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。     

氧化程度对微细鳞片可膨胀石墨结构及膨胀性的影响

以平均粒径为19.71μm的天然微细鳞片石墨为原料,通过化学氧化法制备了具有不同氧化程度的可膨胀石墨,采用XRD、FTIR、Raman、SEM等对可膨胀石墨的结构与膨胀性进行了表征。结果表明：当氧化程度较低时制得的微细鳞片可膨胀石墨由石墨、石墨层间化合物和氧化石墨三相组成;随着氧化程度的增加,氧化石墨相含量与可膨胀石墨结构无序程度逐渐增高,石墨层间化合物相含量先增加后减少,石墨相含量则逐渐降低;氧化促使HSO₄^-或SO₄^2-插入石墨层间,插入层间的HSO₄^-或SO₄^2-量是决定可膨胀石墨膨胀容积的关键因素,制备的微细鳞片膨胀石墨的膨胀容积可达65.9mL·g^-1。     

氧化钛/氧化石墨纳米复合材料的制备、表征及性能

采用四氯化钛(TiCl₄)和氧化石墨为主要原料, 通过原位复合的方法制备了氧化钛/氧化石墨(TiO₂/GO)纳米复合材料. 采用傅里叶变换红外(FTIR)光谱仪、X射线衍射(XRD)仪、热重-差热分析(TG-DTA)仪、X射线光电子能谱(XPS)、透射电子显微镜(TEM)和扫描电子显微镜(SEM)等手段研究了TiO₂/GO纳米复合材料的结构和性能. 结果表明, 石墨在氧化过程中结构层键合大量含氧官能团, 部分含氧官能团进一步与纳米TiO₂以化学键结合; 复合后氧化石墨原有衍射峰消失. 将TiO₂/GO添加到水性聚氨酯(WPU)中, 制备了TiO₂/GO-WPU复合涂膜. 紫外吸收光谱表明, 随着氧化石墨含量的增加, 复合涂膜的紫外吸收能力增强, 当GO含量达到一定数值时, 涂膜的紫外吸收最强, 随着GO含量继续增加吸收又呈下降趋势, 存在一较优浓度值. TiO₂/GO的添加显著提高了聚氨酯涂层的抗紫外线性能, 耐磨损性能和热稳定性能.     

氧化程度对氧化石墨烯a-b轴结构及电学性能的影响

采用改进的Hummers法及超声分散等后续处理制备不同氧化程度的氧化石墨烯样品.用XPS、XRD、AFM、UV-Vis及四探针测试仪对样品官能团变化规律、结构、形貌特征以及电学性能进行表征分析.结果表明,氧化石墨烯在超声波的作用下水相条件下可达单层分散,单层氧化石墨烯厚度约为1.4 nm:成膜过程中,在氢键力的作用下氧化石墨烯片层c轴重叠形成层状凝聚体,结构有序度较好;随氧化剂(KMnO₄)用量增加,碳层平面上含氧官能团含量持续增加,特别是羟基官能团(C-OH)含量的增加,使a-b轴方向最大底面间距(d₁₀₀和d₁₁₀)一直增大,直至KMnO₄用量达4.0 g时,部分C-OH水解,导致d₁₀₀与d₁₁₀略有减小;碳层平面上含氧官能团尤其是环氧官能团(C-O-C)含量的增加,使样品带隙宽度逐渐增大,导电性能越来越差.     

氧化石墨烯/聚吡咯插层复合材料的制备和电化学电容性能

以FeCl₃-甲基橙(MO)为模板, 通过化学原位聚合法成功制备出氧化石墨烯/聚吡咯(GO/PPy)插层复合材料. 采用X射线衍射(XRD)、傅里叶变换红外(FTIR)光谱、扫描电镜(SEM)和透射电镜(TEM)等测试技术对复合材料进行物性表征. 此外, 利用循环伏安、恒电流充放电和交流阻抗测试方法对复合材料在两种不同水系电解液(1 mol·L^-1 Na₂SO₄和1 mol·L^-1 H₂SO₄)中的电化学性能进行了研究. 结果显示: 氧化石墨烯和聚吡咯表现出各自优势并发挥协同作用, 使得GO/PPy插层复合材料在中性和酸性电解液中都显示出可观的比电容. 电流密度为0.5 A·g^-1时, GO/PPy 插层复合材料在Na₂SO₄和H₂SO₄电解液中的比电容分别为449.1 和619.0 F·g^-1, 明显高于纯PPy的比电容. 经过800 次循环稳定性测试后, 两种不同电解液中, 复合材料初始容量的保持率分别为92%和62%. 其中酸性电解液体系中初始容量更大, 而中性溶液中具有更稳定的循环性能.     

