石墨烯研究进展

自2004年安德烈·K·海姆（Andre Geim）教授和科斯佳．诺沃谢洛夫（Kostya Novoselov）研究员首次制备出石墨烯以来,石墨烯受到了全世界科学家的广泛关注。截止到2009年5月26日,关于石墨烯的SCI文章达到2874篇,仅2008年就有1123篇,发表在Science和Nature的相关论文就超过了80篇;其中在2008年,发表在Science和Nature的文章有30多篇。     

石墨烯的光催化研究

石墨烯是一种具有独特的二维平面结构和导电性能好、比表面积大、耐高温等优异性能的新型纳米材料,在物理化学领域应用广泛。本文介绍了利用化学气相沉积法制备单层石墨烯,并以石墨烯和硅作为催化表面,通过表面增强拉曼散射技术研究了对硝基苯硫酚(4NBT)分子的表面催化反应。结果表明,单层石墨烯具有良好的光催化性能。     

石墨烯的量子电容

量子电容在半导体纳米材料和器件中是一个日趋重要的参数,测量和提取石墨烯的量子电容,不仅可以得到石墨烯的重要物理性质,而且对石墨烯晶体管的尺寸缩减行为具有重要指导意义.文章中采用简单工艺在石墨烯上制备出均匀超薄的高质量Y2O3栅介质,其等效栅氧厚度(EOT)可缩减至1.5nm,通过控制栅介质厚度的变化,精确测量并提取了石墨烯量子电容,其电容值在远离狄拉克点时与理论计算相符合;在此基础上,文章作者提出了基于电势涨落的量子电容微观模型,通过采用单一参数——电势涨落δV,可以定量地描述Dirac点附近的量子电容行为,从而在全能量范围内实现对石墨烯量子电容测量值的完美拟合,并得到了石墨烯的相关重要参数.进而,作者从量子电容的角度,探索了石墨烯晶体管的性能极限,并比较其相对于Ⅲ-Ⅴ族场效应晶体管的潜在优势.     

有限尺寸石墨烯的电子态

根据π电子的紧束缚模型, 通过有限系统的Bloch定理方法, 解析计算了有限尺寸石墨烯的电子态和能带. 研究发现, 其电子态有且只有两类, 分别是驻波态和边缘态.驻波态时, 波函数形式是两个方向都是正弦函数; 边缘态时, 波函数形式是Armchair边界的方向是双曲正弦函数, Zigzag边界的方向是正弦函数. 其能带由总碳原子数N个离散的本征值组成, 推导了定量计算边缘态的本征值个数的表达式, 并通过态密度来分析边缘态的存在和与无限大情况的一致性. 所有的分析中数值结果与解析理论都完全一致, 当两个受限方向都变成无限长时, 可以得到与无限大石墨烯相同的结果. 关键词： 紧束缚模型 石墨烯 边缘态 态密度     

发射白光的石墨烯陶瓷

波兰科学家报道称,石墨烯陶瓷在受到可见光或红外光激发时,可让其带隙张开,发出白光。波兰科学院和弗罗茨瓦夫理工大学的Wieslaw Strek及其同事称,宽带发射的中心在650nm处,具有明显阈值的激发激光功率对宽带发射强度有着极强的影响。这些研究人员的分析表明,此发射源在本质上完全是利用电子作用,而与炽热发光     

石墨烯晶体的微观起伏

最近发现石墨烯晶体具有独特的电子结构,其载流子的运动规律与无质量的相对论粒子相同.虽然石墨烯被认为是由碳原子紧密排列而成的单层蜂窝状结构,但其物理结构依然有令人不解之处.     

