Production of graphene layer by liquid-phase exfoliation with low sonication power and sonication time from synthesized expanded graphite

Multi-layer graphene was produced through synthesized expanded graphite (EG) liquid exfoliation using organic solvent. Hexagonal graphite (HG) was used as a starting material. HG was mixed with an acidic mixture, dried, rand subjected to thermal treatment. After this process, EG was obtained. This obtained EG was sonicated for 1 h via an ultrasonic homogenizer by blending an organic solvent. Samples were subjected to SEM, TEM, FTIR, and UV-Vis/NIR spectroscopy investigations. After the investigations, it was shown that nano-size graphene sheets were obtained.     

Generation of soliton and bound soliton pulses in mode-locked erbium-doped fiber laser using graphene film as saturable absorber

We report an observation of soliton and bound-state soliton in passive mode-locked fibre laser employing graphene film as a passive saturable absorber (SA). The SA was fabricated from the graphene flakes, which were obtained from electrochemical exfoliation process. The graphene flakes was mixed with polyethylene oxide solution to form a polymer composite, which was then dried at room temperature to produce a film. The film was then integrated in a laser cavity by attaching it to the end of a fibre ferrule with the aid of index matching gel. The fibre laser generated soliton pulses with a 20.7 MHz repetition rate, 0.88 ps pulse width, 0.0158 mW average output power, 0.175 pJ pulse energy and 18.72 W peak power at the wavelength of 1564 nm. A bound soliton with pulse duration of ~1.04 ps was also obtained at the pump power of 110.85 mW by carefully adjusting the polarization of the oscillating laser. The formation of bound soliton is due to the direct pulse to pulse interaction. The results show that the proposed graphene-based SA offers a simple and cost efficient approach of generating soliton and bound soliton in mode-locked EDFL set-up.     

A novel preparation of water-dispersed graphene and their application to electrochemical detection of dopamine

In the paper, water-dispersed graphene-GQDs composites were prepared by electrochemical exfoliation under alternating voltage combining ultrasonic treatment. The effects of alternating voltage, alternating frequency and the distance between electrodes were carefully explored. The results showed that the quality of composites prepared by alternating voltage was higher than that by direct voltage. The existence of graphene quantum dots (GQDs) hindered the agglomeration of graphene and facilitated dispersion of graphene in water. The sensor based on the obtained graphene-GQDs composites was used to detect dopamine (DA). The electrochemical investigation showed that the sensor had good selectivity and wide linear ranges for the detection of DA (0.1–100 µM). The detection limit could be down to 3 × 10^?8 M (S/N = 3) with a sensitivity of 14.25 µA µM^?1 cm^?2.     

Size controllable synthesis of graphene water nanofluid with enhanced stability

A new preparation scheme of few-layer graphene water nanofluids was developed by exfoliating graphite in water with the help of polymer. The approach used centrifugation to classify the graphene nanosheets that made the graphene nanoflake length controllable. Population balance model was used to study the mechanism of exfoliation of graphite and the results revealed that the abrasion, cleavage and fracture all happened in these different stages of the exfoliation process. Mechanisms behind the size selection were also discussed and the terminal velocity was the critical factor to control the flake length. A simple model was developed to guide future similar experiments to obtain desired length graphene nanofluids. The stability of graphene nanofluid was also investigated and the result revealed that the obtained nanofluid showed enhanced stability suggesting great potential in heat transfer applications.     

Direct exfoliation of graphite into graphene in aqueous solution using a novel surfactant obtained from used engine oil

Large-scale production of high-quality graphene is very critical for practical applications of graphene materials and devices. Exfoliation of graphite in an aqueous solution of surfactants is one of the most promising approaches to produce graphene. In this study, a novel anionic surfactant [sulfonated used engine oil (SUEO)], which was prepared from used engine oil, was employed to exfoliate the graphite nanoplatelets into graphene sheets in an aqueous solution under sonication to form a stable dispersion. The efficiency of SUEO for exfoliating and dispersing graphene was investigated and compared with that of traditional surfactants, such as sodium dodecyl sulfate, sodium dodecyl benzene sulfate, cetyl trimethyl ammonium bromide, and polyvinylpyrrolidone. Result showed that the graphene dispersion with excellent stability had a higher concentration (0.477 mg/mL) than others at 0.5 g/L optimal SUEO dosage in 4 h sonication time. The superior performance of SUEO can be attributed to its special molecular structures, whose hydrophobic moieties contain cycloalkanes/aromatics with different molecular weights and/or side chain –R with different lengths. Structural diversities are very helpful to the “jigsaw-puzzle” process on the graphene surface, where the total interfacial energy of the mixture system was minimized. Microscopic (SEM, TEM, and AFM) and spectroscopic (XRD, XPS, and Raman) measurements revealed that the dispersion consisted of few-layer graphene sheets with lower levels of defects or oxidation. This study presents a new class of dispersing agents for graphene that assists in the exfoliation process in water with high concentration and the stabilization of the graphene sheets against reaggregation.     