氧化程度对氧化石墨结构与阳离子交换容量的影响

通过改进hummers法制备了不同氧化程度的氧化石墨。采用XRD、FTIR及XPS等对不同氧化程度氧化石墨样品的结构特征、含氧官能团种类与含量及阳离子交换容量进行表征。结果表明,石墨经氧化后结构层上键入羟基(C-OH)、环氧基(C-O-C)和羧基(-COOH)等含氧官能团;随氧化程度的增加,石墨结构逐渐全部转化为氧化石墨结构,C-O-C和-COOH的含量逐渐增大,而C-OH的含量先增大后略有减小,阳离子交换容量也表现为先增大后减小,对应的最大值分别为1.70、3.80和4.50 mmol·g^-1;氧化石墨碳平面上C-OH发生去质子化反应在层间产生H⁺,其他阳离子与之交换进入GO层间域,C-OH的含量是影响氧化石墨阳离子交换容量的主要因素,随C-OH含量的增加,氧化石墨样品的阳离子交换容量增大。     

聚乙烯亚胺改性氧化石墨对水中Cr(Ⅵ)的吸附

通过对石墨氧化、酯化,将聚乙烯亚胺耦合接枝到氧化石墨表面,制备聚乙烯亚胺改性氧化石墨(PEI-GO)。通过FTIR、XRD、TEM、RS和XPS等对合成材料进行表征,并研究了其对水中的Cr(Ⅵ)吸附和脱附性能。表征结果表明,聚乙烯亚胺成功嫁接到氧化石墨上,其氨基含量为4.36mmol·g^-1。PEI-GO对水中Cr(Ⅵ)具有很好的吸附性能,吸附等温线符合Freundlich方程,吸附动力学可用拟二级动力学方程来描述。PEI-GO对水中Cr(Ⅵ)的吸附随pH的升高而降低。阴离子的存在降低吸附剂对Cr(Ⅵ)的吸附,不同阴离子的影响大小顺序为PO₄^3- >SO₄^2- >NO₃^- >Cl^-。XPS结果表明,PEI-GO对Cr(Ⅵ)的去除是吸附-化学还原耦合作用的结果。经4次脱附再生循环,PEI-GO对Cr(VI)仍具有较高吸附量,表明该吸附剂再生性好,可循环使用。     

石墨层间化合物FeCl3-CrO3-GIC的制备及性能研究

以天然鳞片石墨、CrO₃、CH₃NO₂、FeCl₃为原料，按物质的量的比34∶1.5∶22∶1，利用化学氧化法制备出低温易膨胀、高膨胀容积的石墨层间化合物，300 ℃时膨胀容积为420 mL·g^-1，800 ℃时达到最大膨胀容积630 mL·g^-1，明显优于传统硫酸、硝酸插层的石墨层间化合物。采用SEM、EDS、FTIR、XRD、TG、VSM等技术对石墨层间化合物的组成、结构、性能进行了表征和分析。     

聚乙烯亚胺改性氧化石墨对水中Cr(Ⅵ)的吸附

通过对石墨氧化、酯化,将聚乙烯亚胺耦合接枝到氧化石墨表面,制备聚乙烯亚胺改性氧化石墨(PEI-GO).通过FTIR、XRD、TEM、RS和XPS等对合成材料进行表征,并研究了其对水中的Cr(Ⅵ)吸附和脱附性能.表征结果表明,聚乙烯亚胺成功嫁接到氧化石墨上,其氨基含量为4.36 mmol·g^-1.PEI-GO对水中Cr(Ⅵ)具有很好的吸附性能,吸附等温线符合Freundlich方程,吸附动力学可用拟二级动力学方程来描述.PEI-GO对水中Cr(Ⅵ)的吸附随pH的升高而降低.阴离子的存在降低吸附剂对Cr(Ⅵ)的吸附,不同阴离子的影响大小顺序为PO₄^3- >SO₄^2- >NO^3- >Cl^-.XPS结果表明,PEI-GO对Cr(Ⅵ)的去除是吸附-化学还原耦合作用的结果.经4次脱附再生循环,PEI-GO对Cr(VI)仍具有较高吸附量,表明该吸附剂再生性好,可循环使用.     

