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。     

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。     

纳米碳材料在可穿戴柔性导电材料中的应用研究进展

可穿戴设备的兴起使得对柔性器件的需求日益提高,柔性导电材料作为可穿戴器件的重要组成部分而成为研究的热点。传统的电极材料主要是金属,因金属材料本身不具有柔性,一般通过降低金属层厚度以及设计波纹结构等策略实现其在柔性器件中的应用,其加工程序复杂,成本较高。以碳纳米管和石墨烯为代表的纳米碳材料兼具良好的柔性和优异的导电性,且具有化学稳定、热稳定、光学透明性等优点,在柔性导电材料领域展现了极大的应用潜力。本文简要综述了近年来纳米碳材料在柔性导电材料领域的研究进展,首先介绍了碳纳米管基柔性导电材料,分别包括基于碳纳米管水平阵列、碳纳米管垂直阵列、碳纳米管薄膜、碳纳米管纤维的柔性导电材料;继而介绍了石墨烯基柔性导电材料,包括基于剥离法制备的石墨烯和化学气相沉积法制备的石墨烯以及石墨烯纤维基柔性导电材料;并简述了碳纳米管/石墨烯复合柔性导电材料;最后论述了纳米碳材料基柔性导电材料所面临的挑战并展望了其未来发展方向。     

层层自组装法制备石墨烯/聚苯胺复合薄膜及在传感器中的应用

利用层层自组装技术,将聚丙烯酸修饰的石墨烯(PAA-Gr)与聚苯胺(PANI)进行层层自组装,制备了石墨烯/聚苯胺{PAA-Gr/PANI}n复合薄膜.聚丙烯酸修饰石墨烯不仅可以提高石墨烯的分散性,而且可以使石墨烯表面带负电荷,为其与带正电的PANI进行层层自组装提供了可能.利用紫外光谱跟踪了{PAA-Gr/PANI}n复合薄膜层层自组装过程.通过红外光谱、X射线衍射、扫描电子显微镜和循环伏安等方法表征了{PAA-Gr/PANI}n复合薄膜的结构.研究了{PAA-Gr/PANI}n复合薄膜的电化学性能,并探讨了复合薄膜在过氧化氢(H2O2)传感器中的应用.{PAA-Gr/PANI}n复合薄膜对H2O2表现出良好的电催化活性,其线性检测范围为0.005~0.3 mmol/L,线性相关系数为0.99858,检测下限为1×10-6mol/L.     

碳纳米管/石墨烯复合结构及其电化学电容行为

本文综述了超级电容器电极材料碳纳米管/石墨烯复合结构的制备方法,以及由该结构和赝电容活性物质形成的三元复合体系的电化学电容行为研究进展,并提出合理设计的碳纳米管和石墨烯复合结构可以有效发挥其高电导率、高比表面积和合理孔隙结构的优势,实现活性物质的高密度负载,从而获得具有高容量、良好倍率特性和长寿命的电化学超级电容器电极材料。     

石墨烯/类金刚石碳复合薄膜的电化学沉积及其场发射性能

采用液相电化学方法在硅基底上制备了石墨烯掺杂的类金刚石碳复合薄膜,探讨了电化学沉积复合薄膜的机理。利用扫描电子显微镜（SEM）、拉曼光谱（Raman）、透射电子显微镜（TEM）和傅里叶变换红外（FTIR）光谱技术对薄膜表面形貌和微观结构进行了分析表征。结果表明,石墨烯片均匀分散沉积在含氢类金刚石碳（a-C：H）基体中,沉积的石墨烯/类金刚石（G/a-C：H）复合薄膜表面相对均匀平整。场发射测试显示石墨烯掺杂使开启电场从4.7 V·μm^-1增加至5.8 V·μm^-1,场发射电流密度从384 μA·cm^-2显著增加至876 μA·cm^-2。     

简易方法制备交叉碳纳米管-石墨烯异质结

发展了一种通过两次高分子辅助转移和选择性氧等离子体刻蚀技术大量制备交叉碳纳米管-石墨烯异质结的无损方法. 拉曼光谱和导电性测试证明, 制备的单层石墨烯薄片在大面积范围内质量均一、导电性好. 而且, 本文所讨论的单层石墨烯的生长和随后的器件制备也提供了大面积制备石墨烯薄片图案化的可重复性方法. 该方法与传统的薄膜技术兼容, 只需简易的几步便可把图案化的石墨烯集成到大规模的微电子器件回路中, 有望实现流线型和自动化的石墨烯微电子器件的大量生产. 这些研究结果为进一步制备分子整流器和其它功能纳米/分子器件提供了技术基础.     

