X-ray Absorption Study of Graphene Oxide and Transition Metal Oxide Nanocomposites.
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ABSTRACT: The surface properties of the electrode materials play a crucial role in determining the performance and efficiency of energy storage devices. Graphene oxide and nanostructures of 3d transition metal oxides were synthesized for construction of electrodes in supercapacitors, and the electronic structure and oxidation states were probed using near-edge X-ray absorption fine structure. Understanding the chemistry of graphene oxide would provide valuable insight into its reactivity and properties as the graphene oxide transformation to reduced-graphene oxide is a key step in the synthesis of the electrode materials. Polarized behavior of the synchrotron X-rays and the angular dependency of the near-edge X-ray absorption fine structures (NEXAFS) have been utilized to study the orientation of the σ and π bonds of the graphene oxide and graphene oxide-metal oxide nanocomposites. The core-level transitions of individual metal oxides and that of the graphene oxide nanocomposite showed that the interaction of graphene oxide with the metal oxide nanostructures has not altered the electronic structure of either of them. As the restoration of the π network is important for good electrical conductivity, the C K edge NEXAFS spectra of reduced graphene oxide nanocomposites confirms the same through increased intensity of the sp(2)-derived unoccupied states π* band. A pronounced angular dependency of the reduced sample and the formation of excitonic peaks confirmed the formation of extended conjugated network.
Project description:Since the commercialization of lithium ion batteries (LIBs), layered transition metal oxides (LiMO2, where M = Co, Mn, Ni, or mixtures thereof) have been materials of choice for LIB cathodes. During cycling, the transition metals change their oxidation states, an effect that can be tracked by detecting energy shifts in the X-ray absorption near edge structure (XANES) spectrum. X-ray absorption spectroscopy (XAS) can therefore be used to visualize and quantify lithiation kinetics in transition metal oxide cathodes; however, in-situ measurements are often constrained by temporal resolution and X-ray dose, necessitating compromises in the electrochemistry cycling conditions used or the materials examined. We report a combined approach to reduce measurement time and X-ray exposure for operando XAS studies of lithium ion batteries. A highly discretized energy resolution coupled with advanced post-processing enables rapid yet reliable identification of the oxidation state. A full-field microscopy setup provides sub-particle resolution over a large area of battery electrode, enabling the oxidation state within many transition metal oxide particles to be tracked simultaneously. Here, we apply this approach to gain insights into the lithiation kinetics of a commercial, mixed-metal oxide cathode material, nickel cobalt aluminium oxide (NCA), during (dis)charge and its degradation during overcharge.
Project description:The fabrication and characterization of graphene oxide (GO) nanosheets and their reaction with Fe3O4 and ZrO2 metal oxides to form two nanocomposites, namely graphene oxide-iron oxide (GO-Fe3O4) and graphene oxide-iron oxide-zirconium oxide (GO-Fe3O4@ZrO2), have been examined. The fabricated nanocomposites were examined using different techniques, e.g.transmission electron microscopy, X-ray diffraction, zeta potential measurement and Fourier transform infrared spectroscopy. Compared to GO, the newly fabricated GO-Fe3O4 and GO-Fe3O4@ZrO2 nanocomposites have the advantage of smaller band gaps, which result in increased adsorption capacity and photocatalytic effects. The results also showed the great effect of the examined GO-metal oxide nanocomposites on the decomposition of cationic rhodamine B dye, as indicated by steady-state absorption and fluorescence, time correlated single photon counting and nanosecond laser photolysis techniques. The antibacterial activity of the fabricated GO and GO-metal oxides has been studied against Gram-positive and Gram-negative bacteria.
