Synthesis of enhanced hydrophilic and hydrophobic graphene oxide nanosheets by a solvothermal method

We report that the hydrophilic affinity of graphene oxide nanosheets can be significantly increased by reacting with allylamine. High resolution transmission electron microscopy and electron diffraction analysis confirmed that the graphene oxide nanosheets were amorphous in structure. Hydrophobic graphene oxide nanosheets were also prepared via functionalising with phenylisocynate (C₆H₅NCO) through a solvothermal synthesis process. Hydrophobic graphene oxide nanosheets can be used as additives in polymer-based composites and other functional applications.     

Graphene nanosheets as cathode catalysts for lithium-air batteries with an enhanced electrochemical performance

Graphene nanosheets have been investigated as cathode catalysts for lithium-air batteries with alkyl carbonate electrolyte. Field emission scanning electron microscopy, transmission electron microscope and Raman spectroscopy have confirmed the high quality of the as-prepared graphene nanosheets and the surface analysis has identified the mesoporous characteristic of graphene nanosheets. The electrochemical properties of graphene nanosheets as cathode catalysts in lithium-air batteries were evaluated by a galvanostatic charge/discharge testing. The reaction products on the graphene nanosheets cathode were analyzed by X-ray diffraction and Fourier transform infrared spectroscopy. The graphene nanosheet electrodes exhibited a much better cycling stability and lower overpotential than that of the Vulcan XC-72 carbon. This work demonstrated that graphene nanosheets could be an efficient catalyst for lithium-air batteries.     

Graphene nanosheets prepared by low-temperature exfoliation and reduction technique toward fabrication of high-performance poly(1-butene)/graphene films

Thermal exfoliation and reduction of graphene oxide (GO) were performed to prepare graphene nanosheets at 300 °C under the ambient atmosphere without any supplementary conditions. The microstructure and morphology of the resulting graphene nanosheets were characterized with scanning electron microscopy, transmission electric microscopy, atomic force microscopy and X-ray photoelectron spectroscopy. The composite films based on poly(1-butene) (PB) and graphene nanosheets were prepared successfully through solution blending and compression molding. The morphological investigation suggested that the graphene nanosheets with nanoscale thickness achieved a homogeneous dispersion in the PB matrix. The composite films exhibited a sharp transition from insulating state to the conducting one with a low percolation threshold, followed by a high electrical conductivity at graphene content higher than 1.6 vol %. The composite films also achieved high dielectric constant with low dielectric loss due to the effective electrical conductive path established by graphene nanosheets in a local range. Moreover, the mechanical evaluation demonstrated that a considerable reinforcement was achieved for the composite films due to the strong interfaces between the graphene nanosheets and PB matrix. The introduction of graphene nanosheets not only enhanced the nucleation capability and crystallinity of PB domain but also improved the thermal stability of the composite films. In addition, the composite films showed an increase in storage modulus and a decrease in loss factors due to the incorporation of graphene nanosheets.     

Silicon nanowire arrays-induced graphene oxide reduction under UV irradiation

This paper reports on efficient UV irradiation-induced reduction of exfoliated graphene oxide. Direct illumination of an aqueous solution of graphene oxide at λ = 312 nm for 6 h resulted in the formation of graphene nanosheets dispersible in water. X-Ray photoelectron spectroscopy (XPS), UV-vis spectroscopy, atomic force microscopy (AFM) and electrochemical measurements (cyclic voltammetry and electrochemical impedance spectroscopy) suggest a restoration of the sp(2) carbon network. The results were compared with graphene nanosheets prepared by photochemical irradiation of a GO aqueous solution in the presence of hydrogenated silicon nanowire (SiNW) arrays or silicon nanowire arrays decorated with silver (SiNW/Ag NPs) or copper nanoparticles (SiNW/Cu NPs). Graphene nanosheets obtained by illumination of the GO aqueous solution at 312 nm for 6 h in the presence of SiNW/Cu NPs exhibited superior electrochemical charge transfer characteristics. This is mainly due to the higher amount of sp(2)-hybridized carbon in these graphene sheets found by XPS analysis. The high level of extended conjugated carbon network was also evident by the water insoluble nature of the resulting graphene nanosheets, which precipitated upon photochemical reduction.     

Synthesis and properties of click coupled graphene oxide sheets with three‐dimensional macromolecules

A facile click chemistry approach to the functionalization of three‐dimensional hyperbranched polyurethane (HPU) to graphene oxide (GO) nanosheets is presented. HPU‐functionalized GO samples of various compositions were synthesized by reacting alkyne‐functionalized HPU with azide‐functionalized GO sheets. The morphological characterization of the HPU‐functionalized GO was performed using transmission electron microscopy and its chemical characterization was carried out using Fourier transform‐infrared spectroscopy, nuclear magnetic resonance spectroscopy, and X‐ray photoelectron spectroscopy. The graphene sheet surfaces were highly functionalized, leading to improved solubility in organic solvents, and consequently, enhanced mechanical, thermal, and thermoresponsive and photothermal shape memory properties. The strategy reported herein provides a very efficient method for regulating composite properties and producing high performance materials. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43358.     

