Graphene Sheet Orientation of Parent Material Exhibits Dramatic Influence on Graphene Properties

The production of graphene from various sources has garnered much attention in recent years with the development of methods that range from “bottom‐up” to “top‐down” approaches. The top‐down approach often requires thermal treatment to obtain a few‐layered and lowly oxygenated graphene sheets. Herein, we demonstrate the production of graphene through oxidation and thermal‐reduction/exfoliation of two sources of differently orientated graphene sheets: multiwalled carbon nanotubes (MWCNTs) and stacked graphene nanofibers (SGNFs). These two carbon‐nanofiber‐like materials have similar axial (length: 5–9 μm) and lateral dimensions (diameter: about 100 nm). We demonstrate that, whereas SGNFs exfoliate along the lateral plane between adjacent graphene sheets, carbon nanotubes exfoliate along its longitudinal axis and leads to opening of the carbon nanotubes owing to the built‐in strain. Subsequent thermal exfoliation leads to graphene materials that have, despite the fact that their parent materials exhibited similar dimensions, dramatically different proportions and, consequently, materials properties. Graphene that was prepared from MWCNTs exhibited dimensions of about 5000×300 nm, whereas graphene that was prepared from SGNFs exhibited sheets with dimensions of about 50×50 nm. The density of defects and oxygen‐containing groups on these materials are dramatically different, as are the electrochemical properties. We performed morphological, structural, and electrochemical characterization based on TEM, SEM, high‐resolution X‐ray photoelectron spectroscopy, Raman spectroscopy, and cyclic voltammetry (CV) analysis on the stepwise conversion of the target source into the exfoliated graphene. Morphological and structural characterization indicated the successful chemical and thermal treatment of the materials. Our findings have shown that the orientation of the graphene sheets in starting materials has a dramatic influence on their chemical, material, and electrochemical properties.     

A General Strategy Towards Encapsulation of Nanoparticles in Sandwiched Graphene Sheets and the Synergic Effect on Energy Storage

A novel and universal approach towards the unique encapsulation of nanoparticles in the sandwiched graphene sheets is presented here. In the method, a low‐cost, sustainable and environmentally friendly carbon source, glucose, is firstly applied to yield the high‐quality, uniform and coupled graphene sheets in a large scale, and the pre‐fabricated hydrated nanosheets act as the sacrificial templates to generate the enveloped metallic nanoparticles. After controllable oxidation or removal of the encapsulated nanoparticles, sandwiched nanocomposite with oxidizes nanoparticles encapsulated in graphene sheets or pure phase of sandwich‐like and coupled graphene sheets would be achieved. Moreover, the synergic effect on energy storage via Li‐ion batteries is solidly verified in the Co₃O₄@graphene nanocomposite. More importantly, the unique structure of the nanoparticles‐encapsulated sandwiched graphene sheets will definitely result in additional applications, such as biosensors, supercapacitors and specific catalyses. These results have enriched the family of graphene‐based materials and recognized some new graphene derivatives, which will be considerably meaningful in chemistry and materials sciences.     

An efficient way to functionalize graphene sheets with presynthesized polymer via ATNRC chemistry

Graphene nanosheets offer intriguing electronic, thermal and mechanical properties and are expected to find a variety of applications in high‐performance nanocomposite materials. The great challenge of exfoliating and dispersing pristine graphite or graphene sheets in various solvents or matrices can be achieved by facilely and properly chemical functionalization of the carbon nanosheets. Here we reported an efficient way to functionalize graphene sheets with presynthesized polymer via a combination of atom transfer nitroxide radical coupling chemistry with the grafting‐onto strategy, which enable us to functionalize graphene sheets with well‐defined polymer synthesized via living radical polymerization. A radical scavenger species, 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO), was firstly anchored onto ? COOH groups on graphene oxide (GO) to afford TEMPO‐functionalized graphene sheets (GS‐TEMPO), meanwhile, the GO sheets were thermally reduced. Next, GS‐TEMPO reacted with Br‐terminated well‐defined poly(N‐isopropylacrylamide) (PNIPAM) homopolymer, which was presynthesized by SET‐LRP, in the presence of CuBr/N,N,N′,N′,N″‐pentamethyldiethylenetriamine to form PNIPAM‐graphene sheets (GS‐PNIPAM) nanocomposite in which the polymers were covalently linked onto the graphene via the alkoxyamine conjunction points. The PNIPAM‐modified graphene sheets are easily dispersible in organic solvents and water, and a temperature‐induced phase transition was founded in the water suspension of GS‐PNIPAM. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Phosphorus and Halogen Co‐Doped Graphene Materials and their Electrochemistry

