Time resolved terahertz spectroscopy of low frequency electronic resonances and optical pump-induced terahertz photoconductivity in reduced graphene oxide membrane

Towards ultrafast optoelectronic applications of single and a few layer reduced graphene oxide (RGO), we study time domain terahertz spectroscopy and optical pump induced changes in terahertz conductivity of self-supported RGO membrane in the spectral window of 0.5-3.5 THz. The real and imaginary parts of conductivity spectra clearly reveal low frequency resonances, attributed to the energy gaps due to the van Hove singularities in the density of states flanking the Dirac points arising due to the relative rotation of the graphene layers. Further, optical pump induced terahertz conductivity is positive, pointing to the dominance of intraband scattering processes. The relaxation dynamics of the photo-excited carriers consists of three cooling pathways: the faster (similar to 450 fs) one due to optical phonon emission followed by disorder mediated large momentum and large energy acoustic phonon emission with a time constant of a few ps (called the super-collision mechanism) and a very large time (similar to 100 ps) arising from the deep trap states. The frequency dependence of the dynamic conductivity at different delay times is analyzed in term of Drude-Smith model. (C) 2014 Published by Elsevier Ltd.

A Continuous Electrical Conductivity Model for Monolayer Graphene From Near Intrinsic to Far Extrinsic Region

We present a closed-form continuous model for the electrical conductivity of a single layer graphene (SLG) sheet in the presence of short-range impurities, long-range screened impurities, and acoustic phonons. The validity of the model extends from very low doping levels (chemical potential close to the Dirac cone vertex) to very high doping levels. We demonstrate complete functional relations of the chemical potential, polarization function, and conductivity with respect to both doping level and temperature (T), which were otherwise developed for SLG sheet only in the very low and very high doping levels. The advantage of the continuous conductivity model reported in this paper lies in its simple form which depends only on three adjustable parameters: the short-range impurity density, the long-range screened impurity density, and temperature T. The proposed theoretical model was successfully used to correlate various experiments in the midtemperature and moderate density regimes.

Hexamethylenetetramine mediated simultaneous nitrogen doping and reduction of graphene oxide for a metal-free SERS substrate

We report a one-pot hydrothermal synthesis of nitrogen doped reduced graphene oxide (N-rGO) and Ag nanoparticle decorated N-rGO hybrid nanostructures from graphene oxide (GO), metal ions and hexamethylenetetramine (HMT). HMT not only reduces GO and metal ions simultaneously but also acts as the source for the nitrogen (N) dopant. We show that the N-rGO can be used as a metal-free surface enhanced Raman spectroscopy (SERS) substrate, while the Ag nano-particles decorated N-rGO can be used as an effective SERS substrate as well as a template for decorating various other nanostructures on N-rGO.

Effect of functional groups on separating carbon dioxide from CO2/N-2 gas mixtures using edge functionalized graphene nanoribbons

Development of microporous adsorbents for separation and sequestration of carbon dioxide from flue gas streams is an area of active research. In this study, we assess the influence of specific functional groups on the adsorption selectivity of CO2/N-2 mixtures through Grand Canonical Monte Carlo (GCMC) simulations. Our model system consists of a bilayer graphene nanoribbon that has been edge functionalized with OH, NH2, NO2, CH3 and COOH. Ab initio Moller-Plesset (MP2) calculations with functionalized benzenes are used to obtain binding energies and optimized geometries for CO2 and N-2. This information is used to validate the choice classical forcefields in GCMC simulations. In addition to simulations of adsorption from binary mixtures of CO2 and N-2, the ideal adsorbed solution theory (IAST) is used to predict mixture isotherms. Our study reveals that functionalization always leads to an increase in the adsorption of both CO2 and N-2 with the highest for COOH. However, significant enhancement in the selectivity for CO2 is only seen with COOH functionalized nanoribbons. The COOH functionalization gives a 28% increase in selectivity compared to H terminated nanoribbons, whereas the improvement in the selectivity for other functional groups are much Enure modest. Our study suggests that specific functionalization with COOH groups can provide a material's design strategy to improve CO2 selectivity in microporous adsorbents. Synthesis of graphene nanoplatelets with edge functionalized COOH, which has the potential for large scale production, has recently been reported (Jeon el, al., 2012). (C) 2014 Elsevier Ltd. All rights reserved,

