抗坏血酸在石墨烯修饰电极的电化学行为研究

以300目鳞片状石墨为原料,采用Hummers法制备氧化石墨并用电化学还原法制备石墨烯修饰电极,分别用X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)对石墨,氧化石墨,氧化石墨烯和石墨烯的结构进行了表征。并以石墨烯修饰电极作为电极,用循环伏安法测试了其在含有一定浓度抗坏血酸的磷酸氢二钠-柠檬酸溶液中的电化学行为,选择了测试的最佳条件。在最佳实验条件下,采用计时电量法、OCPT(开路电位)测试抗坏血酸的电化学行为。实验结果表明,抗坏血酸的电化学氧化是单电子的反应,扩散系数D=3.24×10-6cm2·s~(-1),反应速率常数k0=3.78×10-6cm·s~(-1),电荷传递系数β=0.310。     

新型石墨烯/聚苯胺/银基复合材料的制备

通过对石墨烯(GN)制备、结构改性及与聚苯胺(PANI)、银粒子(Ag)的复合,设计了制备GN/PANI/Ag新型电极复合材料的工艺路线。首先利用Hummers氧化还原法将石墨氧化成氧化石墨烯,利用硼氢化钠将氧化石墨烯还原成石墨烯,将石墨烯与聚苯胺、银粒子反应,最后制得了GN/PANI/Ag复合材料。利用扫描电子显微镜(SEM),透射电子显微镜(TEM),热重分析(TG)和电导率测试对GN和GN/PANI/Ag的形貌,热稳定性和电化学性能进行了分析研究。结果表明,聚苯胺类衍生物、石墨烯以及银粒子三相在整个复合材料中共存,材料的复合使体系热稳定性和电化学性能得到提高。     

KOH活化对超级电容器用氮掺杂石墨烯的影响

为了制备高比表面积、适宜孔径的石墨烯基材料,从而使其具备良好的电化学性能,化学活化法已经被广泛地研究。本文以氧化石墨烯(GO)为基体,密胺树脂预聚体为氮掺杂剂,采用KOH活化法制备超级电容器用氮掺杂石墨烯材料。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积和孔隙度分析(BET)、循环伏安法(CV)及恒电流充放电法(GCD)等对其微观形貌和电化学性质进行分析。结果表明:在活化温度800℃,活化倍率3.0时,样品的比表面积为554.32 m2/g,比电容达到312 F/g,具有更好的电化学特性。     

煤基石墨烯制备及电化学性能研究

以碳化硅冶炼炉同步生产石墨化太西煤为原料,采用改良的Hummers氧化还原法制备了煤基石墨烯,通过FT-IR和XRD对其进行了表征,并利用循环伏安、恒电流充放电等电化学测试方法对其电化学性能进行了测试。结果表明:煤基石墨烯具有良好的电化学性能,在电流密度0.5A·g~(-1)下,充放电1000次后煤基石墨烯电极材料的比电容量为105.5F·g~(-1)。     

氮掺杂石墨烯修饰电极对多巴胺的电化学检测

采用水热法制备了氮掺杂石墨烯材料,利用其修饰玻碳电极,通过电化学方法检测多巴胺。运用X射线衍射,拉曼光谱仪,光电子能谱仪及扫描电镜对氮掺杂石墨烯进行了表征。采用循环伏安法和示差脉冲伏安法研究多巴胺的电化学行为,表明氮掺杂石墨烯修饰的电极对多巴胺的氧化具有良好的催化作用,其对多巴胺的检测范围为0.5~40.0μmol/L,检测限为0.2μmol/L。     

废旧锂电池负极石墨粉制备石墨烯及其电化学研究

以废旧手机锂电池为前驱体,回收负极石墨粉,并以其原料采用氧化还原法制备了石墨烯。通过FT-IR、XRD对其进行了表征和利用交流阻抗、恒电流充放电等电化学测试方法对其电化学性能进行了测试。结果表明:该石墨烯表现出与文献相近的电化学性能,在电流密度0.5A·g~(-1)下,石墨烯电极材料比电容量为113.2F·g~(-1),经1000次循环后比电容可保持93.2%。     

氧化石墨烯掺杂对低碳钢表面硅烷涂层性能的影响

利用浸渍法在Q235低碳钢表面制备了氧化石墨烯(GO)掺杂的双?[3?(三乙氧基)硅丙基]四硫化物(BTESPT)硅烷涂层.分别采用扫描电镜、傅里叶变换红外光谱仪、电化学工作站和摩擦磨损试验机研究了氧化石墨烯掺杂对硅烷涂层的表面形貌、相结构、耐蚀性和耐磨性的影响.结果表明:氧化石墨烯掺杂后硅烷涂层表面更加致密,耐蚀性和耐磨性得到提高.     

