Abstract:In order to progress from the lab to commercial applications it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene.Here we show that high-shear mixing of graphite in suitable, stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. XPS and Raman spectroscopy show the exfoliated flakes to be unoxidised and free of basal plane defects. We have developed a simple model which shows exfoliation to occur once the local shear rate exceeds 10 4 s -1 . By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from 100s of ml up to 100s of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals. Main Text:Due to its ultra-thin, 2-dimensional nature and its unprecedented combination of physical properties, graphene has become the most studied of all nano-materials. In the next decade graphene is likely to find commercial applications in many areas from high-frequency electronics to smart coatings.
In order to fulfil their potential for applications, it will be necessary to develop large-scale production methods for two-dimensional (2D) inorganic nanosheets. Here we demonstrate the large-scale shear-exfoliation of molybdenum disulphide nanosheets in aqueous surfactant solution using a kitchen blender. Using standard procedures, we measure how the MoS2 concentration and production rate scale with processing parameters. However, we also use recently developed methods based on optical spectroscopy to simultaneously measure both nanosheet lateral size and thickness, allowing us to also study the dependence of nanosheet dimensions on processing parameters. We found the nanosheet concentration and production rates to depend sensitively on the mixing parameters (the MoS2 concentration, Ci; the mixing time, t; the liquid volume, V; and the rotor speed, N). By optimising mixing parameters, we achieved concentrations and production rates as high as 0.4 mg/ml and 1.3 mg/min respectively. Conversely, the nanosheet size and thickness were largely invariant with these parameters. The nanosheet concentration is also extremely sensitive to the surfactant concentration. However, more interestingly the nanosheet lateral size and thickness also varied strongly with the surfactant concentration. This allows the mean nanosheet dimensions to be controlled during shear exfoliation at least in the range ~40-220 nm for length and ~2-12 layers for thickness. We demonstrate the importance of this by showing that the MoS2 nanosheets prepared using different surfactant concentrations, and so displaying different nanosheets sizes, perform differently when used as hydrogen evolution catalysts. We find the nanosheets produced using high surfactant concentrations, which gives smaller flake sizes, perform significantly better, consistent with catalysis occurring at nanosheet edges. Finally, we also demonstrate that shear exfoliation using a kitchen blender is not limited to MoS2 but can also be achieved for boron nitride and tungsten disulphide. ToC fig3
Liquid phase exfoliation is a powerful and scalable technique to produce defect-free mono- and few-layer graphene. However, samples are typically polydisperse and control over size and thickness is challenging. Notably, high throughput techniques to measure size and thickness are lacking. In this work, we have measured the extinction, absorption, scattering and Raman spectra for liquid phase exfoliated graphene nanosheets of various lateral sizes (90 ≤ 〈L〉 ≤ 810 nm) and thicknesses (2.7 ≤ 〈N〉 ≤ 10.4). We found all spectra to show well-defined dependences on nanosheet dimensions. Measurements of extinction and absorption spectra of nanosheet dispersions showed both peak position and spectral shape to vary with nanosheet thickness in a manner consistent with theoretical calculations. This allows the development of empirical metrics to extract the mean thickness of liquid dispersed nanosheets from an extinction (or absorption) spectrum. While the scattering spectra depended on nanosheet length, poor signal to noise ratios made the resultant length metric unreliable. By analyzing Raman spectra measured on graphene nanosheet networks, we found both the D/G intensity ratio and the width of the G-band to scale with mean nanosheet length allowing us to establish quantitative relationships. In addition, we elucidate the variation of 2D/G band intensities and 2D-band shape with the mean nanosheet thickness, allowing us to establish quantitative metrics for mean nanosheet thickness from Raman spectra.