基于石墨烯/石墨烯卷轴复合薄膜高灵敏度柔性压力传感器

一维导电材料例如纳米线,大量应用于柔性压力传感器中. 但是一维材料和基底之间接触时相互作用力较弱,使得传感器灵敏度、响应时间、和循环寿命等性能指标有待进一步提高. 针对这些问题,设计了石墨烯/石墨烯卷轴多分子层复合薄膜作为传感器导电层. 石墨烯卷轴具有一维结构,而石墨烯的二维结构可以牢固地固定卷轴,以确保高导电性复合薄膜与基底之间的粘附性,同时整体结构的导电通道得到了增加. 由于一维和二维结构的协同效应,实现了应变灵敏度系数3.5 kPa^-1、 响应时间小于50 ms、能够稳定工作1000次以上的压阻传感器.     

高性能石墨烯霍尔传感器

本文回顾了石墨烯霍尔传感器的相关研究工作.通过改善石墨烯生长转移和霍尔元件的微加工工艺,石墨烯霍尔元件和霍尔集成电路都展示出超越传统霍尔传感器的优异性能.石墨烯霍尔元件的灵敏度、分辨率、线性度和温度稳定性等重要指标都优于传统商用霍尔元件.通过开发一套钝化工艺,霍尔元件的稳定性有了明显提升.结合石墨烯材料的特点,展示了石墨烯在柔性磁传感和多功能传感领域的新颖应用.此外,成功实现了石墨烯/硅互补型金属-氧化物-半导体(CMOS)混合霍尔集成电路,并进行了应用展示.通过发展一套低温加工工艺(不超过180℃),将石墨烯霍尔元件制备在硅基CMOS芯片的钝化层上,从而与硅基CMOS电路实现了单片集成.本文的研究结果表明石墨烯在霍尔磁探测方向拥有重大的性能优势,在产业化应用中有巨大发展潜力.     

石墨烯射频器件研究进展

石墨烯因具有优良的电学特性,在半导体行业中受到广泛关注,特别因其具有超薄的结构和极高的载流子迁移率,为解决短沟道效应提供了可能,并且在高速电子领域具有应用前景.近年来,使用石墨烯作为沟道材料制备射频晶体管及射频电路是发挥石墨烯材料优势的一个重要研究方向.制造高性能的射频器件,首先要制备出高性能的石墨烯材料.在金属衬底上沉积均匀的单层石墨烯材料或者在绝缘衬底上外延生长单层、双层石墨烯材料都是获得高质量石墨烯材料的常用方法.器件结构及工艺流程的设计也是提升晶体管射频性能的重要因素,多指栅结构、T型栅结构、埋栅结构以及自对准工艺的发展能够有效改善石墨烯射频晶体管的截止频率及最大振荡频率.石墨烯晶体管独特的电学特性使得其除了可以构造与其他半导体材料电路相似的射频电路结构,还可以构造出功能完整并且结构更加简单的新型射频电路结构.     

含硫氨基酸与本征及缺陷石墨烯表面的相互作用

半胱氨酸及蛋氨酸是人体的两种含硫氨基酸,在生物活性中发挥着巨大的作用.本研究采用密度泛函理论方法对以上两种氨基酸在本征及缺陷石墨烯表面的吸附机理进行了详细研究.主要考虑了两种吸附体系:半胱氨酸及蛋氨酸平躺在两种石墨烯表面;两种氨基酸垂直地放置于两种石墨烯表面,且含硫的基团靠近表面.研究结果表明,半胱氨酸及蛋氨酸初始构型对它们之间的相互作用有一定的影响.两种氨基酸平躺时有较大的吸附能.此外,吸附能的结果显示两种氨基酸可以更好的与缺陷石墨烯表面紧密结合.同时,蛋氨酸与本征及缺陷石墨烯相互作用均大于半胱氨酸与本征及缺陷石墨烯相互作用.模拟结果有望为含硫氨基酸的石墨烯传感器提供有用的指导.     