High Value of Proton Relaxivity Achieved by Graphene Oxide-Cobalt Ferrite Nanoparticle Composite: A Potential Contrast Agent in Magnetic Resonance Imaging

This work investigates the potential of graphene oxide-cobalt ferrite nanoparticle (GO-CoFe2O4) composite as image contrast enhancing material in Magnetic Resonance Imaging (MRI). In the preset work, GO-CoFe2O4 composites were produced by a two-step synthesis process. In the first step, graphene oxide (GO) was synthesized, and in the second step CoFe2O4 nanoparticles were synthesized in a reaction mixture containing GO to yield graphene GO-CoFe2O4 composite. Proton relaxivity value obtained from the composite was 361 mM(-1)s(-1). This value of proton relaxivity is higher than a majority of reported relaxivity values obtained using several ferrite based contrast agents.

Reduced graphene oxide-titania based platform for label-free biosensor

A label-free biosensor has been fabricated using a reduced graphene oxide (RGO) and anatase titania (ant-TiO2) nanocomposite, electrophoretically deposited onto an indium tin oxide coated glass substrate. The RGO-ant-TiO2 nanocomposite has been functionalized with protein (horseradish peroxidase) conjugated antibodies for the specific recognition and detection of Vibrio cholerae. The presence of Ab-Vc on the RGO-ant-TiO2 nanocomposite has been confirmed using electron microscopy, Fourier transform infrared spectroscopy and electrochemical techniques. Electrochemical studies relating to the fabricated Ab-Vc/RGO-ant-TiO2/ITO immunoelectrode have been conducted to investigate the binding kinetics. This immunosensor exhibits improved biosensing properties in the detection of Vibrio cholerae, with a sensitivity of 18.17 x 10(6) F mol(-1) L-1 m(-2) in the detection range of 0.12-5.4 nmol L-1, and a low detection limit of 0.12 nmol L-1. The association (k(a)), dissociation (k(d)) and equilibrium rate constants have been estimated to be 0.07 nM, 0.002 nM and 0.41 nM, respectively. This Ab-Vc/RGO-ant-TiO2/ITO immunoelectrode could be a suitable platform for the development of compact diagnostic devices.

SnO2 nanowire anchored graphene nanosheet matrix for the superior performance of Li-ion thin film battery anode

All solid state batteries are essential candidate for miniaturizing the portable electronics devices. Thin film batteries are constructed by layer by layer deposition of electrode materials by physical vapour deposition method. We propose a promising novel method and unique architecture, in which highly porous graphene sheet embedded with SnO2 nanowire could be employed as the anode electrode in lithium ion thin film battery. The vertically standing graphene flakes were synthesized by microwave plasma CVD and SnO2 nanowires based on a vapour-liquid-solid (VLS) mechanism via thermal evaporation at low synthesis temperature (620 degrees C). The graphene sheet/SnO2 nanowire composite electrode demonstrated stable cycling behaviours and delivered a initial high specific discharge capacity of 1335 mAh g(-1) and 900 mAh g(-1) after the 50th cycle. Furthermore, the SnO2 nanowire electrode displayed superior rate capabilities with various current densities.

Tailoring the interface of an immiscible polymer blend by a mutually miscible homopolymer grafted onto graphene oxide: outstanding mechanical properties

A unique strategy was adopted here to improve the compatibility between the components of an immiscible polymer blend and strengthen the interface. PMMA, a mutually miscible polymer to both PVDF and ABS, improved the compatibility between the phases by localizing at the blends interface. This was supported by the core-shell formation with PMMA as the shell and ABS as the core as observed from the SEM micrographs. This phenomenon was strongly contingent on the concentration of PMMA in the blends. This strategy was further extended to localize graphene oxide (GO) sheets at the blends interface by chemically coupling it to PMMA (PMMA-g-GO). A dramatic increment of ca. 84% in the Young's modulus and ca. 124% in the yield strength was observed in the presence of PMMA-g-GO with respect to the neat blends. A simultaneous increment in both the strength and the modulus was observed in the presence of PMMA-g-GO whereas, only addition of GO resulted in a moderate improvement in the yield strength. This study reveals that a mutually miscible polymer can render compatibility between the immiscible pair and can improve the stress transfer at the interface.

