Few-layer Graphene Structures Research Articles

Functionalized graphene-based materials for cementitious applications.

Graphene-based materials (GBM) are promising cementitious composite additives that can significantly improve the mechanical characteristics and durability of concrete due to their unique properties, such as high surface area and aspect ratio and excellent tensile strength, to name a few. To display their full potential, GBM have to be homogeneously dispersed into the aqueous environment of cement-based matrices. The present study addresses the issue of limited dispersibility in the aqueous media of GBM through the chemical functionalization of mono- and few-layer graphene structures with hydrophilic aryl sulfonate groups and shows that a series of mortar samples containing modified GBM exhibit increased flexural and compressive strength by up to 17% and 30%, respectively, compared to mortar references without additives.

Few-Layer Graphene Structures as a Promising Mycotoxin Sorbent

Few-Layer Graphene Structures as a Promising Mycotoxin Sorbent

Laser-Induced Graphene Formation on Polyimide Using UV to Mid-Infrared Laser Radiation

Our study presents laser-assisted methods to produce conductive graphene layers on the polymer surface. Specimens were treated using two different lasers at ambient and nitrogen atmospheres. A solid-state picosecond laser generating 355 nm, 532 nm, or 1064 nm wavelengths and a CO2 laser generating mid-infrared 10.6 µm wavelength radiation operating in a pulsed regime were used in experiments. Sheet resistance measurements and microscopic analysis of treated sample surfaces were made. The chemical structure of laser-treated surfaces was investigated using Raman spectroscopy, and it showed the formation of high-quality few-layer graphene structures on the PI surface. The intensity ratios I(2D)/I(G) and I(D)/I(G) of samples treated with 1064 nm wavelength in nitrogen atmosphere were 0.81 and 0.46, respectively. After laser treatment, a conductive laser-induced graphene layer with a sheet resistance as low as 5 Ω was formed. Further, copper layers with a thickness of 3–10 µm were deposited on laser-formed graphene using a galvanic plating. The techniques of forming a conductive graphene layer on a polymer surface have a great perspective in many fields, especially in advanced electronic applications to fabricate copper tracks on 3D materials.

Bubble-Induced Strong Thermal Contraction for Graphene

Abstract The thermal expansion coefficient (TEC) of van der Waals (vdW) layered structures is of crucial importance in governing the dependability and longevity of advanced optoelectronic equipment. Bubbles are commonly found within layered structures, yet their impact on the thermal expansion coefficient of the structure is still not well understood. We derive an analytical formula that describes the influence of bubbles on the variation in length, utilizing both the elastic membrane theory and the improved van der Waals gas state equation. The results demonstrate that as the temperature increases, bubbles can induce significant thermal contraction in few-layer graphene structures. The analytical predictions are validated through molecular dynamic (MD) simulations, confirming the accuracy and reliability of the proposed model. These findings hold significant value in enhancing our understanding of the dependability and durability of functional equipment that relies on van der Waals layered structures.

Direct etching of nano/microscale patterns with both few-layer graphene and high-depth graphite structures by the raster STM electric lithography in the ambient conditions.

The development of raster STM electric lithography has enabled the etching of nano/microscale patterns on both few-layer graphene (FLG) and high-depth graphite structures on the bulk HOPG substrates under ambient conditions. This approach utilises a nanoscale probe tip as a machining tool to directly fabricate conductive sample surfaces without the need for resists or masks. Compared to conventional nano/micro machining methods, the capability of ultraaccurate fabrication of nanoscale patterns using this technique is unmatched. The resulting FLG structures exhibit ultrasmooth flat bottoms and uniformly controlled depths ranging from 0.34 to 3.0nm (less than 10 layers). This work represents a significant advancement as it demonstrates the perfect etching of FLG structures in designated nano/microscale regions using raster STM electric lithography in the constant current mode, which reaches the limitation of top-down manufacturing techniques. Additionally, raster STM electric lithography in the constant height mode can directly etch high-depth structures (up to ∼100nm). The geometric shape and number of layers of the etched graphene structures determined by either local anodic oxidation (LAO) or the electric discharge (ED) mechanism. The LAO mechanism results in less debris and smoother edges compared to the ED mechanism, which is caused by the random electrical discharge between the tip and the sample. The well-controlled raster STM electric lithography technique is believed to be a promising and facile approach for constructing nano/microscale graphene-based devices.