Graphene oxide templated alumina nanosheet for the removal of As(V)

The current paper demonstrates a simple preparative method of alumina nanosheet through controlled hydrolysis and condensation on the surface of graphene oxide (GO). Taking into account the moisture sensitivity of the alumina precursor, its hydrolysis was carried out after introduction of interaction between the functional groups of GO and the alumina precursor in a non-aqueous solvent. On pyrolysis of the aluminum oxide-GO composite, a free-standing alumina nanosheet was obtained, which was further confirmed by XRD, TEM, STEM-EDX, FE-SEM, TGA, and N₂ physisorption. Due to a favorable nanosheet structure, the alumina nanosheets showed a better performance in the removal of As (V) when compared to alumina prepared without GO template, even though the latter had a larger surface area than the alumina nanosheet.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH_2分子相互作用

本研究采用密度泛函理论研究了纯的及V,Fe,Ni,Pd,Si,P,S和Cl掺杂原子的石墨烯和CaH_2分子之间相互作用.研究结果发现CaH_2分子与所有石墨烯表面均具有较大的相互作用,而CaH_2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用,在所有掺杂原子中,其中与Pd掺杂石墨烯具有最大的相互作用,S次之,其它掺杂石墨烯与CaH_2分子相互作用能力相差不大.这些结果表明虽然所有石墨烯均有助于CaH_2中H原子的脱附,但掺杂石墨烯脱附能力仍然大于纯的石墨烯.在掺杂原子中,Pd和S掺杂石墨烯对CaH_2中H原子的脱附效果最好,其它的掺杂原子脱附效果相差不明显.此研究结果将有望为CaH_2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

密度泛函理论研究纯的及不同掺杂原子石墨烯和CaH2分子相互作用

本研究采用密度泛函理论研究了纯的及V, Fe, Ni, Pd, Si, P, S和Cl掺杂原子对石墨烯和CaH2分子之间相互作用. 研究结果发现CaH2分子与所有石墨烯表面均具有较大的相互作用, 而CaH2分子与掺杂石墨烯相互作用都大于与纯石墨烯的相互作用, 在所有掺杂原子中, 其中与Pd掺杂石墨烯具有最大的相互作用, S次之, 其它掺杂石墨烯与CaH2分子相互作用能力相差不大. 这些结果表明虽然所有石墨烯均有助于CaH2中H原子的脱附, 但掺杂石墨烯脱附能力仍然大于纯的石墨烯. 在掺杂原子中, Pd和S掺杂石墨烯对CaH2中H原子的脱附效果最好, 其它的掺杂原子脱附效果相差不明显. 此研究结果将有望为CaH2分子在石墨烯基材料中吸氢-脱氢行为提供有用的理论参考价值.     

Tip-Enhanced Raman Spectroscopy and Mapping of Graphene Sheets

Abstract: Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.     

Preparation and Rheology of Isocyanate Functionalized Graphene Oxide/Thermoplastic Polyurethane Elastomer Nanocomposites

Using monomer-functionalized nanofiller to prepare polymeric nanocomposites is a promising strategy toward achieving enhanced performance. In this study toluene-2,4-diisocyanate (TDI), one of the monomers used for synthesizing polyurethane, was covalently functionalized on graphene oxide (GO) and then the functionalized GO (TDI-GO) was polymerized with polycaprolactone diol (PCL) via in-situ polymerization, leading to chemically linked polyurethane nanocomposites through the covalent bonds between the isocyanate groups on GO and the hydroxyl-terminated PCL. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and dispersion experiments of the nanofillers demonstrated that the TDI was successfully grafted onto the GO. The rheological properties were investigated to establish the structure-property relationships of the nanocomposites. The storage moduli (G’), loss moduli (G”) and complex viscosity (η*) of the samples increased monotonically with TDI-GO content, which is attributed to the strong polymer-filler interactions and the effective dispersion of the nanofillers. Additionally, the tan δ variation with frequency, the intersection of G’ and G”, Han plots, van Gurp-Palmen plots and Cole-Cole plots all showed that the incorporation of TDI-GO decreased the degree of microphase separation and improved the elastic properties of the nanocomposites. We suggest this is related to the enhanced interactions between the polymer and nanofillers, which strongly restricted the mobility and relaxation of the polymer chains.     