Strontium eluting graphene hybrid nanoparticles augment osteogenesis in a 3D tissue scaffold

The objective of this work was to prepare hybrid nanoparticles of graphene sheets decorated with strontium metallic nanoparticles and demonstrate their advantages in bone tissue engineering. Strontium-decorated reduced graphene oxide (RGO_Sr) hybrid nanoparticles were synthesized by the facile reduction of graphene oxide and strontium nitrate. X-ray diffraction, transmission electron microscopy, and atomic force microscopy revealed that the hybrid particles were composed of RGO sheets decorated with 200-300 nm metallic strontium particles. Thermal gravimetric analysis further confirmed the composition of the hybrid particles as 22 wt% of strontium. Macroporous tissue scaffolds were prepared by incorporating RGO_Sr particles in poly(epsilon-caprolactone) (PCL). The PCL/RGO_Sr scaffolds were found to elute strontium ions in aqueous medium. Osteoblast proliferation and differentiation was significantly higher in the PCL scaffolds containing the RGO_Sr particles in contrast to neat PCL and PCL/RGO scaffolds. The increased biological activity can be attributed to the release of strontium ions from the hybrid nanoparticles. This study demonstrates that composites prepared using hybrid nanoparticles that elute strontium ions can be used to prepare multifunctional scaffolds with good mechanical and osteoinductive properties. These findings have important implications for designing the next generation of biomaterials for use in tissue regeneration.

Properties of the chalcogenide-carbon nano tubes and graphene composite materials

Composite can deliver more than the individual elemental property of the material. Specifically chalcogenide- multi walled carbon nano tubes and chalcogenide- bilayer graphene composite materials could be interesting for the investigation, which have been less covered by the investigators. We describe micro structural properties of Se55Te25Ge20, Se55Te25Ge20 + 0.025% multi walled carbon nano tubes and Se55Te25Ge20 + 0.025% bilayer graphene materials. This gives realization of the alloying constituents inclusion/or diffusion inside the multi walled carbon nano tubes and bilayer graphene under the homogeneous parent alloy configuration. Raman spectroscopy, X-ray photoelectron spectroscopy, UV/Visible spectroscopy and Fourier transmission infrared spectroscopy have also been carried out under the discussion. A considerable core energy levels peak shifts have been noticed for the composite materials by the X-ray photoelectron spectroscopy. The optical energy band gaps are measured to be varied in between 1.2 and 1.3 eV. In comparison to parent (Se55Te25Ge20) alloy a higher infrared transmission has been observed for the composite materials. Subsequently, variation in physical properties has been explained on the basis of bond formation in solids. (C) 2014 Elsevier B. V. All rights reserved.

Enhanced photocatalytic efficiency of AuPd nanoalloy decorated ZnO-reduced graphene oxide nanocomposites

Inhibition of electron-hole pair recombination is the most desirable solution for stimulating photocatalytic activity in semiconductor nanostructures. To implement this, herein we study the photocatalytic efficiency of elemental Au, Pd and bimetallic AuPd nanoalloy decorated pristine and reduced graphene oxide (RGO) hybridized ZnO nanorods for degrading rhodamine 6G (R6G) dye. Fabrication of Au, Pd and AuPd nanoalloy on pristine and RGO modified ZnO nanorods is simple and more importantly surfactant or polymer free. AuPd nanoalloyed ZnO-RGO nanocomposites exhibit higher photocatalytic activity for degrading dye than both Au and Pd hybridized ones, indicating the promising potential of bimetallic nanoalloys over elemental components. A non-monotonic dependence on the composite composition was found by analyzing photodegradation efficiency of a series of ZnO-RGO-AuPd hybrid nanostructures with different weight percentages of RGO. The hybrid nanostructure ZnO-RGO (5 wt%)-AuPd (1 wt%) exhibits highest photodegradation efficiency (similar to 100% degradation in 20 min) with an improvement in rate constant (k) by a factor of 10 compared to that of the ZnO-RGO nanocomposite. The enhancement of the photocatalytic activity is attributed to the better separation of photogenerated charge carriers in photocatalysts thereby suggesting possible usefulness in a broad range of applications, such as sensing, photocatalysis and solar energy conversion.

