Synthesis of mono layer graphene oxide from sonicated graphite flakes and their Hall effect measurements

Graphene, a single atom thick sheet is considered a key candidate for the future nanotechnology, due to its unique extraordinary properties. Researchers are trying to synthesize bulk graphene via chemical route from graphene oxide precursor. In the present work, we investigated a safe and efficient way of monolayer graphene oxide synthesis. To get a high degree of oxidation, we sonicated the graphite flakes before oxidation. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirmed graphene oxide formation and high degree of oxidation. Raman spectroscopy and atomic force microscopy (AFM) results revealed a monolayer of graphene oxide (GO) flakes. The sheet like morphology of the GO flakes was further confirmed by scanning electron microscopy (SEM). The Hall effect measurements were performed on the GO film on a silica substrate to investigate its electrical properties. The results obtained, revealed that the GO film is perfectly insulating, having electrical resistivity up to 8.4 × 10⁸ (Ω·cm) at room temperature.     

Graphene/PANI hybrid film with enhanced thermal conductivity by in situ polymerization

Heat dissipation in time is essential for long-term reliability of electrical devices. Graphene, with superior thermal conductivity and excellent flexibility, exhibits a potential to substitute currently used graphite film for thermal management. In this work, a free-standing film with enhanced thermal conductivity and better flexibility was achieved by a facile and environmentally friendly in situ polymerization. The ‘molecular welding’ strategy was introduced for preparation of graphitized graphene oxide/polyaniline (gGO/PANI) hybrid film, and the uniformly distributed PANI, serving as a solder, connected adjacent graphene sheets and filled in air voids of GO films. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction and Raman spectroscopy were used to determine the structure of PANI and the interaction between GO and PANI. The in-plane thermal conductivity of gGO/PANI film is enhanced by 38% to 1019.7 ± 0.1 W m^?1 K^?1 with addition of 12 wt% PANI, compared with that of pristine gGO film. Besides, the gGO/PANI film shows better flexibility than gGO film after 180° bending for 500 times.     

Reduction and disorder in graphene oxide induced by electron-beam irradiation

Structural changes caused by an electron beam with an absorbed dose of 500 kGy were investigated in graphene oxide (GO). In this paper, GO and irradiated GO were characterized by X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy, respectively. It was found that the interlayer spacing of GO was decreased because of the alteration of functional group percent and the reduction effect. The graphitic structure of GO was also found to be disordered slightly. In addition, the samples were reduced partially after irradiation and electron-beam irradiation of GO appeared to be a promising procedure for large-scale synthesis of graphene.     

化学还原氧化石墨烯制备高性能石墨烯自组装水凝胶

提出了一种以抗坏血酸钠为还原剂,通过化学还原氧化石墨烯制备高性能石墨烯自组装水凝胶的方法.用扫描电镜,流变及电导率测试,光电子能谱,X-射线晶体衍射和拉曼光谱等手段对该石墨烯水凝胶的结构与性能进行了表征.结果表明:化学还原氧化石墨烯对形成石墨烯水凝胶具有决定性作用.该石墨烯水凝胶具有优异的导电性(1 S·m-1),机械强度和电化学性能.在1 mol·L-1的硫酸电解质溶液中,通过1.2A·g-1恒电流允放电测试,石墨烯水凝胶电极的比电容高达240F·g-1.

Abstract：

Three-dimensional self-assembled graphene hydrogels (SGHs)have been fabricated by chemical reduction of graphene oxide (GO)with sodium ascorbate. The SGHs were characterized by scanning electron microscopy,rheological tests,electrical conductivity measurements,X-ray photoelectron spectroscopy,X-ray diffraction,and Raman spectroscopy. Results indicate that the reduction of GO promotes the assembly of graphene sheets. The SGHs are electrically conductive(1s·m-1)and mechanically strong and exhibit excellent electrochemical performance.In 1 mol·L-1 aqueous solution of H2SO4,the specific capacitance of SGHs was measured to be about 240F·g-1 at a discharge current density of 1.2·-1.     

A UV-light induced photochemical method for graphene oxide reduction

Chemical reduction of graphene oxide (GO) has been considered as a promising route towards the large scale production of graphene. Herein, a rapid, efficient photochemical method for preparing reduced graphene oxide (RGO) by ultraviolet (UV) irradiation of a mixture solution containing a photoinitiator and Monoethanolamine (MEA) compound in ethanol has been developed. In this route, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (GR-XBPO) was used as the reductant and MEA as the oxygen inhibition agent. After UV irradiation, oxygen-containing groups (OCGs) on GO plane and edges are being largely removed due to the reduction of GO by free radicals generated by photoinitiator decomposition. X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and ultraviolet and visible spectrophotometer showed that GR-XBPO can efficiently reduce GO at room temperature. It is also found that the electrical conductivity of RGO fabricated by this rapid route (~10 min) is more competitive compared to other reported works. Moreover the corresponding reduction mechanism was being discussed. This work puts forward a novel method for preparing graphene, and has great potential in scaling up graphene production and developing graphene materials.     

