Vacancy mediated clipping of multi-layered graphene: A precursor for 1, 2 and 3D carbon structures

Using first principles calculations, we show that the overlapping defects in bi-layer graphene (both AA-and AB-stacked) interact forming inter-layer covalent bonds, giving rise to two-dimensional (2D) clipped structures, without explicit use of functional groups. These clipped structures can be transformed into one-dimensional (1D) double wall nanotubes (DWCNT) or multi-layered three dimensional (3D) bulk structures. These clipped structures show good mechanical strength due to covalent bonding between multi-layers. Clipping also provides a unique way to simultaneously harness the conductivity of both walls of a double wall nanotube through covalently bonded scattering junctions. With additional conducting channels and improved mechanical stability, these clipped structures can lead to a myriad of applications in novel devices. (C) 2015 Elsevier Ltd. All rights reserved.

Graphene scavenges free radicals to synergistically enhance structural properties in a gamma-irradiated polyethylene composite through enhanced interfacial interactions

A unique strategy for scavenging free radicals in situ on exposure to gamma irradiation in polyethylene (PE) nanocomposites is presented. Blends of ultra-high molecular weight PE and linear low-density PE (PEB) and their nanocomposites with graphene (GPEB) were prepared by melt mixing to develop materials for biomedical implants. The effect of gamma irradiation on the microstructure and mechanical properties was systematically investigated. The neat blend and the nanocomposite were subjected to gamma-ray irradiation in order to improve the interfacial adhesion between PE and graphene sheets. Structural and thermal characterization revealed that irradiation induced crosslinking and increased the crystallinity of the polymer blend. The presence of graphene further enhanced the crystallinity via crosslinks between the polymer matrix and the filler on irradiation. Graphene was found to scavenge free radicals as confirmed by electron paramagnetic resonance spectroscopy. Irradiation of graphene-containing polymer composites resulted in the largest increase in modulus and hardness compared to either irradiation or addition of graphene to PEB alone. This study provides new insight into the role of graphene in polymer matrices during irradiation and suggests that irradiated graphene-polymer composites could emerge as promising materials for use as articulating surfaces in biomedical implants.

Electrochemical behavior of Sn-graphene composite coating

The electrochemical properties of pure Sn and Sn-graphene composite coating have been determined and compared. Coatings were electrodeposited on mild steel substrates. Graphene was synthesized by the electrochemical exfoliation process using SO42- ion as the intercalating agent. Morphological and structural characterization results revealed a clear effect of graphene on altering the texture, grain size and morphology of the coating. Corrosion behavior was analyzed through potentiodynamic polarization and electrochemical impedance spectroscopic methods. A significant improvement in the corrosion resistance in terms of reduction in corrosion current and corrosion rate and increase in polarization resistance was noted in case of Sn coating containing graphene.

Ir nanoparticles-anchored reduced graphene oxide as a catalyst for oxygen electrode in Li-O-2 cells

Iridium nanoparticles-anchored reduced graphene oxide (Ir-RGO) was prepared by simultaneous reduction of graphene oxide and Ir3+ ions and its catalytic activity for oxygen electrode in Li-O-2 cells was demonstrated. Ir particles with an average size of 3.9 nm were uniformly distributed on RGO sheets. The oxygen reduction reaction (ORR) was studied on an Ir-RGO catalyst in non-aqueous electrolytes using cyclic voltammetry and rotating disk electrode techniques. Li-O-2 cells with Ir-RGO as a bifunctional oxygen electrode catalyst were subjected to charge-discharge cycling at several current densities. A discharge capacity of 9529 mA h g(-1) (11.36 mA h cm(-2)) was obtained initially at a current density of 0.5 mA cm(-2) (393 mA g(-1)). A decrease in capacity was observed on increasing the current density. Although there was a decrease in capacity on repeated discharge-charge cycling initially, a stable capacity was observed for about 30 cycles. The results suggest that Ir-RGO is a useful catalyst for rechargeable Li-O-2 cells.