石墨烯对PMMA改性材料热稳定性能的影响

研究了氧化石墨烯和石墨烯对聚甲基丙烯酸甲酯(PMMA)材料热稳定性能的影响。采用氧化还原法制备石墨烯,通过浇铸、熔融密炼、模压法制取试验样品;通过电子扫描电镜(SEM)观察试样分散态形貌,采用热分析(TG)研究试样的热降解性能,并利用燃烧法观察试样的宏观燃烧行为。结果显示,氧化石墨烯、石墨烯对PMMA的燃烧行为、热释放速率具有明显的影响。分别添加0.1%(质量份)的氧化石墨烯和石墨烯后,PMMA/石墨烯的半寿温度(失重50%的温度)与纯PMMA相当,而终止温度(最大失重点温度)提高了5℃,PMMA/氧化石墨烯的半寿温度和终止温度分别提高了8和10℃。     

一步法制备硅烷改性氧化石墨烯

采用一步电解剥离法制备硅烷改性氧化石墨烯,通过阳极电泳沉积法得到硅烷改性氧化石墨烯-氧化铝复合薄膜。以傅里叶变换红外光谱(FTIR)、热重分析(TG)、X射线衍射(XRD)、拉曼光谱、扫描电镜(SEM)、电化学阻抗谱等分析方法对其结构进行表征。结果表明,硅烷成功接枝到了氧化石墨烯上,令其热稳定性得以改善。硅烷改性氧化石墨烯表面剥落均匀,石墨的晶格结构在电化学剥离过程中得到保留。与单一氧化铝薄膜相比,硅烷改性氧化石墨烯氧化铝复合薄膜的腐蚀电位正移,腐蚀电流密度降低,阻抗弧半径增大,耐蚀性得到改善,寿命延长。     

银-石墨烯复合材料的原位制备及性能研究

以鳞片石墨为原料,采用Hummers法制备氧化石墨.氧化石墨与硝酸银溶液混合超声处理,通过功能离子预吸附的方式,将银离子有效地分散在氧化石墨烯载体上.以水合肼为还原剂,同时还原氧化石墨和硝酸银溶液中的银离子,原位制备银-石墨烯复合材料.采用X射线衍射仪、扫描电子显微镜对制得的银-石墨烯复合材料进行表征,并对复合材料的电化学性能进行分析.结果显示,制得银-石墨烯复合材料的比电容明显高于单纯的石墨烯材料,电化学性质优异,是理想的电化学电容器电极材料.     

微波法制多孔石墨烯及对亚甲基蓝的吸附性能

以改进的Hummers法合成的氧化石墨烯为自组装原料,通过微波加热的方式制备三维多孔石墨烯材料.并采用场发射扫描电子显微镜、傅立叶红外光谱仪、X射线衍射仪对石墨、氧化石墨烯、三维多孔石墨的微观形貌和内部结构进行表征分析.以亚甲基蓝为吸附质、三维多孔石墨烯为吸附剂,研究其吸附性能.结果表明,三维多孔石墨烯材料的最大吸附量...     

Facile solvothermal synthesis of a graphene nanosheet-bismuth oxide composite and its electrochemical characteristics

This work demonstrates a novel and facile route for preparing graphene-based composites comprising of metal oxide nanoparticles and graphene. A graphene nanosheet-bismuth oxide composite as electrode materials of supercapacitors was firstly synthesized by thermally treating the graphene-bismuth composite, which was obtained through simultaneous solvothermal reduction of the colloidal dispersions of negatively charged graphene oxide sheets in N,N-dimethyl formamide (DMF) solution of bismuth cations at 180 °C. The morphology, composition, and microstructure of the composites together with pure graphite oxide, and graphene were characterized using powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetry and differential thermogravimetry (TG-DTG). The electrochemical behaviors were measured by cyclic voltammogram (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). The specific capacitance of 255 F g⁻¹ (based on composite) is obtained at a specific current of 1 A g⁻¹ as compared with 71 F g⁻¹ for pure graphene. The loaded-bismuth oxide achieves a specific capacitance as high as 757 F g⁻¹ even at 10 A g⁻¹. In addition, the graphene nanosheet-bismuth oxide composite electrode exhibits the excellent rate capability and well reversibility.     

