超声辅助Hummers法制备氧化石墨烯

采用超声辅助Hummers法制备氧化石墨烯,单片层厚～1 nm。本法首先在Hummers法的低温、中温反应阶段加入超声振荡,以此来分别提高石墨的插层效率和氧化程度,然后在高温反应开始时,采用把含有残留浓硫酸的混合液缓慢滴入低温去离子水中再加热的方式,以此减少硫酸分子等插入物因为局部温度过高从石墨层间脱出,最后通过低速离心得到氧化石墨。使用超声辅助Hummers法制备氧化石墨烯既方便快捷,又能有效地增大氧化石墨的层间距,且随着超声功率的提高,所得氧化石墨的层间距呈扩大趋势。     

氧化环境和比例对改性Hummers法制备氧化石墨烯的影响

以鳞片石墨(GR)为原料,采用改性Hummers液相氧化法制备氧化石墨,通过超声剥离获得片状的氧化石墨烯(GO),探讨了H2SO4环境与H2SO4+H3PO4混酸环境和KMn O4与GR的比例对GO制备的影响。采用FT IR,UV,TG,XRD,SEM,Raman和XPS等分析手段对制备的GO进行分析。结果表明,GO外貌呈褶皱片状,在片层上主要有C=O、C—OH、—COOH和C—O—C等官能团,以共价键形式存在石墨层间;通过Raman,TG和XPS数据分析表明在H2SO4+H3PO4混酸环境下制备的GO含氧官能团较多,并且KMn O4与鳞片石墨的最佳比例是1∶4。     

石墨烯的氧化还原法制备及结构表征

采用改进的Hummers法对天然鳞片石墨进行氧化处理制备氧化石墨,经超声分散,然后在水合肼的作用下加热还原制备了在水相条件下稳定分散的石墨烯。用红外光谱、拉曼光谱、扫描探针显微镜和ζ电位仪对样品进行了结构、谱学、形貌和ζ电位分析。结果表明,石墨被氧化后形成以C=O、C-OH、-COOH和C-O-C等官能团形式的共价键型石墨层间化合物;还原氧化石墨后形成的石墨烯表面的官能团与石墨的相似;氧化石墨烯和石墨烯在碱性条件下可形成稳定的悬浮液;氧化石墨烯和石墨烯薄片厚度为1.0nm左右。考察并讨论了还原过程中水合肼用量,体系反应温度、反应时间和pH值对石墨烯还原程度和稳定性的影响,水合肼用量和反应时间是影响石墨烯还原程度的主要因素;pH值对石墨烯稳定性影响较大。     

氧化石墨烯制备过程优化及其吸附特性

为了使改进的Hummers法制备氧化石墨烯(GO)的制备过程更容易控制,以反应温度、KMnO₄加入时间、KMnO₄全部加入后继续反应时间、超声时间为考察因素,亚甲基蓝(MB)的吸附容量为评价指标,在单因素实验基础上,利用响应曲面法对所制备的氧化石墨烯(CGO)的制备工艺进行优化,建立二次多项式回归模型。结果表明,多项式模型的四因素对MB去除效果的影响顺序为:反应温度>KMnO₄加入时间>超声时间>KMnO₄全部加入后继续反应的时间。最佳制备条件为反应温度25℃、KMnO₄加入时间113.25min、t为25min、超声时间6.21h,MB的吸附容量为150mg·g^-1。     

十六烷基三甲基溴化铵改进Hummers法制备石墨烯的研究

将阳离子表面活性剂（十六烷基三甲基溴化铵,CTAB）作为絮凝剂,利用其与氧化石墨烯（GO）产生静电吸引的原理,实现中间产物CTAB-GO复合物的快速分离和纯化,并利用水合肼还原制得还原氧化石墨烯（RGO）。采用UV-Vis、 SEM、 TEM、 AAS和XPS对石墨烯的形貌、纯度、制备过程及机理进行了分析表征。结果显示,CTAB能通过静电力吸附在GO表面,形成CTAB-GO复合物的絮凝沉淀。当CTAB和GO的质量比为1:2时,可以达到最佳的絮凝效果。该絮凝沉淀仅通过低压过滤或低速离心（3 000 rpm, 3 min）便能实现快速分离和纯化,得到CTAB-GO复合物。AAS和XPS证实CTAB-GO复合物中不存在杂质离子。此外,CTAB-GO复合物经过水合肼还原后,CTAB能快速完全脱除,从而得到高纯度RGO。     