TiO2-RGO hybrid nanomaterials for enhanced water splitting reaction

The production of H-2 via photocatalytic water splitting reaction has attracted a great attention as a clean and renewable energy for next generation. Despite tremendous efforts, the present challenge for materials scientist is to develop highly active photo catalysts for splitting of water at low cost. This article reports the synthesis of TiO2-reduced graphene oxide hybrid nanomaterials through ionothermal method using functionalized ionic liquid for the enhanced hydrogen generation via water splitting reaction. The structural and morphological properties of the samples were investigated by XFtD, Raman spectroscopy, TG-DTA, UV-vis spectroscopy and TEM. A substantial increase of H-2 evolution was observed for TiO2-reduced graphene oxide hybrid nanomaterials. This is due to the high migration efficiency of photo-induced electrons and the inhibition of charge carrier recombination due to the electronic interaction between TiO2 and reduced graphene oxide. i.e, reduced graphene oxide acts as an electron-acceptor which effectively hinders the electron hole pair recombination of TiO2. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

High-Performance Sensors Based on Resistance Fluctuations of Single-Layer-Graphene Transistors

One of the most interesting predicted applications of graphenemonolayer-based devices is as high-quality sensors. In this article, we show, through systematic experiments, a chemical vapor sensor based on the measurement of lowfrequency resistance fluctuations of single-layer-graphene field-effect-transistor devices. The sensor has extremely high sensitivity, very high specificity, high fidelity, and fast response times. The performance of the device using this scheme of measurement (which uses resistance fluctuations as the detection parameter) is more than 2 orders of magnitude better than a detection scheme in which changes in the average value of the resistance is monitored. We propose a number-densityfluctuation-based model to explain the superior characteristics of a noisemeasurement-based detection scheme presented in this article.

Dynamic range tuning of graphene nanoresonators

From sensing perspective, smaller electromechanical devices, in general, are expected to be more responsive to the stimuli. This enhanced performance, however, is contingent upon the noise sources remaining unchanged and the onset of nonlinear behavior not being precipitated by miniaturization. In this paper, we study the effect of strain on the nonlinearities and dynamic range in graphene nanoresonators. The dynamic response and the onset of nonlinearity in these devices are sensitive both to the electrostatic field used to actuate the device and the strain. By tuning the strain of the device by two orders of magnitude, we observe an enhancement of 25 dB in the dynamic range leading to a mass resolution of 100 yoctogram. The increase in dynamic range in our devices is modeled as a combined effect of strain and partial cancellation of elastic and electrostatic nonlinearities. (C) 2015 AIP Publishing LLC.

Photoresponse of double-stacked graphene to Infrared radiation

We report the photoresponse of stacked graphene layers towards infrared radiation. Graphene is stacked in two configurations, namely, crossed and parallel layers. Raman analysis demonstrated a strong interaction among the stacked graphene layers. Graphene in the crossed configuration exhibited the presence of both negative and positive conductivities; however, other configurations of graphene exhibited positive conductivity only. The presence of negative photoconductivity is proposed to be due to oxygen or oxygen-related functional group absorbents that are trapped in between two monolayers of graphene and act as scattering centers for free carriers. An interesting trend is reported in differential conductivity when stacked layers are compared with multilayers and parallel-stacked graphene layers.

A galactose-functionalized dendritic siRNA-nanovector to potentiate hepatitis C inhibition in liver cells

A RNAi based antiviral strategy holds the promise to impede hepatitis C viral (HCV) infection overcoming the problem of emergence of drug resistant variants, usually encountered in the interferon free direct-acting antiviral therapy. Targeted delivery of siRNA helps minimize adverse `off-target' effects and maximize the efficacy of therapeutic response. Herein, we report the delivery of siRNA against the conserved 5'-untranslated region (UTR) of HCV RNA using a liver-targeted dendritic nano-vector functionalized with a galactopyranoside ligand (DG). Physico-chemical characterization revealed finer details of complexation of DG with siRNA, whereas molecular dynamic simulations demonstrated sugar moieties projecting ``out'' in the complex. Preferential delivery of siRNA to the liver was achieved through a highly specific ligand-receptor interaction between dendritic galactose and the asialoglycoprotein receptor. The siRNA-DG complex exhibited perinuclear localization in liver cells and co-localization with viral proteins. The histopathological studies showed the systemic tolerance and biocompatibility of DG. Further, whole body imaging and immunohistochemistry studies confirmed the preferential delivery of the nucleic acid to mice liver. Significant decrease in HCV RNA levels (up to 75%) was achieved in HCV subgenomic replicon and full length HCV-JFH1 infectious cell culture systems. The multidisciplinary approach provides the `proof of concept' for restricted delivery of therapeutic siRNAs using a target oriented dendritic nano-vector.

