多孔石墨烯纳米片电学性质的研究

采用紧束缚近似方法,研究了三角形锯齿型石墨烯纳米片(Triangular zigzag graphene nanosheets, TZGN)的电子结构.研究表明单孔TZGN结构的零能级都是外边缘态,跟孔的大小没有关系.多孔TZGN结构受孔间结构的影响,零能级会随着孔数目的增加逐渐出现内外边缘耦合态,导带和价带能级个数也会随着孔的大小和孔的数量的增加而减少.研究结果拓宽了石墨烯纳米结构在纳机电器件方面的应用.     

石墨烯纳米结构的制备及带隙调控研究

石墨烯在未来微电子学领域有极大的应用前景,但是其零带隙的特点阻碍了石墨烯在半导体领域的应用.研究发现,打开室温下可用的石墨烯带隙所需要的石墨烯纳米结构尺度在10 nm以下,这一尺度的纳米结构一方面制备比较困难,另一方面器件可承载的驱动电流较小.因此,如何实现亚10 nm石墨烯纳米结构的有效加工以及如何在有效调控带隙的基础上增大石墨烯器件可承载的驱动电流,还需要进一步的研究.本文首先研究了利用聚甲基丙烯酸甲酯/铬(PMMA/Cr)双层结构工艺,通过刻蚀时间的控制,利用电子束曝光及刻蚀工艺实现了亚10 nm石墨烯纳米结构的可控制备.同时设计并制备了单排孔石墨烯条带结构,该结构打开的带隙远大于相同特征宽度石墨烯纳米带所能打开带隙的大小.该结构在有效打开石墨烯带隙的同时,增加了石墨烯纳米结构可以承载的驱动电流,有利于石墨烯在未来微电子领域的应用.     

石墨烯纳米结构的原子级精准构造

相比单层石墨烯,特定构型的石墨烯纳米结构具有更加新奇的物理性质,被认为是构筑基于石墨烯功能纳米器件的基本单元。由于纳米结构的性质对其局域原子构型非常敏感,可控制备高质量的、原子级精确的石墨烯纳米结构并研究其奇特的电子学和自旋电子学性质是实现其器件应用的必要前提。目前,实验构筑锯齿形石墨烯纳米带及其面内异质结、纳米孔洞以及量子点已取得很多重要进展,但是具有复杂结构的功能化石墨烯纳米结构的构筑与物性研究仍存在挑战。文章介绍作者在原子级精确构造石墨烯纳米结构方面取得的系列科研进展。运用可控制备技术与高精度的极低温强磁场扫描隧道显微镜,探索在不同衬底上制备高质量的、具有特定构型的石墨烯纳米结构,并尝试对制备的石墨烯纳米结构进行原子级精准的操纵,实现构造“用户定制”的功能化石墨烯纳米结构。此系列工作发展了石墨烯纳米结构精确可控制备方法,为研究复杂纳米结构与物性提供了新的思路。     

氟化镧/氧化石墨烯纳米复合物的合成与荧光光谱特征

以化学转化法制备的氧化石墨烯为复合物载体,采用水热法成功合成了氟化镧/氧化石墨烯纳米复合物,使用XRD、SEM对产品进行了表征.结果表明,对反应体系的物料比、反应温度及反应时间的控制是影响产品合成的主要因素.最后,使用室温荧光光谱对复合物的荧光光谱特征进行了分析.     

锯齿型石墨烯纳米带的能带研究

运用π电子紧束缚模型,具体研究了锯齿型石墨烯纳米带(ZGNRs)的边界结构对能带,特别是费米面附近的导带和价带电子的影响.计算了七种不同边界结构的ZGNRs的能带色散关系及费米面附近价带电子在原胞中各原子上的分布情况.计算结果表明:两边界都无悬挂原子的NN-ZGNRs,只有一边界有悬挂原子的DN-ZGNRs,两边界都有五边形环的SPP-ZGNRs和ASPP-ZGNRs为金属性.两边界都有悬挂原子的DD-ZGNRs,一边界为五边形环另一边界无悬挂原子的PN-ZGNRs和一边界为五边形环另一边界有悬挂原子的P 关键词： 锯齿型石墨烯纳米带 紧束缚模型 电子密度分布 缺陷结构     

