An improved Hummers method to synthesize graphene oxide using much less concentrated sulfuric acid

The production of graphene oxide with less acid is beneficial to reduce the costs and lower the impact on the environment, but it is still a great challenge. In this work, a relatively simple, safe method for synthesizing graphene oxide with much less acid (decrease ～40%) is proposed. With assistance of the heat absorbed from environment and reaction system, the temperature of reaction system of low acid can be well controlled. More interestingly, the graphite can be completely oxidized into graphite oxide by using much less acid, with lowering the production of high-concentration aqueous waste acid (> 1 mol/L, decrease ～40%). A series of characterizations show that the prepared graphene oxide has similar yield and functional groups compared with that of using the conventional method. This work provides a safe and environmentally friendly choice for the large-scale production of graphene oxide and its derivative materials.     

Electrochemical oxygen reduction on nitrogen doped graphene sheets in acid media

Nitrogen doped graphene were prepared via exfoliated graphite oxide. This graphene exhibited significantly high oxygen reduction activity. High electric conductivity, high surface area, large amount of edge sites and pyridinic N site in rGS (reduced graphene sheets) contribute to the high ORR (oxygen reduction reaction) activity. The rGS showed a potential to replace expensive Pt for oxygen reduction reaction in PEMFC.     

Ultrafast room-temperature reduction of graphene oxide by sodium borohydride,sodium molybdate and hydrochloric acid

Since graphene-based materials have shown great potential in many fields,it is important to explore ultrafast and high-efficient methods to synthesize reduced graphene oxide(rGO) using inexpensive reducing agents under mild conditions.Here,we reported a novel method for the ultrafast chemical reduction of graphene oxide(GO) at room temperature using sodium borohydride(NaBH₄),sodium molybdate(Na₂MoO₄) and hydrochloric acid(HCl).The reduction was carried out within 2 min.A series of characterization results revealed that the obtained reduced graphene oxide has higher reduction degree than that synthesized by NaBH₄ alone at high temperature.Moreover,rGO electrode based on the present reducing method exhibited a superior specific capacitance of 139.8 F/g at a current density of1 A/g,indicating that it can be used as electrode materials for supercapacitors.     

Synthesis and characterization nanocomposite of the graphene oxide/polyacrylic acid modified with 2-mercaptoethanol

In this research, synthesis and characterization of the nano-graphene oxide (GO) based on the modified polyacrylic acid (PAA) have been carried out. Formation of esteric bonds between the carboxyl functional groups of the GO surface and the hydroxyl groups of PAA was confirmed by FTIR spectroscopy. The result of this synthesis is covalent modification of graphene oxide during the polymerization process and this modification has caused improvement and change in some properties of graphene oxide including solubility of nanocomposite. Additionally, structure and stability of composite were studied by SEM, XRD and TGA.     

Isolation of ellagic acid from pomegranate peel extract by hydrophobic interaction chromatography using graphene oxide grafted cotton fiber adsorbent

Ellagic acid, a natural polyphenol, was isolated from pomegranate peel extract by hydrophobic interaction using graphene oxide grafted cotton fiber as a stationary adsorbent. The grafted graphene oxide moieties served as hydrophobic interaction‐binding sites for ellagic acid adsorption. The graphene oxide grafted cotton fiber was made into a membrane‐like sheet in order to complete ellagic acid purification by using a binding–elution mode. The effects of operational parameters, such as the composition of the binding buffer/elution buffer, buffer pH, and buffer concentration, on the isolation process were investigated. It was found that 5 mmol/L sodium carbonate aqueous solution is a proper‐binding buffer, and sodium hydroxide aqueous solution ranging from 0.04 to 0.06 mol/L is a suitable elution solution for ellagic acid purification. Under the optimized condition, the purity of ellagic acid increased significantly from 7.5% in the crude extract to 75.0–80.0%. The pH value was found to be a key parameter that determines the adsorption and desorption of ellagic acid. No organic solvent is involved in the entire purification process. Thus, a simple and environmentally friendly method is established for ellagic acid purification using a graphene oxide‐modified biodegradable and bio‐sourced fibrous adsorbent.     