Insights on Defect-Mediated Heterogeneous Nucleation of Graphene on Copper

The grain size of monolayer large area graphene is key to its performance. Microstructural design for the desired grain size requires a fundamental understanding of graphene nucleation and growth. The two levers that can be used to control these aspects are the defect density, whose population can be controlled by annealing, and the gas-phase supersaturation for activation of nucleation at the defect sites. We observe that defects on copper surface, namely dislocations, grain boundaries, triple points, and rolling marks, initiate nucleation of graphene. We show that among these defects dislocations are the most potent nucleation sites, as they get activated at lowest supersaturation. As an illustration, we tailor the defect density and supersaturation to change the domain size of graphene from <1 mu m(2) to >100 mu m(2). Growth data reported in the literature has been summarized on a supersaturation plot, and a regime for defect-dominated growth has been identified. In this growth regime, we demonstrate the spatial control over nucleation at intentionally introduced defects, paving the way for patterned growth of graphene. Our results provide a unified framework for understanding the role of defects in graphene nucleation and can be used as a guideline for controlled growth of graphene.

Si-mediated fabrication of reduced graphene oxide and its hybrids for electrode materials

Here, we demonstrate a Si-mediated environmentally friendly reduction of graphene oxide (GO) and the fabrication of its hybrids with multiwall carbon nanotubes and nanofibers. The reduction of GO is facilitated by nascent hydrogen generated by the reaction between Si and KOH at similar to 60 degrees C. The overall process takes 5 to 7 minutes and 10 to 15 mu m of Si is consumed each time. We show that Si can be used multiple times and the rGO based hybrids can be used for electrode materials.

Molecular effects of encapsulation of glucose oxidase dimer by graphene

Knowing the nature of the enzyme-graphene interface is critical for a design of graphene-based biosensors. Extensive contacts between graphene and enzyme could be obtained by employing a suitable encapsulation which does not impede its enzymatic reaction. We have performed molecular dynamics simulations to obtain an insight on many forms of contact between glucose oxidase dimer and the single-layer graphene nano-sheets. The unconnected graphene sheets tended to form a flat stack regardless of their initial positions around the enzyme, whereas the same graphene sheets linked together formed a flower-like shape engendering different forms of wrapping of the enzyme. During the encapsulation no core hydrophobic residues of the enzyme were exposed. Since the polar and charged amino acids populated the enzyme's surface we also estimated, using DFT calculations, the interaction energies of individual polar and charged amino acid residues with graphene. It was found that the negatively charged residues can bind to graphene unexpectedly strongly; however, the main effect of encapsulation comes from the overlap of adjacent edges of graphene sheets.

Chemical Functionalization of Graphene To Augment Stem Cell Osteogenesis and Inhibit Biofilm Formation on Polymer Composites for Orthopedic Applications

Toward designing the next generation of resorbable biomaterials for orthopedic applications, we studied poly(epsilon-caprolactone) (PCL) composites containing graphene. The role, if any, of the functionalization of graphene on mechanical properties, stem cell response, and biofilm formation was systematically evaluated. PCL composites of graphene oxide (GO), reduced GO (RGO), and amine-functionalized GO (AGO) were prepared at different filler contents (1%, 3%, and 5%). Although the addition of the nanoparticles to PCL markedly increased the storage modulus, this increase was largest for GO followed by AGO and RGO. In vitro cell studies revealed that the AGO and GO particles significantly increased human mesenchymal stem cell proliferation. AGO was most effective in augmenting stem cell osteogenesis leading to mineralization. Bacterial studies revealed that interaction with functionalized GO induced bacterial cell death because of membrane damage, which was further accentuated by amine groups in AGO. As a result, AGO composites were best at inhibiting biofilm formation. The synergistic effect of oxygen containing functional groups and amine groups on AGO imparts the optimal combination of improved modulus, favorable stem cell response, and biofilm inhibition in AGO-reinforced composites desired for orthopedic applications. This work elucidates the importance of chemical functionalization of graphene in polymer composites for biomedical applications.