Graphene quantum dots-assisted exfoliation of graphitic carbon nitride to prepare metal-free zero-dimensional/two-dimensional composite photocatalysts

The high aspect-ratio morphology of two-dimensional (2D) nanostructures endues them with distinct advantages for photocatalytic or photoelectrical applications. Although various attempts have been devoted to the liquid exfoliation of graphitic carbon nitride (g-C₃N₄) to obtain ultrathin nanosheets (CNNSs), the high exfoliation efficiency, well preservation of in-planar structure and facile operation cannot be simultaneously realized. Furthermore, functionalization of CNNSs is highly desired to promote the capability of photoabsorption, charge separation and transfer. Herein, we one-step prepared well-dispersed graphene quantum dots (GQDs)-modified CNNSs (GQDs/CNNSs) colloids via a facile and efficient GQDs-assisted exfoliation approach in a normal ultrasonic water bath. The exfoliation procedure was optimized by tuning the dopant in GQDs, ultrasonic time and GQDs dosage. The obtained colloidal GQDs/CNNSs show a typical 2D morphology with lateral size of several 100 nm and ultrathin thickness of 1.5–1.8 nm. What is more, we can tailor the semiconductive behavior of GQDs by heteroatom doping and achieve a p–n-type P-doped GQDs-modified CNNSs colloids. This p–n GQDs/CNNSs material presents the enhanced separation efficiency of photoexcited carriers and photocatalytic activity in comparison with bulky g-C₃N₄ (CN) and other CNNSs materials from acid or alkali exfoliation.     

The production of graphene nano layers by using milling—exfoliation hybrid process

Even though high quality graphene can be produced through chemical exfoliation of Graphite or Expanded graphite (EG), the amount of acquired products is limited. Graphite powders were subjected to a pre-milling process with prevailing shear stress in order to increase the amount of products. Therefore, separation of hexagonal layers through pre-separation process was targeted. The milled powders were firstly mixed in the saturated acid mixture containing H₂SO₄ and HNO₃, and then heated to 950°C. At the end of process, the distance between layers was expanded and the structure called as expanded graphite was obtained. Separation of layers and formation of graphene were provided by stirring expanded graphite within a chemical solvent for a while. The obtained samples were examined by using X-ray analysis, electron microscopy analysis, and Raman spectroscopy analysis. Despite the fact that there is a production method for graphene by chemical exfoliation, addition of the milling into steps of this process is an unusual step. Although a great amount of amorphous structures occurred in the structure at the end of milling process in this study, there were still graphitic structures preserving its hexagonality in the sample even if just a little. Most of amorphous carbon was removed from the structure as a result of applying further steps of process to milled graphite. A great part of graphitic structures apart from amorphous carbon structures were transformed into graphene. Even though amorphous carbon structures and defects were still found in the product, the obtained graphenes were relatively qualified and of high amount.     

Active carbon/graphene hydrogel nanocomposites as a symmetric device for supercapacitors

Activated carbons (ACs) are successfully synthesized from Elaeagnus grain by a simple chemical synthesis methodology and demonstrated as novel, suitable supercapacitor electrode materials for graphene hydrogel (GH)/AC nanocomposites. GH/AC nanocomposites are synthesized via hydrothermal process at temperature of 180°C. The low-temperature thermal exfoliation approach is convenient for mass production of graphene hydrogel (GH) at low cost and it can be used as electrode material for energy storage applications. The GH/AC nanocomposites exhibit better electrochemical performances than the pure GH. Electrochemical performance of the electrodes is studied by cyclic voltammetry, and galvanostatic charge-discharge measurements in 1.0 M H₂SO₄ solution. A remarkable specific capacitance of 602.36 Fg^?1 (based on GH/AC nanocomposites for 0.4 g AC) is obtained at a scan rate of 1 mVs^?1 in 1 M H₂SO₄ solution and 155.78 Fg^?1 for GH. The specific capacitance was increased 3.87 times for GH/AC compared to GH electrodes. Moreover, the GH/AC nanocomposites for 0.2 g AC present excellent long cycle life with 99.8% specific capacitance retained after 1000 charge/discharge processes. Herein, ACs prepared from Elaeagnus grain are synthesized GH and AC supercapacitor device for high-performance electrical energy storage devices as a promising substitute to conventional electrode materials for EDLCs.     

