Graphene fluoride: a stable stoichiometric graphene derivative and its chemical conversion to graphene

Stoichoimetric graphene fluoride monolayers are obtained in a single step by the liquid-phase exfoliation of graphite fluoride with sulfolane. Comparative quantum-mechanical calculations reveal that graphene fluoride is the most thermodynamically stable of five studied hypothetical graphene derivatives; graphane, graphene fluoride, bromide, chloride, and iodide. The graphene fluoride is transformed into graphene via graphene iodide, a spontaneously decomposing intermediate. The calculated bandgaps of graphene halides vary from zero for graphene bromide to 3.1 eV for graphene fluoride. It is possible to design the electronic properties of such two-dimensional crystals.     

Centimeter-scale high-resolution metrology of entire CVD-grown graphene sheets

A high-throughput metrology method for measuring the thickness and uniformity of entire large-area chemical vapor deposition-grown graphene sheets on arbitrary substrates is demonstrated. This method utilizes the quenching of fluorescence by graphene via resonant energy transfer to increase the visibility of graphene on a glass substrate. Fluorescence quenching is visualized by spin-coating a solution of polymer mixed with fluorescent dye onto the graphene then viewing the sample under a fluorescence microscope. A large-area fluorescence montage image of the dyed graphene sample is collected and processed to identify the graphene and indicate the graphene layer thickness throughout the entire graphene sample. Using this metrology method, the effect of different transfer techniques on the quality of the graphene sheet is studied. It is shown that small-area characterization is insufficient to truly evaluate the effect of the transfer technique on the graphene sample. The results indicate that introducing a drop of acetone or liquid poly(methyl methacrylate) (PMMA) on top of the transfer PMMA layer before soaking the graphene sample in acetone improves the quality of the graphene dramatically over immediately soaking the graphene in acetone. This work introduces a new method for graphene quantification that can quickly and easily identify graphene layers in a large area on arbitrary substrates. This metrology technique is well suited for many industrial applications due to its repeatability and flexibility.     

石墨烯/氧化石墨烯-聚乳酸的制备与表征

通过优化Hummers法制备了氧化石墨烯,并用水合肼还原法制备了石墨烯,且对自制的石墨烯和氧化石墨烯进行了测试及分析;然后通过溶液插层法制得纳米级聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料,并对其分散性、热学性能以及力学性能进行了分析。对石墨烯和氧化石墨烯的表征结果说明,水合肼可以还原氧化石墨,所制备的石墨烯纯度较高。对聚乳酸/石墨烯和聚乳酸/氧化石墨烯复合材料的性能分析结果表明,在聚乳酸的结晶度、结晶速率和对聚乳酸的结晶成核上,石墨烯比氧化石墨烯具有更优异的表现,但在热稳定性能方面,氧化石墨烯比石墨烯优异;在力学性能方面,有增强和降低两种影响,添加少量氧化石墨烯时聚乳酸的力学性能降低,而含质量分数为0.5%的石墨烯复合材料在拉伸实验和冲击实验中的增强效果较为明显。     

掺杂和修饰的石墨烯对半胱氨酸吸附性能的密度泛函理论研究

使用密度泛函理论计算了掺杂或修饰Al或Mn原子的石墨烯对半胱氨酸的吸附性能。计算结果表明,掺杂或修饰Al或Mn原子后,Graphene与半胱氨酸之间结合稳定,具有较大的结合能。其中掺杂或修饰Mn原子的体系的吸附能整体高于掺杂或修饰Al原子的体系。石墨烯上修饰或掺杂Al或Mn原子,增加了石墨烯基底与半胱氨酸之间的电荷转移,特别是修饰方式显著改变了费米能级附近的性质,同时改变了Graphene的电导性质。Al或Mn原子修饰或者掺杂的Graphene除了增加对半胱氨酸吸附能力外,也是一种潜在的检测半胱氨酸的传感器材料,进而在生物领域得到更广泛的应用,比如用来检测富含半胱氨酸的金属硫蛋白。     

Laser‐Induced Direct Graphene Patterning and Simultaneous Transferring Method for Graphene Sensor Platform

General methods utilized in the fabrication of graphene devices involve graphene transferring and subsequent patterning of graphene via multiple wet‐chemical processes. In the present study, a laser‐induced pattern transfer (LIPT) method is proposed for the transferring and patterning of graphene in a single processing step. Via the direct graphene patterning and simultaneous transferring, the LIPT method greatly reduces the complexity of graphene fabrication while augmenting flexibility in graphene device design. Femtosecond laser ablation under ambient conditions is employed to transfer graphene/PMMA microscale patterns to arbitrary substrates, including a flexible film. Suspended cantilever structures are also demonstrated over a prefabricated trench structure via the single‐step method. The feasibility of this method for the fabrication of functional graphene devices is confirmed by measuring the electrical response of a graphene/PMMA device under laser illumination.     

