正丁基氯化镁还原氧化石墨烯的表征

采用元素分析、红外光谱(FTIR)、X射线光电子能谱(XPS)、拉曼光谱、X射线衍射(XRD)、固体¹³C核磁共振波谱(¹³C MAS NMR)、热失重分析(TGA)、导电率测试以及原子力显微镜(AFM)等手段对正丁基氯化镁还原的氧化石墨烯进行了系统的表征. 结果表明, 正丁基氯化镁可以有效还原氧化石墨烯, 随着其用量的增加, 氧化石墨烯还原程度增加, 碳/氧摩尔比升高, 片层间距减小, 热稳定性增强, 导电率增大(可达3.6×10² S/m). 还原后部分氧化石墨烯片层发生聚集.     

石墨烯/铁氰化钴复合膜修饰玻碳电极同时测定对苯二酚、邻苯二酚和间苯二酚

采用滴涂法和电沉积法制备了石墨烯/铁氰化钴复合膜修饰玻碳电极. 用扫描电镜对该纳米复合膜进行了表征.用循环伏安法研究了对苯二酚(HQ)、邻苯二酚(CT)和间苯二酚(RS)在修饰电极上的电化学行为. 实验结果表明, 相对于裸玻碳电极和石墨烯修饰电极, HQ, CT 和RS 在石墨烯/铁氰化钴修饰电极上的氧化峰电流显著提高. 利用差分脉冲伏安法测定, HQ, CT 和RS 分别在1.0×10^－6～1.5×10^－4 mol/L, 1.0×10^－6～2.0×10^－4 mol/L 和3.5×10^－6～2.5×10^－4 mol/L浓度范围内与氧化峰电流呈良好的线性关系, 相关系数分别为0.991, 0.993 和0.992. 信噪比为3 时, HQ, CT 和RS 检出限分别为2.0×10^－7, 2.1×10^－7 和3.5×10^－7 mol/L. 将该方法用于水样分析, 回收率为95.6%～106.1%.     

激光直写微型RGO/MWCNT/CF平面柔性超级电容器的制备及性能

将采用改性Hummers法制备的氧化石墨烯与多壁碳纳米管(MWCNT)复合, 通过激光直写的方法制备了以棉织物(Cotton fabric, CF)为基底的石墨烯复合碳纳米管的同心圆形织物柔性平面超级电容器(RGO/MWCNT/CF). 通过扫描电子显微镜、 X 射线衍射和拉曼光谱技术对RGO/MWCNT/CF进行了表征, 并对超级电容器的电导率和电化学性能进行了测试. 结果表明, 电极材料经激光还原后导电率达到了7.19×10 ⁴ S/m, 表现出良好的导电性能. 以RGO/MWCNT/CF为工作电极、 PVA/LiCl凝胶为电解质组装的超级电容器具有良好的电化学性能, 在电位窗口为0~1 V、 电流密度为40.8 mA/cm ²时比电容达到24 mF/cm ², 功率密度为61 mW·h/kg, 能量密度为1.22 mW·h/kg, 且循环1000次仍能保持92%的比电容.     

纳米纤维素/还原氧化石墨烯复合材料用于高性能超级电容器

以高浓度氧化石墨烯(GO)溶液作为反应前驱体,纳米纤维素(NC)作为物理间隔物和电解液储存器,通过简单的一步水热法制备了纳米纤维素/还原氧化石墨烯(NC/rGO)复合材料,并探究了其作为超级电容器电极材料的潜力。结果如下：NC添加量为1 mL所制备的NC/rGO-1具有最佳电化学性能。基于NC/rGO-1的无黏合剂对称型超级电容器在0.3 A·g^-1的电流密度下显示出了269.33 F·g^-1和350.13 F·cm^-3的高质量和体积比电容,并在10.0 A·g^-1时仍能达到215.88 F·g^-1和280.62 F·cm^-3(其初始值的80.15%)。组装器件还显示出了较高的质量和体积能量密度(9.3 Wh·kg^-1和12.13 Wh·L^-1)和出色的循环性能(10 A·g^-1下10 000次循环后其初始比电容仅减少6.02%)。     

