Graphene-oxide-modified β-tricalcium phosphate bioceramics stimulate in vitro and in vivo osteogenesis

Graphene oxide (GO) has attracted much interest for applications in bone tissue engineering; however, until now the interaction between GO and stem cells, and the in vivo bone-forming ability of GO has not been explored. The aim of this study was to produce a GO-modified β-tricalcium phosphate (β-TCP-GRA) biceramics and then explore the material’s osteogenic capacity in vitro and in vivo, as well as unravel some of the molecular mechanisms behind this. β-TCP-GRA disks and scaffolds were successfully prepared by a simple GO/water suspension soaking method in combination with heat treatment. These scaffolds were found to significantly enhance the proliferation, alkaline phosphatase activity and osteogenic gene expression of human bone marrow stromal cells (hBMSCs), when compared to β-TCP without GO modification (controls). Activation of the Wnt/β-catenin signaling pathway in hBMSCs appears to be the mechanism behind this osteogenic induction by β-TCP-GRA. β-TCP-GRA scaffolds led to an increased rate of in vivo new bone formation compared to β-TCP controls, indicative of the stimulatory effect of GO on in vivo osteogenesis, making GO modification of β-TCP a very promising method for applications in bone tissue engineering, in particular for the regeneration of large bone defects.

Interlaminar mechanical properties of carbon fiber reinforced plastic laminates modified with graphene oxide interleaf

By taking the advantage of the excellent mechanical properties and high specific surface area of graphene oxide (GO) sheets, we develop a simple and effective strategy to improve the interlaminar mechanical properties of carbon fiber reinforced plastic (CFRP) laminates. With the incorporation of graphene oxide reinforced epoxy interleaf into the interface of CFRP laminates, the Mode-I fracture toughness and resistance were greatly increased. The experimental results of double cantilever beam (DCB) tests demonstrated that, with 2 g/m2 addition of GO, the Mode-I fracture toughness and resistance of the specimen increase by 170.8% and 108.0%, respectively, compared to those of the plain specimen. The improvement mechanisms were investigated by the observation of fracture surface with scanning electron microscopies. Moreover, finite element analyses were performed based on the cohesive zone model to verify the experimental fracture toughness and to predict the interfacial tensile strength of CFRP laminates.

Pentacene on Ni(111): room-temperature molecular packing and temperature-activated conversion to graphene

We investigate, using scanning tunnelling microscopy, the adsorption of pentacene on Ni(111) at room temperature and the behaviour of these monolayer films with annealing up to 700 °C. We observe the conversion of pentacene into graphene, which begins from as low as 220 °C with the coalescence of pentacene molecules into large planar aggregates. Then, by annealing at 350 °C for 20 minutes, these aggregates expand into irregular domains of graphene tens of nanometers in size. On surfaces where graphene and nickel carbide coexist, pentacene shows preferential adsorption on the nickel carbide phase. The same pentacene to graphene transformation was also achieved on Cu(111), but at a higher activation temperature, producing large graphene domains that exhibit a range of moiré superlattice periodicities.

Synthesis, characterization and applications of graphene oxide-polymer nanocomposites

Graphene has emerged as one of the most exciting materials of the 21st century due to its unique properties which have demonstrated great potential for applications in energy storage, flexible electronics and multifunctional composites. This thesis has established a new technique for investigating the structure-property relationship of graphene-polymer nanocomposites at micro and nanoscales. The outcomes can help gain a fundamental understanding of the toughening mechanism in these novel nanocomposites and benefit the development of broad graphene based materials and devices.

Effect of covalent functionalisation on thermal transport across graphene-polymer interfaces

This paper is concerned with the interfacial thermal resistance for polymer composites reinforced by various covalently functionalised graphene. By using molecular dynamics simulations, the obtained results show that the covalent functionalisation in graphene plays a significant role in reducing the graphene-paraffin interfacial thermal resistance. This reduction is dependent on the coverage and type of functional groups. Among the various functional groups, butyl is found to be the most effective in reducing the interfacial thermal resistance, followed by methyl, phenyl and formyl. The other functional groups under consideration such as carboxyl, hydroxyl and amines are found to produce negligible reduction in the interfacial thermal resistance. For multilayer graphene with a layer number up to four, the interfacial thermal resistance is insensitive to the layer number. The effects of the different functional groups and the layer number on the interfacial thermal resistance are also elaborated using the vibrational density of states of the graphene and the paraffin matrix. The present findings provide useful guidelines in the application of functionalised graphene for practical thermal management.