Graphene growth on a Pt(111) substrate by surface segregation and precipitation

We report on the fabrication of a sizable graphene sheet on a carbon-doped Pt(111) substrate through surface segregation and precipitation. Scanning Auger electron spectroscopy (AES) reveals that the graphene covered more than 98% of the substrate surface. Our graphene consists of single-layer graphene across the substrate with fractions of several micrometer wide bi- and tri-layer graphene islands. We also show that the number of graphene layers can be precisely determined by analyzing AES data. While Raman spectroscopy is usually used to study graphene on SiO?, we show that AES is a powerful tool to characterize graphene grown on metal substrates.     

Finite element analysis of the effect of interlayer on interfacial stress transfer in layered graphene nanocomposites

Understanding the roles of interlayers in reinforcement efficiencies by layered graphene is very important in order to produce strong and light graphene based nanocomposites. The present paper uses the finite element method to evaluate the interfacial strain transfers and reinforcement efficiencies in layered graphene-polymer composites. Results indicate that the presence of compliant interlayers in layered graphene plays significant roles in the transfers of strain/stress from matrix to graphene and subsequently the reinforcement effectiveness of layered graphene. In general, the magnitude of shear strain transferred onto the rigid graphene decreases as the thickness of the interlayer increases. This trend becomes insignificant as the graphene becomes sufficiently large (s>25,000). The shear strain at the interface of graphene-matrix is also greatly influenced by the interlayer modulus. A stiffer interlayer would result in a higher shear strain transferred on the graphene. The performance of the interlayers is further affected by the property of the composite and the architecture of the layered graphene stack. If a composite contains more graphene phase, the efficiency of reinforcement by a layered graphene becomes improved. If a graphene stack contains more interlayers, the effectiveness of reinforcement at the edges of the graphene becomes negatively affected.     

Copper‐Vapor‐Assisted Growth and Defect‐Healing of Graphene on Copper Surfaces

Although there is significant progress in the chemical vapor deposition (CVD) of graphene on Cu surfaces, the industrial application of graphene is not realized yet. One of the most critical obstacles that limit the commercialization of graphene is that CVD graphene contains too many vacancies or sp³‐type defects. Therefore, further investigation of the growth mechanism is still required to control the defects of graphene. During the growth of graphene, sublimation of the Cu catalyst to produce Cu vapor occurs inevitably because the process temperature is close to the melting point of Cu. However, to date few studies have investigated the effects of Cu vapor on graphene growth. In this study, how the Cu vapor produced by sublimation affects the chemical vapor deposition of graphene on Cu surfaces is investigated. It is found that the presence of Cu vapor enlarges the graphene grains and enhances the efficiency of the defect‐healing of graphene by CH₄. It is elucidated that these effects are due to the removal by Cu vapor of carbon adatoms from the Cu surface and oxygen‐functionalized carbons from graphene. Finally, these insights are used to develop a method for the synthesis of uniform and high‐quality graphene.     

石墨烯均匀分散问题研究进展

具有优良性能的石墨烯常被作为增强体加入基体材料中以改进其性能。研究发现,石墨烯增强复合材料的性质在很大程度上取决于石墨烯在基体中的均匀分散程度。而石墨烯增强体在基体中的均匀分散问题一直是研究的难点,这就限制了石墨烯增强复合材料性能的提升及其开发应用。总结了石墨烯在基体中均匀分散方法的研究进展,并展望了其研究方向及发展趋势。     