Graphene nanosheets for enhanced lithium storage in lithium ion batteries

Graphene nanosheets were synthesized in large quantities using a chemical approach. Field emission electron microscope observation revealed that loose graphene nanosheets agglomerated and crumpled naturally into shapes resembling flower-petals. High resolution transmission electron microscope analysis, Raman spectroscopy and ultraviolet-visible spectroscopy measurements confirmed the graphitic crystalline structure of the graphene nanosheets. The nanosheets exhibited an enhanced lithium storage capacity as anodes in lithium-ion cells and good cyclic performance.     

Utilization of multiple graphene nanosheets in fuel cells: 2. The effect of oxidation process on the characteristics of graphene nanosheets

Structural properties of graphene nanosheets that will be used as electrode material in fuel cells were investigated at different oxidation times. As the oxidation time was increased, the strong bonding between graphene layers in graphite was reduced and graphene layers started to exfoliate forming clusters with a few number of graphene layers. The variations in interplanar spacings, layer number and percent crystallinity indicated how stepwise chemical procedure influenced the morphology of graphite. It was possible to produce relatively flat graphene clusters with definite number of layers by controlling the oxidation time. Graphene nanosheets were characterized in detail by scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman spectroscopy, and thermal gravimetric analyzer.     

Furfuryl alcohol functionalized graphene nanosheets for synthesis of high carbon yield novolak composites

Graphene oxide and furfuryl alcohol modified graphene nanosheets (G‐FA) were used to prepare graphene/novolak composites. Effect of graphene compatibilization on the properties of the composites especially carbon yield value is evaluated. Both types of graphene nanosheets were dispersed uniquely in the novolak matrix as proved by X‐ray diffraction analysis. However, modification of graphene sheets by furfuryl alcohol results in more improved dispersions. Thermogravimetric analysis confirms the elevated thermal stability of the nanocomposites in comparison with the neat novolak. In addition, G‐FA containing composites have higher carbon yield values. A shift in the wave number of characteristic bonds of graphene after oxidation and modification with furfuryl alcohol, O? H, C?O, and C? O bonds, are seen in the Fourier transform infrared spectroscopy spectra. Raman results and scanning electron microscopy images show that graphene nanosheets reduced in size and wrinkled by oxidation and functionalization. Transmission electron microscopy image of the composite with 0.2 wt % of G‐FA reveals the presence of nanosheets with curvature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40273.     

Revelation of graphene-Au for direct write deposition and characterization

Graphene nanosheets were prepared using a modified Hummer''s method, and Au-graphene nanocomposites were fabricated by in situ reduction of a gold salt. The as-produced graphene was characterized by X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy (HR-TEM). In particular, the HR-TEM demonstrated the layered crystallites of graphene with fringe spacing of about 0.32 nm in individual sheets and the ultrafine facetted structure of about 20 to 50 nm of Au particles in graphene composite. Scanning helium ion microscopy (HIM) technique was employed to demonstrate direct write deposition on graphene by lettering with gaps down to 7 nm within the chamber of the microscope. Bare graphene and graphene-gold nanocomposites were further characterized in terms of their composition and optical and electrical properties.     

Ammonia borane assisted solid exfoliation of graphite fluoride for facile preparation of fluorinated graphene nanosheets

Fluorinated graphene, which combines the unique properties of graphite fluoride and graphene, has attracted considerable attention in recent years. Here, we developed a facile, efficient, and scalable method for high-yield exfoliation of graphite fluoride into fluorinated graphene (fluorographene) nanosheets. The exfoliation approach consists of solid ball milling of graphite fluoride with ammonia borane and followed washing with ethanol to get rid of ammonia borane from the products. The majority of the as-synthesized fluorographene nanosheets consist of 1–6 atomic layers with grain sizes in the range of 0.3–1 μm. X-ray diffraction, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy demonstrated that fluorographene has the same structure as pristine graphite fluoride.     

