Graphene-based composite materials

Graphene sheets--one-atom-thick two-dimensional layers of sp2-bonded carbon--are predicted to have a range of unusual properties. Their thermal conductivity and mechanical stiffness may rival the remarkable in-plane values for graphite (approximately 3,000 W m(-1) K(-1) and 1,060 GPa, respectively); their fracture strength should be comparable to that of carbon nanotubes for similar types of defects; and recent studies have shown that individual graphene sheets have extraordinary electronic transport properties. One possible route to harnessing these properties for applications would be to incorporate graphene sheets in a composite material. The manufacturing of such composites requires not only that graphene sheets be produced on a sufficient scale but that they also be incorporated, and homogeneously distributed, into various matrices. Graphite, inexpensive and available in large quantity, unfortunately does not readily exfoliate to yield individual graphene sheets. Here we present a general approach for the preparation of graphene-polymer composites via complete exfoliation of graphite and molecular-level dispersion of individual, chemically modified graphene sheets within polymer hosts. A polystyrene-graphene composite formed by this route exhibits a percolation threshold of approximately 0.1 volume per cent for room-temperature electrical conductivity, the lowest reported value for any carbon-based composite except for those involving carbon nanotubes; at only 1 volume per cent, this composite has a conductivity of approximately 0.1 S m(-1), sufficient for many electrical applications. Our bottom-up chemical approach of tuning the graphene sheet properties provides a path to a broad new class of graphene-based materials and their use in a variety of applications.     

膨胀石墨制备石墨烯的可行性研究

本文以鳞片石墨为原料,采用化学法经氧化酸化插层、水洗、干燥、高温膨胀过程制备膨胀石墨,再采用超声剥离法制备出少层数石墨烯片;并对制备膨胀石墨时的相关影响因素及插层机理作了初步探讨。结果表明：对不同工艺条件下制备的膨胀石墨,其层间距变化非常微小,但是其衍射强度却有明显下降;不管是细鳞片石墨还是大鳞片石墨制备成膨胀石墨,再次进行酸化处理后,加入插层剂后经过超声剥离就可以得到少层数的片状石墨烯。膨胀石墨制备石墨烯,不失为一种能高效、可行地方法。     

氧化石墨烯制备及其结构表征

本文以不同类型的石墨为原料,采用密闭氧化法制备了氧化石墨,并通过超声剥离得到氧化石墨烯,利用氨肼还原法将氧化石墨烯还原得到石墨烯。讨论了不同类型石墨原料对所制备氧化石墨烯微观形貌的影响,并且利用高分辨率扫描电子显微镜（SEM）和X射线衍射仪（XRD）对所制备的氧化石墨烯和石墨烯进行了结构表征,结果表明,在以不同类型石墨为原料所制备的氧化石墨烯中,50目天然鳞片制备的氧化石墨烯的微观形貌最好,呈波浪褶皱状。     

非气态原料制备垂直石墨烯

垂直石墨烯是由石墨烯片垂直于基底生长而形成的一种新型3维碳材料结构,由于其独特的生长取向,可以有效减轻石墨烯层与层之间的堆叠,使石墨烯充分发挥其优异的特性.等离子体增强化学气相沉积技术作为合成垂直石墨烯的主要手段常需引入化工合成气为碳源,原料灵活性低.该文综述了非气态碳源用于垂直石墨烯的制备,介绍了所合成的垂直石墨烯在多种领域中的应用,并讨论了其生长机理.     

氧化石墨烯/磷钼酸复合物的制备及其液晶性研究

由Hummer's方法制备的氧化石墨烯负载磷钼酸,制备了氧化石墨烯/磷钼酸复合物,其水溶液展现出较好的溶致液晶性.透射电镜分析表明,纯氧化石墨烯呈现出透明的褶皱薄纱状形貌,氧化石墨烯/磷钼酸复合物中磷钼酸微粒均匀分布在氧化石墨烯片层中.红外光谱说明氧化石墨烯和磷钼酸之间存在较强的相互作用.所得氧化石墨烯/磷钼酸复合物在偏振光下具有明显的溶致液晶性.相比相同条件下的纯氧化石墨烯,磷钼酸的引入没有破坏氧化石墨液晶体系的介晶结构,复合物表现出更明显的明暗交织的液晶织构,旨在将多酸嵌入氧化石墨液晶体系中并为多酸和氧化石墨烯的应用开拓一个新思路.     