单层石墨烯水分子吸附对其光学性质的影响

用MS软件对水分子吸附在单层石墨烯表面进行计算,采用第一性原理中的密度泛函理论。使用广义梯度近似和周期性平面模型,得到不同数量的水分子吸附在石墨烯表面上的吸附能,并且计算了相对应的光学性质。得到的结果是吸附能很小,主要是范德瓦尔斯相互作用。石墨烯具有高疏水性,水分子在石墨烯表面对石墨烯的电子结构几乎没有作用,吸附不同个数的水分子后对石墨烯的光学性质有一定影响,其中吸附单个水分子后变化并不明显,吸附2或3个水分子后吸收率和光电导率略有下降;折射率和消光率下降不明显,说明吸附水对石墨烯的透明度影响不大;介电函数的实数部分变化趋于平缓,虚数部分有明显下降;能量损失增加。     

单层石墨烯水分子吸附对其光学性质的影响

用基于第一性原理中的密度泛函理论MS软件对水分子吸附在单层石墨烯表面进行计算,使用广义梯度近似和周期性平面模型,得到不同数量的水分子吸附在石墨烯表面上的吸附能,并且计算了相对应的光学性质.得到的结果是吸附能很小,主要是范德瓦尔斯相互作用.石墨烯具有高疏水性,水分子在石墨烯表面对石墨烯的电子结构几乎没有作用,吸附不同个数的水分子后对石墨烯的光学性质有一定影响,其中吸附单个水分子后变化并不明显,吸附2或3个水分子后吸收率和光电导率略有下降;折射率和消光率下降不明显,说明吸附水对石墨烯的透明度影响不大;介电函数的实数部分变化趋于平缓,虚数部分有明显下降;能量损失增加.     

Probing the role of hydrolytically stable, 3-aminopropyl triethoxysilane crosslinked chitosan/graphene oxide membrane towards Congo red dye adsorption

In this investigation, the practicability of utilizing 3-aminopropyl triethoxysilane (3-APTES) crosslinked chitosan (Ch)/graphene oxide (GO) membranes were explored for adsorptive removal of anionic dyes from aqueous medium. Membranes were successfully fabricated through solution casting technique. Strong interactions amongst matrix (chitosan), 3-APTES, polyvinylpyrrolidone (PVP) and GO were confirmed by Infrared spectroscopy. Thermal stability of the chitosan was improved by adding graphene oxide and results were verified via thermogravimetric (TGA) analysis. Swelling and hydrolytic results confirmed that 2 %-Ch/PVP was a stable membrane while increasing the amount of 3-APTES in the chitosan nanocomposites membrane decreased its stability in aqueous medium. The adsorption characteristics of the membranes were evaluated by the adsorption of Congo red (CR) dye from aqueous medium. The adsorbent can remove 80% of CR from aqueous medium and follows second order kinetics. This study outlines the possibility of exploring green membranes which can be easily fit in various flow systems.     

Graphene oxide thin film coated quartz crystal microbalance for humidity detection

In this paper, we demonstrated that chemically derived graphene oxide (GO) thin film as a humidity sensitive coating deposited on quartz crystal microbalances (QCMs) for humidity detection. By exposing GO thin film coated QCMs to various relative humidity (RH) environments at room temperature, the humidity sensing characteristics of the QCMs such as sensitivity and linearity, response and recovery, humidity hysteresis were investigated. The experiment results show that GO thin film coated QCMs exhibit an excellent humidity sensing performance. Moreover, the possible humidity sensing mechanism of GO thin film coated QCMs was also investigated by monitoring the crystal's motional resistance change. It is suggested that the frequency response of the QCMs is dependent on water molecules adsorbed/desorbed masses on GO thin film in the low RH range, and on both water molecules adsorbed/desorbed masses on GO thin film and variations in interlayer expansion stress of GO thin film derived from swelling effect in the high RH range.