The mechanics of graphene nanocomposites: A review

The preparation and characterisation of the different forms of graphene are reviewed first of all. The different techniques that have been employed to prepare graphene such as mechanical and solution exfoliation, and chemical vapour deposition are discussed briefly. Methods of production of graphene oxide by the chemical oxidation of graphite are then described. The structure and mechanical properties of both graphene and graphene oxide are reviewed and it is shown that although graphene possesses superior mechanical properties, they both have high levels of stiffness and strength. It is demonstrated how Raman spectroscopy can be used to characterise the different forms of graphene and also follow the deformation of exfoliated graphene, with different numbers of layers, in model composite systems. It is shown that continuum mechanics can be employed to analyse the behaviour of these model composites and used to predict the minimum flake dimensions and optimum number of layers for good reinforcement. The preparation of bulk nanocomposites based upon graphene and graphene oxide is described finally and the properties of these materials reviewed. It is shown that good reinforcement is only found at relatively low levels of graphene loading and that, due to difficulties with obtaining good dispersions, challenges still remain in obtaining good mechanical properties for high volume fractions of reinforcement.     

Peptide-functionalized colloidal graphene via interdigited bilayer coating and fluorescence turn-on detection of enzyme

Synthesis of colloidal functional graphene is challenging because graphene is water-insoluble and its relatively inert surface made the functionalization a difficult task. Here we report interdigited bilayer type coating that provide both colloidal stability and functionalization option for graphene. Colloidal graphene oxide is first converted into interdigited bilayer coated graphene oxide and next they are transformed into colloidal graphene by hydrazine reduction. These coated graphenes can be further transformed into colloidal functional graphene using covalent conjugation chemistry. Functional graphene has been synthesized for optical detection of enzyme where a fluorescent dye is covalently linked through a peptide so that the dye fluorescence is quenched by graphene but switches on once enzymes cleave the peptide bond. The interdigited bilayer coating reported here is unique as it provides coating thickness <3 nm, offering optically responsive graphene-fluorophore substrate with high colloidal stability.     

The Enhancing Ionic Current Rectification in Single Graphene Conical Nanochannel

Enhanced ionic current rectification induced by the concentration gradient has been reported recently owing to the development of asymmetric nanofluidic system, in particular graphene nanochannels. However, the reasons for the enhancement of ionic current rectification of graphene conical nanochannels are not well understood. Herein, a finite element model of a single graphene conical nanochannel is established to explore the fundamental mechanisms of the ionic current rectification. The model proves that the highest cation concentration caused by graphene is almost 42 times higher than the bulk ion concentration. Compared with the nongraphene model, the graphene with higher surface charge density can absorb more cation in the tip (the small pore) of graphene conical nanochannel. Besides, the nanoscale corner consisting of graphene membrane and the wall of the conical nanochannel is a semihermetic reservoir for cation accumulation. It demonstrates that the enhancement of ionic current rectification is mainly ascribed to the unique structure of the graphene nanochannel and the graphene membrane with a high surface charge density. This work provides a new mechanism explanation about the influence of graphene in ionic current rectification.     

Polymeric Graphene Bulk Materials with a 3D Cross‐Linked Monolithic Graphene Network

Although many great potential applications are proposed for graphene, till now none are yet realized as a stellar application. The most challenging issue for such practical applications is to figure out how to prepare graphene bulk materials while maintaining the unique two‐dimensional (2D) structure and the many excellent properties of graphene sheets. Herein, such polymeric graphene bulk materials containing three‐dimensional (3D) cross‐linked networks with graphene sheets as the building unit are reviewed. The theoretical research on various proposed structures of graphene bulk materials is summarized first. Then, the synthesis or fabrication of these graphene materials is described, which comprises mainly two approaches: chemical vapor deposition and cross‐linking using graphene oxide directly. Finally, some exotic and exciting potential applications of these graphene bulk materials are presented.     

3D打印石墨烯制备技术及其在储能领域的应用研究进展

石墨烯优异的力学和物理性能使其成为理想的储能材料。因结构精确可控,易实现规模化制备,3D打印石墨烯材料有望在储能领域得到广泛应用。本文全面综述了3D打印石墨烯制备技术及其在储能领域的应用研究进展。石墨烯墨水的黏度和可打印性是实现石墨烯3D打印的制约因素。实现工艺简单、浓度可控、无黏结剂石墨烯墨水的规模化打印将成为3D打印石墨烯制备技术未来的研究热点。石墨烯超级电容器、锂硫电池、锂离子电池等储能元件一体化打印成型是3D打印石墨烯在储能领域应用的发展方向。     

Hydrophilicity of Graphene in Water through Transparency to Polar and Dispersive Interactions

Establishing contact angles on graphene‐on‐water has been a long‐standing challenge as droplet deposition causes free‐floating graphene to rupture. The current work presents ice and hydrogels as substrates mimicking water while offering a stable support for graphene. The lowest water contact angles on graphene ever measured, namely on graphene‐on‐ice and graphene‐on‐hydrogel, are recorded. The contact angle measurements of liquids with a range of polarities allow the transparency of graphene toward polar and dispersive interactions to be quantified demonstrating that graphene in water is hydrophilic. These findings are anticipated to shed light on the inconsistencies reported so far on the wetting properties of graphene, and most particularly on their implications toward rationalizing how molecules interact with graphene in water.     