Photocatalytic synthesis of aniline from nitrobenzene using Ag-reduced graphene oxide nanocomposite

We used a UV-irradiation reduction method to prepare Ag-reduced graphene oxide (RGO) composite by reducing graphite oxide and silver ion in ethanol. Transmission electron microscopy (TEM), X-ray diffraction spectroscopy (XRD), UV–vis absorption spectrophotometry (UV–vis), and X-ray photoelectron spectroscopy (XPS) characterized the prepared samples. Ag–RGO nanocomposite was tested for reduction of nitrobenzene to aniline under visible light. The Ag–RGO nanocomposites have a high efficiency to convert nitrobenzene to aniline under visible-light irradiation. Therefore, Ag-reduced graphene oxide nanocomposite can be used as a photocatalyst for organic synthesis.     

Direct electrochemistry of horseradish peroxidase on graphene-modified electrode for electrocatalytic reduction towards H2O2

Graphene was synthesized by a chemical method to reduce graphite oxide and well characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectra. Horseradish peroxidase (HRP) immobilized on a graphene film glassy carbon electrode was found to undergo direct electron transfer and exhibited a fast electron transfer rate constant of 4.63 s⁻¹. The HRP-immobilized electrode was investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The CV results showed that the modified electrode gave rise to well-defined peaks in phosphate buffer, corresponding to the electrochemical redox reaction between HRP–Fe(III) and HRP–Fe(II). The obtained electrode also displayed an electrocatalytic reduction behavior towards H₂O₂. The new H₂O₂ sensor shows a linear range of 0.33–14.0 μM (R² = 0.9987) with a calculated detection limit of 0.11 μM (S/N = 3). Furthermore, the biosensor exhibits both good operational storage and storage stability.     

The synthesis of graphene sheets with controlled thickness and order using surfactant-assisted electrochemical processes

An electrochemical route is reported for the production of graphene sheets using the following steps: electrochemical intercalation of sodium dodecyl sulfate (SDS) into graphite followed by electrochemical exfoliation of a SDS-intercalated graphite electrode. These electrochemical processes yield a stable colloidal graphene/SDS suspension. The potential value for SDS intercalation into graphite plays an important role in determining the structural order, size, and number of layers of synthesized graphene sheets. Raman spectroscopy and transmission electron microscopy results indicate that graphene sheets with the highest structural order and lowest number of layers can be obtained by using relatively high intercalation potentials. Average size and thickness of graphene sheets prepared at high potentials for SDS intercalation into graphite were measured to be about 500 and 1 nm, respectively, indicating presence of graphene sheets as thin as a monolayer. UV–vis spectra of graphene/SDS suspensions show that a large amount of the reduced form of graphene flakes is obtained after successive electrochemical intercalation and exfoliation processes.     

Thermally reduced graphenes exhibiting a close relationship to amorphous carbon

Graphene is an important material for sensing and energy storage applications. Since the vast majority of sensing and energy storage chemical and electrochemical systems require bulk quantities of graphene, thermally reduced graphene oxide (TRGO) is commonly employed instead of pristine graphene. The sp(2) planar structure of TRGO is heavily damaged, consisting of a very short sp(2) crystallite size of nanometre length and with areas of sp(3) hybridized carbon. Such a structure of TRGO is reminiscent of the key characteristic of the structure of amorphous carbon, which is defined as a material without long-range crystalline order consisting of both sp(2) and sp(3) hybridized carbons. Herein, we describe the characterization of TRGO, its parent graphite material and carbon black (a form of amorphous carbon) via transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry experiments. We used the data obtained as well as consideration of practical factors to perform a comparative assessment of the relative electrochemical performances of TRGO against amorphous carbon. We found out that TRGO and amorphous carbon exhibit almost identical characteristics in terms of density of defects in the sp(2) lattice and a similar crystallite size as determined by Raman spectroscopy. These two materials also exhibit similar amounts of oxygen containing groups as determined by XPS and nearly indistinguishable cyclic voltammetric response providing almost identical heterogeneous electron transfer constants. This leads us to conclude that for some sensing and energy storage electrochemical applications, the use of amorphous carbon might be a much more economical solution than the one requiring digestion of highly crystalline graphite with strong oxidants to graphite oxide and then thermally exfoliating it to thermally reduced graphene oxide.     