Doping of graphene materials with heteroatoms is important as it can change their electronic and electrochemical properties. Here, graphene is co‐doped with n‐type dopants such as phosphorus and halogen (Cl, Br, I). Phosphorus and halogen are introduced through the treatment of graphene oxide with PX₃ gas (PCl₃, PBr₃, and PI₃). Graphene oxides are prepared through chlorate and permanganate routes. Detailed chemical and structural characterization demonstrates that the graphene sheets are covered homogeneously by phosphorus and halogen atoms. It is found that the amount of phosphorus and halogen introduced depends on the graphene oxide preparation method. The electrocatalytic effect of the resulting co‐doped materials is demonstrated for industrially relevant electrochemical reactions such as the hydrogen evolution and oxygen reduction reactions.     

Hybrid Hydrogels of Porous Graphene and Nickel Hydroxide as Advanced Supercapacitor Materials

Graphene‐based hydrogels can be used as supercapacitor electrodes because of their excellent conductivity, their large surface area and their high compatibility with electrolytes. Nevertheless, the large aspect ratio of graphene sheets limits the kinetics of processes occurring in the electrode of supercapacitors. In this study, we have introduced in‐plane and out‐of‐plane pores into a graphene–nickel hydroxide (Ni(OH)₂) hybrid hydrogel, which facilitates charge and ion transport in the electrode. Due to its optimised chemistry and architecture, the hybrid electrode demonstrates excellent electrochemical properties with a combination of high charge storage capacitance, fast rate capability and stable cycling performance. Remarkably, the Ni(OH)₂ in the hybrid contributes a capacitance as high as 3138.5 F g^?1, which is comparable to its theoretical capacitance, suggesting that such structure facilitates effectively charge‐transfer reactions in electrodes. This work provides a facile pathway for tailoring the porosity of graphene‐based materials for improved performances. Moreover, this work has also furthered our understanding in the effect of pore and hydrogel structures on the electrochemical properties of materials.     

Recent advances in the use of graphene-family nanoadsorbents for removal of toxic pollutants from wastewater

Adsorption technology is widely considered as the most promising and robust method of purifying water at low cost and with high-efficiency. Carbon-based materials have been extensively explored for adsorption applications because of their good chemical stability, structural diversity, low density, and suitability for large scale production. Graphene – a single atomic layer of graphite – is the newest member in the family of carbon allotropes and has emerged as the “celeb” material of the 21st century. Since its discovery in 2004 by Novoselov, Geim and co-workers, graphene has attracted increased attention in a wide range of applications due to its unprecedented electrical, mechanical, thermal, optical and transport properties. Graphene's infinitely high surface-to-volume ratio has resulted in a large number of investigations to study its application as a potential adsorbent for water purification. More recently, other graphene related materials such as graphene oxide, reduced graphene oxide, and few-layered graphene oxide sheets, as well as nanocomposites of graphene materials have also emerged as a promising group of adsorbent for the removal of various environmental pollutants from waste effluents. In this review article, we present a synthesis of the current knowledge available on this broad and versatile family of graphene nanomaterials for removal of dyes, potentially toxic elements, phenolic compounds and other organic chemicals from aquatic systems. The challenges involved in the development of these novel nanoadsorbents for decontamination of wastewaters have also been examined to help identify future directions for this emerging field to continue to grow.     