Synthesis and electrochemical performance of sandwich-like polyaniline/graphene composite nanosheets

Sandwich-like polyaniline/graphene composite nanosheets have been synthesized by chemical oxidation polymerization of aniline monomer on the surfaces of reduced graphene oxide nanosheets in the absence of any surfactants. The influences of the mass ratios of aniline and reduced graphene oxide on the sizes and morphologies of polyaniline/graphene nanocomposites have been investigated. As the mass ratio of aniline and reduced graphene oxide is smaller than 12:1, polymerization reaction of aniline occurs on the surfaces of reduced graphene oxide by heterogeneous nucleation to form sandwich-like polyaniline/graphene composite nanosheets. However, besides sandwich-like polyaniline/graphene composite nanosheets, polyaniline nanofibers are formed by homogeneous nucleation. In comparison with reduced graphene oxide and polyaniline nanofibers, the obtained sandwich-like polyaniline/graphene composite nanosheets exhibit good electrochemical performances due to the synergistic effect between graphene and polyaniline.     

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。     

Synthesis of reduced graphene oxide and its electrocatalytic properties

The method of the chemical synthesis of reduced graphene oxide was developed. Sodium hypophosphite and sulfi te were used as reducing agents. The formation of reduced graphene oxide was confi rmed by several methods. Volt-ampere characteristics of electrodes based on reduced graphene oxide were investigated in an experimental model of an oxygen fuel cell with an alkaline electrolyte. Characteristics of oxygen electrodes based on reduced graphene oxide were stable over semiannual tests. The resulting reduced graphene oxide is a promising material for oxygen electrodes of chemical current sources.     

Zinc oxide nanoparticles immobilized on graphene flake

Interactions of ZnO nanoparticles with graphene oxide in isopropanol were studied; graphene oxide was shown to perform as an efficient substrate to immobilize zinc oxide nanoparticles on its surface. Interactions of nanocomposites consisting of graphene oxide-zinc oxide nanoparticles with supercritical isopropanol were studied. The conversion of graphene oxide into graphene does not appreciably changes the composition, morphology, or structure of ZnO nanoparticles.     

石墨烯纳米载药体系的制备及对人口腔鳞癌细胞杀伤效果

利用化学氧化还原法制备了氧化石墨烯,进一步超声破碎剥离,得到纳米氧化石墨烯,并对其进行聚乙二醇(PEG)的功能化修饰后载药顺铂。 采用扫描电子显微镜(SEM)、紫外-可见吸收光谱(UV-Vis)、傅立叶变换红外光谱(FTIR)对石墨烯纳米载药体系进行表征,细胞存活率实验(MTT)法检验石墨烯纳米载药体系对人口腔鳞癌(KB)细胞的杀伤作用。 结果表明,石墨烯纳米载药体系对顺铂的负载率为42.4%,聚乙二醇修饰后可以降低纳米氧化石墨烯的细胞毒性并提高生物相容性,对KB细胞具有双重的杀伤作用,为纳米氧化石墨烯在肿瘤治疗的临床应用提供了理论依据。     

氧化石墨烯吸附亚甲基蓝的分子动力学模拟

采用分子动力学方法研究了亚甲基蓝在不同氧化度的氧化石墨烯表面的吸附行为及其动力学性质, 从微观角度讨论了亚甲基蓝由体相到氧化石墨烯表面的吸附过程及主要作用机制, 并通过亚甲基蓝分子动力学性质解释了氧化石墨烯的氧化度和含氧官能团类型对吸附行为的影响. 结果表明, 吸附过程中, 亚甲基蓝主要受氧化石墨烯表面含氧官能团的静电作用, 以近似垂直氧化石墨烯表面的方向进入, 并以平行的方式吸附于氧化石墨烯表面; 亚甲基蓝不易脱离高氧化度氧化石墨烯的吸附位点; 吸附平衡过程中, 相对于低氧化度的氧化石墨烯, 高氧化度氧化石墨烯对亚甲基蓝的束缚性更强, 同时与亚甲基蓝间相互作用更强; 含氧官能团中的环氧基与亚甲基蓝间的作用势能更强, 且羟基能够与亚甲基蓝间形成氢键结构, 共同保障了亚甲基蓝吸附层的稳定性.     