采用连续电位阶跃方法研究聚吡咯在电解质水溶液中的氧化还原稳定性

连续电位阶跃方法是一种研究氧化还原稳定性的有效方法. 本文采用连续电位阶跃方法研究了以对甲苯磺酸钠为掺杂剂的聚吡咯(ppy)膜的电化学氧化还原稳定性, 通过计算聚吡咯在阶跃电位下的还原电量(Q_red), 还原和氧化电量的比值(Q_red/Q_ox)考察聚吡咯在H₂SO₄、Na₂SO₄和NaOH溶液中在不同电位下的氧化还原可逆性. 结果发现聚吡咯过氧化的发生强烈依赖支持电解质的pH值和阶跃电位. 在H₂SO₄溶液中, 过氧化的起始电位为0.8 V, 而在Na₂SO₄溶液中, 过氧化的起始电位为0.5 V. 在NaOH溶液中, 过氧化在任何电位均可发生, 表明溶液中OH^- 的存在是过氧化发生的直接原因.     

Preparing graphene oxide–copper composite material from spent lithium ion batteries and catalytic performance analysis

The wide use of lithium ion batteries (LIBs) has created much waste, which has become a global issue. It is vital to recycle waste LIBs considering their environmental risks and resource characteristics. Anode graphite from spent LIBs still possess a complete layer structure and contain some oxygen-containing groups between layers, which can be reused to prepare high value-added products. Given the intrinsic defect structure of anode graphite, copper foils in LIB anode electrodes, and excellent properties of graphene, graphene oxide–copper composite material was prepared in this work. Anode graphite was firstly purified to remove organic impurities by calcination and remove lithium. Purified graphite was used to prepare graphene oxide–copper composite material after oxidation to graphite oxide, ultrasonic exfoliation to graphene oxide (GO), and Cu²⁺ adsorption. Compared with natural graphite, preparing graphite oxide using anode graphite consumed 40% less concentrated H₂SO₄ and 28.6% less KMnO₄. Cu²⁺ was well adsorbed by 1.0 mg L^?1 stable GO suspension at pH 5.3 for 120 min. Graphene oxide–copper composite material could be successfully obtained after 6 h absorption, 3 h bonding between GO and Cu²⁺ with 3/100 of GO/CuSO₄ mass ratio. Compared to CuO, graphene oxide–copper composite material had better catalytic photodegradation performance on methylene blue, and the electric field further improved the photodegradation efficiency of the composite material.     

Mass transfer kinetics of graphene oxide prepared by chemical oxidation intercalationg assisted ultrasonic field

The key step of the control reaction for the preparation of graphene oxide (GO) by chemical oxidation of KMnO₄/ concentrated H₂SO₄ oxidation system is the intercalation mass transfer process of oxidizer in graphite. Ultrasonic field can promote the intercalation mass transfer process, but the mass transfer kinetics remains unclear. In this paper, the kinetic model of mass transfer coefficient of graphene oxide sheet intercalated by Mn₂O₇ oxidizer in ultrasonic field was established. The Mn₂O₇ intercalation process after the intervention of the ultrasonic was simulated by COMSOL Multiphysics 5.5 simulation software. The results show that the ultrasonic field makes the Mn₂O₇ solution inside and outside the graphite layer turbulent, and the ultrasonic intervening time has little influence on the concentration distribution and diffusion rate of the solution outside the graphite layer, while it has great influence on the concentration distribution and little influence on the diffusion rate change inside the graphite layer. These results contribute to the improvement of the mass transfer theory for the preparation of GO by ultrasonic assisted chemical oxidation.     

Studies on thermal decomposition of electrochemically oxidized glass-like carbon

Glass-like carbon (GC) tiles were electrochemically oxidized in 1 mol·dm^?3 H₂SO₄ solution at a potential of 2.3 V/SCE. The surfaces of the oxidized samples were examined by scanning electron microscopy (SEM). The solid oxidation products were studied by derivatographic (TG, DTG and DTA) and elemental analyses. The solid products of electrochemical oxidation of GC, with the general formula C₈O_4.2H_2.3 were thermolabile and revealed properties similar to those of graphite oxide. They are hydrophylic and their thermal decomposition proceeds in three steps: (i) evaporation of-chemisorbed water (320–400 K), (ii) exothermic decomposition of graphite oxide (370–430 K), and (iii) gradual decomposition of the oxidation products (>430 K).     