An electrochemical route to graphene oxide

Large-scale graphene oxide (GO) with adjustable resistivity was synthesized from graphite via an electrochemical method using KCl solution as an effective electrolyte. During the exfoliation process, electrostatic force intercalates chloride ions between the expanded graphite layers on the anode. These chloride ions form small gas bubbles between the graphite layers in the electrochemical reaction. It is believed that the gas bubbles expand the gap between graphite sheets and produce a separating force between adjacent graphene layers. This separating force overcomes the Van der Waals force between adjacent sheets and exfoliates graphene layers from the starting graphite. Because the graphene is electrochemically oxidized by chorine during the exfoliation, the exfoliated GO sheets are hydrophilic and easily dispersed in the electrolyte solution. The GO solution prepared by the electrochemical exfoliation can be simply sprayed or spin-coated onto any substrate for device applications. The measured average thicknesses of a monolayer, bilayer, and trilayer exfoliated GO on SiO2 substrate were 1.9, 2.8, and 3.9 nm, respectively. It was observed that the measured resistance of the exfoliated GO sheets increases due to electrochemical oxidation in the solution. This electrochemical approach offers a low-cost and efficient route to the fabrication of graphene based devices.     

One pot synthesis of a highly water-dispersible hybrid glucose carbides and reduced graphene oxide material with superior electrical capacitance

In this paper, reduced graphene oxide with glucose carbides (RGO-GC) was synthesized in a simple one pot synthesis via a hydrothermal approach. Graphene oxide (GO) dispersion was dissolved together with glucose in water, and the mixture was heated to 180 °C in an autoclave. After hydrothermal treatment, a thin GO-like glucose carbides (GC) film grows in situ on the RGO surface. Differing from RGO, the obtained RGO-GC not only has a much better dispersion in water, but also can be used as a support and a green reductant to fabricate Ag-decorated RGO-GC. Moreover, the maximum specific capacitance of the RGO-GC reaches as high as 247 F g^?1 at a charging/discharging current density of 0.1 A g^?1 in 1 M H₂SO₄ solution. After 1000 charging/discharging cycles, the specific capacitance still retains 95 % of its initial specific capacitance. The greatly improved electrochemical performance is attributed to the increased surface wettability, more effective ionic diffusion, and a higher conductivity arising from the hydrophilic GO-like GC grown on the RGO surfaces.     

Preparation and properties of polystyrene nanocomposites with graphite oxide and graphene as flame retardants

In this study, graphite oxides (GOs) with different oxidation degrees and graphene nanosheets were prepared by a modified Hummers method and thermal exfoliation of the prepared GO, respectively. Polystyrene (PS)/GO and PS/graphene nanocomposites were prepared via melt blending. X-ray diffraction results showed that GOs and graphene were exfoliated in the PS composites. It could be observed from the scanning electron microscope images that GOs and graphene were well dispersed throughout the matrix without obvious aggregates. Dynamic mechanical thermal analysis suggested that the storage modulus for the PS/GO1 and PS/graphene nanocomposites was efficiently improved due to the low oxygen content of GO1 and the elimination of the oxygen groups from GO. The flammability of nanocomposites was evaluated by thermal gravimetric analysis and cone calorimetry. The results suggested that both the thermal stability and the reduction in peak heat release rate (PHRR) decreased with the increasing of the oxygen groups in GOs or graphene. The optimal flammability was obtained with the graphene (5 wt%), in which case the reduction in the PHRR is almost 50 % as compared to PS.     

Production of graphene nanosheets by supercritical CO2 process coupled with micro-jet exfoliation

A facile and cost-effective method which combines supercritical CO₂ and micro-jet exfoliation has been developed for producing graphene nanosheets with high-quality. CO₂ molecules can intercalate into the interlayer of graphite because of their high diffusivity and small molecule size in supercritical operation. The tensile stress induced by graphite interfacial reflection of compressive waves exert on the graphite flakes, which lead to further exfoliation of graphite. Scanning electron microscope (SEM), transmission electron microscope (TEM), atomic force microscopy (AFM), Raman spectrum and X-ray diffraction (XRD) are used to identify morphology and quality of the exfoliated graphene nanosheets, which reveal that the graphite was successfully exfoliated into graphene and more than 88% of graphene nanosheets are less than three layers. The yield of graphene nanosheets is about 28 wt% under optimum conditions, which can be greatly improved by repeated exfoliation of the graphene sediment. The pure graphene film has a high conductivity of 2.1 × 10⁵ S/m.     