CoP/EEBP/N-FLGS Nanocomposite as an Efficient Electrocatalyst of Hydrogen Evolution Reaction in Alkaline Media

The search for new hydrogen evolution reaction (HER) electrocatalysts with lower cost and higher activity and stability than noble metal catalysts is essential. In this regard cobalt phosphide is considered one of the most promising nanomaterials. The present work proposes a simple and efficient method for the synthesis of a nanocomposite of graphene–phosphorene structures decorated with CoP nanoparticles 2–5 nm in size via the electrochemical exfoliation of black phosphorus carried out in the presence of nitrogen-doped few-layer graphene structures and followed by solvothermal synthesis in a Co2+-containing solution. The obtained CoP/EEBP/N-FLGS nanocomposite demonstrates high electrocatalytic activity and stability towards HER in an alkaline medium. The nanocomposite is characterized by an overpotential of 190 mV at a current density of 10 mA cm−2 as well as a small Tafel slope (78 mV dec−1). These characteristics make the CoP/EEBP/N-FLGS nanocomposite superior to most electrocatalysts based on cobalt phosphides. The results of this study could be in demand for the future design and improvement of HER electrocatalysts.

In English

In presented work we have reported that polyvinylpyrrolidone (PVP) is suitable organic solvent for mechanical exfoliation of crystalline graphite to graphene in aqueous solution through kitchen blender technique. Morphological, structural and optical, properties of graphene samples were characterized by scanning electron microscopy, Raman scattering and UV-Visible spectroscopy. Scanning electron microscopy demonstrates folded morphology of graphene flakes with ~4 nm thickness. Raman scattering was revealed the high-quality graphene with low levels of defects after the exfoliation process of graphite/PVP dispersions. The G band at ~1582 cm−1 on Raman spectra is related with stretching vibrations of carbon atoms. The broadening of the G band is not observed, that indicated on absence of the basal plane defects in the graphene structure, which can be introduced during exfoliation by the kitchen blender. The ratio of the intensity of 2D and G bands equal to 1.66 (I2D/IG>1) and the value of 2D band full width at half maximum is 79.88 cm–1, indicated a few-layer graphene (FLG) structure. The defects quantity identified by the intensity ratio of the D and G bands, ID/IG is 0.18, significantly lower than that reported for graphene oxide with basal plane defects (> 1) and for sonication dispersed graphene (~ 0.6). The graphene dispersions were characterized by UV–Vis spectroscopy, minimum transmittance observed at around 270 nm is attributed to the π→π* transitions of aromatic C–C bonds in graphene. The optical transmittance minimum and the overall high transmittance decreasing values observed between 270 and 800 nm strongly suggest the presence of two-dimensional material in the dispersion, thus confirming the successful exfoliation of graphite to graphene by blending. We demonstrate the simple and nontoxic method to product high-quality FLG sheets, free from defects, using a kitchen blender and eco-friendly polyvinylpyrrolidone as an organic exfoliant.

Bithiophene as a Sulfur-Based Promotor for the Synthesis of Carbon Nanotubes and Carbon-Carbon Composites.

We assess bithiophene (C8H6S2) as a novel sulfur-based promotor for the growth of single-walled carbon nanotubes (SWCNTs) in the aerosol (floating catalyst) CVD method. Technologically suitable equilibrium vapor pressure and an excess of hydrocarbon residuals formed under its decomposition make bithiophene an attractive promoter for the production of carbon nanotubes in general and specifically for ferrocene-based SWCNT growth. Indeed, we detect a moderate enhancement in the carbon nanotube yield and a decrease in the equivalent sheet resistance of the films at a low bithiophene content, indicating the improvement of the product properties. Moreover, the relatively high concentrations and low temperature stability of bithiophene result in non-catalytical decomposition, leading to the formation of pyrolytic carbon deposits; the deposits appear as few-layer graphene structures. Thus, bithiophene pyrolysis opens a route for the cheap production of hierarchical composite thin films comprising carbon nanotubes and few-layer graphene, which might be of practical use for hierarchical adsorbents, protective membranes, or electrocatalysis.