石墨烯气凝胶的可控组装

石墨烯气凝胶一般是由石墨烯片层经过湿法化学组装或气相化学生长获得的一种具有连通多孔网络结构的石墨烯三维宏观体材料,表现出极高的比表面积、良好的导电性以及优异的机械性能等,在电化学储能、吸附、催化以及传感等领域有着极为重要的应用。本文从石墨烯气凝胶的结构设计与组装策略出发,综述了近年来石墨烯纳米结构单元在石墨烯气凝胶材料（氧化石墨烯、还原氧化石墨烯、化学气相沉积（CVD）石墨烯、以及复合气凝胶等）中的组装行为,并对石墨烯气凝胶目前的现状及今后发展方向做了简要评述。     

基于石墨烯基材料的非金属液相催化反应

非金属碳基催化剂因其具有合成简单、结构稳定、比表面积大、可调控性强等特点受到了研究者的关注,已成为最活跃的研究领域之一。以二维、单原子层、六方结构的碳为基础的石墨烯和其高度氧化形态——氧化石墨烯是一类新兴的碳基材料。这类材料在催化领域的应用在近五年内才刚刚兴起。此类材料可用于烃类转化、有机化学合成、能源转化等多种催化反应,本文主要综述了采用化学氧化还原法制备的石墨烯和氧化石墨材料为催化剂的各类催化反应的最新研究进展。     

Modulating Aβ33–42 Peptide Assembly by Graphene Oxide

Graphene oxide (GO) is utilized as the modulator to tune the formation and development of amyloid fibrils (Aβ_33–42). Atomic force microscopy temporal evolution measurements reveal that the initial binding between the peptide monomer and the large available surface of the GO sheets can redirect the assembly pathway of amyloid beta. The results support the possibility to develop graphene‐based materials to inhibit amyloidosis.     

Green and facile microwave-assisted synthesis of TiO2/graphene nanocomposite and their photocatalytic activity for methylene blue degradation

TiO₂ (P25)/graphene nanocomposite photocatalyst have been successfully synthesized with P25 and different ratios of graphene oxide through a green and facile one-step microwave-assisted method. Graphene oxide was restored to graphene sheets and P25 was coated on it simultaneously during the reaction. The method offers easy access to the semiconductor/graphene nanocomposites with a uniform coating and strong interactions between semiconductor and the underlying graphene sheets. The prepared P25/graphene nanocrystals hybrid has superior photocatalytic activity in the degradation of methylene blue, showing an impressive photocatalytic enhancement over P25. The improved photocatalytic activities may be attributed to increased adsorptivity of dyes, extended light absorption range, and efficient charge separation properties of a two-dimensional graphene network.     

Graphene and its derivatives: switching ON and OFF

As the thinnest material ever known in the universe, graphene has been attracting tremendous amount of attention in both materials science and condensed-matter physics since its successful isolation a few years ago. This one-atom-thick two-dimensional pseudo-infinite nano-crystal consists of sp(2)-hybridized aromatic carbon atoms covalently packed into a continuous hexagonal lattice. Graphene exhibits a range of unique properties, viz., high three-dimensional aspect ratio and large specific surface area, superior mechanical stiffness and flexibility, remarkable optical transmittance, extraordinary thermal response and excellent electronic transport properties, promising its applications in the next generation electronics. To switch graphene and its derivatives between ON and OFF states in nanoelectronic memory devices, various techniques have been developed to manipulate the carbon atomic sheets via introducing the valence-conduction bandgap and to enhance their processability. In this article, we review the utilization of electrically, thermally and chemically modified graphene and its polymer-functionalized derivatives for switching and information storage applications. The challenges posed on the development of novel graphene materials and further enhancements of the device switching performance have also been discussed.     

Degradation of Single‐Layer and Few‐Layer Graphene by Neutrophil Myeloperoxidase

Biodegradability of graphene is one of the fundamental parameters determining the fate of this material in vivo. Two types of aqueous dispersible graphene, corresponding to single‐layer (SLG) and few‐layer graphene (FLG), devoid of either chemical functionalization or stabilizing surfactants, were subjected to biodegradation by human myeloperoxidase (hMPO) mediated catalysis. Graphene biodegradation was also studied in the presence of activated, degranulating human neutrophils. The degradation of both FLG and SLG sheets was confirmed by Raman spectroscopy and electron microscopy analyses, leading to the conclusion that highly dispersed pristine graphene is not biopersistent.     

