Electrical Conductivity and Ferromagnetism in a Reduced Graphene–Metal Oxide Hybrid

The rare coexistence of ferromagnetism and electrical conductivity is observed in the reduced graphene oxide–metal oxide hybrids, rGO-Co, rGO-Ni, and rGO-Fe, using chemical reduction with hydrazine or ultraviolet photoirradiation of the graphene oxide–metal complexes, GO-Co, GO-Ni, and GO-Fe. The starting and final materials are characterized by X-ray photoelectron spectroscopy, transmission electron microscopy (TEM), elemental analysis, Mossbauer spectroscopy, and Raman spectroscopy. In contrast to graphene, where the electrical conductivity and magnetic properties are controlled by carrier (electron or hole) doping, those of graphene oxide can be controlled by complexation with Co2+, Ni2+, and Fe3+ cations through the strong electrostatic affinity of negatively charged graphene oxide towards metal cations. The presence of ferromagnetism and electrical conductivity in these hybrids can promote significant applications including magnetic switching and data storage.

[1]  Xinyong Li,et al.  A structured macroporous silicon/graphene heterojunction for efficient photoconversion. , 2010, Angewandte Chemie.

[2]  Prashant V. Kamat,et al.  Electrocatalytically Active Graphene-Platinum Nanocomposites. Role of 2-D Carbon Support in PEM Fuel Cells , 2009 .

[3]  Xin Wang,et al.  Graphene−Metal Particle Nanocomposites , 2008 .

[4]  J. Heath,et al.  Crystalline, Shape, and Surface Anisotropy in Two Crystal Morphologies of Superparamagnetic Cobalt Nanoparticles by Ferromagnetic Resonance , 2001 .

[5]  P. Bloemen,et al.  Magnetic anisotropy of multilayers , 1991 .

[6]  A. Scherz,et al.  Manipulation of the Curie temperature and the magnetic moments of ultrathin Ni and Co films by Cu-capping , 2000 .

[7]  Prashant V Kamat,et al.  Graphene-semiconductor nanocomposites: excited-state interactions between ZnO nanoparticles and graphene oxide. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[8]  Michio Koinuma,et al.  Photoreaction of Graphene Oxide Nanosheets in Water , 2011 .

[9]  M. Fröba,et al.  Silica-based mesoporous organic-inorganic hybrid materials. , 2006, Angewandte Chemie.

[10]  S. Blundell,et al.  Coexistence of superconductivity and magnetism by chemical design. , 2010, Nature chemistry.

[11]  Jin Zhai,et al.  Two-dimensional graphene bridges enhanced photoinduced charge transport in dye-sensitized solar cells. , 2010, ACS nano.

[12]  Yongsheng Chen,et al.  Room-temperature ferromagnetism of graphene. , 2009, Nano letters.

[13]  Chappert,et al.  Ferromagnetic resonance studies of very thin cobalt films on a gold substrate. , 1986, Physical review. B, Condensed matter.

[14]  L. W. Vernon,et al.  The Magnetic Properties of the Cobalt Oxide–Alumina System , 1958 .

[15]  M. Tokumoto,et al.  Antiferromagnetic Organic Metal Exhibiting Superconducting Transition, κ-(BETS)2FeBr4 [BETS = Bis(ethylenedithio)tetraselenafulvalene] , 1999 .

[16]  M I Katsnelson,et al.  Modeling of graphite oxide. , 2008, Journal of the American Chemical Society.

[17]  Shifeng Hou,et al.  Graphene-supported platinum and platinum–ruthenium nanoparticles with high electrocatalytic activity for methanol and ethanol oxidation , 2010 .

[18]  Dongmin Chen,et al.  Synthesis and Solid-State NMR Structural Characterization of 13C-Labeled Graphite Oxide , 2008, Science.

[19]  E. Yoo,et al.  Enhanced cyclic performance and lithium storage capacity of SnO2/graphene nanoporous electrodes with three-dimensionally delaminated flexible structure. , 2009, Nano letters.