One-Step Plasma-Assisted Electrochemical Synthesis of Nanocomposites of Few-Layer Graphene Structures with Manganese Oxides as Electrocatalysts for Oxygen Reduction Reaction

Using the method of plasma-assisted electrochemical exfoliation of graphite, a nanocomposite, which consists of few-layer graphene structures with surface decorated with manganese oxides nanoparticles, is synthesized in one-step process. It is found that this material exhibits a high electrocatalytic activity towards the oxygen reduction reaction due to the presence of manganese in the +2 and +3 oxidation states, and also carbonyl (quinone) functional groups on the surface of graphene structures.

One-Step Plasma-Assisted Electrochemical Synthesis of Nanocomposites of Few-Layer Graphene Structures with Manganese Oxides as Electrocatalysts for Oxygen Reduction Reaction

One-Step Plasma-Assisted Electrochemical Synthesis of Nanocomposites of Few-Layer Graphene Structures with Manganese Oxides as Electrocatalysts for Oxygen Reduction Reaction

Plasma Electrochemical Synthesis of Graphene-Phosphorene Composite and Its Catalytic Activity towards Hydrogen Evolution Reaction

For the first time, graphene-phosphorene structures were synthesized using the plasma-assisted electrochemical method. The catalytic activity of the composite obtained in the electrolytic plasma mode and its mixtures with few-layer graphene structures toward the hydrogen evolution reaction was studied. A substantial increase in the catalytic activity of the phosphorene structures towards the hydrogen evolution reaction was realized by mixing them with few-layer graphene structures. The catalyst demonstrates excellent activity towards the hydrogen evolution reaction in alkaline media with a low overpotential of 940 mV at a current density of 10 mA·cm−2 and a small Tafel slope of 130 mV dec−1.

A Surface Modification Strategy Towards Reversible Na-ion Intercalation on Graphitic Carbon Using Fluorinated Few-Layer Graphene

Na-ion batteries (NIBs) are proposed as a promising candidate for beyond Li-ion chemistries, however, a key challenge associated with NIBs is the inability to achieve intercalation in graphite anodes. This phenomenon has been investigated and is believed to arise due to the thermodynamic instability of Na-intercalated graphite. We have recently demonstrated theoretical calculations showing it is possible to achieve thermodynamically stable Na-intercalated graphene structures with a fluorine surface modifier. Here, we present experimental evidence that Na+ intercalation is indeed possible in fluorinated few-layer graphene (F-FLG) structures using cyclic voltammetry (CV), ion-sensitive scanning electrochemical microscopy (SECM) and in situ Raman spectroscopy. SECM and Raman spectroscopy confirmed Na+ intercalation in F-FLG, while CV measurements allowed us to quantify Na-intercalated F-FLG stoichiometries around NaC14–18. These stoichiometries are higher than the previously reported values of NaC186 in graphite. Our experiments revealed that reversible Na+ ion intercalation also requires a pre-formed Li-based SEI in addition to the surface fluorination, thereby highlighting the critical role of SEI in controlling ion-transfer kinetics in alkali-ion batteries. In summary, our findings highlight the use of surface modification and careful study of electrode-electrolyte interfaces and interphases as an enabling strategy for NIBs.