钒酸银/氧化石墨烯复合物的制备和可见光催化性能

通过改进Hummers法制备了氧化石墨烯(GO),采用液相沉淀法合成了Ag₃VO₄/GO复合物,利用X射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见(UV-Vis)漫反射光谱等技术手段对样品进行了测试表征;并在可见光辐射下(λ≥420 nm)考察了复合物催化剂中GO含量对Ag₃VO₄光催化降解甲基橙溶液(MO)的性能影响。 结果表明,掺杂质量分数2%的GO复合物光催化活性提高最显著,30 min内对MO的降解率可达到89%以上,是纯Ag₃VO₄光催化活性的3倍。     

石墨烯和氧化石墨烯的表面功能化改性

石墨烯和氧化石墨烯由于特殊的电子、光学、力学性能已成为当今科学研究的热点.重点综述了近年来石墨烯和氧化石墨烯的表面功能化改性研究进展.首先介绍了石墨烯、氧化石墨烯的基本结构与性质.然后将表面功能化分为非共价键结合改性、共价键结合改性和元素掺杂改性.非共价键结合的功能化改性分为四类：π-π键相互作用、氢键作用、离子键作用以及静电作用.共价键结合的功能化改性分为四类：碳骨架功能化、羟基功能化、羧基功能化和环氧基功能化.元素掺杂改性分为N、B、P等不同元素的掺杂功能化.总结了石墨烯、氧化石墨烯基体与改性分子的相互作用和反应类型,以及改性产物的性能与应用.最后对石墨烯和氧化石墨烯在表面功能化改性方面的发展前景作了展望和预测.     

球磨辅助氧化还原法制备石墨烯

本文利用天然石墨作为原材料,采用改进的Hummers法制备氧化石墨(GO)。首先将氧化石墨在低能球磨机中球磨10 h,然后超声剥离得到氧化石墨烯。最后利用水合肼作为还原剂,通过磁力搅拌回流反应得到石墨烯。利用SEM,AFM,XRD,Raman,FTIR,TEM对所制备的石墨烯的形貌和结构进行表征。同时将经低能球磨制备的石墨烯与未经低能球磨制备的石墨烯进行比较,分析了在不同工艺条件下制备的石墨烯的效果。结果表明低能球磨有利于减薄氧化石墨,促进氧化石墨的剥离。并且有利于氧化石墨的还原,从而缩短回流还原反应时间,提高了制备石墨烯的效率。     

氧化石墨烯增强卡拉胶复合膜的制备与性能

在Hummers法基础上制得了氧化石墨烯(GO), 采用流延法制备了氧化石墨烯/κ-卡拉胶(GO/κ-Car)复合膜材料. 结合红外光谱、 扫描电子显微镜及热重分析对其结构进行表征. 探讨了不同条件所得膜的成膜性、 溶解性、 透气性和力学性能, 得到性质稳定GO/κ-Car复合膜的制备条件为15.0 g 3%的κ-Car溶液、0.040 g GO粉末及5.0 g 8%的PVA溶液于75 ℃搅拌混合5 h后, 流延铺平, 于30 ℃烘干6.5 h. GO质量分数为5%的GO/κ-Car复合膜的最大负荷、 拉伸强度及杨氏模量分别是对照组κ-Car膜的1.5倍、 1.5倍和1.6倍. 同时, GO/κ-Car复合膜具有较强的透气性能, 且保留了κ-Car清除羟基自由基的生物性能.     