Effect of SiC whiskers and graphene nanosheets on the mechanical properties of ZrB2-SiCw-Graphene ceramic composites

Ultrahigh temperature ZrB₂-SiC_w-Graphene ceramic composites are fabricated by hot pressing ZrB₂-SiC_w-Graphene oxide powders at 1950 °C and 30 MPa for 1 h. The microstructures of the composites are characterized by Scanning electron microscopy, Raman spectroscopy and X-ray diffraction. The results show that multilayer graphene nanosheets are achieved by thermal reduction of graphene oxide during sintering process. Compared with monolithic ZrB₂ materials, flexural strength and fracture toughness are both improved due to the synergistic effect of SiC whisker and graphene nanosheets. The toughening mechanisms mainly are the combination of SiC whisker and graphene nanosheets crack bridging, pulling out.     

Investigation of thermal properties and mechanical properties of reduced graphene oxide/polyimide resin composites

In this article, reduced graphene oxide/polyimide resin composites which exhibited enhancements in mechanical properties were successfully fabricated by hot‐pressing, and reduced graphene oxide nanosheets were synthesized by thermal reduced method, which can readily mix with PI powders in aqueous solution by sonication process. The chemical structures of rGO were carefully characterized by X‐ray diffraction, Fourier transfer infrared spectroscopy and X‐ray photoelectron spectroscopy. The field emission scanning electron microscopy observations showed that the rGO displayed excellent dispersibility and compatibility with the PI matrix. The mechanical analysis indicated that the tensile and flexural strength values of the rGO/PI resin composite with 1.5 wt% rGO loading reached 80.7 and 133.3 MPa, respectively. Compared with pure PI, the optimized rGO/PI resin composite exhibited an enhancement of 30% in tensile strength, 19% in flexural strength and 27% in impact strength, due to the fine dispersion of high specific surface area of graphene nanosheets and the good adhesion between the rGO and the matrix. In addition, thermogravimetric analysis, dynamic mechanical analysis, and dielectric properties were also investigated. POLYM. COMPOS., 38:2321–2331, 2017. © 2015 Society of Plastics Engineers     

The effect of heat treatment on formation of graphene thin films from graphene oxide nanosheets

Graphene thin films with very low concentration of oxygen-containing functional groups were produced by reduction of graphene oxide nanosheets (prepared by using a chemical exfoliation) in a reducing environment and using two different heat treatment procedures (called one and two-step heat treatment procedures). The effects of heat treatment procedure and temperature on thickness variation of graphene platelets and also on reduction of the oxygen-containing functional groups of the graphene oxide nanosheets were studied by atomic force microscopy and X-ray photoelectron spectroscopy. While formation of the thin films composed of single-layer graphene nanosheets with minimum thickness of 0.37 nm and nearly without any functional group bonds was observed at the high temperature of 1000 °C in the one-step reducing procedure, similar high quality graphene thin films were obtained at the lower temperature of 500 °C in our two-step reducing temperature. The results also indicated possibility of efficient reduction of the graphene oxide thin films at even lower heat treatment temperatures (?500 °C).     

Graphene nanosheets production using liquid-phase exfoliation of pre-milled graphite in dimethylformamide and structural defects evaluation

The non-oxidation-based procedure is proposed for the production of high-quality graphene nanosheets using graphite as the raw materials. This research demonstrated a hybrid two-step production method by liquid-phase exfoliation (LPE) of Premilled graphite in Dimethylformamide (DMF) and compared it with the purely milled and just sonicated samples. However, a simple physical separation procedure composed of two centrifuge processes also designed for the separation of the products in each step. By this process, the exfoliated graphite, less-exfoliated ones and produced nanoparticles are separated, and the less-exfoliated ones are reused again in moderate sonication process. Two grades of graphene nanosheets and a grade of graphitic nanoparticles result at the end. The quality and the nature of defects in all graphene samples produced from LPE, wet milling of graphite and a combination of both, was investigated and discussed by Raman spectroscopy related indices. Raman spectra analysis indicates the adverse effect of sonication power on the in-plane defects formation in the graphene nanosheets which could be hindered by the reduction in power of sonication along with the pre-milling of the graphite. Also inductively-coupled plasma (ICP) and field emission scanning electron microscopy (FE-SEM) analysis used for further characterization of the milled-sonicated sample.     

RESS制备石墨烯纳米片及防止其再团聚的新方法

本文以天然鳞片石墨为原料,利用超临界状态下二氧化碳的快速膨胀（RESS）来剥离石墨产生石墨烯纳米片。电子显微镜（SEM）表征证实RESS可有效地实现石墨的剥离,并产生了一些石墨烯纳米片层。同时,为了解决再团聚难题,提出利用碳纳米管在产生石墨烯纳米片间穿层的方法和利用小分子包覆法来防止其再团聚,实验证实都起到良好的效果。     

Incorporate boron and nitrogen into graphene to make BCN hybrid nanosheets with enhanced microwave absorbing properties

This work demonstrates the conversion of graphene oxide into BCN hybrid nanosheets by reaction with boric acid and urea at 900 °C, during which boron and nitrogen atoms are incorporated into the graphene atomic sheets. X-ray diffraction pattern and X-ray photoelectron spectroscopy reveal the existence of h-BN. High-resolution electron microscopy and Raman spectrum indicate the presence of graphene-like layers with h-BN nanodomains. The content of h-BN in the BCN nanosheets can also be tuned by further heat-treatment in an ammonia environment, which in turn affects the band gap of these nanosheets. The electromagnetic parameters suggest that these samples can be used as good microwave absorbing materials at G band (5.6–8.2 GHz) and X band (8.2–12.4 GHz). This study provides a simple route to BCN hybrid nanosheets with tunable band gap and adjustable conductivity for microwave absorbing applications.     

