镧修饰羧基化氧石墨烯的抑菌性能

在氧化石墨烯(GO)的研究和应用中,为充分发挥其优良性质,必须对其进行功能化。笔者将稀土La3+离子接枝到羧基化的GO(GO-COOH)片层上,制备了一种功能化的镧修饰羧基化氧石墨烯(La/GO-COOH)。利用红外光谱、热重分析和透射电镜等手段对合成的La/GO-COOH进行了表征,结果表明,La3+已通过化学和物理作用吸附在GO片层上。通过细菌生长动力学实验评价了La/GO-COOH的抑菌性能,结果表明,La/GO-COOH对大肠杆菌有很好的抑菌效果,当浓度为0.5 mg/mL,抑菌率达96.40%;对金黄色葡萄球菌和铜绿假单胞菌也均有抑菌效果,因此La/GO-COOH是具有抑菌性能的新型GO负载物;与未剥离的镧修饰氧化石墨(La/GTO)相比,由于剥离的GO片层的比表面积大,其吸附La3+离子的量高于氧化石墨(GTO),故La/GO-COOH复合物的抑菌性远优于La/GTO。     

通过pH值调控的氧化石墨烯片层尺寸、表面化学和电化学性质(英文)

通过调节氧化石墨烯水溶胶的pH值,可以得到尺寸和表面化学性质可控的氧化石墨烯片层。由于氧化石墨烯片层上的羧基在酸性条件下质子化,而在碱性条件下部分被脱除,因此可以通过调控氧化石墨烯水溶胶的pH值对具有不同片层大小和官能团的氧化石墨烯进行筛选。研究发现,羧基的存在可提高氧化石墨烯的电化学活性,而且较大的片层也同样有利于电化学活性的提高。另外,氧化石墨烯对H2O2的检测具有较高的活性,因而在生物传感器上具有广阔的应用前景。     

端羟基超支化聚(胺-酯)非共价改性氧化石墨烯

采用改进的Hummer方法制备了氧化石墨烯(GO),并利用端羟基超支化聚(胺-酯)对其非共价功能化。采用傅里叶变换红外光谱(FT-IR)、拉曼光谱(Raman)、X射线衍射(XRD)、扫描电镜(SEM)和热重分析(TG)及紫外可见分光光度等方法对氧化石墨烯表面改性的性能进行了分析。FT-IR,Raman,XRD和TG分析结果表明,超支化聚(胺-酯)分子成功改性了氧化石墨烯;XRD分析表明,随着超支化聚(胺-酯)含量的增加,石墨烯片层层间距增大,这说明超支化分子能够渗透插入到氧化石墨烯片层之间;Raman分析表明,吸附在氧化石墨烯表面的超支化聚(胺-酯)提高了氧化石墨烯表面的无序化程度和石墨烯结构的不完善程度。SEM形貌分析表明超支化聚(胺-酯)大分子覆盖在氧化石墨烯的表面上,且通过对改性前后氧化石墨烯在乙醇和正己烷中透光率的对比,表明改性后的氧化石墨烯分散性能得到了明显提高。     

功能化石墨烯选择性吸附重金属离子

重金属离子污染日益严重,石墨烯作为一种新型碳材料在吸附重金属离子方面具有巨大潜力。本文通过尝试,探索出基于酯化反应将功能团乙二胺四乙酸(EDTA)连接到氧化石墨烯(GO)表面合成功能化氧化石墨烯(EDTA-GO)的新方法。研究结果显示:EDTA-GO饱和吸附量高达(355±17)mg/g,较改性之前提高了17.5%,并且符合Langmuir单层吸附模型。随着pH值的升高,EDTA-GO的吸附性能越来越强。吸附平衡时间在4分钟以内。通过将Pb~(2+)与Cd~(2+)和Cu~(2+)相比较,发现在pH=4.6的条件下Pb~(2+)的饱和吸附量远大于后两者,表现出良好的选择性吸附特点。     

基于离子液体功能化石墨烯/碳纳米管的葡萄糖传感器的研究(英文)

将离子液体功能化的石墨烯/碳纳米管(G-IL/CNTs)修饰到玻碳电极上,再固载上葡萄糖氧化酶(GOD)和辣根过氧化物酶(HRP),构筑了新型的(G-IL/CNTs)/(GOD+HRP)/GC双酶葡萄糖传感器。用SEM观察电极形貌,发现碳纳米管类似于导线穿插在石墨烯片层中,连接了各石墨烯片层,两者结合形成了三维立体结构,明显提高了石墨烯的分散性,同时由于功能化后的石墨烯与碳纳米管的协同作用,该传感器在葡萄糖的检测上表现了良好的分析性能,传感器的线性范围为0. 004～5 mmol/L,灵敏度为53. 89μA mmol/L~(-1)cm~(-2),检出限为3. 99×10~(-7)mol/L(S/N=3)。     

水合肼还原氧化石墨烯的研究

通过改进的Hummers法制备氧化石墨,将获得的氧化石墨进行热剥离以及超声剥离得到双层甚至单层的氧化石墨烯片.然后采用化学还原-水合肼还原的方法去除氧化石墨烯所含的羧基COOH、羟基OH、羰基C=O和环氧基等化学基团.本实验着重研究了还原剂的用量和反应时间对各个化学基团的影响规律.     