To facilitate progression from the lab to commercial applications, it will be necessary to develop simple, scalable methods to produce high quality graphene. Here we demonstrate the production of large quantities of defect-free graphene using a kitchen blender and household detergent. We have characterised the scaling of both graphene concentration and production rate with the mixing parameters: mixing time, initial graphite concentration, rotor speed and liquid volume. We find the production rate to be invariant with mixing time and to increase strongly with mixing volume, results which are important for scale-up. Even in this simple system, concentrations of up to 1 mg ml À1 and graphene masses of >500 mg can be achieved after a few hours mixing. The maximum production rate was $0.15 g h À1 , much higher than for standard sonication-based exfoliation methods. We demonstrate that graphene production occurs because the mean turbulent shear rate in the blender exceeds the critical shear rate for exfoliation.Over the last decade, graphene has become one of the most studied of all nano-materials due to its 2-dimensional structure and its unique set of physical properties. 1,2 During this period, the focus of much of the research community has been on mapping out and understanding the fundamental physics and chemistry of graphene. However, in recent years, the emphasis has started to shi slightly towards the demonstration of applications. 3 Over the next few years, we expect the emphasis to shi further as both academic and industrial researchers concentrate on fullling the applications potential of graphene, eventually leading to a range of graphene-enabled products.However, before this can be achieved, it will be critically important to develop industrially scalable production methods for graphene. While graphene can be produced by a range of techniques, many applications will require solution-processed 4 graphene. In particular, a number of applications will require access to large volumes of graphene dispersions or inks. Using standard solution deposition techniques such as inkjet printing 5,6 or spray coating, 7,8 such inks can be used to prepare a range of lms, coatings or patterned structures. In particular, applications in areas such as printed electronics will require the production of conductive lms or traces. Here, defect free graphene performs particularly well, giving high conductivity structures without high temperature post treatments. 5 Thus, it is clear that large scale production techniques for defect-free graphene are urgently required.Defect free graphene is generally produced by sonicating graphite powder either in certain solvents 9-16 or aqueous surfactant 17-23 solutions. The sonication tends to break up the graphite crystallites as well as exfoliating them to give large number of graphene nanosheets. 11 Raman spectroscopy 15,24,25 shows this method to produce negligible quantities of basal plane defects while XPS shows the akes to be un-oxidised. 14 While the graphene produced by this m...
We have prepared polymer nanocomposites reinforced with exfoliated graphene layers solely via melt blending. For this study polyethylene terephthalate (PET) was chosen as the polymer matrix due to its myriad of current and potential applications. PET and PET/graphene nanocomposites were melt compounded on an internal mixer and the resulting materials were compression molded into films. Transmission electron microscopy and scanning electron microscopy revealed that the graphene flakes were randomly orientated and well dispersed inside the polymer matrix. The PET/graphene nanocomposites were found to be characterized by superior mechanical properties as opposed to the neat PET. Thus, at a nanofiller load as low as 0.07 wt%, the novel materials presented an increase in the elastic modulus higher than 10% and an enhancement in the tensile strength of more than 40% compared to pristine PET.The improvements in the tensile strength were directly correlated to changes in elongation at break and indirectly correlated to the fracture initiation area. The enhancements observed in the mechanical properties of polymer/graphene nanocomposites achieved at low exfoliated graphene loadings and manufactured exclusively via melt mixing may open the door to industrial manufacturing of economical novel materials with superior stiffness, strength and ductility.3
The systematic study of nanoparticle–biological interactions requires particles to be reproducibly dispersed in relevant fluids along with further development in the identification of biologically relevant structural details at the materials–biology interface. Here, we develop a biocompatible long-term colloidally stable water dispersion of few-layered graphene nanoflakes in the biological exposure medium in which it will be studied. We also report the study of the orientation and functionality of key proteins of interest in the biolayer (corona) that are believed to mediate most of the early biological interactions. The evidence accumulated shows that graphene nanoflakes are rich in effective apolipoprotein A-I presentation, and we are able to map specific functional epitopes located in the C-terminal portion that are known to mediate the binding of high-density lipoprotein to binding sites in receptors that are abundant in the liver. This could suggest a way of connecting the materials' properties to the biological outcomes.
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