石墨烯和铂/石墨烯的合成及其表征

以天然鳞状石墨为原料,采用化学氧化法合成氧化石墨,在此基础上采用低温热解膨胀结合微波加热乙二醇还原法合成石墨烯(Gr)以及铂/石墨烯(Pt/Gr)复合材料。SEM和TEM显示所制备的石墨烯为层状结构的半透明薄膜。采用X射线光电子能谱(XPS)和傅立叶转换红外光谱(FTIR)分别确定氧化石墨、膨胀石墨及石墨烯表面含氧官能团的数量和性质。以所制备的碳氧原子比5.94的石墨烯作为载体制备出可用于质子交换膜燃料电池的高负载量的Pt/Gr催化剂,在铂载量高达60%时,表面铂粒子依然具有高分散性,平均粒径为3.8 nm。     

壳聚糖/氮掺杂还原氧化石墨烯修饰电极对黄嘌呤的检测及尿酸抑制的研究

用碳热还原法制备氮掺杂还原氧化石墨烯（N-RGO）,用壳聚糖（CS）的乙酸溶液作为氮掺杂还原氧化石墨烯（N-RGO）的分散剂,将其修饰在玻碳电极表面,用于检测黄嘌呤（xanthine）.该传感器对黄嘌呤展现出优异的电化学响应,线性范围为2.99×10^-8~1.07×10^-4 mol/L,检测限为9.96×10^-9 mol/L（S/N=3）.此外,利用循环伏安法（CV）对黄嘌呤电化学行为进行了研究.最后,用电化学的方法研究了非布索坦（Febuxostat）和别嘌呤醇（Allopurinol）两种药物对尿酸生成的抑制.本工作为痛风的诊断和治疗提供了重要的信息.     

柔性复合织物电极Graphene/Cotton和MnO2/Graphene/Cotton的合成及在电化学电容器中的应用

通过热还原法成功地制备出了柔性复合织物电极石墨烯/棉布(graphene/cotton)。热还原条件对电极的导电性能具有较大的影响。导电柔性织物电极graphene/cotton特有的多级结构使其既有利于进一步负载膺电容材料,又有利于电子和电解质离子的传输与扩散。通过电化学沉积方法,利用导电柔性织物电极graphene/cotton进一步制备出了电极MnO₂/graphene/cotton。利用扫描电子显微镜(SEM),傅里叶变换红外(FTIR)光谱,四探针测试法等表征技术对电极的结构进行了较为详细的表征。结果表明电极MnO₂/graphene/cotton的比电容可以达到536 F·g^-1。良好的电化学性能和柔性使得此类电极在柔性储能材料应用中具有极大的应用前景。     

多孔石墨烯分离CH4/CO2的分子动力学模拟

采用分子动力学方法模拟CH₄/CO₂混合气体在多孔石墨烯分离膜中的分离过程, 分析了3 种纳米孔功能化修饰(N/H 修饰、全H修饰和N/―CH₃修饰)对分离过程的影响规律. 模拟结果表明气体分子会在石墨烯表面形成吸附层, CO₂分子的吸附强度高于CH₄分子. 纳米孔的功能化修饰不仅减小了纳米孔的可渗透面积, 还通过影响纳米孔边缘原子的电荷分布提高了气体分子的吸附强度, 进而影响了混合气体分子在多孔石墨烯分离膜中的渗透性和选择性. CO₂分子在多孔石墨烯中的渗透率能达到10⁶ GPU (1 GPU=3.35×10^-10 mol·s^-1·m^-2·Pa^-1), 远远高于传统的聚合物分离膜. 研究表明多孔石墨烯分离膜在天然气处理、CO₂捕获等工业气体分离过程中具有广泛的应用前景.     

影响热还原氧化石墨烯超级电容器性能的因素比较

通过改进的Hummer法制得氧化石墨烯,并在不同温度的氩气气氛中还原得到一系列热还原氧化石墨烯（T-RGO）. 电化学测试表明,T-RGO作为超级电容器电极材料时,良好的导电性是必需的,但石墨烯表面含氧官能团对其电容性能的影响要远大于导电性和比表面积的影响,900 °C还原的T-RGO比表面积为314 m²·g^-1电导率为2421 S·m^-1,但其容量只有56 F·g^-1,然而300 °C还原的T-RGO比表面积为18.8 m²·g^-1电导率为574 S·m^-1,其容量却达到281 F·g^-1. 材料表征分析表明,300 °C 还原的石墨烯之所以有更高的电容,是因为除双电层电容外,更多的是由其表面含氧官能团提供的赝电容,这使作者以后在设计制备超级电容器等储能设备用石墨烯基电极材料时更加有针对性.     