氧化石墨烯与淀粉样短肽相互作用的理论研究

利用副本交换分子动力学方法,对比研究了淀粉样短肽Aβ_(16-22)在加入石墨烯以及氧化石墨烯前后的聚集状况.我们发现相比石墨烯,氧化石墨烯能够明显地抑制淀粉样短肽Aβ_(16-22)的聚集.其原因是氧化石墨烯与Aβ_(16-22)片段中氨基酸的疏水相互作用以及氧化石墨烯表面的极性基团与Aβ_(16-22)形成的氢键大大地弱化了Aβ_(16-22)氨基酸链间的相互作用,最终抑制了Aβ_(16-22)的纤维化.我们的研究将为基于碳纳米颗粒治疗淀粉样变性病的药物设计与开发提供新思路.     

石墨烯纳米带电子结构的紧束缚法研究

在推导出的一般复式格子的π电子紧束缚能量色散关系的基础上,通过假定石墨烯纳米带的电子横向限制势为无穷大硬壁势,导出石墨烯纳米带的能量色散关系及石墨烯纳米带或为金属或为半导体的条件.结果表明：石墨烯纳米带的电子结构与其几何构型（对称性及宽度）密切相关,所以通过控制几何构型,可将其调制成金属或不同带隙的半导体.这意味着石墨烯纳米带对于发展新型纳米器件具有重要意义. 关键词： 石墨烯纳米带 复式格子 紧束缚模型 电子结构     

成分和拓扑形貌可控的氧化锌/氧化钛复合反蛋白石的合成及其光催化性

利用自组装胶体晶体模板导向电沉积制备氧化锌反蛋白石,利用液相沉积法在室温下制备复合氧化锌/氧化钛反蛋白石. 当对氧化锌反蛋白石进行20 min的液相沉积处理时,可以获得具有非密堆积三维有序多孔结构的氧化锌/氧化钛复合反蛋白石. 当液相沉积时间达到60 min时,则得到壁厚明显增强的纯氧化钛反蛋白石(TIO-LPD60). 讨论了样品成分和拓扑形貌变化的机理. 紫外光催化性能的初步研究显示,反蛋白石膜的光催化性能同时受到来自成分和拓扑形貌两方面的显著影响. 对比纯的氧化锌或者氧化钛反蛋白石,尽管样品具有相似的反蛋白石壁厚,ZnO/TiO₂复合反蛋白石被证实具有明显增强的光催化活性. 然而,当反蛋白石壁厚从约52 nm增加到约90 nm时,TIO-LPD60显示了最高的光催化活性.     

采用溶胶凝胶协同自组装与光刻相结合的方法在反蛋白石结构薄膜中引入二维缺陷

采用溶胶凝胶协同自组装与光刻相结合的方法,在光子晶体反蛋白石结构中引入缺陷,通过溶胶凝胶协同自组装方法在硅片上垂直沉积胶体晶体复合薄膜,把BP212正性光刻胶均匀旋涂在复合薄膜上,通过曝光、显影等光刻工艺,把掩膜版图案复制在复合薄膜上,用此样品再次垂直沉积一层复合薄膜,使图案被复合薄膜覆盖.最后去除胶体微球与光刻胶图案,从而在反蛋白石结构中引入缺陷,用扫描电子显微镜对样品进行表征.分析了光刻胶图案对胶体微球排列的影响.     

水热法制备二氧化钛纳米管-石墨烯复合光催化剂及其光催化性能

采用水热法制备了二氧化钛纳米管-石墨烯的复合光催化剂。利用X射线衍射仪、扫描电镜、透射电镜和拉曼光谱仪对复合材料进行了表征与分析,并对其光催化性能进行了测试。结果显示,同纯二氧化钛纳米管相比,二氧化钛纳米管-石墨烯的光催化性能较高。石墨烯与二氧化钛纳米管复合,充当电子受体,载流子迁移率得到提高,从而提升了光催化性能。     