Synthesis of 3-dimensional porous graphene nanosheets using electron cyclotron resonance plasma enhanced chemical vapour deposition

Microwave plasma driven chemical vapour deposition was used to synthesize graphene nanosheets from a mixture of acetylene and hydrogen gas molecules. In this plasma, acetylene decomposes to carbon atoms that form nanostructures in the outlet plasma stream and get deposited on the substrate. The GNS consists of a few layers of graphene aligned vertically to the substrate. Graphene layers have been confirmed by high-resolution transmission electron microscopy, and Raman spectral studies were conducted to observe the defective nature of the sample. The growth of nanosheets in a vertical direction is assumed to be due to the effect of electric field and from the difference in the deposition rate in the axial and parallel directions. These vertical graphene sheets are attractive for various applications in energy storage and sensors.

Tailored nitrogen dioxide sensing response of three-dimensional graphene foam

Ultralight and macroporous three-dimensional reduced graphene oxide (rGO) foams are prepared by lyophilization (freeze-drying) technique to avoid a conventional template method. This method allows tailoring the porosity of the foams by varying the weight percentages of graphene oxide dispersions in water. Three different rGO foams of 0.2, 0.5 and 1.0 wt% are used for NO2 sensing. Sensing response from the tailored structure of rGO is found to be directly related to the density. A maximum of 20% sensing response is observed for a higher porosity of the structure, better than the known results so far on graphene foams in the literature. (C) 2015 Elsevier B.V. All rights reserved.

A 1 V supercapacitor device with nanostructured graphene oxide/polyaniline composite materials

Polyaniline and graphene oxide composite on activated carbon cum reduced graphene oxide-supported supercapacitor electrodes are fabricated and electrochemically characterized in a three-electrode cell assembly. Attractive supercapacitor performance, namely high-power capability and cycling stability for graphene oxide/polyaniline composite, is observed owing to the layered and porous-polymeric-structured electrodes. Based on the materials characterization data in a three-electrode cell assembly, 1 V supercapacitor devices are developed and performance tested. A comparative study has also been conducted for polyaniline and graphene oxide/polyaniline composite-based 1 V supercapacitors for comprehending the synergic effect of graphene oxide and polyaniline. Graphene oxide/polyaniline composite-based capacitor that exhibits about 100 F g(-1) specific capacitance with faradaic efficiency in excess of 90% has its energy and power density values of 14 Wh kg(-1) and 72 kW kg(-1), respectively. Cycle-life data for over 1000 cycles reflect 10% capacitance degradation for graphene oxide/polyaniline composite supercapacitor.

Rational molecular dynamics scheme for predicting optimum concentration loading of nano-additive in phase change materials

The present study deals with the diffusion and phase transition behaviour of paraffin reinforced with carbon nano-additives namely graphene oxide (GO) and surface functionalized single walled carbon nanotubes (SWCNT). Bulk disordered systems of paraffin hydrocarbons impregnated with carbon nano-additives have been generated in realistic equilibrium conformations for potential application as latent heat storage systems. Ab initio molecular dynamics(MD) in conjugation with COMPASS forcefield has been implemented using periodic boundary conditions. The proposed scheme allows determination of optimum nano-additive loading for improving thermo-physical properties through analysis of mass, thermal and transport properties; and assists in determination of composite behaviour and related performance from microscopic point of view. It was observed that nanocomposites containing 7.8% surface functionalised SWCNT and 55% GO loading corresponds to best latent heat storage system. The propounded methodology could serve as a by-pass route for economically taxing and iterative experimental procedures required to attain the optimum composition for best performance. The results also hint at the large unexplored potential of ab-initio classical MD techniques for predicting performance of new nanocomposites for potential phase change material applications. (C) 2015 Author(s).

ZnO quantum dots and graphene based heterostructure for excellent photoelastic and highly sensitive ultraviolet photodetector

Heterostructures comprised of zinc oxide quantum dots (ZnO QDs) and graphene are presented for ultraviolet photodetectors (UV PD). Graphene-ZnO QDs-graphene (G-ZnO QDs-G) based PD demonstrated an excellent UV photoresponse with outstanding photoelastic characteristics when illuminated for several cycles with a periodicity 5 s. PD demonstrated faster detection ability with the response and recovery times of 0.29 s in response to much lower UV illumination. A direct variation in photoresponse is revealed with the bias voltage as well as UV illumination intensity. A drastic reduction in the dark current is noticed due to potential barrier formation between adjacent ZnO QDs and the recombination rate reduces by directly transferring photogenerated charge carriers from ZnO QDs to graphene for enhanced the charge mobility.