Substrate effects in the supramolecular assembly of 1,3,5-benzene tricarboxylic acid on graphite and graphene

The behavior of small molecules on a surface depends critically on both molecule–substrate and intermolecular interactions. We present here a detailed comparative investigation of 1,3,5-benzene tricarboxylic acid (trimesic acid, TMA) on two different surfaces: highly oriented pyrolytic graphite (HOPG) and single-layer graphene (SLG) grown on a polycrystalline Cu foil. On the basis of high-resolution scanning tunnelling microscopy (STM) images, we show that the epitaxy matrix for the hexagonal TMA chicken wire phase is identical on these two surfaces, and, using density functional theory (DFT) with a non-local van der Waals correlation contribution, we identify the most energetically favorable adsorption geometries. Simulated STM images based on these calculations suggest that the TMA lattice can stably adsorb on sites other than those identified to maximize binding interactions with the substrate. This is consistent with our net energy calculations that suggest that intermolecular interactions (TMA–TMA dimer bonding) are dominant over TMA–substrate interactions in stabilizing the system. STM images demonstrate the robustness of the TMA films on SLG, where the molecular network extends across the variable topography of the SLG substrates and remains intact after rinsing and drying the films. These results help to elucidate molecular behavior on SLG and suggest significant similarities between adsorption on HOPG and SLG.

Sodium and lithium storage properties of spray-dried molybdenum disulfide-graphene hierarchical microspheres

Developing nano/micro-structures which can effectively upgrade the intriguing properties of electrode materials for energy storage devices is always a key research topic. Ultrathin nanosheets were proved to be one of the potential nanostructures due to their high specific surface area, good active contact areas and porous channels. Herein, we report a unique hierarchical micro-spherical morphology of well-stacked and completely miscible molybdenum disulfide (MoS2) nanosheets and graphene sheets, were successfully synthesized via a simple and industrial scale spray-drying technique to take the advantages of both MoS2 and graphene in terms of their high practical capacity values and high electronic conductivity, respectively. Computational studies were performed to understand the interfacial behaviour of MoS2 and graphene, which proves high stability of the composite with high interfacial binding energy (−2.02 eV) among them. Further, the lithium and sodium storage properties have been tested and reveal excellent cyclic stability over 250 and 500 cycles, respectively, with the highest initial capacity values of 1300 mAh g−1 and 640 mAh g−1 at 0.1 A g−1.

The effect of graphene oxide and its oxidized debris on the cure chemistry and interphase structure of epoxy nanocomposites

The influence of graphene oxide (GO) and its surface oxidized debris (OD) on the cure chemistry of an amine cured epoxy resin has been investigated by Fourier Transform Infrared Emission Spectroscopy (FT-IES) and Differential Scanning Calorimetry (DSC). Spectral analysis of IR radiation emitted at the cure temperature from thin films of diglycidyl ether of bisphenol A epoxy resin (DGEBA) and 4,4'-diaminodiphenylmethane (DDM) curing agent with and without GO allowed the cure kinetics of the interphase between the bulk resin and GO to be monitored in real time, by measuring both the consumption of primary (1°) amine and epoxy groups, formation of ether groups as well as computing the profiles for formation of secondary (2°) and tertiary (3°) amines. OD was isolated from as-produced GO (aGO) by a simple autoclave method to give OD-free autoclaved GO (acGO). It has been found that the presence of OD on the GO prevents active sites on GO surfaces fully catalysing and participating in the reaction of DGEBA with DDM, which results in slower reaction and a lower crosslink density of the three-dimensional networks in the aGO-resin interphase compared to the acGO-resin interphase. We also determined that OD itself promoted DGEBA homopolymerization. A DSC study further confirmed that the aGO nanocomposite exhibited lower Tg while acGO nanocomposite showed higher Tg compared to neat resin because of the difference in crosslink densities of the matrix around the different GOs.

Reversible Conversion of Dominant Polarity in Ambipolar Polymer/Graphene Oxide Hybrids

The possibility to selectively modulate the charge carrier transport in semiconducting materials is extremely challenging for the development of high performance and low-power consuming logic circuits. Systematical control over the polarity (electrons and holes) in transistor based on solution processed layer by layer polymer/graphene oxide hybrid system has been demonstrated. The conversion degree of the polarity is well controlled and reversible by trapping the opposite carriers. Basically, an electron device is switched to be a hole only device or vice versa. Finally, a hybrid layer ambipolar inverter is demonstrated in which almost no leakage of opposite carrier is found. This hybrid material has wide range of applications in planar p-n junctions and logic circuits for high-throughput manufacturing of printed electronic circuits.

Nanosheets Co3O4 interleaved with graphene for highly efficient oxygen reduction

Efficient yet inexpensive electrocatalysts for oxygen reduction reaction (ORR) are an essential component of renewable energy devices, such as fuel cells and metal-air batteries. We herein interleaved novel Co3O4 nanosheets with graphene to develop a first ever sheet-on-sheet heterostructured electrocatalyst for ORR, whose electrocatalytic activity outperformed the state-of-the-art commercial Pt/C with exceptional durability in alkaline solution. The composite demonstrates the highest activity of all the nonprecious metal electrocatalysts, such as those derived from Co3O4 nanoparticle/nitrogen-doped graphene hybrids and carbon nanotube/nanoparticle composites. Density functional theory (DFT) calculations indicated that the outstanding performance originated from the significant charge transfer from graphene to Co3O4 nanosheets promoting the electron transport through the whole structure. Theoretical calculations revealed that the enhanced stability can be ascribed to the strong interaction generated between both types of sheets.