氢氧化镍纳米线/三维石墨烯复合材料的制备及其电化学性能

采用水热法制备了氢氧化镍纳米线/三维石墨烯复合材料及作为比较的三维石墨烯、氢氧化镍纳米线、还原氧化石墨烯和氢氧化镍纳米线/还原氧化石墨烯, 通过X射线衍射、扫描电镜、热失重分析和氮气吸脱附表征了材料的形貌、结构和组成, 并采用循环伏安法和恒电流充放电测试了复合材料的电化学性能. 结果表明: 氢氧化镍纳米线/三维石墨烯复合材料中直径为20-30 nm的氢氧化镍纳米线和三维结构的石墨烯紧密结合, 相互交联形成网状结构, 其比表面积达到136 m²·g^-1, 孔径分布20-50 nm, 氢氧化镍纳米线的含量达到88% (w,质量分数). 在6 mol·L^-1的KOH电解液中, 复合材料的比电容在1 A·g^-1电流密度下达到1664 F·g^-1, 在1 A·g^-1电流密度下循环3000 次后的比电容保持率为93%. 将复合材料的比电容和循环性能与氢氧化镍纳米线、氢氧化镍纳米线/还原氧化石墨烯、三维石墨烯和还原氧化石墨烯的性能进行比较, 发现三维石墨烯较还原氧化石墨烯具有更高的比表面积和三维多孔结构, 可以更大地提高活性物质的利用率, 进而提高复合材料的比电容和稳定性.     

Low‐Temperature Solid‐State Microwave Reduction of Graphene Oxide for Transparent Electrically Conductive Coatings on Flexible Polydimethylsiloxane (PDMS)

Microwaves (MWs) are applied to initialize deoxygenation of graphene oxide (GO) in the solid state and at low temperatures (～165 °C). The Fourier‐transform infrared (FTIR) spectra of MW‐reduced graphene oxide (rGO) show a significantly reduced concentration of oxygen‐containing functional groups, such as carboxyl, hydroxyl and carbonyl. X‐ray photoelectron spectra confirm that microwaves can promote deoxygenation of GO at relatively low temperatures. Raman spectra and TGA measurements indicate that the defect level of GO significantly decreases during the isothermal solid‐state MW‐reduction process at low temperatures, corresponding to an efficient recovery of the fine graphene lattice structure. Based on both deoxygenation and defect‐level reduction, the resurgence of interconnected graphene‐like domains contributes to a low sheet resistance (～7.9×10⁴ Ω per square) of the MW‐reduced GO on SiO₂‐coated Si substrates with an optical transparency of 92.7 % at ～547 nm after MW reduction, indicating the ultrahigh efficiency of MW in GO reduction. Moreover, the low‐temperature solid‐state MW reduction is also applied in preparing flexible transparent conductive coatings on polydimethylsiloxane (PDMS) substrates. UV/Vis measurements indicate that the transparency of the thus‐prepared MW‐reduced GO coatings on PDMS substrates ranges from 34 to 96 %. Correspondingly, the sheet resistance of the coating ranges from 10⁵ to 10⁹ Ω per square, indicating that MW reduction of GO is promising for the convenient low‐temperature preparation of transparent conductors on flexible polymeric substrates.     

石墨烯/银复合薄膜的制备及表征

采用静电自组装技术,通过交替沉积聚(二烯丙基二甲基氯化铵)(PDDA)(或硝酸银)和氧化石墨烯,制备氧化石墨烯/PDDA薄膜和氧化石墨烯/硝酸银复合薄膜。然后在600℃下通入氩气和氢气进行气氛还原得到石墨烯薄膜和石墨烯/银复合薄膜。采用AFM、SEM、XPS、UV-Vis以及四探针电阻仪等对薄膜结构及性质进行表征。结果表明,通过静电自组装法可以获得生长均匀的薄膜。对比于相同自组装次数的石墨烯薄膜,石墨烯/银复合薄膜具有更好的透光性和更低的薄膜方块电阻。在λ=500 nm时,四层石墨烯/银复合薄膜的透过率为85%左右,而石墨烯薄膜的透过率为72%左右;石墨烯薄膜的方阻为161.39 kΩ.□-1,而石墨烯/银复合薄膜的方阻为99.11 kΩ.□-1。     

Transparent and conductive thin films of graphene/polyaniline nanocomposites prepared through interfacial polymerization

This communication reports a simple, one-pot procedure for the synthesis and processing of transparent and conductive thin films of graphene/polyaniline nanocomposites based on an interfacial polymerization. Thin films presenting transmittance of 89% and sheet resistance of 60.6 ? sq(-1) are spontaneously obtained and can be easily transferred to suitable substrates.     