Properties of polyamide 6 and thermoplastic polyurethane blends containing modified montmorillonites

In this paper are reported some experimental data related to the influence of preparation regimes and characteristics of exfoliated graphite based sorbents produced by thermal expansion of H₂SO₄-graphite intercalation compounds (H₂SO₄-GICs) on their sorption properties. Investigations involving X-ray diffraction analyses, surface area, bulk density and oil sorption capacity measurements, have been performed. Sorption capacity was discussed as a function of bulk density, total pore volume and surface area. Some empirical correlation between studied characteristics of exfoliated graphite have been found. The differences among the obtained samples, as a consequence of synthesis conditions, were also put in evidence by thermal analysis (TG, DTG and DTA) performed after their exposure to oil sorption.It was found that thermal analysis method could provide information about the exfoliated graphite pore system related to the sorbed oil oxidation rate. The capacity for oil uptake was also discussed in the case of graphite oxide soot.     

Electrochemical Synthesis of Co-intercalation Compounds in the Graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-H<Subscript>3</Subscript>PO<Subscript>4</Subscript>System

Anodic oxidation of highly oriented pyrolytic graphite in an electrolyte containing concentrated sulfuric and anhydrous phosphoric acids is studied for the first time. The synthesis was carried out under galvanostatic conditions at a current I = 0.5 mA and an elevated temperature (t = 80°C). Intercalation compounds of graphite (ICG) are shown to form at all concentration ratios of H₂SO₄ and H³PO⁴ acids. The intercalation compound of step I forms in solutions containing more than 80 wt % H₂SO₄, a mixture of compounds of intercalation steps I and II forms in 60% H²SO⁴, intercalation step II is realized in the sulfuric acid concentration range from 10 to 40%, and a mixture of compounds of intercalation steps III and II is formed in 5% H₂SO₄ solutions. The threshold concentration of H₂SO₄ intercalation is ∼2%. With the decrease in active intercalate (H₂SO₄) concentration, the charging curves are gradually smoothed, the intercalation step number increases, and the potentials of ICG formation also increase. As the sulfuric acid concentration in the electrolyte changes from 96 to 40 wt %, the filled-layer thickness d _i in ICG monotonously increases from 0.803 to 0.820 nm, which apparently is associated with the greater size of phosphoric acid molecules. With further increase in H₃PO₄ concentration in solution, d _i remains unchanged. According to the results of chemical analysis, both acids are simultaneously incorporated into the graphite interplanar spacing and their ratio in ICG is determined by the electrolyte composition.__________Translated from Elektrokhimiya, Vol. 41, No. 5, 2005, pp. 651–655.Original Russian Text Copyright © 2005 by Leshin, Sorokina, Avdeev.     

Effect of the graphite oxide composition on the structure of products obtained by sulfuric acid treatment at elevated temperatures

The electronic structure and functional composition of products of the graphite oxide (GO) interaction with concentrated sulfuric acid (H₂SO₄) are studied, depending on the oxygen content in the precursor and the treatment temperature. X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure (NEXAFS) measured at the CK edge, and infrared spectroscopy are used to show the recovery of the π electron system of graphene planes at a temperature of 200 °C. Aggregation of functional groups in GO containing more than 40% of oxygen causes the formation of vacancy defects in the planes with treatment. When the GO treatment temperature rises to 280 °C, the oxidation of the basal plane π-regions occurs. The results can underlie the control of the functional composition, vacancy number, and size in graphite materials.     

Behaviors of Perfluorocarbon Emulsion during Dissolution of Oxide Layers

This study investigates the dissolution behavior of oxide layers containing radionuclides using perfluorocarbon (PFC) emulsion as a reusable medium. Chemicals such as PFC, anionic surfactant, and H₂SO₄ are used for preparing the PFC emulsion, and emulsified using an ultrasonication process. The FTIR results show O–H stretching that is formed by the interaction of the carboxyl group of the anionic surfactant with the hydroxyl group of water containing H₂SO₄, and find that the H₂SO₄ can be homogeneously dispersed in the PFC–anionic surfactant–H₂SO₄ emulsion. The dissolution test of the simulated Cr₂O₃ specimen is conducted using PFC emulsion containing KMnO₄. Through the weight losses of specimens and Scanning Electron Microscope-Energy Dispersive X-ray Spectrometer (SEM-EDS) analysis, it is confirmed that the Cr₂O₃ layer on the SUS304 specimen is easily dissolved using PFC emulsion. During the dissolution of the Cr₂O₃, it is observed that the dispersed H₂SO₄–KMnO₄ became unstable and separated from PFC emulsion. Based on these results, the behavior of the PFC emulsion during the dissolution of the oxide layer is explained.     