Project description:The reduced graphene oxide/iron oxide (rGO/Fe2O3) and reduced graphene oxide/cobalt oxide (rGO/Co3O4) composite anodes have been successfully prepared through a simple and scalable ball-milling synthesis. The substantial interaction of Fe2O3 and Co3O4 with the rGO matrix strengthens the electronic conductivity and limits the volume variation during cycling in the rGO/Fe2O3 and rGO/Co3O4 composites because reduced graphene oxide (rGO) helps the metal oxides (MOs) to attain a more efficient diffusion of Li-ions and leads to high specific capacities. As anode materials for LIBs, the rGO/Fe2O3 and rGO/Co3O4 composites demonstrate overall superb electrochemical properties, especially rGO/Fe2O3T-5 and rGO/Co3O4T-5, showcasing higher reversible capacities of 1021 and 773 mAhg-1 after 100 cycles at 100 mAg-1, accompanied by the significant rate performance. Because of their superior electrochemical efficiency, high capacity and low cost, the rGO/Fe2O3 and rGO/Co3O4 composites made by ball milling could be outstanding anode materials for LIBs. Due to the excellent electrochemical performance, the rGO/Fe2O3 and rGO/Co3O4 composites prepared via ball milling could be promising anode materials with a high capacity and low cost for LIBs. The findings may provide shed some light on how other metal oxides wrapped by rGO can be prepared for future applications.
Project description:Graphene-based membranes have great potential to revolutionize nanofiltration technology, but achieving high solute rejections at high water flux remains extremely challenging. Herein, a family of ultrafine metal oxide/reduced graphene oxide (rGO) nanocomposites are synthesized through a heterogenous nucleation and diffusion-controlled growth process for dye nanofiltration. The synthesis is based on the utilization of oxygen functional groups on GO surface as preferential active sites for heterogeneous nucleation, leading to the formation of sub-3 nm size, monodispersing as well as high-density loading of metal oxide nanoparticles. The anchored ultrafine nanoparticles could inhibit the wrinkling of the rGO nanosheet, forming highly stable colloidal solutions for the solution processing fabrication of nanofiltration membranes. By functioning as pillars, the nanoparticles remarkably increase both vertical interlayer spacing and lateral tortuous paths of the rGO membranes, offering a water permeability of 225 L m-2 h-1 bar-1 and selectivity up to 98% in the size-exclusion separation of methyl blue.
Project description:Anisotropic Fe3O4 nanoparticle and a series of its graphene composites have been successfully prepared as high-frequency absorbers. The crystal structure, morphology and magnetic property of the samples were detailed characterized through X-ray diffractometer (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). The high-frequency absorbing performance of the composites is evaluated within 2.0-18.0 GHz. Combining reduced graphene oxide (RGO) to Fe3O4 helps to adjust the permittivity and permeability of the composite, balance the dielectric loss and magnetic loss, consequently improve the absorbing performance in view of the impedance matching characteristic. The optimal reflection loss of the pure Fe3O4 sample reaches -38.1 dB with a thickness of 1.7 mm, and it increases to -65.1 dB for the sample grafted with 3 wt.% RGO. The addition of proper content of RGO both improves the reflection loss and expands the absorbing bandwidth. This work not only opens a new method and an idea for tuning the electromagnetic properties and enhancing the capacity of high-efficient absorbers, but also broadens the application of such kinds of lightweight absorbing materials frameworks.
Project description:An acetylcholinesterase biosensor modified with graphene and transition metal carbides was prepared to detect organophosphorus pesticides. Cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy were used to characterize the electrochemical catalysis of the biosensor: acetylcholinesterase/chitosan-transition metal carbides/graphene/glassy carbon electrode. With the joint modification of graphene and transition metal carbides, the biosensor has a good performance in detecting dichlorvos with a linear relationship from 11.31 μM to 22.6 nM and the limit of detection was 14.45 nM. Under the premise of parameter optimization, the biosensor showed a good catalytic performance for acetylcholine. Compared to the biosensors without modification, it expressed a better catalytic performance due to the excellent electrical properties, biocompatibility and high specific surface area of graphene, transition metal carbides. Finally, the biosensor exhibits good stability, which can be stored at room temperature for one month without significant performance degradation, and has practical potential for sample testing.