通过“点击化学”对石墨烯和氧化石墨烯进行功能化改性

点击化学具有操作简单方便、灵活高效等特点,在石墨烯的功能化改性上具有极其重要的应用.本工作针对点击化学对石墨烯和氧化石墨烯功能化改性方面进行了综述.将石墨烯点击功能化改性方法分为两种情况:共价键结合的点击功能化改性和非共价键作用的点击功能化改性,其中共价键结合又可细分为边缘点击功能化改性和表面点击功能化改性.首先,本工作对石墨烯点击功能化改性的反应过程和反应条件及其研究方法作了详细的归类和系统的总结.一方面,在石墨烯点击功能化改性的分类上包括:氧化石墨烯边缘点击,氧化石墨烯表面点击,石墨烯表面点击,石墨烯表面经过Diels-Alder[4+2]的点击反应,以及通过非共价键作用的π-π堆积之后的点击反应;另一方面,在点击反应的合成路线上,详细列出了对石墨烯或者氧化石墨烯进行炔基化或者叠氮基化以及功能化分子进行相应地叠氮基化或者炔基化的连接方法和反应条件,通过点击反应将两部分连接起来,并指出石墨烯功能化复合物的功能特性和应用前景.对这部分工作进行列表总结,然后作图列出石墨烯和氧化石墨烯的点击功能化反应的具体分类和反应过程.另外,本工作列表总结了IR,Raman,UV,1H NMR,13C NMR,XPS,XRD,AFM,TEM,SEM,CV,TGA等对石墨烯和氧化石墨烯进行表征的常用方法,指出了常见的出峰位置以及表征结果和测试目的,并作了简要的分析和说明.最后,对点击化学在石墨烯和氧化石墨烯上的功能化应用作出了总结和展望.     

Enhanced enantioselective oxidation of olefins catalyzed by Mn-porphyrin immobilized on graphene oxide

An efficient enantioselective heterogeneous catalyst, GO-[Mn(TPyP)tart], was prepared by covalent attachment of Mn(III) complex of H₂TPyP via the propyl linkage to graphene oxide (GO) nanosheet and using chiral tartrate counter ion. The catalyst was characterized by Fourier transform infrared (FT-IR), diffuse reflectance ultraviolet–visible (DR UV–Vis) spectroscopy, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman and thermogravimetric analysis (TGA). The graphene-supported Mn-porphyrin showed higher activity for the enantioselective epoxidation of unfunctionalized olefins with molecular oxygen in the presence of isobutyraldehyde. It could be recovered easily and reused in asymmetric oxidation of styrene precursor in a five-step sequence without any considerable loss of its catalytic activity and selectivity. The obtained optically epoxide selectivities were achieved in 86% to 100%.     

改性氧化石墨烯膜的制备及其性能研究

为了改善氧化石墨烯(GO)膜的低渗透性和不稳定性,本文采用过氧化氢对GO进行改性后抽滤成膜,并在不同温度下对膜进行热还原.采用超高性能全自动气体吸附仪、透射电镜、扫描电镜、拉曼光谱仪、接触角、X射线衍射等对材料进行结构和形貌表征.分析不同HGO(H2O2改性GO)负载量和不同温度热还原对膜水通量和截留率的影响.在优化条...     

Simultaneous removal of uranium and humic acid by cyclodextrin modified graphene oxide nanosheets

Cyclodextrin-modified graphene oxide nanosheets (denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid (HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a “bridge” between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.     

Effects of curing agents and modified graphene oxide on the properties of XNBR composites

This paper investigates the effects of crosslinking methods on the incorporation of graphene oxide (GO) in carboxylated nitrile butadiene rubber (XNBR) in the process of producing nanocomposites for chemical-resistant protective clothing and gloves. The novel aspect of the study is a comprehensive approach involving both unmodified GO as well as GO that was carboxylated to increase its affinity to XNBR and to facilitate its application. The nanostructure of XNBR composites was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Fourier transform infrared spectroscopy (FTIR) was used to elucidate the chemical structure of the composites. Thermal stability studies were performed using differential scanning calorimetry (DSC). The barrier properties of the composites were determined based on swelling, crosslinking density, and permeation by mineral oils. The mechanical tests included resistance to puncture and abrasion, stress at strain, and tensile strength. Contact angle was measured to determine the degree of hydrophobicity of the obtained composites.AFM and SEM images revealed the effects of different curing agents (sulfur, magnesium oxide, or a hybrid system) as well as GO type on the surface morphology of XNBR composites. The type of curing agent was found to affect the kind of crosslinks formed and their spatial network structure, as confirmed by FTIR. The DSC curves showed that the crosslinking methods of XNBR did not affect glass transition temperature, but led to large changes observed in the temperature range of 130–220 °C.The type of crosslinking method affected the degree of swelling. It was found that the incorporation of carbon nanofillers led to an improvement in the abrasion and puncture resistance as well as tensile strength of XNBR composites. The water contact angle of the composites indicated hydrophobicity. The properties of XNBR composites containing GO revealed their substantial application potential in protective clothing.     

Tailoring thermal conductivity of bulk graphene oxide by tuning the oxidation degree

The thermal conductivity of graphene oxides can be tailored by tuning oxidation degree due to the introduction of atomic- and nano-scale phonon scattering centers.     