Triethylenetetramine/hydroxyethyl cellulose-functionalized graphene oxide monoliths for the removal of copper and arsenate ions

Nitrogen-doped graphene oxide monoliths (GOMs) were readily constructed by crosslinking graphene oxide (GO) using triethylenetetramine (TETA) and hydroxyethyl cellulose (HEC). The addition of HEC was beneficial to the formation of a network structure compared to that in the absence of HEC. The generated monoliths have shown various morphologies with different d spacing, layer thickness, and micropore size. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses provided evidences for the formation of covalent C–N bonds and some nitrogen-containing heterocyclic composition inside the graphene oxide sheet, indicating that the interaction of GO with the amine crosslinker involved the crosslinking reaction between GO epoxides and amine groups. HEC was also involved in the N-doping reaction via the partial reduction of oxygen in HEC molecules. Analysis of X-ray diffraction (XRD) results indicated that the lattice distance between GO sheets increased after TETA/HEC crosslinking. Thermogravimetric analysis (TGA) confirmed the successful incorporation of crosslinker moieties on the surface of GO sheets. The fabricated GOMs could be used to efficiently adsorb metal ions and arsenate by the introduced polar functional groups on GO sheets and porous structures based on hydrogen bonds, whose morphologies and compositions were confirmed via XRD, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS).     

功能化石墨烯片的表面性能调控

以氧化石墨为前驱体,采用真空辅助热膨胀法在低温下即获得功能化石墨烯片。将所得石墨烯在不同温度下热处理,制备了表面化学结构不同的石墨烯片,并用透射电子显微镜、X射线衍射、X射线光电子能谱、傅里叶变换红外光谱等方法对样品进行分析表征。结果表明,还原氧化石墨烯片中含氧官能团的种类和数量均随热还原温度的升高而减小。     

亲水型功能化石墨烯的分散性及其对水泥基复合材料力学性能的影响

为了解决石墨烯纳米片在水泥基体中的分散问题,采用芳基重氮盐(F)对氧化石墨烯(GO)进行改性,制备了一种新型亲水型功能化石墨烯(FG)。结果表明,FG在水溶剂中最大的分散浓度能够达到2.1 mg/mL。FTIR、拉曼光谱和XPS结果表明F成功对石墨烯进行了表面改性。对比纯水泥基体材料,本文所制备的亲水型FG/水泥复合材料的28天抗折强度和抗压强度相对提高了95.3%和78.3%。F对GO进行改性,实现了石墨烯在水泥基材料中的均匀分散及对其力学性能的提升。      

Facile synthesis of reduced graphene oxide nanosheets by a sodium diphenylamine sulfonate reduction process and its electrochemical property

We report a new method to convert graphene oxide (GO) to stable colloidal dispersion of reduced graphene oxide nanosheets (RGONS) using sodium diphenylamine sulfonate (SDAS) as a reductant, as well as itself and its redox product as the stabilizer. The as-prepared RGONS have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, UV–visible spectroscopy, thermo-gravimetric analysis, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, atomic force microscopy and Raman spectroscopy. The results indicate that the bulk of oxygen-containing functional groups from GO have been removed. Based on the cyclic voltammogram (CV) analyses, it is found that the RGONS-based material exhibits better electrochemical activity in sensing ascorbic acid than GO. The simple method provides a new efficient route for the synthesis of water-soluble RGONS on a large scale and novel composites.     

Structural,optical, and photocatalytic investigation of nickel oxide@graphene oxide nanocomposite thin films by RF magnetron sputtering

Despite the recent advancement in graphene oxide (GO) as a host material in energy and environmental sectors, its composite thin films with metal oxides such as nickel oxide (NiO) and its optical, structural, chemical state, and photocatalytic activities have been poorly explored. Herein, we have reported the GO/NiO thin films preparation by a combination of chemical and physical deposition techniques (i.e. spin coating followed by DC/RF sputtering). The as-prepared composites thin films were characterised using Raman spectroscopy, X-ray diffraction/photoelectron spectroscopy scanning electron microscopy, and atomic force microscopy. The surface topography confirmed the uniform deposition of NiO over thin films of GO. The XPS results showed the formation of NiC along with the partial reduction in GO into graphene with their existing four constituents, i.e. NiO, NiC, GO, in the thin film composites. The classical plasmon, Wemple and Didomenico model, was first time applied for GO/NiO to compute energy loss functions, and dispersion energy parameters. The theoretical calculated values for the deposited GO/NiO thin films were found to be in very close agreement to the standard classical plasmon values. The change in spin orbital movement of Ni is considered due to the interaction between its nanoparticles and basal planes of GO. Thin films applied for the photodegradation of recalcitrant organic pollutant 2-chlorophenol (2-CP) revealed the dependence of photocatalytic efficiency on particle size and also on the interaction of GO with NiO rather than the ratio of NiO and GO in the films.     