石墨烯/有机物复合吸附剂的设计及其在水处理中的应用

当今,资源和能源极度紧缺,改良传统吸附剂,开发高效、低成本、高性能的复合吸附剂成为一大研究课题。石墨烯/有机物复合吸附剂结合了无机材料石墨烯和有机材料的优势,在水处理吸附领域有着广阔的应用前景。目前有关石墨烯/有机物复合吸附剂的设计思路、合成方法及其在水处理中的应用缺少相关的综述。因此,本文对近些年在石墨烯/有机物复合吸附剂的制备及其应用等方面取得的进展进行了综述,探讨和分析了不同类型石墨烯/有机物复合吸附剂的性能以及存在的问题,对其发展方向进行了展望,为后续开展石墨烯/有机物复合吸附剂的相关研究及应用提供了参考。     

一步法制备TiO_2/石墨烯复合多孔薄膜应用于增强光催化活性及光伏性能（英文）

纳米二氧化钛具有制备简单、成本低、化学稳定性好及光响应度高等诸多优势,因而广泛应用于光催化及太阳能转化等诸多领域中.然而,传统TiO_2纳米材料受限于较高光电子空穴复合率,导致其光催化活性及光电转化效率较低.为解决这一问题,研究者采用多种方法用以改善纳米TiO_2的结构,包括化学掺杂、半导体材料插层、碳材料杂化等;另一方面则关注材料结构的设计,例如将合成的纳米材料进一步加工为多孔薄膜,以增大材料比表面积及器件稳定性,以增强其器件性能.其中,将石墨烯引入纳米TiO_2中,形成复合纳米材料,以提升材料本身的光电子传输效率,降低光生载流子复合率,为制备高性能光催化剂及光伏器件开辟了一条可行之路.然而,目前制备的纳米TiO_2/石墨烯复合材料的性能仍不理想,其中常见的问题为合成的材料团聚严重,导致光生载流子在界面传输阻力及复合率都十分高,限制其实际应用.此外,当前大多数关于纳米TiO_2/石墨烯的制备方法仍为溶胶凝胶法、水热法等,所得材料需要进一步进行微纳加工方能形成介孔结构;这些加工方式往往需要二次退火处理,这会进一步加重纳米材料的团聚现象,导致孔隙率分布混乱、材料界面缺陷增多等不良结果.因此,本文采用一步法-蒸汽热法成功制备了TiO_2/石墨烯复合多孔薄膜,无需二次热处理.实验结果表明,所制TiO_2/石墨烯复合物(VTH)的形貌为二维结构,其比表面积高达260 m~2g~(–1),获得的多孔薄膜无明显团聚且孔隙分布集中.当复合物中还原氧化石墨烯含量为5.0wt%时,其光催化活性最高,高于单一的TiO_2薄膜近3倍;将还原氧化石墨烯含量为0.75wt%的复合物用于染料敏化太阳能电池的光阳极时,光电转化效率达到7.58%,明显高于传统方法制备的单一TiO_2的(4.38%).     

石墨烯-氧化钨复合薄膜的制备及界面电子传输特性

以偏钨酸铵为钨源、聚乙烯吡咯烷酮为连接剂,采用浸渍提拉法制备了石墨烯-氧化钨复合薄膜,利用X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）及Raman光谱等方法对复合结构材料进行了表征,并利用光电流测试、交流阻抗谱（EIS）、瞬态光电流谱和强度调制光电流谱等方法,研究复合薄膜电极在光电作用下界面上的载流子转移过程和电荷传输行为. 结果表明,组成薄膜的氧化钨纳米颗粒与石墨烯充分复合,光电性能显著提高;与石墨烯复合后,薄膜的瞬态时间常数增大,电子-空穴对寿命延长;电子传输时间减少,为纯氧化钨薄膜的47.5%.     

Rational design of three-dimensional nitrogen and phosphorus co-doped graphene nanoribbons/CNTs composite for the oxygen reduction

In the present work, we report nitrogen and phosphorus co-doped 3-D structured carbon nanotube intercalated graphene nanoribbon composite. The graphene nanoribbons are prepared via partial exfoliation of multi-walled carbon nanotubes. In the graphene nanoribbons/CNTs composite, carbon nanotubes play a role of skeleton and support the exfoliated graphene nanoribbons to form the stereo structure. After high temperature heat-treatment with ammonium dihydrogen phosphate, the unique structure reserves both the properties of carbon nanotube and graphene, exhibiting excellent catalytic performance for the ORR with excellent onset and half-wave potential, which is similar to commercial Pt/C electrocatalysts.     