Hysteresis I–V nature of mechanically exfoliated graphene FET

Graphene is an attractive material for device applications due to its excellent electrical and mechanical properties. The mechanical exfoliation is an attractive method to fabricate graphene devices using mono and multilayer graphene flakes. As the graphene is very sensitive to atmosphere the occurrence of hysteresis and p-doping is common. This paper reports electrical characterization and hysteresis effect of graphene field effect transistor (FET) fabricated using mechanically exfoliated graphene flakes. Raman spectra and atomic force microscopy techniques have been used to examine the quality and thickness of the exfoliated graphene. This fabricated graphene FET has shown hysteresis nature with p-type doping. The possible reason for the observed hysteresis and p-doping has been explained.     

石墨烯涂层对直升机旋翼防/除冰组件传热的影响

采用水性和油性石墨烯涂层对复合材料防/除冰组件进行测温及防/除冰实验.针对直升机旋翼对结冰的敏感等特点,提出了旋翼防/除冰组件包铁表面涂覆石墨烯涂层改性传热性能的方法,从而提高旋翼防/除冰组件除冰效率.为验证石墨烯涂层对防/除冰组件传热效率具有显著的提高作用,采用搭建的除冰实验平台并对涂覆的旋翼防/除冰组件进行传热实验...     

Layer-dependent fluorination and doping of graphene via plasma treatment

In this work, the fluorination of n-layer graphene is systematically investigated using CHF? and CF? plasma treatments. The G and 2D Raman peaks of graphene show upshifts after each of the two kinds of plasma treatment, indicating p-doping to the graphene. Meanwhile, D, D' and D + G peaks can be clearly observed for monolayer graphene, whereas these peaks are weaker for thicker n-layer graphene (n ≥ 2) at the same experimental conditions. The upshifts of the G and 2D peaks and the ratio of I(2D)/I(G) for CF? plasma treated graphene are larger than those of CHF? plasma treated graphene. The ratio of I(D)/I(G) of the Raman spectra is notably small in CF? plasma treated graphene. These facts indicate that CF? plasma treatment introduces more p-doping and fewer defects for graphene. Moreover, the fluorination of monolayer graphene by CF? plasma treatment is reversible through thermal annealing while that by CHF? plasma treatment is irreversible. These studies explore the information on the surface properties of graphene and provide an optimal method of fluorinating graphene through plasma techniques.     

Defects in Graphene:Generation,Healing,and Their Effects on the Properties of Graphene:A Review

Graphene has attracted immense investigation since its discovery.Lattice imperfections are introduced into graphene unavoidably during graphene growth or processing.These structural defects are known to significantly affect electronic and chemical properties of graphene.A comprehensive understanding of graphene defect is thus of critical importance.Here we review the major progresses made in defectrelated engineering of graphene.Firstly,we give a brief introduction on the types of defects in graphene.Secondly,the generation and healing of the graphene defects are summarized.Then,the effects of defects on the chemical,electronic,magnetic,and mechanical properties of graphene are discussed.Finally,we address the associated challenges and prospects on the future study of defects in graphene and other nanocarbon materials.     

Evaluation of Constants of Electron–Phonon Coupling between Gas Molecules and Graphene

The adsorption of CO, NO, NO₂, Н₂О, and NH₃ molecules on ideal graphene and graphene doped with aluminum is analyzed using simple models. The constants of electron–phonon coupling are evaluated with the Lennard-Jones 6–12 potential for ideal graphene and the 2–4 potential for doped graphene. It is demonstrated that the dimensionless electron–phonon-coupling constant for ideal graphene is ζ ? 1, while ζ ~ 1 corresponds to graphene doped with aluminum. Ways to use both types of graphene as a resistive gas sensor are discussed.