Rapid and effective functionalization of graphene oxide by ionic liquid

Functionalized graphene oxide (DDIB-GO) sheets, which can be homogeneously distributed into ortho-dichlorobenene, were obtained via rapid and effective covalent functionalization with imidazolium ionic liquids (1,3-didodecylimidazolium bromine) through ion exchange. The resulting DDIB-GO sheets were characterized by Fourier transform infrared spectroscopy (FTIR), UV Vis NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), Atomic force microscopy (AFM). Furthermore, FTIR, XPS and TGA show that the 1,3-didodecylimidazolium have been covalently attached to the GO sheets. UV Vis NIR, TEM, and AFM demonstrate that after functionalization, the size and shape of DDIB-GO sheets had little change compared with GO sheets and it was mostly dispersed in single layer. And good electronic conductivity of the film prepared from DDIB-GO in ODCB was obtained after high temperature annealing.     

Surfactant-assisted synthesis of reduced graphene oxide/polyaniline composites by gamma irradiation for supercapacitors

A series of graphene materials are prepared by intercalation of graphene oxide (GO) with different surfactants, cetyltrimethylammonium bromide (CTAB), n-octyltrimethylammonium bromide, tetramethylammonium bromide, and sodium dodecylbenzene sulfonate, subsequently by γ-ray induced reduction in N-methyl-2-pyrrolidone (NMP) at room temperature. GO can be reduced by the electrons generated from the radiolysis of NMP under γ-ray irradiation, and reduced GO is simultaneously functionalized by the radiolytic product of NMP. Cationic surfactant CTAB with longer alkyl chains can effectively promote the reduction process of GO by preventing the aggregation of graphene sheets, which has been testified by X-ray photoelectron spectroscopy, X-ray diffraction, thermogravimetric analysis, Raman spectroscopy, and Fourier transform infrared spectroscopy analyses. Furthermore, when the as-prepared graphene/polyaniline composites are used for supercapacitor electrode materials, there is a highest specific capacitance of 484 F g^?1 at a current density of 0.1 A g^?1 for the graphene produced in the presence of cationic surfactant CTAB.     

Effect of the exposure time of hydrazine vapor on the reduction of graphene oxide films

Preparation of highly uniform graphene with superior electrical properties is one of the key issues in graphene researches. The use of hydrazine vapor for reducing the graphene oxide (GO) has attracted considerable attention in recent year due to the simplicity, reproduciblilty and availibility of one-step procedure. Here, we investigated the effect of the exposure time of hydrazine vapor on the reduction of GO films. Raman spectroscopy, UV-vis spectroscopy, X-ray photoelectron spectrophotometer, and X-ray diffraction results showed that the reduction rate of the GO films by hydrazine vapor was very fast in the initial 10 min, and thereafter the reduction rate slowed down. Upon 12 hours of hydrazine vapor treatment, the reduction came to a level that further hydrazine vapor treatment did not bring about significant improvement of the reduction. We demonstrated that this might be attributed to the slow penetration of hydrazine vapor into the GO films in order to reduce the inner sheets of the GO films.     

Synthesis of high-performance graphene nanosheets by thermal reduction of graphene oxide

High-performance graphene nanosheets have been synthesized by thermal reduction of graphene oxide (GO) under ethanol atmosphere. The reduced GO nanosheets were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy and electrical transport measurements, respectively. The results indicated that the thermal reduction of GO under ethanol atmosphere can effectively remove the oxygen-containing functional groups and restore its graphic structure compared to the ones obtained using hydrazine or hydrogen. The electrical measurements indicated that the electrical mobility of single-layer graphene sheet reduced under ethanol atmosphere at 900 °C can reach 29.08 cm² V⁻¹ S⁻¹.     