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

[21]  Diandra L. Leslie-Pelecky,et al.  Magnetic Properties of Nanostructured Materials , 1996 .

[22]  Michio Koinuma,et al.  Simple photoreduction of graphene oxide nanosheet under mild conditions. , 2010, ACS applied materials & interfaces.

[23]  Anthony K. Cheetham,et al.  There's Room in the Middle , 2007, Science.

[24]  John Silcox,et al.  Atomic and electronic structure of graphene-oxide. , 2009, Nano letters.

[25]  Bei Wang,et al.  HYDROTHERMAL SYNTHESIS AND OPTICAL, MAGNETIC, AND SUPERCAPACITANCE PROPERTIES OF NANOPOROUS COBALT OXIDE NANORODS , 2009 .

[26]  S. Tolbert,et al.  Controlling Magnetic Coupling between Cobalt Nanoparticles through Nanoscale Confinement in Hexagonal Mesoporous Silica , 2003 .

[27]  V. Laukhin,et al.  Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound , 2000, Nature.

[28]  J. J. Gracio,et al.  Surface Modification of Graphene Nanosheets with Gold Nanoparticles: The Role of Oxygen Moieties at Graphene Surface on Gold Nucleation and Growth , 2009 .

[29]  M. Popall,et al.  Applications of hybrid organic–inorganic nanocomposites , 2005 .

[30]  How graphene is cut upon oxidation? , 2009, Journal of the American Chemical Society.

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

[32]  Feng Li,et al.  Anchoring Hydrous RuO2 on Graphene Sheets for High‐Performance Electrochemical Capacitors , 2010 .

[33]  Augustine Urbas,et al.  Ultrafast Intersystem Crossing: Excited State Dynamics of Platinum Acetylide Complexes , 2009 .

[34]  SUPARNA DUTTASINHA,et al.  Graphene: Status and Prospects , 2009, Science.

[35]  H. R. Krishnamurthy,et al.  Monitoring dopants by Raman scattering in an electrochemically top-gated graphene transistor. , 2008, Nature nanotechnology.

[36]  Itaru Honma,et al.  Enhanced electrocatalytic activity of Pt subnanoclusters on graphene nanosheet surface. , 2009, Nano letters.

[37]  Andre K. Geim,et al.  The rise of graphene. , 2007, Nature materials.

[38]  Xingfa Gao,et al.  Hydrazine and Thermal Reduction of Graphene Oxide: Reaction Mechanisms, Product Structures, and Reaction Design , 2010 .

[39]  P. Kamat,et al.  Electron transfer cascade by organic/inorganic ternary composites of porphyrin, zinc oxide nanoparticles, and reduced graphene oxide on a tin oxide electrode that exhibits efficient photocurrent generation. , 2011, Journal of the American Chemical Society.

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

[41]  Ado Jorio,et al.  General equation for the determination of the crystallite size La of nanographite by Raman spectroscopy , 2006 .

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

[43]  A. Xu,et al.  Highly Durable N-Doped Graphene/CdS Nanocomposites with Enhanced Photocatalytic Hydrogen Evolution from Water under Visible Light Irradiation , 2011 .

[44]  C. Rao,et al.  Novel Magnetic Properties of Graphene: Presence of Both Ferromagnetic and Antiferromagnetic Features and Other Aspects , 2009, 0904.2739.

[45]  Frederic Chaput,et al.  Optical Properties of Functional Hybrid Organic–Inorganic Nanocomposites , 2003 .

[46]  Ji‐Guang Zhang,et al.  Self-assembled TiO2-graphene hybrid nanostructures for enhanced Li-ion insertion. , 2009, ACS nano.

[47]  H. Tajima,et al.  Magnetic properties of NiO nanoparticles , 2003 .

[48]  Yongsheng Chen,et al.  Flexible, Magnetic, and Electrically Conductive Graphene/Fe3O4 Paper and Its Application for Magnetic-Controlled Switches , 2010 .

[49]  Xixiang Zhang,et al.  Microstructural and magnetic properties of passivated Co nanoparticle films , 2004 .