Effects of green solvents and surfactants on the characteristics of few-layer graphene produced by dual-frequency ultrasonic liquid phase exfoliation technique

Nowadays, one of the promising methods for scalable graphene production is ultrasound-aided liquid phase exfoliation (ULPE) of graphite. Two current limiting factors of ULPE are the use of harmful solutions (such as N-Methyl-2-pyrrolidone or Dimethylformamide) and a relatively low graphene yield. In this study, we demonstrate a new dual frequency (20 kHz and 1174 kHz) ULPE approach in various eco-friendly media, which enabled us to produce various few-layer graphene (FLG) solutions of high quality. By implementing sophisticated characterisation techniques consisting of Raman spectroscopy, UV–vis spectroscopy and high-resolution electron microscopy, the final graphene flakes structure was confirmed to correlate the properties of each individual solution. The thinner (∼3 layers) and larger (∼1.5 μm2) flakes were observed while using just water, with the highest yield (11%) of smaller FLG flakes to be achieved in the mixture of water and a surfactant. In order to understand the cavitation mechanism in different solutions, the ULPE process was investigated by acoustic measurements. This study demonstrates the crucial role of ethanol (as a solvent) and surfactants as it regulates the cavitation power and intensity of the ultrasonic field and, thereby, the cavitation effectiveness. It is suggested that the mixture of water, ethanol and a surfactant is the best medium for ULPE process where a high yield of low-defective FLG flakes can be obtained in a solution stable at least for 3 months (around 80%)

Temperature as a key parameter for graphene sono-exfoliation in water

Graphene dispersions in water are highly desirable for a range of applications such as biomedicines, separation membranes, coatings, inkjet printing and more. Recent novel research has been focussed on developing a green approach for scalable production of graphene. However, one important parameter, which is often neglected is the bulk temperature of the processing liquid. This paper follows our earlier work where optimal sono-exfoliation parameters of graphite in aqueous solutions were determined based on the measured acoustic pressure fields at various temperatures and input powers. Here, we take the next step forward and demonstrate using systematic characterisation techniques and acoustic pressure measurements that sonication-assisted liquid phase exfoliation (LPE) of graphite powder can indeed produce high quality few layer graphene flakes in pure water at a specific temperature, i.e. 40 °C, and at an optimised input generator power of 50%, within 2-h of processing. UV–vis analysis also revealed that the exfoliation, stability and uniformity of dispersions were improved with increasing temperature. We further confirmed the successful exfoliation of graphene sheets with minimal level of defects in the optimized sample with the help of Raman microscopy and transmission electron microscopy. This study demonstrated that understanding and controlling processing temperature is one of the key parameters for graphene exfoliation in water which offers a potential pathway for its large-scale production

An eco-friendly solution for liquid phase exfoliation of graphite under optimised ultrasonication conditions

Ultrasonic assisted liquid phase exfoliation (ULPE) is a promising method for the large scale production of 2D materials. Currently, toxic solvents such as N-Methyl-2-pyrrolidone (NMP) are commonly used for the production of graphene. In this paper four solvents; three green solvents (water, ethanol and water/ethanol) plus NMP for comparison, were sonicated and examined in terms of their bubble dynamics and acoustic emissions. Advanced fundamental analysis was conducted using high-speed imaging synchronised with acoustic pressure measurements complemented by shadowgraphic photography of the emitted shockwaves, in order to determine a suitable eco-friendly solvent medium from a cavitation bubbles dynamics perspective. Thereafter, ULPE of graphite in the optimum solvent took place for 2 h under controlled ultrasonication parameters. The produced graphene samples were characterised by employing a series of techniques consisting of Ultraviolet–visible (UV–Vis) and Raman spectroscopy as well as transmission electron microscopy (TEM). A mixture of deionised water and ethanol was shown to produce a yield twice that of pure water, comprising of high quality few layer graphene (3–5 Ls) with an average area of ∼1.15 (μm)2 and stability of ∼78% for the duration of six months. This combination is a promising eco-friendly substitute for future commercial manufacturing of graphene

Subchronic Toxicity of Copper Oxide Nanoparticles and Its Attenuation with the Help of a Combination of Bioprotectors

In the copper metallurgy workplace air is polluted with condensation aerosols, which a significant fraction of is presented by copper oxide particles <100 nm. In the scientific literature, there is a lack of their in vivo toxicity characterization and virtually no attempts of enhancing organism’s resistance to their impact. A stable suspension of copper oxide particles with mean (±SD) diameter 20 ± 10 nm was prepared by laser ablation of pure copper in water. It was being injected intraperitoneally to rats at a dose of 10 mg/kg (0.5 mg per mL of deionized water) three times a week up to 19 injections. In parallel, another group of rats was so injected with the same suspension against the background of oral administration of a “bio-protective complex” (BPC) comprising pectin, a multivitamin-multimineral preparation, some amino acids and fish oil rich in ω-3 PUFA. After the termination of injections, many functional and biochemical indices for the organism’s status, as well as pathological changes of liver, spleen, kidneys, and brain microscopic structure were evaluated for signs of toxicity. In the same organs we have measured accumulation of copper while their cells were used for performing the Random Amplification of Polymorphic DNA (RAPD) test for DNA fragmentation. The same features were assessed in control rats infected intraperitoneally with water with or without administration of the BPC. The copper oxide nanoparticles proved adversely bio-active in all respects considered in this study, their active in vivo solubilization in biological fluids playing presumably an important role in both toxicokinetics and toxicodynamics. The BPC proposed and tested by us attenuated systemic and target organs toxicity, as well as genotoxicity of this substance. Judging by experimental data obtained in this investigation, occupational exposures to nano-scale copper oxide particles can present a significant health risk while the further search for its management with the help of innocuous bioprotectors seems to be justified