电子受体材料功能化还原氧化石墨烯的结构和光学性能

采用Hummers法制备氧化石墨烯(GO),利用水热法对GO分别还原5 h和10 h制得两种还原氧化石墨烯(5-RGO和10-RGO),进一步用异氰酸苯酯对还原前后的氧化石墨烯材料进行改性,即得功能化氧化石墨烯和功能化还原氧化石墨烯(SPFGO、5-SPFRGO和10-SPFRGO)。以功能化还原氧化石墨烯材料为电子受体,聚3-己基噻吩(P3HT)为电子给体,制备复合膜。结果表明:GO由3-5层组成,经水热还原后样品表面仍含有—CO,—COOH等含氧官能团;功能化后石墨烯在邻二氯苯中分散性良好,与P3HT能级相匹配,满足作为聚合物太阳能电池受体材料要求;以5-SPFRGO做为受体材料与P3HT复合制备的复合膜表面规整致密,光吸收强度高,荧光光谱强度低,性能最优。     

羧基功能化和表面活性剂修饰对石墨烯电化学性能的影响

通过简单的两步溶液法对石墨烯进行羧基接枝和表面活性剂修饰, 并研究其电化学性能。研究结果表明, 与纯石墨烯(比电容50 F/g)相比, 表面活性剂本身并不能有效提高石墨烯的比电容(45 F/g), 羧基功能化可以将石墨烯的比电容提高至130 F/g。而羧基功能化和表面活性剂修饰双处理工艺能够将石墨烯的比电容提高到230 F/g, 且经800次充放电循环后其比电容仍然具有95%的保持率, 表明该材料具有良好的循环稳定性。因此, 调控石墨烯的表面化学特性对提高其电化学性能具有重要的意义。     

功能化多壁碳纳米管负载铁离子改性双极膜的制备与表征

分别用未功能化的多壁碳纳米管(MWCNTs)、羟基化多壁碳纳米管(MWCNTs-OH)、羧基化多壁碳纳米管(MWCNTs-COOH)、磺酸基化多壁碳纳米管(MWCNTs-SO3H)改性羧甲基纤维素钠(CMC)-聚乙烯醇(PVA)/壳聚糖(CS)-聚乙烯醇双极膜(BPM)的阳离子交换膜层。采用力学性能分析、接触角测定、电流密度-槽电压曲线等对改性前后双极膜的性能进行表征,并测定了改性前后双极膜中Fe~(3+)的流失量。结果表明,经功能化多壁碳纳米管改性后,双极膜的亲水性和力学性能得到了显著提高。功能化多壁碳纳米管和Fe~(3+)对催化中间界面层水解离有协同作用,大大提高了中间界面层水解离效率,降低了双极膜的膜阻抗和槽电压。此外,改性后双极膜中Fe~(3+)的流失量有了明显的下降,从而保持了双极膜结构和催化水解离性能的稳定性。     

石墨烯/聚苯胺/四氧化三锰纳米复合材料的制备

成功制备了石墨烯/聚苯胺/四氧化三锰(RGO/PANI/Mn_3O_4)纳米复合材料。首先,以过硫酸铵(APS)为氧化剂,在氧化石墨烯(GO)片层上氧化聚合苯胺单体,制备氧化石墨烯/聚苯胺(GO/PANI),再通过水热法将GO还原并热解Mn(Ac)_2·4H_2O从而制得RGO/PANI/Mn_3O_4复合材料。形貌和结构表征结果表明Mn_3O_4纳米颗粒均匀生长在以PANI为导电连接层的RGO片层上。     

Mechanical properties of graphene oxide: A molecular dynamics study

In this paper, the mechanical properties of graphene oxide are obtained using the molecular dynamics analysis, including the ultimate stress, Young modulus, shear modulus and elastic constants, and the results are compared with those of pristine graphene. It is observed that the increase of oxide agents (–O) and (–OH) leads to the increase of C–C bond length at each hexagonal lattice and as a result, alter the mechanical properties of the graphene sheet. It is shown that the elasticity modulus and ultimate tensile strength of graphene oxides (–O) and (–OH) decrease significantly causing the failure behavior of graphene sheet changes from the brittle to ductile. The results of shear loading tests illustrate that the increase of oxide agents (–O/–OH) results in the decrease of ultimate shear stress and shear module of the graphene sheet. It is shown that the increase of oxide agents in the graphene sheet leads to decrease of the elastic constants, in which the reduction of elastic properties in the armchair direction is more significant than the zigzag direction. Moreover, the graphene sheet with oxide agents (–O) and (–O/–OH) presents an anisotropic behavior.     

