氧化石墨还原法制备石墨烯及其吸附性能

利用液相化学氧化法制备氧化石墨,通过水合肼还原氧化石墨制备石墨烯.采用X射线衍射分析、激光拉曼光谱和透射电子显微镜等测试方法,对石墨烯材料的结构和吸附性能进行分析表征.结果表明,通过氧化石墨还原法制得的石墨烯晶体结构完整性有所降低;石墨烯对极性较大的有机染料亚甲基蓝、甲基橙和罗丹明B的吸附率都在95%以上,对极性较小的有机污染物苯酚和氯苯酚的吸附能力较弱.     

直接液相剥离法制备无缺陷石墨烯

石墨烯优良的物理和化学性能,使它日益得到广泛的关注.如何获得高质量高产量的石墨烯对石墨烯未来的开发和应用至关重要.直接液相剥离法制备石墨烯是一种有望实现高质量石墨烯量产化的方法.该方法是在一定介质中通过超声手段将石墨烯晶体从石墨中剥离出来,形成胶体溶液,从而得到石墨烯.通过剥离介质(溶剂及辅助试剂)的筛选可以有效地提高石墨烯的剥离效率.本文主要介绍近年来液相剥离法制备石墨烯的研究进展,讨论了在不同的剥离介质、剥离条件下制得的石墨烯的质量和产量.旨在为未来液相剥离法制备石墨烯的发展提供参考,开发更加有效的剥离体系,研究能够高效生产高性能石墨烯的新方法.     

氧化石墨烯水悬浮液的非等温结晶过程

采用添加石墨烯纳米材料形成悬浮液的方法可以有效地提高相变储能材料的导热系数,石墨烯纳米材料的存在将对悬浮液的固液相变行为产生可观的影响. 利用差示扫描量热仪对低质量分数的氧化石墨烯水悬浮液进行非等温结晶实验观测,对比分析不同质量分数（最高为1%）的悬浮液在不同降温速率情况下过冷度的变化规律. 实验结果表明,由于氧化石墨烯的存在,悬浮液的过冷度较纯水有所降低. 随着质量分数的提高,悬浮液的过冷度呈逐步下降的趋势,当最高质量分数为1%时,悬浮液的过冷度较纯水下降了近5 ℃. 悬浮液的过冷度随着降温速率的增大会略微升高,但降温速率对过冷度随悬浮液质量分数的相对变化没有影响. 采用氧化石墨烯水悬浮液作为蓄冷工质能够有效地降低水的过冷度,但对整个非等温结晶过程未体现出加速的效果．     

Tuning microstructure and surface chemistry of reduced graphene oxide by mild reduction

Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp~2 domains have smaller sizes and larger quantity. The content of sp~2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.     

Synthesis of zinc oxide nanoparticles with good photocatalytic activities under stabilization of bovine serum albumin

Zinc oxide nanoparticles were synthesized using bovine serum albumin as stabilizers through a facile one-pot strategy in aqueous media. The morphology and crystal phase of the zinc oxide nanoparticles were determined by transmission electron microscopy, X-ray diffractograms, and Fourier transform infrared spectroscopy. The synthesized ZnO nanoparticles exhibited strong absorption and photoluminescence properties in the visible wavelength region based on the fluorescence and UV-visible spectroscopy. Based on the results, the zinc oxide nanoparticles could effectively degrade the organic dyes through the mediation of the hydroxyl radical under visible light irradiation. Furthermore, the zinc oxide nanoparticles show good recycling stability during the photocatalytic experiments. These results suggested that the as-prepared zinc oxide nanoparticles might be used as a potential photocatalyst to efficiently treat the organic pollutants.     