Sensitive detection of luteolin based on poly(diallyldimethylammonium chloride)-functionalized graphene-carbon nanotubes hybrid/β-cyclodextrin composite film

Poly(diallyldimethylammonium chloride) (PDDA)-functionalized graphene sheets-multiwalled carbon nanotubes (G-CNTs) hybrid materials (PDDA-G-CNTs) were successfully synthesized. The materials were characterized by transmission electron microscopy (TEM) and Fourier transform infrared (FT-IR) spectra. Then, an electrochemical sensor based on PDDA-G-CNTs/β-cyclodextrin (PDDA-G-CNTs/β-CD) was fabricated for the sensitive determination of luteolin. In 0.2 M HAc–NaAc buffer solution (pH 5.0), the redox peak currents of luteolin increased significantly on PDDA-G-CNTs/β-CD modified glassy carbon electrode (GCE), suggesting that the composite film not only showed excellent electronic properties of PDDA-G-CNTs but also exhibited high molecular recognition capability of β-CD. The chronocoulometry investigation demonstrated that the composite could effectively increase the electrochemical active surface. Under the optimal conditions, the oxidation peak current of luteolin increased linearly with increasing the concentration in the range from 0.05 to 60 μM with the detection limit of 0.02 μM (S/N?=?3). The developed electrochemical sensor exhibited high selectivity, good stability and reproducibility, and also successfully determined luteolin in drug samples.     

Preparation of antistatic high‐density polyethylene composites based on synergistic effect of graphene nanoplatelets and multi‐walled carbon nanotubes

Graphene nanoplatelets are promising candidates for enhancing the electrical conductivity of composites. However, because of their poor dispersion, graphene nanoplatelets must be added in large amounts to achieve the desired electrical properties, but such large amounts limit the industrial application of graphene nanoplatelets. Multi‐walled carbon nanotubes also possess high electrical conductivity accompanied by poor dispersion. Therefore, a synergistic effect was generated between graphene nanoplatelets and multi‐walled carbon nanotubes and used for the first time to prepare antistatic materials with high‐density polyethylene via 1‐step melt blending. The synergistic effect makes it possible to significantly improve the electrical properties by adding a small amount of untreated graphene nanoplatelets and multi‐walled carbon nanotubes and increases the possibility of using graphene nanoplatelets in industrial applications. When only 1 wt% graphene nanoplatelets and 0.5 wt% multi‐walled carbon nanotubes were added, the surface and volume resistivity values of the composites were much lower than those of the composites that were only added 3 wt% graphene nanoplatelets. Additionally, as a result of the synergistic effect of graphene nanoplatelets and multi‐walled carbon nanotubes, the composites met the requirements for antistatic materials.     

Electrochemical study of single wall carbon nanotubes/graphene/ferritin composite for biofuel cell applications

A single wall carbon nanotubes (SWNTs)/graphene/ferritin/GOx layer on a glassy carbon electrode (GCE) acting as a biofuel cell anode was fabricated using a SWNTs/graphene/ferritin composite as an electron transfer mediator from the enzyme to the electrode. In the presence of glucose, the SWNTs/graphene/ferritin/GOx composite showed a higher current response than SWNTs/graphene/GOx composite and the electrocatalytic oxidation of glucose on the anode increased linearly with increasing concentration of glucose. The highly distributed SWNTs/graphene/ferritin composite acts as a platform for enzyme immobilization resulted in an enhanced electrocatalytic activity towards glucose. The SWNTs/graphene/ferritin composite showed an enhanced electron transfer from enzyme to the electrode; therefore, SWNTs/graphene/ferritin/GOx composite can be used as an anode in biofuel cells.     