Enhanced Performance of Transfer-Free Graphene Transparent Conductive Films on Insulating Substrates by Introducing Array Nanostructure

Graphene is one of the most prevailing materials to replace traditional transparent conductive films (TCFs). In order to improve the performance of graphene TCFs, it is proposed to directly deposit graphene on insulating substrates via assisted catalysis of Cu foil to avoid intricate transfer process, and further effectively enhance the optical performance by introducing the close-packed antireflection array nanostructure. The graphene TCFs grown on bare quartz substrates have sheet resistance of 0.766 kΩ sq⁻¹ and transmittance of 86.83 %. Graphene composite TCFs with transmittance of 95.79 % were obtained by introducing the close-packed solid/hollow SiO₂ nanospheres antireflection array nanostructure. Compared with graphene TCFs, transmittance of graphene composite TCFs increased significantly, while the sheet resistance remained at the same level. This method combining direct synthesis technique with novel antireflection array nanostructure provides a significant design idea to grow transfer-free graphene with controllable optoelectronic properties and promotes the application and development of the future electronic devices.     

石墨烯的制备、表征及其在透明导电膜中的应用

近年来,石墨烯因其优异的电学和光学等特性,越来越受到人们的广泛关注。研究人员应用多种方法来合成石墨烯并且探讨其潜在的应用价值。本文首先简要介绍了石墨烯的结构及其基本的物理性质,并简单回顾了石墨烯的合成方法和表征手段。在此基础上,讨论了石墨烯/银复合薄膜在透明导电膜中的应用,并详细介绍了我们在该领域的研究成果。用化学气相沉积法（CVD）和多羟基法分别制备了双层石墨烯及银纳米线,成功合成了石墨烯/银复合薄膜,结果表明复合薄膜的方块电阻可降低至26 Ω·□-1,展示了其在光电器件上广泛的应用前景。     

Inspired by Grape Seed and Wine: Tannic Acid as a Modified Coating for Fabricating Highly Flexible,Transparent and Conductive Film

The application of transparent conductive films in flexible electronics has shown promising prospects recently. Tannic acid(TA) was successfully applied to modifying the surface of polydimethylsiloxane(PDMS) to fhbricate highly flexible, transparent and conductive Ag nanowires(NWs) based films. TA modification transformed the PDMS surface from hydrophobicity into hydrophilicity without decreasing the transparence. A sheet resistance(Rs) of 80 Ω/cm^2 with an optical transmittance of 94% was achieved, which was superior to that of indium tin oxide(ITO) films. More importantly, the TA layer enhanced the interaction between Ag NWs and the PDMS substrate. The Ag NWs films on TA modified PDMS substrate exhibited excellent stability in Rs when subjected to a bending test.     

Ga对在AlN衬底上直接生长石墨烯的远程催化

通过镓(Ga)远程催化, 采用化学气相沉积(CVD)方法在氮化铝(AlN)衬底上直接生长石墨烯薄膜. 研究了生长温度、 催化剂距离对石墨烯生长及其光学性质和电学性质的影响规律. 结果表明, 在生长温度1070 ℃下可以制备厚度约为5层的石墨烯薄膜, Ga周围1.4 cm范围内可以得到厚度均匀的石墨烯薄膜. 通过透光率和方阻表征了石墨烯的光学和电学性质, 结果表明, 400~800 nm波长范围内石墨烯薄膜透光率可达90%以上, 方阻约为230 Ω/□. 第一性原理计算结果表明, 石墨烯仍保持金属性, AlN衬底对石墨烯有吸附掺杂作用, 可有效降低石墨烯的方阻, 改善石墨烯和衬底的电学接触.     