Nanoarchitectonics effect of few-layer graphene on the properties of cement mortar

• The number of layers is an important indicator to measure the properties of graphene. • Few-layer graphene can improve the mechanical properties of cement mortar. • Within the scope of test, the optimal dosage of Few-layer graphene is 0.04% ∼ 0.06%. To further study graphene/mortar composites, the effects of few-layer graphene (FLG) on the fluidity, mechanical properties (compressive strength and flexural strength) and electrical properties of cement mortar were systematically studied in this paper, through SEM, XRD and EDS to analyze the mechanism. Meanwhile, AFM, Raman and SEM were used to characterize the layer number and structure of FLG. The results show that the layer number of FLG is between 3 and 6 layers, which shows a hexagonal honeycomb structure and interlayer stacking phenomenon. The addition of FLG can reduce the fluidity of mortar, while improve the conductivity of mortar, and FLG/mortar composites present NTC effect. 28 d compressive strength and flexural strength of mortar increased by 38.1% and 58.03% respectively with the addition of FLG. FLG has the effect of nano filling and overlapping hydration products, which can promote the better connection between cement paste and aggregate, thus the structure of mortar more dense.

One-step synthesis of nitrogen-doped few-layer graphene structures decorated with Mn1.5Co1.5O4 nanoparticles for highly efficient electrocatalysis of oxygen reduction reaction

A nanocomposite consisting of nitrogen-doped few-layer graphene structures, the surface of which is decorated with nanocrystallites of Mn1.5Co1.5O4 spinel oxide, was prepared by a single-stage method of plasma-assisted electrochemical exfoliation of graphite in a solution of 1 M NaNO3 + 0.005 M MnSO4 + 0.005 M CoSO4 + 0.01 M melamine. The high catalytic activity of the synthesized catalyst in the oxygen reduction reaction is due to pyridine nitrogen atoms and Mn1.5Co1.5O4 spinel nanoparticles.

A Quantitative Chemical Method for Determining the Surface Concentration of Stone-Wales Defects for 1D and 2D Carbon Nanomaterials.

A quantitative method is proposed to determine Stone–Wales defects for 1D and 2D carbon nanostructures. The technique is based on the diene synthesis reaction (Diels–Alder reaction). The proposed method was used to determine Stone–Wales defects in the few-layer graphene (FLG) nanostructures synthesized by the self-propagating high-temperature synthesis (SHS) process in reduced graphene oxide (rGO) synthesized based on the method of Hammers and in the single-walled carbon nanotubes (SWCNT) TUBAL trademark, Russia. Our research has shown that the structure of FLG is free of Stone–Wales defects, while the surface concentration of Stone–Wales defects in TUBAL carbon nanotubes is 1.1 × 10−5 mol/m2 and 3.6 × 10−5 mol/m2 for rGO.

Enhanced thermal energy storage performance of hydrous salt phase change material via defective graphene

Structural modification of two-dimensional materials has a significant influence on performance. In this work, a novel preparation method is presented to get defective graphene and the as-obtained defective graphene shows great benefits for the thermal energy storage performance of phase change material (PCM). Based on the experimental results, we found the structure of few-layer graphene becomes weak at high temperatures (1200 °C) under the protection of N2, and then some micro-defects could be formated in the surface of graphene at a suitable thermal treatment schedule in air atmosphere. Owing to the unique nature of defective graphene, the PCM/defective graphene composite showed a higher thermal conductivity than barium hydroxide octahydrate (Ba(OH)2·8H2O) as the pure PCM. Scanning electron microscopy (SEM) and thermal cycling tests revealed that the defective graphene can be acted as the nucleating agent, which reduced the supercooling degree of Ba(OH)2·8H2O. Furthermore, thermal cycle stability tests showed the composite PCM had outstanding thermal cycling stability, and the defective graphene can also be acted as a kind of stabilizer. We showed the excellent application values of defective graphene in the PCM field for energy storage. This work is beneficial to the development of graphene and PCM composites.