Fabrication of graphene/prussian blue composite nanosheets and their electrocatalytic reduction of H2O2

In this work, graphene/prussian blue (PB) composite nanosheets with good dispersibility in aqueous solutions have been synthesized by mixing ferric-(III) chloride and potassium ferricyanide in the presence of graphene under ambient conditions. Transmission electron microscopy (TEM) shows that the average size of the as-synthesized PB nanoparticles on the surface of graphene nanosheets is about 20 nm. Fourier-transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) patterns have been used to characterize the chemical composition of the obtained graphene/PB composite nanosheets. The graphene/PB composite nanosheets exhibit good electrocatalytic behavior to detection of H₂O₂ at an applied potential of −0.05 V. The sensor shows a good linear dependence on H₂O₂ concentration in the range of 0.02-0.2 mM with a sensitivity of 196.6 μA mM⁻¹ cm⁻². The detection limit is 1.9 μM at the signal-to-noise ratio of 3. Furthermore, the graphene/PB modified electrode exhibits freedom of interference from other co-existing electroactive species. This work provides a new kind of composite modified electrode for amperometric biosensors.     

Graphene nanosheets toughened TiB2-based ceramic tool material by spark plasma sintering

One kind of TiB₂/TiC composite ceramic tool material toughened by graphene nanosheets was fabricated by spark plasma sintering. Effects of graphene nanosheets on microstructure, mechanical properties and toughening mechanisms were investigated. The results indicated that TiB₂/TiC with 0.1?wt% graphene nanosheets sintered at 1800?°C with the holding time of 5?min obtained full densification and optimal mechanical properties. Its fracture toughness and Vickers hardness were 7.9?±?1.2?MPa?m^1/2 and 20.0?±?0.7?GPa, respectively. Excess graphene nanosheets had no effects to toughness improvement. Fracture toughness was increased by 31.7% in comparison with the TiB₂/TiC without graphene nanosheets. Toughness enhancement mainly benefited from crack bridging, also slip-stick effect of graphene made it hard to detach and effectively restrained crack extension.     

Enhanced interfacial interaction for effective reinforcement of poly(vinyl alcohol) nanocomposites at low loading of graphene

The graphene/poly(vinyl alcohol) (PVA) nancomposites with homogeneous dispersion of the nanosheet and enhanced nanofiller–matrix interfacial interaction were fabricated via water blending partially reduced graphene oxide and PVA. The nanocomposites were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetry. The graphene nanosheets were fully exfoliated in the PVA matrix and a new covalent linkage was formed between graphene and PVA matrix. Uncommon to conventional method, the enhanced interfacial adhesion resulted from covalent interaction and hydrogen bondings between graphene and PVA backbone. The mechanical and thermal properties of the nanocomposites were significantly improved at low graphene loadings. An 116% increase in tensile strength and a 19 °C improvement of onset thermal degradation temperature were achieved by the addition of only 0.8 wt% graphene.     

Glucose sensing,photocatalytic and antibacterial properties of graphene–ZnO nanoparticle hybrids

A simple and efficient approach was developed to uniformly decorate graphene nanosheets with zinc oxide (ZnO) nanoparticles. A single source precursor, zinc benzoate dihydrazinate complex, has been used for the in situ generation of ZnO nanoparticles onto graphene at a relatively low temperature, 200 °C. Physico chemical analyses such as X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that ZnO nanoparticles were finely dispersed on the surface of graphene. ZnO–graphene hybrids were further characterized by Raman spectroscopy and ultraviolet visible spectroscopy and room-temperature photoluminescence. The materials exhibited excellent photocatalytic activity as evident from the degradation of methylene blue in ethanol under UV irradiation. An electrochemical glucose biosensor was fabricated by immobilization of glucose oxidase on the ZnO–graphene hybrids. This biosensor showed improved sensitivity towards glucose as compared to graphene. Also, the hybrids showed significant antibacterial activity against E. coli, gram negative bacteria. This simple and economical preparation strategy may be extended for the preparation of other graphene-based hybrids.