Recent advances in graphene based photoresponsive materials

Recent scientific interests reveal that graphene, with its flexibility, chemical stability, thermal conductivity,unique electronic band structure and optical transmittance, has emerged as the novel supporting material for nanocomposites for various applications. Research interests have flourished regarding decoration of conventional materials with modified graphene for achieving better optical properties. More concern is given for achieving improved photoresponse with graphene as the supporting material. The giant electron mobility and transparency of graphene enables the photo-induced electron transfer in the hybrid material, resulting in enhanced behaviour. Graphene oxide is able to effectively convert near infrared energy into heat, potentially acting as a photo-thermal switch. They act as potential candidates for photo-catalysts, sensors, photo-current switching,photo-detectors and other optical applications. In this review, we summarized the recent developments on fabrication and properties of graphene based photoresponsive materials.     

石墨烯/聚合物纳米复合材料研究进展

 石墨烯是由单层碳原子通过共价键结合形成的二维片层状结构,是一种新型碳类纳米材料,具有优异的力学、电学和热学等性能,被认为是一种非常有前景的材料,近年来广泛用于改性各种聚合物。本文回顾了石墨烯/聚合物纳米复合材料的制备方法、性能和应用现状;综述了石墨烯/聚合物纳米复合材料的强度、刚度、韧性、电学和热学等性能的研究进展。主要内容包括石墨烯改性聚合物常见的3种制备方法(溶液共混、熔融共混和原位聚合)及其对石墨烯在聚合物基体中分散性的影响,石墨烯/聚合物纳米复合材料力学性能变化规律与作用机理,石墨烯微观结构等因素对材料热学性能以及导电阈值的影响等;讨论了石墨烯/聚合物纳米复合材料的潜在应用和面临的挑战和机遇,并展望了其低成本产业化的发展前景。     

化学法制备石墨烯对环氧树脂导电性能的影响

通过化学氧化热解膨胀还原法制备了石墨烯,并对石墨烯的化学结构及微观形貌进行表征.将自制的石墨烯以及商业级的碳纳米管、富勒烯、石墨分别作为纳米导电填料加入到环氧树脂中,考察不同碳纳米材料对环氧树脂导电性能的影响.结果表明:所制备的石墨烯是不同于氧化石墨烯和热解膨胀石墨薄层的单层或少数层的二维材料;当石墨烯体积分数为0.25%时,复合材料的电导率发生渗流突变,而当体积分数增大到0.50%时,其电导率为2.02×10-7 S·m-1,导电性能得到显著增强.     

Direct evidence for atomic defects in graphene layers

Atomic-scale defects in graphene layers alter the physical and chemical properties of carbon nanostructures. Theoretical predictions have recently shown that energetic particles such as electrons and ions can induce polymorphic atomic defects in graphene layers as a result of knock-on atom displacements. However, the number of experimental reports on these defects is limited. The graphite network in single-walled carbon nanotubes has been visualized by transmission electron microscopy (TEM) and their chiral indices have been determined. But the methods used require a long image acquisition time and intensive numerical treatments after observations to find an 'average' image, which prevents the accurate detection and investigation of defect structures. Here we report observations in situ of defect formation in single graphene layers by high-resolution TEM. The observed structures are expected to be of use when engineering the properties of carbon nanostructures for specific device applications.     