Graphene for Cleanup in Trace Analysis of Pyrethroid Insecticides in Cucumber and Spinach

Graphene, a novel class of carbon nanostructure, possesses an ultra-high specific surface area (theoretical value 2,630 m² g⁻¹), and both sides of the planar sheets of graphene are available for molecule adsorption. Graphene has already been used for preconcentration, extraction, and electrochemical selective determination. In this study, we used graphene to clean up pigments in cucumber for analysis, and measured eight pyrethroid model analytes using GC with electron capture detection (ECD). The recoveries of the 8 pyrethroids were 75–116 % with RSDs below 10 %, and LOQs ranged from 2.5 to 10 μg kg⁻¹. Comparative studies showed that graphene was superior to graphitized carbon black for the purification of pigments. We also investigated the ability of graphene to clean up spinach. A promising new adsorbent for pesticide residue analysis was developed. Graphene has significant potential as an effective adsorbent of pigments.

     

Electrochemical property of graphene oxide/polyaniline composite prepared by in situ interfacial polymerization

Graphene oxide–polyaniline composites were synthesized by an interfacial method using two green solvents, water and an ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), as the two phases. The interfacial polymerization of aniline was carried out at room temperature in the presence of graphene oxide dispersed in the aqueous phase. The analysis revealed the surface of the graphene sheets to be coated with a smooth thin layer of polyaniline. The thermal stability of the composites was much better than that of bare graphene oxide. The composites were used to modify the glass carbon electrodes for the chemical detection of hydrogen peroxide in aqueous media. This method is a facile, efficient, and green route for the development of doped polyaniline materials suitable for chemical sensors.     

Selective Removal of Hydroxyl Groups from Graphene Oxide

Graphene has a wide range of potential applications, thus tremendous efforts have been put into ensuring that the most direct and effective methods for its large‐scale production are developed. The formation of graphene materials from graphene oxide through a chemical reduction method is still one of the most preferred routes. Numerous methods starting from various reducing agents have been developed to obtain near‐pristine graphene sheets. However, most of the reducing agents are not mechanistically supported by classical organic chemistry knowledge and of those that are supported, they are only theoretically capable of, at most, reducing oxygen‐containing groups on graphene oxide to hydroxyl groups. Herein, we present a mechanistically proven method for the selective defunctionalisation of hydroxyl groups from graphene oxide that is based on ethanethiol–aluminium chloride complexes and provides a graphene material with improved properties. The structural, morphological and electrochemical properties of the graphene materials have been fully characterised based on high‐resolution X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, Raman spectroscopy, scanning electron microscopy, electrochemical impedance spectroscopy and cyclic voltammetry techniques. Our analyses showed that the obtained graphene materials exhibited high heterogeneous electron‐transfer rates, low charge‐transfer resistance and high conductivity as compared to the parent graphene oxide. Moreover, the selective defunctionalisation of hydroxyl groups could potentially allow for the tailoring of graphene properties for various applications.     

石墨烯化聚合物:一种兼具电子和离子传输通道的三维富碳高分子能源材料

近年来,用于电化学能源存储和转化的石墨烯材料,得到了研究者们越来越多的关注。但是,这些石墨烯材料不同于严格定义的单原子碳层结构,往往具有孔洞、杂原子和化学官能团等缺陷结构。由于制备方法的不同,缺陷结构各不相同,其电化学性能也表现各异。结构分析表明,这类材料是由类似石墨烯片段的单元与聚合物链共价连接而成,使其具有石墨烯和聚合物的双重特性,我们称之为石墨烯化聚合物。由小分子通过自下而上的方法制备的多孔聚合物,也可以通过进一步热交联等方法,使其形成包含石墨烯片段单元与聚合物链的化学结构。这些材料与石墨烯衍生材料一起组成了石墨烯化聚合物的整个谱系;这个谱系涵盖了由聚合物到石墨烯的过渡区。更重要的是,这类材料特殊的结构与性质,使其成为一种兼具电子和离子传输通道的三维富碳高分子材料,非常适合作为电极材料应用于电化学能源存储和转化,这为我们深入研究储能器件中电极材料的结构与性能的相关关系提供了很好的材料平台。     