高温还原氧化石墨烯膜及其导热性能

采用氧化还原法制备了结构致密且具有较高柔韧性的石墨烯薄膜,探究了薄膜经过较高退火温度还原后结构变化,并通过T型稳态法测量了其热导率,研究了还原温度对薄膜热导率和力学性能的影响。结果表明,高温还原有助于氧化石墨烯中含氧官能团的去除和sp2杂化碳晶格的恢复,并且温度越高还原效果越好。当还原温度高达2800℃时,在200~350 K温度范围内石墨烯膜的热导率在336.9~436 W·m^-1·K^-1之间,伴随着温度的升高,热导率有先增大后减小的趋势。     

Functionalization of Graphene Oxide and its Biomedical Applications

Graphene oxide (GO) offers interesting physicochemical and biological properties for biomedicine due to its versatility, biocompatibility, small size, large surface area, and its ability to interact with biological cells and tissues. GO is a two-dimensional material of exceptional strength, unique optical, physical, mechanical, and electronic properties. Ease of functionalization and high antibacterial activity are two major properties identified with GO. Due to its excellent aqueous processability, amphiphilicity, surface functionalization capability, surface enhanced Raman scattering (SERS), and fluorescence quenching ability, GO chemically exfoliated from oxidized graphite is considered a promising material for biological applications. In addition, due to π-π* transitions, a low energy is required for electron movement, a property important in Biosensor and Bioimaging applications of GO. In this article, we present an overview of current advances in GO applications in biomedicine and discuss future perspectives. We conclude that GO is going to play a vital role in Biomedical applications in the near future.     

Unique Morphology in Polylactide/Graphene Oxide Nanocomposites

Polylactide (PLA)/graphene oxide (GO) nanocomposites with different GO loadings were prepared by solution blending using tetrahydrofuran (THF) as solvent. The morphologies of the nanocomposites in the cast films and in subsequently isothermally crystallized samples were investigated separately. According to polarized optical microscopy images of the composites after isothermal crystallization, it was deduced that GO had nucleation effects on the crystallization of PLA and led to the size of spherulites decreasing and the number of spherulites increasing. However, by virtue of SEM, unique microsphere morphologies were found in the cast films of the PLA/GO composites. It was found that the features of this kind of microsphere were not influenced by the compositions but by the evaporation rate of the solvent during the preparation of the cast films. A faster evaporation rate of solvent resulted in smaller size of the microspheres. Based on DSC and FTIR results, it was proposed that the forming of this kind of microsphere was related to hydrogen bonds being formed between PLA and GO. The unique microsphere morphology is suggested to provide a new method to prepare PLA microsphere-based scaffolds.     

Oxygenated Functional Group Density on Graphene Oxide: Its Effect on Cell Toxicity

The association of cellular toxicity with the physiochemical properties of graphene‐based materials is largely unexplored. A fundamental understanding of this relationship is essential to engineer graphene‐based nanomaterials for biomedical applications. Here, an in vitro toxicological assessment of graphene oxide (GO) and reduced graphene oxide (RGO) and in correlation with their physiochemical properties is reported. GO is found to be more toxic than RGO of same size. GO and RGO induce significant increases in both intercellular reactive oxygen species (ROS) levels and messenger RNA (mRNA) levels of heme oxygenase 1 (HO1) and thioredoxin reductase (TrxR). Moreover, a significant amount of DNA damage is observed in GO treated cells, but not in RGO treated cells. Such observations support the hypothesis that oxidative stress mediates the cellular toxicity of GO. Interestingly, oxidative stress induced cytotoxicity reduces with a decreasing extent of oxygen functional group density on the RGO surface. It is concluded that although size of the GO sheet plays a role, the functional group density on the GO sheet is one of the key components in mediating cellular cytotoxicity. By controlling the GO reduction and maintaining the solubility, it is possible to minimize the toxicity of GO and unravel its wide range of biomedical applications.     