水热法制备氟化石墨烯

以石墨为原料,由Hummers法的改进方法制备氧化石墨烯,再采用水热法对氧化石墨烯进行氟化,获得氟化石墨烯。利用X射线衍射（XRD）、傅立叶红外光谱（FTIR）、拉曼光谱（Raman）、原子力显微镜（AFM）对其结构和微观形貌进行表征。FTIR和Raman结果表明氟化产物的化学结构中存在C-F键,且D峰（1350 cm-1处）和G峰（1580 cm-1处）所对应的强度比ID/IG在氟化后明显变大,即氟化造成碳结构缺陷,规整性下降。AFM显示氟化石墨烯具有纳米层状结构,厚度约为4 nm。该法成本较低,工艺简单,易于控制,对设备要求不高,有望实现氟化石墨烯的大规模制备。     

Efficient Preparation and Characterization of Functional Graphene with Versatile Applicability

Graphene, as star versatile materials having extraordinarily high electric conductivity, electron mobility, thermal conductivity, thermal stability, optical transparency, and mechanical strength, has attracted much attention from scientists and engineers in the field of materials, chemistry, physics, energy, and environment in the last decade and achieved fruitful accomplishment. This review discusses preparation strategies, functionality, characterization, and applications for two dimensional nanosheet and quasi-one-dimensional nanoribbon of graphene through direct exfoliation of graphite, chemical vapor deposition of hydrocarbon, laser-induced direct synthesis of graphene, laser etched graphene oxide in the dry state without the use of toxic reducing agent hydrazine, unzipping carbon nanotube, and polycondensation of polycyclic aromatics on the basis of 178 representative references mostly in 2015. The stabilization of graphene oxide prepared in chemical preparation in "top-down" is emphasized. Several vital classic methods of characterizing molecular structure, C/O ratio, defect, morphology, single-or few-layered (2 to 10 layers) structure, porous and hollow structures, including Raman spectroscopy, AFM, SEM, TEM, STM, electron diffraction, X-ray diffraction, and X-ray photoelectron spectroscopy are systematically introduced. Because graphene possesses novel incomparable multifunctionalities, its versatile applications as novel conducting additives, reinforcing filler, separation membrane, sensor, anticorrosive coating, catalyst, electromagnetic shield, lubricant, and flexible electrode materials in electrochemical and electronic devices, including photovoltaic cells, supercapacitors, rechargeable batteries, sensors, field effect transistors, light emitting diodes, separation membranes, adsorbents and absorbents, catalysts, electro-optic modulator, terahertz emitter and detector, and semiconductors, have been mentioned.Especially in the aspect of both high performance and cost-effectiveness, graphene is expected to be even superior to the expensive carbon nanotubes.     

甲基橙掺杂聚吡咯/氧化石墨烯复合材料

为了得到新型导电聚合物/石墨烯纳米复合材料,采用偶氮染料甲基橙为掺杂剂,过硫酸铵为氧化剂,一步法制备了纳米片状的聚吡咯/氧化石墨烯复合材料,通过傅里叶红外光谱、扫描电子显微镜等测试,对聚吡咯/氧化石墨烯复合材料的结构和形貌进行表征;通过循环伏安法对其进行电化学性能测试.结果表明:由于甲基橙分子中含有的磺酸根阴离子,甲基橙分子掺杂在聚吡咯分子链中,影响了聚吡咯分子的共轭结构;在聚吡咯/氧化石墨烯复合材料中保留了氧化石墨烯的片状结构,表明吡咯单体首先被吸附到氧化石墨表面,进而在氧化石墨烯表面发生聚合.聚吡咯/氧化石墨烯复合材料均匀的片状纳米结构,在循环伏安测试中显现出具有良好的电容特性,将来可以应用到商业电容器领域.     

石墨烯化石墨/聚苯胺电极的制备及电容特性

通过电解剥落得到的表面石墨烯化的石墨电极(graphene layers/graphite plate, GL/GP)为基底,在硫酸介质中以苯胺为单体,采用循环伏安法(cyclic voltammetry, CV)制备了表面石墨烯化的石墨/聚苯胺(graphene layers/graphite plate/polyaniline, GL/GP/PANI)电极,并探究聚合圈数对GL/GP/PANI电极比电容的影响。利用场发射扫描电镜(scanning electron microscope, SEM)对电极材料的形貌进行表征。在0.5 M H₂SO₄电解液中,对合成的电极材料进行循环伏安、恒电流充放电(chronopotentiometry, CP)和电化学稳定性测试。结果表明,在表面石墨烯化的石墨电极上合成的PANI具有棒状结构,电流密度为0.085 mA/cm²时, GL/GP/PANI电容器的比电容可达1 042.8 F/g。提供了一种新的超级电容材料基底电极的构建方式。     