氧化石墨烯在生物医学领域的应用

氧化石墨烯(GO)是石墨烯的衍生物,具有较高的比表面积和丰富的官能团:底面含羟基和环氧基,边缘含羧基。这些官能团赋予了氧化石墨烯良好的亲水性、分散性和生物相容性,易于修饰和功能化,加之其优良的光学性质,使得氧化石墨烯在生物医学领域具有广阔的应用前景。着重介绍了氧化石墨烯在生物传感器、生物成像、药物/基因传送、光热/光动力治疗、抗菌材料、生物安全性方面的研究现状和进展。     

Synthesis of graphene-gold nanocomposites via sonochemical reduction

A Reduced reduced graphene oxide (RGO)-gold (Au) nanoparticle (NP) nanocomposite was synthesized by simultaneously reducing the Au ions and depositing Au NPs on onto the surface surface of the RGOsRGO simultaneously. To facilitate the reduction of Au ions and the generation of oxygen functionalities for anchoring the Au NPs on the RGOsRGO, ultrasound irradiation was applied to the mixture of reactants. The functional groups were investigated with FT-IR spectra. From the Raman and XPS spectra, the oxygen groups were identified as hydroxyl, epoxy, and carboxyl groups, the same as the one from graphene oxide (GO). As a result, the dense and uniform deposition of nanometer-sized Au NPs with nanometer size was observed on the RGO sheets sheet was observed with from the TEM imagesimage. The Oxygen oxygen functional groups that formed on the surface surface of the RGOs RGO seemed to have served serve as links for Au NPs NP attachment, through the electrostatic attraction of Au ions. Hybrid materials could thus be produced in a short time, with a high yield, by via ultrasound application. Besides, it ultrasound application could can readily take goldAu- binding- peptide (GBP)-modified biomolecules, readily implying its possibility in possible biological applications.     

氧化石墨烯的制备及其对NH3的敏感特性研究

石墨烯独特的原子结构赋予其电学、热学、力学等方面的优异性能,在诸多领域具有广泛的应用。氧化石墨烯不仅具有石墨烯结构特点,而且具有大量的含氧官能团,增强了对气体的吸附能力,更适合应用于气敏传感器。通过改进的Hummer方法制备了片状多层氧化石墨烯,并对不同浓度的NH3进行敏感特性测试。结果表明氧化石墨烯对NH3具有良好的响应,在(1.5～3.5)×10-4范围内呈线性关系。     

Synthesis of mono layer graphene oxide from sonicated graphite flakes and their Hall effect measurements

Graphene, a single atom thick sheet is considered a key candidate for the future nanotechnology, due to its unique extraordinary properties. Researchers are trying to synthesize bulk graphene via chemical route from graphene oxide precursor. In the present work, we investigated a safe and efficient way of monolayer graphene oxide synthesis. To get a high degree of oxidation, we sonicated the graphite flakes before oxidation. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirmed graphene oxide formation and high degree of oxidation. Raman spectroscopy and atomic force microscopy (AFM) results revealed a monolayer of graphene oxide (GO) flakes. The sheet like morphology of the GO flakes was further confirmed by scanning electron microscopy (SEM). The Hall effect measurements were performed on the GO film on a silica substrate to investigate its electrical properties. The results obtained, revealed that the GO film is perfectly insulating, having electrical resistivity up to 8.4 × 10⁸ (Ω·cm) at room temperature.     

Graphene-based materials: synthesis, characterization, properties, and applications

Graphene, a two-dimensional, single-layer sheet of sp(2) hybridized carbon atoms, has attracted tremendous attention and research interest, owing to its exceptional physical properties, such as high electronic conductivity, good thermal stability, and excellent mechanical strength. Other forms of graphene-related materials, including graphene oxide, reduced graphene oxide, and exfoliated graphite, have been reliably produced in large scale. The promising properties together with the ease of processibility and functionalization make graphene-based materials ideal candidates for incorporation into a variety of functional materials. Importantly, graphene and its derivatives have been explored in a wide range of applications, such as electronic and photonic devices, clean energy, and sensors. In this review, after a general introduction to graphene and its derivatives, the synthesis, characterization, properties, and applications of graphene-based materials are discussed.     