Analytical applications of nanomaterials in electrogenerated chemiluminescence

This critical review covers the use of carbon nanomaterials (single-wall carbon nanotubes, multi-wall carbon nanotubes, graphene, and carbon quantum dots), semiconductor quantum dots, and composite materials based on the combination of the aforementioned materials, for analytical applications using electrogenerated chemiluminescence. The recent discovery of graphene and related materials, with their optical and electrochemical properties, has made possible new uses of such materials in electrogenerated chemiluminescence for biomedical diagnostic applications. In electrogenerated chemiluminescence, also known as electrochemiluminescence (ECL), electrochemically generated intermediates undergo highly exergonic reactions, producing electronically excited states that emit light. These electron-transfer reactions are sufficiently exergonic to enable the excited states of luminophores, including metal complexes, quantum dots and carbon nanocrystals, to be generated without photoexcitation. In particular, this review focuses on some of the most advanced and recent developments (especially during the last five years, 2010–2014) related to the use of these novel materials and their composites, with particular emphasis on their use in medical diagnostics as ECL immunosensors.     

Nickel oxide coated on ultrasonically pretreated carbon nanotubes for supercapacitor

Nickel oxide/carbon nanotubes (NiO/CNTs) composite materials for supercapacitor are prepared by chemically depositing nickel hydroxide onto carbon nanotubes pretreated by ultrasonication and followed by thermal annealing at 300 °C. A series of NiO/CNTs composites with different weight ratios of nickel oxide versus carbon nanotubes are synthesized via the same route. The high-resolution TEM and SEM results show that a lot of nicks, which favored the nucleation of the nickel hydroxide formed on the outer walls of carbon nanotubes due to ultrasonic cavitations, and then nickel oxide coated uniformly on the outer surface of the individual carbon nanotubes. The NiO/CNTs electrode presents a maximum specific capacitance of 523 F/g as well as a good cycle life during 1,000 cycles in 6 M KOH electrolyte. The good electrochemical characteristics of NiO/CNTs composite can be attributed to the three-dimensionally interconnected nanotubular structure with a thin film of electroactive materials.     

Graphene and carbon nanotube composite electrodes for supercapacitors with ultra-high energy density

We describe a graphene and single-walled carbon nanotube (SWCNT) composite film prepared by a blending process for use as electrodes in high energy density supercapacitors. Specific capacitances of 290.6 F g(-1) and 201.0 F g(-1) have been obtained for a single electrode in aqueous and organic electrolytes, respectively, using a more practical two-electrode testing system. In the organic electrolyte the energy density reached 62.8 Wh kg(-1) and the power density reached 58.5 kW kg(-1). The addition of single-walled carbon nanotubes raised the energy density by 23% and power density by 31% more than the graphene electrodes. The graphene/CNT electrodes exhibited an ultra-high energy density of 155.6 Wh kg(-1) in ionic liquid at room temperature. In addition, the specific capacitance increased by 29% after 1000 cycles in ionic liquid, indicating their excellent cyclicity. The SWCNTs acted as a conductive additive, spacer, and binder in the graphene/CNT supercapacitors. This work suggests that our graphene/CNT supercapacitors can be comparable to NiMH batteries in performance and are promising for applications in hybrid vehicles and electric vehicles.     

Application of carbon-based nanomaterials in sample preparation: A review

In this paper, a broad overview on the applications of different carbon-based nanomaterials, including nanodiamonds, fullerenes, carbon nanotubes, graphene, carbon nanofibers, carbon nanocones-disks and nanohorns, as well as their functionalized forms, in sample preparation is provided. Particular attention has been paid to graphene because many papers regarding its application in this research field are becoming available. The distinctive properties, derivatization methods and application techniques of these materials were summarized and compared. According to their research status and perspective, these nanomaterials were classified in four groups (I: graphene and carbon nanotubes; II: carbon nanofibers; III: fullerenes; and IV: nanodiamonds, carbon nanocones/disks and carbon nanohorns) and characteristics and future trends of every group were discussed.     

聚合物/无机纳米粒子复合膜在气体分离中的研究进展

由于聚合物膜具有可高度设计、机械性能好、易于加工 等优点,是理想的气体分离材料。然而,聚合物膜在气体选择性和渗透性方面存在平衡限制,在聚合物中引入纳米粒子,是提高气体分离性能的一种有效手段。本文基于聚合物/无机纳米粒子复合膜在气体分离领域的研究现状,重点阐述了零维纳米粒子（二氧化硅、二氧化钛）、一维纳米粒子（碳纳米管）、二维纳米粒子（氧化石墨烯、二维过渡金属氧化物）、三维纳米粒子（金属有机框架、沸石）对气体分离性能的影响,并展望了聚合物复合分离膜的发展趋势,为未来高效分离膜的研发提供了参考。