石墨烯/SnO_2/聚苯胺纳米复合材料的制备与表征

石墨烯具有独特的纳米结构和一系列极具吸引力的特性,成为新型纳米复合材料的理想载体,如纳米复合材料分散的基体.提出了一种以石墨,苯胺,四氯化锡为原料制备石墨烯/二氧化锡/聚苯胺的新方法.通过X-射线衍射,红外光谱,透射电子显微镜,扫描电子显微镜以及紫外-可见光谱对合成的材料进行表征.结果表明：二氧化锡纳米粒子原位吸附在石墨烯的表面,有效地避免了石墨烯片的堆叠,聚苯胺加入后可大大提高二氧化锡的电化学性质.     

Graphene Quantum Dots Derived from Carbon Fibers for Oxidation of Dopamine

We demonstrated a facile method to prepare photoluminescent graphene quantum dots using commercial polyacrylonitrile(PAN) based carbon fibers(CFs) as the raw material by facile chemical oxidation and exfoliation method. The as-prepared GQDs with uniform size exhibit an excitation-independent photoluminescence behavior, which is similar to other semiconductor quantum dots. Moreover, when acting as catalyst the uniform GQDs have better activity for electrochemical oxidation of dopamine(DA) than graphene oxides(GOs). The square wave voltammogram(SWV) peak values of GQDs are in good correspondence with DA concentrations and can act as a sensor of DA.     

Supercapacitors based on high-surface-area graphene

Exfoliated graphite oxide was prepared by an improved Hummers method and was then reduced to graphene with hydrazine in the presence of ammonium hydroxide.N2adsorption–desorption measurement showed that graphene so obtained had a specific surface area as high as 818 m2/g.Galvanostatic charge/discharge curves demonstrated that the as-prepared graphene exhibited a specific capacitance of 186.9 F/g at a current density of 0.1 A/g and that about 96%of the specific capacitance was retained after 2000 cycles at a current density of 5 A/g.     

石墨烯与四氧化三铁复合材料的制备与性能

为了得到具有良好吸附性能的石墨烯与含铁氧化物的复合材料,在碱性条件下通过亚铁离子与氧化石墨烯的一步反应制备石墨烯与四氧化三铁复合材料. 采用Ｘ射线衍射、扫描电子显微镜和热失重分析对该复合材料的结构与微观形貌进行表征,并研究了石墨烯与四氧化三铁复合材料对罗丹明Ｂ的吸附性能. 实验结果表明,亚铁离子在碱性条件下生成的四氧化三铁纳米颗粒较均匀地分布在石墨烯表面,破坏了石墨烯原有的结晶结构. 与单独的石墨烯或者四氧化三铁相比,复合材料对罗丹明Ｂ有良好的吸附性能. 吸附染料的复合材料可以用磁铁从溶液中移出,有利于复合材料的回收与重复使用. 研究其吸附动力学和吸附等温线发现,该复合材料吸附罗丹明Ｂ符合准二级动力学方程和Ｌａｎｇｍｕｉｒ吸附模型.     

石墨烯/ Pd复合材料的制备及其形成机制研究

采用氯化双乙二胺钯Pd(en)2Cl2为钯的前驱体、氧化石墨为炭的前驱体,先将Pd(en)22+插入氧化石墨层中,再用NaBH4化学还原插层的氧化石墨,从而制备出石墨烯/Pd复合材料。并用X衍射(XRD)、场扫描电镜(FE-SEM)、透射电镜(TEM)和N2吸附表征复合材料的结构,且在此基础上推导出石墨烯/Pd复合材料的形成机制。     