Electrochromatographic performance of graphene and graphene oxide modified silica particles packed capillary columns

Graphene oxide functionalized silica microspheres (GO@SiO₂) were synthesized based on condensation reaction between amino from aminosilica particles and carboxyl groups from GO. Reduction of GO@SiO₂ with hydrazinium hydroxide generated graphene modified silica particles (G@SiO₂). GO@SiO₂ and G@SiO₂ packed capillary columns for capillary electrochromatography were thereafter fabricated by pressure slurry packing with single‐particle frits. GO of 0.3 mg/mL in dispersion solution for GO@SiO₂ synthesis was considered as a compromise between retaining and column efficiency whereas GO@SiO₂ of 20 mg/mL in slurries for column packing was chosen for a homogenous and tight bed. Optimum mobile phases were acquired considering both electroosmotic flow and resolution at an applied voltage of −6 kV as the following: acetonitrile/phosphate buffer (10 mM, pH 7.0), 75:25 (v/v) for polycyclic aromatic hydrocarbons and 50:50 (v/v) for aromatic compounds. A comparison was made between electrochromatographic performances for three PAHs (naphthalene, fluorene and phenanthrene) and three aromatic compounds of various polarities (toluene, aniline and phenol) on bare aminosilica, GO@SiO₂ and G@SiO₂ packed columns, which proved the contribution of alone or combinational actions of solvophobic effect and π‐π electron stacking as well as hydrogen bonds to retaining behaviors by GO@SiO₂ and G@SiO₂. Well over‐run, over‐day and over‐column precisions (retention time: 0.3–1.4, 1.1–3.8 and 2.8–5.2%, respectively; peak area: 2.6–6.5, 4.8–8.3 and 6.5–12.6%, respectively) of GO@SiO₂ packed columns were a powerful proof for good reproducibility. Analytical characteristics of GO@SiO₂ packed capillary columns in CEC analysis of fresh water were evaluated with respect to linearity (R² = 0.9961–0.9989) over the range 0.1 to 100 mg/L and detection limits of 9.5 for naphthalene, 12.6 for fluorene and 16.2 μg/L for phenanthrene. Further application to fresh water increased the visibility of the proposed material, where good spike recoveries in the range 89–96% were offered.     

氧化石墨烯的制备及低温还原研究

用化学氧化法制备氧化石墨烯,并用一种新型的低温化学还原方法将其还原。用红外光谱、拉曼光谱、X射线衍射、X射线光电子能谱、扫描电镜、原子力显微镜等多种手段表征氧化石墨烯和还原氧化石墨烯的结构与形貌。结果表明,即使在低温条件下,壳聚糖依然可以还原氧化石墨烯,从而预示,在低温条件下,能够在同一环境下实现氧化石墨烯的还原和石墨烯的应用。     

Effect of preparation methods of graphene oxide on permeability of free-standing membranes against polar and nonpolar species

ABSTRACT

In this study, graphene oxide (GO) was synthesized using Hummers, modified Hummers and improved Hummers methods, and then freestanding membranes were prepared based on these materials. Effects of different GO preparation methods on C/O ratio and interlayer spacing of freestanding membranes were studied. Structure of these membranes was studied by X-ray diffraction, contact angle, XRF, FT-IR, and FESEM methods. Also, permeability of ammonia, dichloromethane, and water vapor was investigated through these membranes. Results showed that, the sample prepared by the Hummers method had lower C/O ratio, smoother surface and lower permeability for polar species, such as water and ammonia vapors, than nonpolar materials. Membranes prepared using Improved Hummers method showed the least permeability against nonpolar vapors such as dichloromethane.     

Dispersion of graphene oxide and its flame retardancy effect on epoxy nanocomposites

Graphene oxide was prepared by ultrasonication of completely oxidized graphite and used to improve the flame retardancy of epoxy.The epoxy/graphene oxide nanocomposite was studied in terms of exfoliation/dispersion,thermal stability and flame retardancy.X-ray diffraction and transmission electron microscopy confirmed the exfoliation of the graphene oxide nanosheets in epoxy matrix.Cone calorimeter measurements showed that the time to ignition of the epoxy/graphene oxide nanocomposite was longer than that of neat epoxy.The heat release rate curve of the nanocomposite was broadened compared to that of neat epoxy and the peak heat release rate decreased as well.