Surfactant assisted exfoliation of high purity graphene in aqueous solution as a nanofluid using kitchen blender: Influence on dispersion,thermal conductivity and rheological properties

In this work, graphene is exfoliated from graphite flakes in distilled water solution containing Tween 80 as surfactant and by using the mechanical exfoliation method through a kitchen blender. The blending time is an important parameter for the size reduction and concentration of graphene exfoliation in a nanofluid. Graphene obtained using a kitchen blender is of high purity having no basal plane defects, as depicted from Raman spectroscopic investigation. The viscosity of graphene nanofluid increases with blending time up to 7 h and thereafter the viscosity decreases. All graphene nanofluid samples prepared using different blending time shows shear thinning behavior by fitting the power law of non-linear viscoelastic measurement data. The linear viscoelastic region measured was in the strain range of 0.01–0.8%. Further, the frequency sweep measurement using a rheometer has indicated the gel-like behavior of graphene nanofluid in a certain frequency range and depends on the concentration of graphene. The use of two-dimensional nanosheets-based nanofluid has attracted the attention of researchers for improving pool boiling properties. Herein, the pool boiling of graphene nanofluid at 7 h of blending shows the 77.4% enhancement in critical heat flux (CHF). This work has established mechanical exfoliation as a process to synthesize the graphene nanofluid and can be used for heat transfer applications.     

Non-covalently modified reduced graphene oxide/polyurethane nanocomposites with good mechanical and thermal properties

Non-covalently modified graphene nanosheets were prepared by reduction graphene oxide with hydrazine hydrate and simultaneous non-covalent functionalization via 1-allyl-methylimidazolium chloride (AmimCl) ionic liquid. Atomic force microscopy revealed that AmimCl ionic liquid modified graphene (IL-G) was well-dispersed in a single exfoliation with a thickness of around 0.96 nm in DMF. Subsequently, the prepared IL-G nanosheets were incorporated into polyurethane (PU) to fabricate IL-G/PU nanocomposites by solution blending. X-ray diffraction disclosed an exfoliated morphology of IL-G nanosheets dispersed in the PU matrix, while the fractured morphology of the IL-G/PU nanocomposites showed that IL-G nanosheets presented a wrinkled morphology when dispersed in the matrix. Both techniques revealed homogeneous dispersion and good compatibility of IL-G nanosheets with PU matrix, indicating the existence of interfacial interactions. At 0.608 wt% loadings of IL-G nanosheets, the tensile strength and storage modulus of the composites were increased by 68.5 and 81.1 %, respectively. High thermal properties were also achieved at a low loading of IL-G nanosheets. An approximately 40 °C improvement in temperature of 5 % weight loss and 34 % increase in thermal conductivity were obtained at just 0.608 wt% loading of IL-G nanosheets.     

Electrochemical determination of hydrazine based on polydopamine-reduced graphene oxide nanocomposite

In this work, a simple and mild procedure was employed to synthesize polydopamine-reduced graphene oxide (PDA-RGO) nanocomposites, where the sheets of graphene oxide were functionalized firstly with PDA through self-polymerization. FTIR was used to confirm that the GO sheets had been functionalized successfully with PDA and reduced. Besides, UV-Vis and X-ray diffraction spectroscopy were employed to further demonstrate the formation of RGO. The electrochemical property of the PDA-RGO has been studied by the determination of hydrazine. The results indicated that the electrochemical oxidation of hydrazine was significantly improved by the obtained PDA-RGO nanocomposite due to the increased available surface area of electrode. A quick amperometric response was observed with the electrochemical sensor based on PDA-RGO nanocomposite for the hydrazine measurement in a wide linear range of 0.03–100 μM, where the limit of the detection was 0.01 μM.     

Effects of stage, intercalant species and expansion technique on exfoliation of graphite intercalation compound into graphene sheets

Graphite is composed of a series of stacked parallel graphene layers bonded by weak van der Waals forces. Although the weak interactions that hold the graphene sheets together allow them to slide readily over each other, the numerous weak bonds make it difficult to separate the sheets. A graphene sheet is a two-dimensional platelet consisting of a few graphene layers with an overall thickness in nanometer scale. Graphene sheets can be obtained from intercalation and subsequent exfoliation of graphite. To realize the expansion and exfoliation behaviors of graphite, graphite intercalation compound (GIC) is produced using an electrochemical method and three important factors, namely stage structure of GIC, intercalant species and expansion techniques, are taken into account. Graphene sheets produced from a lower stage FeCl3-GIC display the best exfoliation behavior in terms of specific surface area, total pore volume and expansion volume. Microwave irradiation gives rise to a more explosive expansion than heating in a furnace.     