Unique synthesis of graphene-based materials for clean energy and biological sensing applications

Graphene has unique physical properties,and a variety of proof-of-concept devices based on graphene have been demonstated.A prerequisite for the application of graphene is its production in a controlled manner because the number of graphene layers and the defects in these layers significantly influence transport properties.In this paper,we briefly review our recent work on the controlled synthesis of graphene and graphene-based composites,the development of methods to characterize graphene layers,and the use of graphene in clean energy applications and for rapid DNA sequencing.For example,we have used Auger electron spectroscopy to characterize the number and structure of graphene layers,produced single-layer graphene over a whole Ni film substrate,synthesized well-dispersed reduced graphene oxide that was uniformly grafted with unique gold nanodots,and fabricated graphene nanoscrolls.We have also explored applications of graphene in organic solar cells and direct,ultrafast DNA sequencing.Finally,we address the challenges that graphene still face in its synthesis and clean energy and biological sensing applications.     

纳米石墨片的制备与表征

以74μm天然鳞片石墨为原料,采用Hummers法制备氧化石墨。微波加热膨胀处理的氧化石墨,经超声振荡,氧化石墨片层剥离。通过水热法,在还原剂硼氢化钠的作用下得到纳米石墨片分散液。利用透射电子显微镜(TEM)、拉曼光谱和X射线衍射仪(XRD)对所制备的纳米石墨片进行表征。实验结果表明:该纳米石墨片呈现透明的薄片状,片层边缘存在褶皱形貌,片层间距为0.39 nm,层数约为12层。氧化石墨的剥离程度和还原程度均较高,其晶体结构中的缺陷得到了修复。     

Growth of nanowire superlattice structures for nanoscale photonics and electronics

The assembly of semiconductor nanowires and carbon nanotubes into nanoscale devices and circuits could enable diverse applications in nanoelectronics and photonics. Individual semiconducting nanowires have already been configured as field-effect transistors, photodetectors and bio/chemical sensors. More sophisticated light-emitting diodes (LEDs) and complementary and diode logic devices have been realized using both n- and p-type semiconducting nanowires or nanotubes. The n- and p-type materials have been incorporated in these latter devices either by crossing p- and n-type nanowires or by lithographically defining distinct p- and n-type regions in nanotubes, although both strategies limit device complexity. In the planar semiconductor industry, intricate n- and p-type and more generally compositionally modulated (that is, superlattice) structures are used to enable versatile electronic and photonic functions. Here we demonstrate the synthesis of semiconductor nanowire superlattices from group III-V and group IV materials. (The superlattices are created within the nanowires by repeated modulation of the vapour-phase semiconductor reactants during growth of the wires.) Compositionally modulated superlattices consisting of 2 to 21 layers of GaAs and GaP have been prepared. Furthermore, n-Si/p-Si and n-InP/p-InP modulation doped nanowires have been synthesized. Single-nanowire photoluminescence, electrical transport and electroluminescence measurements show the unique photonic and electronic properties of these nanowire superlattices, and suggest potential applications ranging from nano-barcodes to polarized nanoscale LEDs.     

Growth of graphene from solid carbon sources

Monolayer graphene was first obtained as a transferable material in 2004 and has stimulated intense activity among physicists, chemists and material scientists. Much research has been focused on developing routes for obtaining large sheets of monolayer or bilayer graphene. This has been recently achieved by chemical vapour deposition (CVD) of CH(4) or C(2)H(2) gases on copper or nickel substrates. But CVD is limited to the use of gaseous raw materials, making it difficult to apply the technology to a wider variety of potential feedstocks. Here we demonstrate that large area, high-quality graphene with controllable thickness can be grown from different solid carbon sources-such as polymer films or small molecules-deposited on a metal catalyst substrate at temperatures as low as 800?°C. Both pristine graphene and doped graphene were grown with this one-step process using the same experimental set-up.     