Fast growth of polycrystalline graphene by chemical vapor deposition of ethanol on copper

High conductive graphene films can be grown on metal foils by chemical vapor deposition (CVD). We here analyzed the use of ethanol, an economic precursor, which results also safer than commonly-used methane. A comprehensive range of process parameters were explored in order to obtain graphene films with optimal characteristics in view of their use in optoelectronics and photovoltaics. Commercially-available and electro-polished copper foils were used as substrates. By finely tuning the CVD conditions, we obtained few-layer (2-4) graphene films with good conductivity (-500 Ohm/sq) and optical transmittance around 92-94% at 550 nm on unpolished copper foils. The growth on electro-polished copper provides instead predominantly mono-layer films with lower conductivity (>1000 Ohm/sq) and with a transmittance of 97.4% at 550 nm. As for the device properties, graphene with optimal properties as transparent conductive film were produced by CVD on standard copper with specific process conditions.

MnOx/carbon nanotube/reduced graphene oxide nanohybrids as high-performance supercapacitor electrodes

Nanohybrids consisting of both carbon and pseudocapacitive metal oxides are promising as high-performance electrodes to meet the key energy and power requirements of supercapacitors. However, the development of high-performance nanohybrids with controllable size, density, composition and morphology remains a formidable challenge. Here, we present a simple and robust approach to integrating manganese oxide (MnOx) nanoparticles onto flexible graphite paper using an ultrathin carbon nanotube/reduced graphene oxide (CNT/RGO) supporting layer. Supercapacitor electrodes employing the MnOx/CNT/RGO nanohybrids without any conductive additives or binders yield a specific capacitance of 1070 F g−1 at 10 mV s−1, which is among the highest values reported for a range of hybrid structures and is close to the theoretical capacity of MnOx. Moreover, atmospheric-pressure plasmas are used to functionalize the CNT/RGO supporting layer to improve the adhesion of MnOx nanoparticles, which results in theimproved cycling stability of the nanohybrid electrodes. These results provide information for the utilization of nanohybrids and plasma-related effects to synergistically enhance the performance of supercapacitors and may create new opportunities in areas such as catalysts, photosynthesis and electrochemical sensors

Directional synthesis of tin oxide@graphene nanocomposites via a one-step up-scalable wet-mechanochemical route for lithium ion batteries

Directional synthesis of SnO2@graphene nanocomposites via a one-step, low-cost, and up-scalable wetmechanochemical method is achieved using graphene oxide and SnCl2 as precursors. The graphene oxides are reduced to graphene while the SnCl2 is oxidized to SnO2 nanoparticles that are in situ anchored onto the graphene sheets evenly and densely, resulting in uniform SnO2@graphene nanocomposites. The prepared nanocomposites possess excellent electrochemical performance and outstanding cycling in Li-ion batteries.

Biological application of carbon nanotubes and graphene

Carbon nanotubes (CNTs) and graphene are two representative nanomaterials comprised of purely element carbon [1,2]. Graphene is the two-dimensional, hexagonal sp2-carbon ring networks with one atomic layer thickness, while CNTs can be envisaged as one or several graphene sheets concentrically rolled up into a one-dimensional cylindrical structure, so-called singlewalled (SW) or multi-walled (MW) CNTs, respectively. Figure 12.1 shows the schematic diagram of structures of graphene, SWCNT and MWCNT. Owing to their exceptional mechanical, electrical, optical and thermal properties, CNTs and graphene have been widely considered as a new type of materials with great potentials to revolutionalize many of the biological and medical fields [3–5].

Copper nanoparticles on graphene support: An efficient photocatalyst for coupling of nitroaromatics in visible light

Copper is a low-cost plasmonic metal. Efficient photocatalysts of copper nanoparticles on graphene support are successfully developed for controllably catalyzing the coupling reactions of aromatic nitro compounds to the corresponding azoxy or azo compounds under visible-light irradiation. The coupling of nitrobenzene produces azoxybenzene with a yield of 90 % at 60 °C, but azobenzene with a yield of 96 % at 90 °C. When irradiated with natural sunlight (mean light intensity of 0.044 W cm−2) at about 35 °C, 70 % of the nitrobenzene is converted and 57 % of the product is azobenzene. The electrons of the copper nanoparticles gain the energy of the incident light through a localized surface plasmon resonance effect and photoexcitation of the bound electrons. The excited energetic electrons at the surface of the copper nanoparticles facilitate the cleavage of the NO bonds in the aromatic nitro compounds. Hence, the catalyzed coupling reaction can proceed under light irradiation and moderate conditions. This study provides a green photocatalytic route for the production of azo compounds and highlights a potential application for graphene.