Effect of in situ oxidization with potassium permanganate on the morphologies of SEBS membranes

The morphologies of the asymmetric membranes of polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) prepared and simultaneously oxidized with different substrate solutions were investigated with atomic force microscopy (AFM), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and attenuated total reflectance infrared spectroscopy (ATR-FTIR). We used the KMnO₄ aqueous solution and KMnO₄/H₂SO₄ mixture solution as solvent-casting substrates, as well as oxidized reagents. The surface composition and functional groups of membranes were also measured. The effect of casting substrates on morphological changes was discussed through possible chemical reactions. It was found that the SEBS membranes were transformed from an ordered microphase-separated structure to disordered nodular or sponge-like structures. The former might be contributed to MnO₂ depositions while the latter was caused by the bond interruption, after KMnO₄ or KMnO₄/H₂SO₄ oxidizing.     

Synergistic effect of hybrid graphene and boron nitride on the cure kinetics and thermal conductivity of epoxy adhesives

In the present study, the synergistic effect of hybrid boron nitride (BN) with graphene on the thermal conductivity of epoxy adhesives has been reported. Graphene was prepared by chemical reduction of graphite oxide (GO) in a mixture of concentrated H₂SO₄/H₃PO₄ acid. The particle size distribution of GO was found to be ~10 μm and a low contact angle of 54° with water indicated a hydrophilic surface. The structure of prepared graphene was characterized by Fourier transform infrared (FTIR), X‐ray diffraction (XRD), Raman spectroscopy and atomic force microscopy (AFM). The thermal conductivity of adhesives was measured using guarded hot plate technique. Test results indicated an improvement in the thermal conductivity up to 1.65 W/mK, which was about ninefold increase over pristine epoxy. Mechanical properties of different epoxy formulations were also measured employing lap shear test. The surface characterization of different epoxy adhesive systems was characterized through XRD, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies. Fourier transform infrared also served to determine the nature of interactions between filler particles and epoxy resin. Non‐isothermal differential scanning calorimetric (DSC) technique was used to investigate the effects of graphene and BN particles on the cure kinetics and cross‐linking reaction of epoxy cured with amine curing agent. The Kissinger equation, the model‐free isoconversional Flynn–Wall–Ozawa method and the Ozawa model were used to analyze the kinetic parameter. Copyright © 2017 John Wiley & Sons, Ltd.     

The use of the rotating pt-electrode at zero applied e. m. f. for the microdetermination of monovalent phosphorus in hypophosphorous acid or hypophosphite

Summary An amperometric method is described for the microdetermination of monovalent phosphorus using the rotating Pt-electrode vs S. C. E. and zero applied e. m. f. It is based on oxidation of hypophosphorous acid and hypophosphite with KMnO₄ to phosphorous acid and phosphite respectively under the following conditions: Acidity 0.05–0.6 and 0.2–1.68N H₂SO₄ for H₃PO₂ and NaH₂PO₂ respectively; NaF: 0.4–1.5%; amounts of P (I): 2.4g-2.1 mg and 5.4g-7.24 mg corresponding to hypophosphorous acid and hypophosphite respectively. The method is accurate and can be utilized at concentrations lower than that with the potentiometric method.

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Die Verwendung einer rotierenden Pt-Elektrode bei EMK=0 zur Mikrobestimmung von P (I) in unterphosphoriger Säure oder Hypophosphit

Zusammenfassung Die amperometrische Mikrobestimmung einwertigen Phosphors mit einer rotierenden Pt-Elektrode gegen eine ges. Kalomelelektrode bei EMK=0 wurde beschrieben. Sie beruht auf der Oxydation der unterphosphorigen Säure bzw. des Hypophosphits mit KMnO₄ zu phosphoriger Säure bzw. Phosphit bei einer Acidität von 0,05-0,6 bzw. 0,2-1,68N H₂SO₄ für H₃PO₂ bzw. NaH₂PO₂; 0,4-1,5% NaF; 2,4g-2,1 mg bzw. 5,4g-7,24 mg P (I) als H₃PO₂ bzw. H₂PO₂ ^–. Das Verfahren ist genau und für geringere Konzentrationen geeignet als die Potentiometrie.