Geometry-dependent electrochemistry of graphene oxide family

The influence of graphene oxide geometry on electrochemical performance is of great interest, but there are few reports on this subject. Three different members of the graphene oxide family, graphene oxide nanosheets, graphene oxide nanoribbons, and graphene oxide quantum dots were comparatively investigated as electrode materials to systematically study the effect of geometric structure. The results showed that, as the geometric structure varies, the three graphene oxide materials possess different electrical conductivities, various defect densities and oxygen contents, as well as diverse electrode surface chemistry and microstructures, which combine together to result in the distinct electrochemical responses for the modified electrodes, depending on the redox system involved. This work broadens the method of studying the electrochemical performance of many other materials from the perspective of geometry.     

Increasing the Sensitivity and Single‐Base Mismatch Selectivity of the Molecular Beacon Using Graphene Oxide as the “Nanoquencher”

Here, we report a novel, highly sensitive, selective and economical molecular beacon using graphene oxide as the “nanoquencher”. This novel molecular beacon system contains a hairpin‐structured fluorophore‐labeled oligonucleotide and a graphene oxide sheet. The strong interaction between hairpin‐structured oligonucleotide and graphene oxide keep them in close proximity, facilitating the fluorescence quenching of the fluorophore by graphene oxide. In the presence of a complementary target DNA, the binding between hairpin‐structured oligonucleotide and target DNA will disturb the interaction between hairpin‐structured oligonucleotide and graphene oxide, and release the oligonucleotide from graphene oxide, resulting in restoration of fluorophore fluorescence. In the present study, we show that this novel graphene oxide quenched molecular beacon can be used to detect target DNA with higher sensitivity and single‐base mismatch selectivity compared to the conventional molecular beacon.     

还原态氧化石墨烯载Pd纳米催化剂对甲酸氧化的电催化性能

采用改进的Hummers法氧化石墨后,对其超声剥离成氧化石墨烯水溶液,继之通过乙二醇还原Pd金属离子和氧化石墨烯,得到了还原态氧化石墨烯（RGO）负载Pd纳米催化剂,并用于甲酸的电催化氧化.透射电子显微镜和X射线衍射结果显示：负载于RGO上的Pd粒子平均粒径为3.8nm,其优先在RGO的褶皱和边缘处生长.电化学测试表明：RGO上残存的含氧基团降低了Pd催化剂受CO毒化的程度,Pd/RGO催化剂表现出了较商业化Pd/C更高的电催化活性和更好的稳定性.     

氧化石墨烯-海藻酸钠-壳聚糖复合支架的制备及表征

通过冷冻干燥技术,将不同量的氧化石墨烯与海藻酸钠和壳聚糖复合,构建复合支架材料.研究了不同的氧化石墨烯含量(质量分数0, 0.3%, 0.5%, 0.7%, 1%)对支架材料微观结构、孔隙率、溶胀比、体外降解性能、机械性能及生物相容性的影响,以确定复合支架中最佳氧化石墨烯含量.研究结果表明,复合材料呈固态海绵状结构,具有一定的形态可塑性;扫描电子显微镜观察发现,各组支架均为三维网状结构,随着氧化石墨烯含量的增加,孔隙尺寸逐渐降低,孔壁厚度增加,孔隙尺寸在140～240μm之间;随氧化石墨烯含量的增加,复合支架溶胀比和体外降解速率逐渐降低,而机械强度明显增强;体外细胞毒性显示,当氧化石墨烯质量分数为0.3%时,细胞存活率最高,而当氧化石墨烯含量增高时,细胞活性会被明显抑制,造成细胞死亡.因此,氧化石墨烯在复合支架中最佳含量为0.3%.     

Preparation and investigation of tribological properties of ultra‐high molecular weight polyethylene (UHMWPE)/graphene oxide