MgH2-graphene复合储氢材料吸放氢性能

通过球磨制备MgH2,MgHz-GMgHz-graphene储氢材料,研究石墨烯添加对MgH2吸放氢性能的影响。结果表明,石墨和石墨烯对球磨过程中MgHz的细化有促进作用;石墨和石墨烯的添加对MgH2的吸放氢动力学有良好的改善作用;特别是MgH2-graphene储氢材料有优良的吸放氢性能,在573K下于5,2min内放氢和再吸氢质量分数都为7．0％,且其放氢起始温度较MgH2的低50K。     

机械剥离法制备高质量石墨烯的初步研究

采用机械剥离法制备了高质量的石墨烯。利用光学显微镜、原子力显微镜和拉曼光谱仪分析了石墨烯的厚度、形貌和结构。结果表明剥离的石墨薄层包含了高质量的单层及2~3层石墨烯。机械剥离法是制备高质量石墨烯最简单的方法。     

A Comparative Study of Electrochemical Capacitance of Graphene Oxide Affected by Oligomers of p-phenylenediamine and Hydrazine Hydrate in Solvothermal Condition

A systematic investigation of the graphene oxide composite reduced by either p-phenylenediamine oligomers or hydrazine hydrate was performed with field emission scanning electron microscopy,high resolution transmission electron microscopy,X-ray diffraction,fourier transform infrared,and X-ray photoelectron spectroscopy analyses.The electrical capacitance of the composite was evaluated by a cyclic voltammetry technique,while the properties of these prototype supercapacitors were measured by a chronopotentiometry technique.It was found that,under the solvothermal condition,the graphene oxide reduced by p-phenylenediamine oligomers was observed to have higher electrical capacitance than that reduced by hydrazine.The improved electrical capacitance can be attributed to that p-phenylenediamine oligomers are the more effective spacers for graphene layers;and they could also provide some pseudo-capacitance to the graphene oxide composite based on their conjugate structure.The results imply that graphene oxide modified by diamine oligomers has a good potential in energy storage devices.     

Synthesis and characterization of amphiphilic graphene

A simple and effective method for the preparation of amphiphilic graphene (AG) is presented under an organic solvent-free synthetic condition. The synthetic route first involves a cyclization reaction between carboxylic groups on graphene oxide and the amino groups on 5,6-diaminopyrazine-2,3-dicarbonitrile, and subsequent reduction by hydrazine. Results of UV-vis spectroscopy, Fourier transformed infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and Raman spectroscopy have confirmed that the covalent functionalization of graphene can be achieved through the formation of imidazo[4,5-b]pyrazine on the graphene sheets. As a result, AG can be successfully dispersed in water and common organic solvents. This work successfully provides a facile and efficient way to fabricate AG and may extend the potential applications of graphene-based materials in nanoelectronic devices, polymer fillers and biological field.     

水热法制备聚苯胺/石墨烯复合材料的研究

以氧化石墨烯（GO）与苯胺作为前驱物,在高温高压下一步水热反应,合成了聚苯胺/石墨烯（PANI/Gr）复合材料。利用紫外可见光谱、傅里叶变换红外光谱、扫描电子显微镜研究了PANI/Gr复合材料的结构和微观形貌,进一步利用电化学工作站探究了PANI/Gr复合材料的电化学性能。研究了水热反应时苯胺与GO的投料质量比对所得复合材料的结构与电化学性能的影响。循环伏安法和恒电流充放电测试结果表明由于聚苯胺与石墨烯的相互作用,复合材料的电容性能比单组分的聚苯胺和石墨烯要高。这说明通过GO与苯胺的一步水热反应成功制备了具有优良电容性能的PANI/Gr复合材料。     

氧化石墨片层中含氧官能团的探讨

采用Hummers法合成了氧化石墨（GO）产物,并通过XRD、IR、SEM和XPS等分析方法对产物进行表征分析.结果表明石墨被氧化为氧化石墨后仍具有层状结构,层间距比石墨大,层间含有大量的含氧功能性极性基团,包括羟基、羧基、醚基,未发现文献报道的环氧基团.