Vacuum-assisted microwave reduction/exfoliation of graphite oxide and the influence of precursor graphite oxide

One-step synthesis of high quality graphene at gram-scale quantities is important for industrial applications, e.g. in electrochemistry for sensing and energy storage. Currently, thermal reduction/exfoliation of graphite oxide (GO) is a typical method of choice. However, it has the drawback of requiring specialized equipment for rapid thermal shock. A recent alternative method, microwave-assisted exfoliation, usually suffers from poor reduction of graphite oxide and thus low C/O ratios. Herein we show that vacuum-assisted microwave reduction/exfoliation of graphite oxide in a closed system leads to high C/O ratios and partial hydrogenation of graphene (2.6 at.% of H). Microwave irradiation of graphite oxide in vacuum leads to outgassing from GO and the creation of plasma which aids temperature distribution and hydrogenation. This plasma is quickly extinguished by further dramatic evolution of gases from GO and consequent pressure increase. We assess the influence of precursor graphite oxide, prepared by Hummers, Staudenmaier, and Hofmann methods, upon the materials properties of microwave exfoliated graphene. We show that microwave-exfoliated graphenes prepared from different graphite oxides show very fast heterogeneous electron transfer rates, with similar electrochemical behaviour to thermally reduced graphene oxide.     

Graphenes prepared by Staudenmaier, Hofmann and Hummers methods with consequent thermal exfoliation exhibit very different electrochemical properties

Large-scale fabrication of graphene is highly important for industrial and academic applications of this material. The most common large-scale preparation method is the oxidation of graphite to graphite oxide using concentrated acids in the presence of strong oxidants and consequent thermal exfoliation and reduction by thermal shock to produce reduced graphene. These oxidation methods typically use concentrated sulfuric acid (a) in combination with fuming nitric acid and KClO(3) (Staudenmaier method), (b) in combination with concentrated nitric acid and KClO(3) (Hofmann method) or (c) in the absence of nitric acid but in the presence of NaNO(3) and KMnO(4) (Hummers method). The evaluation of quality and applicability of the graphenes produced by these various methods is of high importance and is attempted side-by-side for the first time in this paper. Full-scale characterization of thermally reduced graphenes prepared by these standard methods was performed with techniques such as transmission and scanning electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Their applicability for electrochemical devices was further evaluated by means of cyclic voltammetry techniques. We showed that while Staudenmaier and Hofmann methods (methods that do not use potassium permanganate as oxidant) generated thermally reduced graphenes with comparable electrochemical properties, the graphene prepared by the Hummers method which uses permanganate as oxidant showed higher heterogeneous electron transfer rates and lower overpotentials as compared to graphenes prepared by the Staudenmaier or Hofmann methods. This clearly shows that the methods of preparations have dramatic influences on the materials properties and, thus, such findings are of eminent importance for practical applications as well as for academic research.     

Microwave syntheses of graphene and graphene decorated with metal nanoparticles

We report a simple and rapid method to synthesize pure graphene sheets and those decorated with metal nanoparticles by combining chemical foaming agents, green oxidizers, and microwave radiation. Under microwave radiation, an intercalated foaming agent between graphite oxide layers plays a key role in the rapid and large expansion of the graphene worm along the thickness direction and in the reduction process of the graphite oxide. By adding metal precursors to the reactant mixture, this technique can also be extended to a one-pot method to synthesize graphene decorated with metal nanoparticles. A variety of metal precursors was used to yield iron, platinum, and palladium decorated graphene sheets. These were tested for their electrocatalytic performance in organic glucose sensing and inorganic electro-active compounds, all of which showed a remarkable increase in electrochemical performance for all cases.     

One-pot electrochemical synthesis of graphene by the exfoliation of graphite powder in sodium dodecyl sulfate and its decoration with platinum nanoparticles for methanol oxidation

We demonstrate a method which directly grows large areas of graphene on carbon paper and glassy carbon (GC) substrates from graphite powder and anionic surfactant, sodium dodecyl sulfate, assisted electrochemical exfoliation. The electrochemically reduced graphene has been carefully characterized by scanning electron microscopy (SEM) and electrochemical techniques. Particularly, SEM images show enhanced growth of graphene structures formed of ‘urchin’ objects. The CV spectra illustrate that a variety of the oxygen-containing functional groups has been thoroughly removed from the graphite plane via electrochemical reduction. Potential peak (Ep) of graphene electrode in [Fe(CN)₆]^3−/4− solution is as small as 212 mV which is 168 mV smaller than that of graphite electrode. This could be attributed to the high quality graphene accelerating the electron transfer rate in [Fe(CN)₆]^3−/4− electrochemistry. Finally, platinum was electro reduced onto the GC and graphene modified GC based electrodes for use in methanol oxidation. The catalytic activities of graphene-supported Pt nanoparticles and Pt-GC electrocatalysts for methanol oxidation were 1900 and 915.5 A g⁻¹ Pt, which can reveal the particular properties of the exfoliated graphene supports.