Project description:Heterostructures consisting of two-dimensional materials have shown new physical phenomena, novel electronic and optical properties, and new device concepts not observed in bulk material systems or purely three dimensional heterostructures. These new effects originated mostly from the van der Waals interaction between the different layers. Here we report that a new optical and electronic device platform can be provided by heterostructures of 2D graphene with a metal oxide (TiO2). Our novel direct synthesis of graphene/TiO2 heterostructure is achieved by C60 deposition on transition Ti metal surface using a molecular beam epitaxy approach and O2 intercalation method, which is compatible with wafer scale growth of heterostructures. As-grown heterostructures exhibit inherent photosensitivity in the visible light spectrum with high photo responsivity. The photo sensitivity is 25 times higher than that of reported graphene photo detectors. The improved responsivity is attributed to optical transitions between O 2p orbitals in the valence band of TiO2 and C 2p orbitals in the conduction band of graphene enabled by Coulomb interactions at the interface. In addition, this heterostructure provides a platform for realization of bottom gated graphene field effect devices with graphene and TiO2 playing the roles of channel and gate dielectric layers, respectively.
Project description:Recently, graphene-based nanomaterials, in the form of two dimensional substrates or three dimensional foams, have attracted considerable attention as bioactive scaffolds to promote the differentiation of various stem cells towards specific lineages. On the other hand, the potential advantages of using graphene-based hybrid composites directly as factors inducing cellular differentiation as well as tissue regeneration are unclear. This study examined whether nanocomposites of reduced graphene oxide (rGO) and hydroxyapatite (HAp) (rGO/HAp NCs) could enhance the osteogenesis of MC3T3-E1 preosteoblasts and promote new bone formation. When combined with HAp, rGO synergistically promoted the spontaneous osteodifferentiation of MC3T3-E1 cells without hindering their proliferation. This enhanced osteogenesis was corroborated from determination of alkaline phosphatase activity as early stage markers of osteodifferentiation and mineralization of calcium and phosphate as late stage markers. Immunoblot analysis showed that rGO/HAp NCs increase the expression levels of osteopontin and osteocalcin significantly. Furthermore, rGO/HAp grafts were found to significantly enhance new bone formation in full-thickness calvarial defects without inflammatory responses. These results suggest that rGO/HAp NCs can be exploited to craft a range of strategies for the development of novel dental and orthopedic bone grafts to accelerate bone regeneration because these graphene-based composite materials have potentials to stimulate osteogenesis.
Project description:We introduce a general approach for synthesizing multicomponent metal-decorated crumpled reduced graphene oxide nanocomposites using a one-step, continuous flame-based process. Crumpled reduced graphene oxide balls (CGB) were produced from graphene oxide (GO) in a High Temperature Reducing Jet (HTRJ) reactor. Moreover, CGBs were simultaneously decorated with different transition metal nanoparticles, including cobalt (Co), nickel (Ni), iron (Fe), and palladium (Pd). Various metal alloy-decorated crumpled reduced graphene oxide balls (M-CGBs) including CoPd-, CoNi-, CoPdNi-, and CoNiFe-CGBs were successfully synthesized using a general recipe. The key advantage of the HTRJ system over common flame-based aerosol synthesis methods is the separation of flame and product formation zones, which allows production and/or reduction of nanomaterials that can be reduced by H2 in the presence of H2O. Nanomaterials are produced from aqueous precursors containing low-cost metal salts and dispersed GO. Electron microscopy and other characterization methods show the decoration of the CGBs with sub-4 nm diameter binary and ternary alloy, non-oxide transition metal nanoparticles of controlled compositions. The nanostructures made by this process can potentially be used as electrocatalysts for fuel cells, electrodes in batteries and supercapacitors, conductive inks for printed electronics, catalysts in wastewater treatment, and many other applications where a graphitized carbon-metal nanomaterial is needed.
Project description:Graphene has evoked extensive interests for its abundant physical properties and potential applications. It is reported that the interfacial electronic interaction between metal and graphene would give rise to charge transfer and change the electronic properties of graphene, leading to some novel electrical and magnetic properties in metal-graphene heterostructure. In addition, large specific surface area, low density and high chemical stability make graphene act as an ideal coating material. Taking full advantage of the aforementioned features of graphene, we synthesized graphene-coated Fe nanocomposites for the first time and investigated their microwave absorption properties. Due to the charge transfer at Fe-graphene interface in Fe/G, the nanocomposites show distinct dielectric properties, which result in excellent microwave absorption performance in a wide frequency range. This work provides a novel approach for exploring high-performance microwave absorption material as well as expands the application field of graphene-based materials.