In-situ intercalation polymerization synthesis and electromagnetic wave absorption property of graphene/PANI/CuO ternary composites

Based on in-situ intercalation polymerization of PANI, graphene/PANI/CuO ternary nanocomposites were synthesized by hydrothermal reaction at 160 °C followed by heat treatment at 280 °C. The morphology and electromagnetic wave absorption property of as-prepared products were investigated. Result shows that the physical exfoliation of graphite into graphene takes place mainly in the hydrothermal process. After hydrothermal reaction for 4 h, prolongation of the reaction time has no obvious effect on graphene exfoliation and the electromagnetic wave absorption of graphene/PANI/CuO. The synthesized graphene/PANI/CuO ternary nanocomposite is a promising candidate for electromagnetic wave absorbing. Double-layer absorbers using graphene/PANI/CuO as absorbing layer present excellent performances. Both effective absorption bandwidths of DB-1 and DB-2 exceed 10.0 GHz when the total thickness is only 3.0 mm. The maximum reflection loss for DB-1 is up to 39.4 dB at 16.1 GHz and that for DB-2 is???47.3 dB at 11.0 GHz.

     

Exfoliation and dispersion of graphene in ethanol-water mixtures

Graphene has attracted much attention as a new nano-carbon for its unique structure and properties. However, production and dispersion of unfunctionalized graphene are still big challenges. Herein, we demonstrate a simple method for preparation and dispersion of such graphene with low cost and non toxicum. This approach is achieved by exfoliating graphite in an ethanol/water mixture and forming stable dispersion of mono- and few-layer graphenes. The ratio of ethanol/water in the mixture is found to be crucial to both the exfoliation and dispersion processes. Exfoliation in pure water or pure ethanol produces no graphene. This method avoids the conventional use of harsh oxidants and surfactants; therefore, the graphitic structure is well maintained without destruction. Benefiting from the use of ethanol and water, it can be easy to prepare transparent and conductive graphene films by vacuum filtering or spray method, and does not need special post-treatment to remove the impurity, which could be beneficial for potential applications in electronic, optic and energy areas.     

Conducting polymer and reduced graphene oxide Langmuir–Blodgett films: a hybrid nanostructure for high performance electrode applications

In this work, we prepared a reduced graphene oxide (RGO)/poly(3,4-ethylenedioxythiophene) (PEDOT) hybrid composite with well defined nanostructure. The graphene oxide (GO) was first deposited on substrate through the Langmuir–Blodgett (LB) deposition, which provided a tunable and ordered GO arrangement on substrate. Then the GO LB films were reduced to RGO by following thermal treatment, and a ultrathin conducting polymer (CP) PEDOT was directly coated on RGO through a vapor phase polymerization process. The RGO/PEDOT nanocomposite exhibits excellent electrical conductivity about 377.2 S/cm. Electrochemical activity investigation revealed that this nanocomposite exhibits 213 F/g high specific capacitance at a 0.5 A/g current density and shows better capacitance retention rate than pure PEDOT. The detailed study also confirmed that the arrangement of RGO shows distinct influence on the electrical and electrochemical properties of obtained nanocomposite. Large area RGO/PEDOT nanocomposite with high conductivity and electrochemical activity can be deposited on different substrates. Such high conductivity and electrochemical activity RGO/CP nanocomposite shows promising application future in organic and flexible electrode materials for sustainable energy storage.     

Facile and size-controllable preparation of graphene oxide nanosheets using high shear method and ultrasonic method

ABSTRACT

The lateral size of the graphene oxide (GO) nanosheets could be controlled by preparation method, and a simple and effective strategy to adjust the lateral size of GO nanosheets by selecting suitable method is presented. The high shear method was introduced to produce GO nanosheets, and the GO nanosheets (few micrometres) prepared by high shear method is about one order of magnitude larger than GO nanosheets (few hundred nanometres) obtained by ultrasonic method, as evidenced by atomic force microscopy. The FTIR, XPS and Raman analysis revealed that there are no distinct differences in composition and functional groups between the GO nanosheets produced by high shear method and ultrasonic method. The cavitation in the procedure of ultrasonic method is favourable for GO exfoliation, but it also could result in damage to GO nanosheets. The shearing force in the process of high shear method is effective for GO delamination with minimal fragmentation. The results indicated that the high shear method proposed in this paper is an efficient exfoliation means to produce single-layer GO nanosheets.