Reduction and functionalization of graphene oxide sheets using biomimetic dopamine derivatives in one step

An easy and environmentally friendly chemical method for the simultaneous reduction and noncovalent functionalization of graphene oxide (GO) using dopamine derivatives is described. The reaction takes place at room temperature under ultrasonication of an aqueous suspension of GO and a dopamine derivative. X-ray photoelectron spectroscopy, FT-IR spectroscopy, and cyclic voltammetry characterizations revealed that the resulting material consists of graphene functionalized with the dopamine derivative. This one-step protocol is applied for simultaneous reduction and functionalization of graphene oxide with a dopamine derivative bearing an azide function. The chemical reactivity of the azide function was demonstrated by a postfunctionalization with ethynylferrocene using the Cu(I) catalyzed 1,3-dipolar cyloaddition.     

Simple facile route for the preparation of graphite oxide and graphene

A simple method is reported for the preparation of graphite oxide (GO) and graphene using KCIO3/NaNO3/H2SO4 and Na2S as oxidizing agent as oxidizing and reducing agents respectively. The formation of GO and graphene have also been confirmed by X-ray diffraction studies, UV-visible, spectroscopy, FTIR and Raman spectroscopy. The morphology, surface charge characteristic and thermal stability behaviour have been studied by SEM/TEM, Zeta potential measurements, thermogravimetric analysis.     

Synthesis of graphene soluble in organic solvents by simultaneous ether-functionalization with octadecane groups and reduction

Octadecane-functionalized graphene (OD-G) soluble in organic solvents was produced by combining the Hummers process for graphite oxidation and a simultaneous ether-functionalization and reduction approach with 1-bromooctadecane in pyridine and dimethylformamide (DMF). The exfoliated OD-Gs were testified to be monolayer sheets by transmission electron microscope (TEM) and atomic force microscopy (AFM). The functionalization with octadecane (OD) groups and the effective deoxygenation of graphene oxide (GO) were confirmed by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). It is proved that the effective reduction and functionalization of GO could be simultaneously completed during the refluxing process. The functionalization with OD groups can effectively prevent the aggregation of GO during the reduction.     

Thermal and electrical conductivity of Al(OH)<Subscript>3</Subscript> covered graphene oxide nanosheet/epoxy composites

Al(OH)₃ functionalized graphene composites (Al–GO) were prepared using a simple sol–gel method. In this protocol, graphene oxide (GO) was prepared according to the Hummers method and functionalized to enhance its reactivity with aluminum isopropoxide by a LiAlH₄ treatment. The functionalized graphene sheets were characterized by X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy. These analyses confirmed that GO had been fabricated and the Al(OH)₃ layer could have a homogeneous distribution with large and dense coverage onto GO sheets. In addition, the thermal and electrical conductivity of the epoxy composites with GO and Al–GO fillers were measured. The thermal conductivities of the composites with graphene-based fillers were enhanced by the addition of fillers. In particular, the thermal conductivity of GO/epoxy composite containing 3 wt% was approximately two times higher than that of pure epoxy resin. In addition, the electrical conductivity of Al–GO embedded composites degenerated compared to GO composites.     

Production of graphene nanospheres by annealing of graphene oxide in solution

We report a simple method to produce graphene nanospheres (GNSs) by annealing graphene oxide (GO) solution at high-temperature with the assistance of sparks induced by the microwave absorption of graphite flakes dispersed in the solution. The GNSs were formed by rolling up of the annealed GO, and the diameters were mostly in the range 300–700 nm. The GNS exhibited a hollow sphere structure surrounded by graphene walls with a basal spacing of 0.34 nm. Raman spectroscopy and X-ray photoelectron spectroscopy of the GNSs confirmed that the GO was efficiently reduced during the fabrication process. The resulting GNSs may open up new opportunities both for fundamental research and applications, and this method may be extended to the synthesis of other nanomaterials and the fabrication of related nanostructures.      

氧化锡粒子/石墨烯纳米复合材料真空热还原制备及其在近红外胰腺癌热疗中的应用

利用真空热还原法制备得到氧化锡粒子/石墨烯纳米复合材料(SnO2/GR),该过程中,石墨烯氧化物原料既是氧化锡粒子的有效载体来源,也是新型的活泼氧给体,可同步将零价锡氧化为正四价锡,石墨烯氧化物原料则被还原为石墨烯。利用透射电镜(TEM)、扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱等分别对氧化锡粒子/石墨烯纳米复合材料的形貌和尺寸、结构进行了表征。利用该新型材料在近红外(NIR)激光照射下的强光热转化性能,使相比健康细胞更易受到温度影响的胰腺肿瘤细胞内部产生过高热(Hyperthermia),从而诱导胰腺肿瘤细胞热损伤及细胞凋亡。实验结果表明,在1064nm近红外激光照射下,对照组胰腺肿瘤细胞仍保持较高活性,而实验组的胰腺肿瘤细胞活力则大幅降至5.03%,充分显示了氧化锡粒子/石墨烯纳米复合材料在胰腺肿瘤热疗领域的潜力。