Few-Layer Graphene Structures as a Promising Mycotoxin Sorbent

It has been experimentally established that samples of low-layer graphene, synthesized by carbonization of plant materials (lignin, cellulose, and spruce bark) under conditions of self-propagating high-temperature synthesis, are effective sorbents for mycotoxin T-2 under conditions simulating the environment in the gastrointestinal tract of mammals, and are capable of irreversibly sorb at least 94.6% of mycotoxin with a sorption capacity of 1 mg of mycotoxins per 1 g of sorbent. Key words: few-layer graphene, self-propagating high-temperature synthesis, specific surface area, mycotoxin sorption. Keywords: few-layer graphene, self-propagating high-temperature synthesis, specific surface, sorption of mycotoxins.

Microwave-Assisted Coal-Derived Few-Layer Graphene as an Anode Material for Lithium-Ion Batteries.

A few-layer graphene (FLG) composite material was synthesized using a rich reservoir and low-cost coal under the microwave-assisted catalytic graphitization process. X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy were used to evaluate the properties of the FLG sample. A well-developed microstructure and higher graphitization degree were achieved under microwave heating at 1300 °C using the S5% dual (Fe-Ni) catalyst for 20 min. In addition, the synthesized FLG sample encompassed the Raman spectrum 2D band at 2700 cm−1, which showed the existence of a few-layer graphene structure. The high-resolution TEM (transmission electron microscopy) image investigation of the S5% Fe-Ni sample confirmed that the fabricated FLG material consisted of two to seven graphitic layers, promoting the fast lithium-ion diffusion into the inner surface. The S5% Fe-Ni composite material delivered a high reversible capacity of 287.91 mAhg−1 at 0.1 C with a higher Coulombic efficiency of 99.9%. In contrast, the single catalyst of S10% Fe contained a reversible capacity of 260.13 mAhg−1 at 0.1 C with 97.96% Coulombic efficiency. Furthermore, the dual catalyst-loaded FLG sample demonstrated a high capacity—up to 95% of the initial reversible capacity retention—after 100 cycles. This study revealed the potential feasibility of producing FLG materials from bituminous coal used in a broad range as anode materials for lithium-ion batteries (LIBs).

A Simplified Method for Patterning Graphene on Dielectric Layers.

The large-scale formation of patterned, quasi-freestanding graphene structures supported on a dielectric has so far been limited by the need to transfer the graphene onto a suitable substrate and contamination from the associated processing steps. We report μm scale, few-layer graphene structures formed at moderate temperatures (600–700 °C) and supported directly on an interfacial dielectric formed by oxidizing Si layers at the graphene/substrate interface. We show that the thickness of this underlying dielectric support can be tailored further by an additional Si intercalation of the graphene prior to oxidation. This produces quasi-freestanding, patterned graphene on dielectric SiO2 with a tunable thickness on demand, thus facilitating a new pathway to integrated graphene microelectronics.

Structure of Coal-Derived Metal-Supported Few-Layer Graphene Composite Materials Synthesized Using a Microwave-Assisted Catalytic Graphitization Process.

Metal-supported few-layer graphene (FLG) was synthesized via microwave-assisted catalytic graphitization owing to the increasing demand for it and its wide applications. In this study, we quickly converted earth-abundant and low-cost bituminous coal to FLG over Fe catalysts at a temperature of 1300 °C. X-ray diffraction, Raman spectroscopy, transmission electron microscopy, and N2 adsorption–desorption experiments were performed to analyze the fabricated metal-supported FLG. The results indicated that the microwave-irradiation temperature at a set holding-time played a critical role in the synthesis of metal-supported FLG. The highest degree of graphitization and a well-developed pore structure were fabricated at 1300 °C using a S10% Fe catalyst for 20 min. High-resolution transmission electron microscopy analysis confirmed that the metal-supported FLG fabricated via microwave-assisted catalytic graphitization consisted of 3–6 layers of graphene nanosheets. In addition, the 2D band at 2700 cm−1 in the Raman spectrum of the fabricated metal-supported FLG samples were observed, which indicated the presence of few-layer graphene structure. Furthermore, a mechanism was proposed for the microwave-assisted catalytic graphitization of bituminous coal. Here, we developed a cost-effective and environmental friendly metal-supported FLG method using a coal-based carbonaceous material.