基于氧化石墨烯荧光适体传感器的多巴胺检测

以修饰有荧光基团(FAM)的多巴胺核酸适体作为识别元件,氧化石墨烯为猝灭剂,构建了光学适体传感器用于检测多巴胺。通过π-π堆积作用力,氧化石墨烯以共振方式把核酸适体上FAM能量转移到其表面,荧光信号消失;加入多巴胺后荧光恢复,荧光强度恢复的大小与多巴胺浓度呈正相关关系。实验优化结果表明,在反应时间5 min和10μg/mL氧化石墨烯条件下,氧化石墨烯可以达到对FAM的最高猝灭效率;25min孵育后,多巴胺恢复荧光强度达到稳定;传感器线性检测范围为1~500μmol/L,检测限达到1μmol/L。所制备传感器具有检测范围宽、检测速度快、特异性强以及检测成本低等优点。     

Preparation and Characterization of Grafted Natural Rubber/Graphene Oxide Nanocomposites

Vinyltriethoxysilane (VTES) was grafted onto natural rubber (NR) in latex form, using potassium persulfate (KPS) as initiator. The VTES grafted NR (NR-g-VTES) was then further reinforced with graphene oxide (GO) by a mechanical mixing method with different GO loadings to get the rubber composite (GO/NR-g-VTES). The NR-g-VTES was characterized and confirmed by attenuated total teflectance-Fourier transforms infrared spectroscopy (ATR-FTIR). The effect of GO content on the curing characteristics and resulting mechanical properties of the GO/NR-g-VTES were studied and compared with neat NR filled with GO (NR/GO). The maximum and minimum torque and the tensile and tear strength of the NR-g-VTES/GO composites were higher than that of NR/GO. The samples containing low GO concentration showed maximum torque and tensile and tear strength. Dynamic mechanical analysis showed that the interaction between GO and NR-g-VTES was better than that of the GO-reinforced NR.     

Synthesis of Fluorinated Graphene Oxide and its Amphiphobic Properties

The richly functionalized basal plane bonded to polar organic moieties makes graphene oxide (GO) innately hydrophilic. Here, a methodology to synthesize fluorinated graphene oxide by oxidizing the basal plane of fluorinated graphite, allowing for tunable hydrophobicity of GO, is reported. Fluorine exists as tertiary alkyl fluorides covalently bonded to graphitic carbons, and using magic‐angle spinning (MAS) ¹³C NMR as a primary tool chemical structures for the two types of synthesized fluorinated graphene oxides (FGOs) with significantly different fluorine contents are proposed. The low surface energy of the C–F bond drastically affects GO's wetting behavior, leading to amphiphobicity in its highly fluorinated form. Ease of solution processing enables the fabrication of inks that are spray‐painted on various porous/non‐porous substrates. These coatings maintain amphiphobicity for solvents with surface tensions down to 59 dyn/cm, thus bypassing existing lithographic means to create similar surfaces. The approach towards fluorinating GO and fabricating graphene‐based surfaces with tunable wettability opens the path towards unique, accessible, carbon‐based amphiphobic coatings.     

Quantification of the Particle Size and Stability of Graphene Oxide in a Variety of Solvents

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta‐stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene‐based materials.     

Natural Rubber/Graphene Oxide Nanocomposites Prepared by Latex Mixing

Natural rubber/graphene oxide (NR/GO) nanocomposites were prepared by latex mixing. The dispersion state of GO and the mechanical properties of the nanocomposites were studied. It was found that a uniform dispersion of GO in the NR matrix was achieved with the latex mixing method. The well-distributed GO was remarkably effective in improving the tensile strength and storage modulus of NR at very low filler contents, without sacrificing the ultimate strength. The percolation point of GO in the nanocomposites took place at a content of less than 0.1 parts by weight per hundred parts of rubber. The Halpin-Tsai model was used to analyze the reinforcement effect of GO for NR.     

电化学法制备的还原氧化石墨烯薄膜及其光电性能研究

通过电化学方法在FTO导电玻璃上沉积了不同还原程度(C/O)的还原氧化石墨烯薄膜(rGO),其中rGO薄膜由未经处理的GO电解液制备,A-rGO由碱处理后的电解液制备,B-rGO由NaBH4处理后的电解液制备。利用XRD、XPS、SEM、UV-Vis对薄膜的化学结构和微观形貌进行了表征,并研究了薄膜在可见光照射下的光电性能。结果表明:在1.8 V下沉积的不同C/O比的rGO薄膜中,B-rGO薄膜的C/O比最高(8.1),带隙最小(0.54 eV),导带最靠近FTO的导带位置。在可见光照射下,几种薄膜均产生了阴极电流,电流密度随C/O比的增大而增大,其中B-rGO最大达1μA·cm-2。本文提供了一种通过控制C/O比来控制rGO薄膜光电性能的方法。