High electron mobility, quantum Hall effect and anomalous optical response in atomically thin InSe

A decade of intense research on two-dimensional (2D) atomic crystals has revealed that their properties can differ greatly from those of the parent compound. These differences are governed by changes in the band structure due to quantum confinement and are most profound if the underlying lattice symmetry changes. Here we report a high-quality 2D electron gas in few-layer InSe encapsulated in hexagonal boron nitride under an inert atmosphere. Carrier mobilities are found to exceed 103cm2V-1s-1and 104cm2V-1s-1at room and liquid-helium temperatures, respectively, allowing the observation of the fully developed quantum Hall effect. The conduction electrons occupy a single 2D subband and have a small effective mass. Photoluminescence spectroscopy reveals that the bandgap increases by more than 0.5eV with decreasing the thickness from bulk to bilayer InSe. The band-edge optical response vanishes in monolayer InSe, which is attributed to the monolayer's mirror-plane symmetry. Encapsulated 2D InSe expands the family of graphene-like semiconductors and, in terms of quality, is competitive with atomically thin dichalcogenides and black phosphorus.EU, EPSRC. The Royal Societ

CVD graphene recrystallization as a new route to tune graphene structure and properties

International audienceWe report here on a new way to tailor the structure of large-scale graphene during its growth. Monolayer graphene formed on Pt substrate using a modified hot-filament-assisted chemical vapor deposition setup, which does not require any control of crystal nucleation and orientation. The underlying growth mechanism includes a stage of structural evolution from nanocrystalline to microcrystalline graphene film. An enhanced recrystallization process in the graphene film is assessed by means of Raman spectroscopy and atomic resolution transmission electron microscopy. Moreover we demonstrate that the rotational angle between neighboring graphene grains can be tuned to 30 degrees or to small misalignment about 1-2 degrees only. This process opens a new route to control the electrical properties of large-scale uniform graphene film. (C) 2016 Elsevier Ltd. All rights reserved

Environment friendly dual-frequency ultrasonic exfoliation of few-layer graphene

Ultrasound-aided liquid phase exfoliation (ULPE) of graphene in pure water is environment-friendly. Two limiting factors of ULPE are the non-uniform thickness of few-layer graphene (FLG) and a relatively low graphene yield. Here we describe ULPE in water that enables us to produce FLG flakes with a thickness of 3 layers and the flake sizes exceeding 1 micron2 in just 2 h. This process is based on using a combination of two ultrasound sources of high and low frequencies: 1174 kHz and 20 kHz. Two different frequencies generate a wider population and size distribution of cavitation bubbles that act through a number of mechanisms towards the exfoliation of graphene. For the first time ULPE was characterized by acoustic measurements. Results show that a high graphene yield (10%) can be achieved. This study demonstrates that the use of a dual frequency ultrasonic source and control of acoustic pressure is critical in optimizing the quality and yield of the cavitation assisted LPE of graphene in pure water. It is suggested that the width of the acoustic pressure peak reflecting shock-wave emissions can be used as an indicator of ULPE completeness, opening for the first time a way of in-situ monitoring of the process

Indirect to Direct Gap Crossover in Two-Dimensional InSe Revealed by Angle-Resolved Photoemission Spectroscopy

Atomically thin films of III–VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductors that feature a strong variation of their band gap as a function of the number of layers in the crystal and, specifically for InSe, an expected crossover from a direct gap in the bulk to a weakly indirect band gap in monolayers and bilayers. Here, we apply angle-resolved photoemission spectroscopy with submicrometer spatial resolution (μARPES) to visualize the layer-dependent valence band structure of mechanically exfoliated crystals of InSe. We show that for one-layer and two-layer InSe the valence band maxima are away from the Γ-point, forming an indirect gap, with the conduction band edge known to be at the Γ-point. In contrast, for six or more layers the band gap becomes direct, in good agreement with theoretical predictions. The high-quality monolayer and bilayer samples enable us to resolve, in the photoluminescence spectra, the band-edge exciton (A) from the exciton (B) involving holes in a pair of deeper valence bands, degenerate at Γ, with a splitting that agrees with both μARPES data and the results of DFT modeling. Due to the difference in symmetry between these two valence bands, light emitted by the A-exciton should be predominantly polarized perpendicular to the plane of the two-dimensional crystal, which we have verified for few-layer InSe crystals