络合法制备均匀γ-Fe2O3纳米颗粒@多层石墨烯复合材料研究

采用水热反应中的金属离子络合一步制备均匀超细磁性γ-Fe₂O₃纳米颗粒@多层石墨烯复合材料, 无需对石墨烯进行氧化处理。采用超声法制备多层石墨烯作为基片, 制备方法简单, 石墨烯表面的含氧官能团少。以FeCl₂为反应物, 以DMF(N, N二甲基甲酰胺)和水混合液作为溶剂, 其中DMF能起到络合金属离子的作用。实验研究了乙酸钠、反应温度及填充度对制备产物的影响。采用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)对复合材料进行微结构分析, 采用振动样品磁强计(VSM)测试了复合材料的磁性能。研究结果表明: 利用亚铁离子与DMF形成的络合物与碳环的π-π吸附作用可以在多层石墨烯表面生成铁氧化物。通过控制亚铁离子的氧化速度和氧化铁的生长速度, 在多层石墨烯表面获得了尺寸小于10 nm的均匀γ-Fe₂O₃纳米颗粒, 复合材料具有良好的磁性能。     

Triethylenetetramine/hydroxyethyl cellulose-functionalized graphene oxide monoliths for the removal of copper and arsenate ions

Nitrogen-doped graphene oxide monoliths (GOMs) were readily constructed by crosslinking graphene oxide (GO) using triethylenetetramine (TETA) and hydroxyethyl cellulose (HEC). The addition of HEC was beneficial to the formation of a network structure compared to that in the absence of HEC. The generated monoliths have shown various morphologies with different d spacing, layer thickness, and micropore size. Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses provided evidences for the formation of covalent C–N bonds and some nitrogen-containing heterocyclic composition inside the graphene oxide sheet, indicating that the interaction of GO with the amine crosslinker involved the crosslinking reaction between GO epoxides and amine groups. HEC was also involved in the N-doping reaction via the partial reduction of oxygen in HEC molecules. Analysis of X-ray diffraction (XRD) results indicated that the lattice distance between GO sheets increased after TETA/HEC crosslinking. Thermogravimetric analysis (TGA) confirmed the successful incorporation of crosslinker moieties on the surface of GO sheets. The fabricated GOMs could be used to efficiently adsorb metal ions and arsenate by the introduced polar functional groups on GO sheets and porous structures based on hydrogen bonds, whose morphologies and compositions were confirmed via XRD, scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS).     

Molecular dynamics study of the effect of chemical functionalization on the elastic properties of graphene sheets

In this study, the effects of chemical functionalization on the elastic properties of graphene sheets are investigated by using molecular dynamics (MD) and molecular mechanics (MM) simulations. The influences of the degree of functionalization, which is defined as the ratio of the number of the total sp3-hybridized atoms to the number of the total carbon atoms of the graphene sheet, the chirality of graphene sheets, the molecular structure and molecular weight of functional groups on Young's modulus are studied. The dependence of shear modulus and wrinkling properties on the functional groups are also investigated. The simulation results indicate that Young's modulus depends strongly on the degree of functionalization and the molecular structure of the functional groups, while the effects of chirality of the graphene sheets and the molecular weight of the functional groups are negligible. The chemical functionalization also reduces the shear modulus and critical strain, beyond which the wrinkling instability occurs.     

Direct nucleation of silver nanoparticles on graphene sheet

Silver (Ag) nanoparticles were synthesized on the surface of graphene sheet by the simultaneous reduction of Ag+ and graphene oxide (GO) in the presence of simple reducing agent, hydrazine hydrate (N2H4 x H2O). Both the Ag+ and GO were reduced and Ag+ was nucleated onto graphene. GO flakes were prepared by conventional chemical exfoliation method and in the presence of strong acidic medium of potassium chlorate. Silver nanoparticles were prepared using 0.01 M AgNO3 solution. The reduced GO sheet decorated with Ag is referred as G-Ag sample. G-Ag was characterized by FTIR (Fourier transform infrared) spectroscopy using GO as standard. An explicit alkene peak appeared around 1625 cm(-1) was observed in G-Ag sample. Besides, the characteristic carbonyl and hydroxyl peaks shows well reduction of GO. The FTIR therefore confirms the direct interaction of Ag into Graphene. SEM (scanning electron microscopy) and TEM (transmission electron microscopy) analysis were performed for morphological probing. The average size of Ag nanoparticles was confirmed by around 5-10 nm by the high-resolution TEM (HRTEM). The Ag quantum dots incorporated nanocomposite material could become prominent candidate for diverse applications including photovoltaic, catalysis, and biosensors etc.