Ultralight,Ultraflexible, Anisotropic,Highly Thermally Conductive Graphene Aerogel Films

Graphene aerogels have attracted much attention as a promising material for various applications. The unusually high intrinsic thermal conductivity of individual graphene sheets makes an obvious contrast with the thermal insulating performance of assembled 3D graphene materials. We report the preparation of anisotropy 3D graphene aerogel films (GAFs) made from tightly packed graphene films using a thermal expansion method. GAFs with different thicknesses and an ultimate low density of 4.19 mg cm⁻³ were obtained. GAFs show high anisotropy on average cross-plane thermal conductivity (K_⊥) and average in-plane thermal conductivity (K_||). Additionally, uniaxially compressed GAFs performed a large elongation of 11.76% due to the Z-shape folding of graphene layers. Our results reveal the ultralight, ultraflexible, highly thermally conductive, anisotropy GAFs, as well as the fundamental evolution of macroscopic assembled graphene materials at elevated temperature.     

Graphene‐Based Composite with γ‐Fe2O3 Nanoparticle for the High‐Performance Removal of Endocrine‐Disrupting Compounds from Water

Graphene is a 2D sp²‐hybridized carbon sheet and an ideal material for the adsorption‐based separation of organic pollutants. However, such potential applications of graphene are largely limited, owing to their poor solubility and extensive aggregation properties through graphene? graphene interactions. Herein, we report the synthesis of graphene‐based composites with γ‐Fe₂O₃ nanoparticle for the high‐performance removal of endocrine‐disrupting compounds (EDC) from water. The γ‐Fe₂O₃ nanoparticles partially inhibit these graphene? graphene interactions and offer water dispersibility of the composite without compromising much of the high surface area of graphene. In their dispersed form, the graphene component offers the efficient adsorption of EDC, whilst the magnetic iron‐oxide component offers easier magnetic separation of adsorbed EDC.     

Electrocatalytic Oxidation of Glucose by the Glucose Oxidase Immobilized in Graphene‐Au‐Nafion Biocomposite

Graphene was successfully prepared and well separated to individual sheets by introducing  SO₃⁻. XRD and TEM were employed to characterize the graphene. UV‐visible absorption spectra indicated that glucose oxidase (GOx) could keep bioactivity well in the graphene‐Au biocomposite. To construct a novel glucose biosensor, graphene, Au and GOx were co‐immobilized in Nafion to further modify a glassy carbon electrode (GCE). Electrochemical measurements were carried out to investigate the catalytic performance of the proposed biosensor. Cyclic voltammograms (CV) showed the biosensor had a typical catalytic oxidation response to glucose. At the applied potential +0.4 V, the biosensor responded rapidly upon the addition of glucose and reached the steady state current in 5 s, with the present of hydroquinone. The linear range is from 15 μM to 5.8 mM, with a detection limit 5 μM (based on the S/N=3). The Michaelis‐Menten constant was calculated to be 4.4 mM according to Lineweaver–Burk equation. In addition, the biosensor exhibits good reproducibility and long‐term stability. Such impressive properties could be ascribed to the synergistic effect of graphene‐Au integration and good biocompatibility of the hybrid material.     

疏水石墨烯水相分散液的制备及电化学性能

通过未添加表面活性剂和稳定剂而得到均匀的石墨烯水相分散液的方法,近来来成为研究的一大热点.本工作通过提高水合肼的用量,来替代表面活性剂或者其它稳定剂的作用,得到了良好的均匀的水相石墨烯分散液,可长期稳定存放,6个月内未发生团聚现象.其Zeta电位低于-32.5 mV(pH值为5.89),原子力显微镜和透射电子显微镜图像表明产物为具有褶皱结构的、六方晶系的单层石墨烯结构,厚度为0.38 nm.XPS分析显示这种方法对于除去羟基和环氧基团起到了有效的作用.利用这种分散液所制备的石墨烯-玻碳电极(GE-GCE)在检测抗坏血酸(AA)和尿酸(UA)时,比普通玻碳电极(GCE)显示出更良好的电化学响应.