Self-assembled graphene/azo polyelectrolyte multilayer film and its application in electrochemical energy storage device

Graphene/azo polyelectrolyte multilayer films were fabricated through electrostatic layer-by-layer (LbL) self-assembly, and their performance as electrochemical capacitor electrode was investigated. Cationic azo polyelectrolyte (QP4VP-co-PCN) was synthesized through radical polymerization, postpolymerization azo coupling reaction, and quaternization. Negatively charged graphene nanosheets were prepared by a chemically modified method. The LbL films were obtained by alternately dipping a piece of the pretreated substrates in the QP4VP-co-PCN and nanosheet solutions. The processes were repeated until the films with required numbers of bilayers were obtained. The self-assembly and multilayer surface morphology were characterized by UV-vis spectroscopy, AFM, SEM, and TEM. The performance of the LbL films as electrochemical capacitor electrode was estimated using cyclic voltammetry. Results show that the graphene nanosheets are densely packed in the multilayers and form random graphene network. The azo polyelectrolyte cohesively interacts with the nanosheets in the multilayer structure, which prevents agglomeration of graphene nanosheets. The sheet resistance of the LbL films decreases with the increase of the layer numbers and reaches the stationary value of 1.0 × 10(6) Ω/square for the film with 15 bilayers. At a scanning rate of 50 mV/s, the LbL film with 9 bilayers shows a gravimetric specific capacitance of 49 F/g in 1.0 M Na(2)SO(4) solution. The LbL films developed in this work could be a promising type of the electrode materials for electric energy storage devices.     

Free-standing highly conductive transparent ultrathin single-walled carbon nanotube films

Transparent and conductive single-walled carbon nanotube (SWNT) films are of great importance to a number of applications such as optical and electronic devices. Here, we describe a simple approach for preparing free-standing highly conductive transparent SWNT films with a 20-150 nm thickness by spray coating from surfactant-dispersed aqueous solutions of SWNTs synthesized by an improved floating-catalyst growth method. After the HNO(3) treatment, dipping the SWNT films supporting on glass substrates in water resulted in a quick and nondestructive self-release to form free-standing ultrathin SWNT films on the water surface. The obtained films have sufficiently high transmittance (i.e., 95%), a very low sheet resistance (i.e., ～120 Ω/sq), and a small average surface roughness (i.e., ～3.5 nm for a displayed 10 × 10 μm area). Furthermore, the floating SWNT films on the water surface were easily transferred to any substrates of interest, without intense mechanical and chemical treatments, to preserve their original sizes and network structures. For example, the transferred SWNT films on poly(ethylene terephthalate) films are mechanically flexible, which is a great advantage over conventional indium-tin oxide (ITO) and therefore strongly promise to be "post ITO" for many applications.     

石墨烯玻璃透明薄膜加热特性

Graphene has become a research focus in recent years owing to its excellent characteristics, and glass is a commonly used material with high transparency and low cost. Graphene glass combines the excellent properties of both graphene and glass; graphene glass has not only high thermal conductivity, high electrical conductivity, and good surface hydrophobicity but also exhibits superior electrothermal conversion and wide-spectrum high-light-transmittance characteristics. Therefore, the study of graphene glass films is of theoretical value and practical significance. In this study, a high-purity glass-based (JGS1 quartz glass) multilayer graphene film was developed based on an atmospheric-pressure chemical vapor deposition (APCVD) method, and its electrical characteristics, light transmittance, and electrical heating characteristics were experimentally investigated in detail. The results show that graphene glass with different surface resistance values obtained through direct growth on a high-purity quartz glass substrate using the APCVD method, not only has excellent uniformity and quality, but also has considerably flat and high transmittance across the entire visible light region and exhibits excellent heating performance and fast response time. For graphene glass with a surface resistance of 1500 Ω·sq^-1, the light transmittance can reach 74%, and the saturation temperature can rise to 185 ℃ by applying a bias voltage of 40 V. In addition, when the resistance value of the graphene glass is 420 Ω·sq^-1, the graphene glass reaches a high saturation temperature of 325 ℃ in 40 s, and the corresponding heating rate can exceed 18 ℃·s^-1, achieving a significantly higher heating rate than other heating films at the same voltage. Compared with the polyethylene-terephthalate- (PET-) based and silicon-based graphene films obtained by the transfer, graphene glass has a higher saturation temperature, shorter thermal response time, and faster heating rate. Furthermore, graphene glass exhibits better heating cycle stability and longer-term heating stability at a constant voltage. In addition, an experiment using the graphene glass to thermally tune the wavelength of a vertical-cavity surface-emitting laser was conducted and gave good results. The position of the laser peak controlled by the graphene glass was red-shifted by 1.78 nm by applying a voltage of 20 V, and the wavelength tuning efficiency reached 0.059 nm·℃^-1. Compared with PET-based and silicon-based graphene films, the actual electrical heating capacity of graphene glass increased by 195%. These experimental findings demonstrate that graphene glass transparent films with excellent electric heating characteristics can be used in various transparent electric heating fields and have relatively wide application prospects.