石墨烯专利技术国际研发态势分析

石墨烯是物理学、化学、材料科学等领域近年来的研究热点之一。因其集优异的电学、力学、光学、化学和热学等性能于一身,石墨烯已经成为一个备受关注、竞争非常激烈的新兴技术领域,近年来全球相关专利申请数量持续快速增长。该文基于DII数据库,利用TDA、Aureka等分析工具,对全球石墨烯相关专利进行了分析,揭示了全球石墨烯相关专利技术的研发和竞争态势。     

石墨烯吸附材料的制备与应用研究进展

石墨烯具有独特的结构、优异的性能,在诸多领域有广泛的应用.石墨烯层的原子均为表面原子,其表面积非常大,是天然的吸附材料.其易于制备、成本低廉等优势使得石墨烯吸附材料成为水处理研究中的热点.石墨烯及其复合材料已经在重金属、染料、杀虫剂、抗生素、石油等污染物的治理方面得到应用.综述了石墨烯吸附材料的制备方法以及其在污水处理方面的应用.分析了污染物在石墨烯吸附材料上的吸附行为,并讨论了石墨烯与污染物的相互作用.着重关注官能团对石墨烯吸附材料性能的影响,从化学视角提出了设计高效石墨烯吸附剂的思路.     

功能化石墨烯在生物医学研究中的应用

石墨烯以其独特的二维结构和优良的电学、光学、热学和机械性能,自2004年来倍受研究人员的高度关注,迅速成为材料、化学、物理和医学领域的热点研究课题.在简要介绍石墨烯基本情况的基础上,重点阐述了石墨烯在生物传感器、靶向给药中的应用.     

Rapid Preparation and Characterization of Graphene/Carbon Nanotube Hybrid Materials

In this work,a stable,large area sandwich structure of material consisted of carboxylic multiwall carbon nanotubes(c-MWCNTs) and polymer-modified graphene(G) via a self-assembly process was prepared.Positively charged nanomaterial of polymer-modified graphene were prepared via in situ reduction of graphite oxide in the presence of poly(diallyldimethylammonium chloride)(PDDA).Then c-MWCNTs were added into the water-soluble PDDA-modified graphene to form hybrid carbon material via sequential electrostatic self-assembly.Transmission electron microscope(TEM) and scanning electron microscopy(SEM) were used to characterize those hybrid materials.From the figures we can learn that this method has successfully led to the fabrication of a reasonably uniform film with well-interconnected carbon-based hybrid materials.     

Preparation of three-dimensional graphene foam for high performance supercapacitors

Supercapacitor is a new type of energy-storage device, and has been attracted widely attentions. As a two dimensional (2D) nanomaterials, graphene is considered to be a promising material of supercapacitor because of its excellent properties involving high electrical conductivity and large surface area. In this paper, the large-scale graphene is successfully fabricated via environmental-friendly electrochemical exfoliation of graphite, and then, the three dimensional (3D) graphene foam is prepared by using nickel foam as template and FeCl3/HCl solution as etchant. Compared with the regular 2D graphene paper, the 3D graphene foam electrode shows better electrochemical performance, and exhibits the largest specific capacitance of approximately 128 F/g at the current density of 1 A/g in 6 M KOH electrolyte. It is expected that the 3D graphene foam will have a potential application in the supercapacitors.     

Heteroatom-doped graphene for electrochemical energy storage

The increasing energy consumption and envi- ronmental concerns due to burning fossil fuel are key drivers for the development of effective energy storage systems based on innovative materials. Among these materials, graphene has emerged as one of the most promising due to its chemical, electrical, and mechanical properties. Heteroatom doping has been proven as an effective way to tailor the properties of graphene and render its potential use for energy storage devices. In this view, we review the recent developments in the synthesis and applications of heteroatom-doped graphene in supercapacitors and lithium ion batteries.     

膨胀石墨氧化制备石墨烯

在氧化还原法制备石墨烯的工艺中,氧化石墨的制备尤为重要。以大鳞片石墨制备的膨胀石墨为原料,采用改进的Hummers法制备氧化程度高、可剥离度高的氧化石墨稀,研究中温氧化时间、氧化剂用量及高温反应对氧化石墨烯结构、形貌及氧化程度的影响,对样品进行扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)表征。结果表明:硫酸与膨胀石墨用量比为75 mL∶1 g,高锰酸钾与石墨用量比为4 g∶1 g,35℃水浴反应24 h,制备得到氧化程度高的大片氧化石墨烯。该方法工艺简单、反应温度低,无须进行高温反应,可以解决大鳞片石墨制备氧化石墨烯难度大,氧化效率低的问题。