 2007 .

[25]  Mohamed Ali Hajjaji,et al.  Influence of operating conditions on methylene blue uptake by a smectite rich clay fraction , 2009 .

[26]  H. Boehm.,et al.  Some aspects of the surface chemistry of carbon blacks and other carbons , 1994 .

[27]  Felix Franks,et al.  Water:A Comprehensive Treatise , 1972 .

[28]  L. Staudenmaier,et al.  Verfahren zur Darstellung der Graphitsäure , 1898 .

[29]  José L. Figueiredo,et al.  Adsorption of dyes on activated carbons: influence of surface chemical groups , 2003 .

[30]  Chun Li,et al.  Flexible graphene films via the filtration of water-soluble noncovalent functionalized graphene sheets. , 2008, Journal of the American Chemical Society.

[31]  Ulrich Hofmann,et al.  Das Adsorptionsverhalten sehr dünner Kohlenstoff‐Folien , 1962 .

[32]  I. Dékány,et al.  Selective liquid sorption properties of hydrophobized graphite oxide nanostructures , 1998 .

[33]  J. Robertson,et al.  Interpretation of Raman spectra of disordered and amorphous carbon , 2000 .

[34]  Jacobs,et al.  Spectroscopy of Methylene Blue-Smectite Suspensions. , 1999, Journal of colloid and interface science.

[35]  Zhuang Liu,et al.  PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. , 2008, Journal of the American Chemical Society.

[36]  M. Pospíšil,et al.  Composition, structure, and luminescence of montmorillonites saturated with different aggregates of methylene blue. , 2007, Journal of colloid and interface science.

[37]  Carla C Schmitt,et al.  Influence of the layer charge and clay particle size on the interactions between the cationic dye methylene blue and clays in an aqueous suspension. , 2002, Journal of colloid and interface science.

[38]  Janos H. Fendler,et al.  Preparation and Characterization of Ultrathin Films Layer-by-Layer Self-Assembled from Graphite Oxide Nanoplatelets and Polymers , 2000 .

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

[40]  Yang Yang,et al.  High-throughput solution processing of large-scale graphene. , 2009, Nature nanotechnology.

[41]  F. Tuinstra,et al.  Raman Spectrum of Graphite , 1970 .

[42]  C. Párkányi,et al.  A quantitative study of the effect of solvent on the electronic absorption and fluorescence spectra of substituted phenothiazines: evaluation of their ground and excited singlet-state dipole moments , 1993 .

[43]  E. Samulski,et al.  Synthesis of water soluble graphene. , 2008, Nano letters.

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

[45]  SonBinh T. Nguyen,et al.  Aqueous Suspension and Characterization of Chemically Modified Graphene Sheets , 2008 .

[46]  Prashant V. Kamat,et al.  Decorating Graphene Sheets with Gold Nanoparticles , 2008 .

[47]  E. Bekyarova,et al.  Chemical modification of epitaxial graphene: spontaneous grafting of aryl groups. , 2009, Journal of the American Chemical Society.

[48]  S. Stankovich,et al.  Synthesis of graphene-based nanosheets via chemical reduction of exfoliated graphite oxide , 2007 .

[49]  I. Yamazaki,et al.  Fluorescence decays and spectral properties of rhodamine B in submono-, mono-, and multilayer systems , 1986 .