This article has been devoted to investigation of the tribological properties of ultra‐high molecular polyethylene/graphene oxide nanocomposite. The nanocomposite of ultra‐high molecular polyethylene/graphene oxide was prepared with 0.5, 1.5, and 2.5 wt% of graphene oxide and with a molecular weight of 3.7 × 10⁶ by in‐situ polymerization using Ziegler–Natta catalyst. In this method, graphene oxide was used along with magnesium ethoxide as a novel bi‐support of the Ziegler–Natta catalyst. Analyzing the pin‐on‐disk test, the tribological properties of the nanocomposite, such as wear rate and mean friction coefficient, were investigated under the mentioned contents of graphene oxide. The results showed that an increase in graphene oxide content causes a reduction in both wear rate and mean coefficient friction. For instance, by adding only 5 wt% graphene oxide to the polymeric matrix, the wear rate and mean coefficient friction decreased about 34% and 3.8%, respectively. Also, the morphological properties of the nanocomposite were investigated by using X‐ray diffraction and scanning electron microscopy. In addition, thermal properties of the nanocomposite were analyzed using differential scanning calorimetry, under various contents of graphene oxide. The results of the morphological test indicated that the graphene oxide was completely exfoliated into the polymeric matrix without any agglomeration. Copyright © 2016 John Wiley & Sons, Ltd.     

石墨烯/铂复合材料的制备及电化学性能研究

采用Hummers法制备氧化石墨,再超声分散于去离子水中形成稳定的氧化石墨分散液。分散液与氯铂酸溶液混合后,氧化石墨烯还原氯铂酸产生大量铂纳米粒子,铂粒子被牢固地锚在氧化石墨烯片上,最后将所得到的氧化石墨烯/铂复合物置于管式炉中在Ar/H2气氛中于800℃下热裂解制备出石墨烯/铂复合材料。形貌与纳米结构分析表明,氧化石墨已被彻底还原成石墨烯,铂纳米粒子均匀分散在褶皱的石墨烯纳米片间。电化学阻抗研究进一步揭示复合材料的电子转移阻抗明显小于石墨烯,呈示铂纳米粒子掺入石墨烯片层大大改善了导电性。石墨烯/铂复合材料应用于对苯二酚的电化学检测,检出限达1.6×10-7mol.L-1,这说明该材料具有优异的电催化性能。     

Determination of Lysozyme by Graphene Oxide–Polyethylene Glycol-Based Fluorescence Resonance Energy Transfer

The surface of graphene oxide was modified by bis(3-aminopropyl)-terminated polyethylene glycol to produce a composite graphene–polyethylene glycol. The graphene oxide/polyethylene glycol maximum absorption peak in the ultraviolet–visible spectrum was redshifted, and transmission electron microscope images showed that graphene oxide was cleaved into small nanosheets to form graphene oxide/polyethylene glycol. The dispersibility of graphene oxide/polyethylene glycol in physiological solution was higher than for graphene oxide. The optimum composite of graphene oxide/polyethylene glycol was used as a quencher in a fluorescence resonance energy transfer aptasensor for the determination of lysozyme detection. The results showed that graphene oxide/polyethylene glycol rapidly and efficiently quenched the fluorescence of the dye-labeled aptamer. The fluorescence was recovered by adding lysozyme to the system. The aptamer fluorescence intensity exhibited a strong linear dependence on the lysozyme concentration from 50 to 300?nM, and the lysozyme detection limit was approximately 11?nM. This method was used for the determination of lysozyme in egg whites, demonstrating that this approach is a promising alternative for the determination of lysozyme.     

氧化石墨烯在辣根过氧化物酶传感器中的应用研究

本文研究氧化石墨烯的合成方法及其在生物传感器中的应用.通过Hummer法氧化天然石墨粉制得氧化石墨,在蒸馏水中利用超声分散将氧化石墨剥片,从而合成了氧化石墨烯(GO).通过透射电镜图表征了氧化石墨烯的形貌并通过红外光谱证实氧化石墨烯的形成.将所合成的氧化石墨烯与三角形貌的金纳米颗粒(prism AuNPs)、辣根过氧化...     

Experimental test and curve fitting of creep recovery characteristics of modified graphene oxide natural rubber and its relationship with temperature

The creep recovery properties of different graphene-doped rubber and the effect of temperature on them were studied. Doping graphene, especially with the surface functional group or surface microstructure, can significantly improve the creep resistance of natural rubber (NR). The permanent creep of each composite tested under the same conditions for 20 min. Graphene oxide, hydrazine hydrate reduced graphene oxide, and 3-aminopropyltriethoxysilane (APTS) grafted graphene oxide was 33%, 16%, and 51% lower than those filled with carbon black respectively. Four parameter model and Weibull distribution function used to analyze and evaluate the creep and recovery test results of composite rubber. These curve fitting results can adequately describe the influence of different types of nanofillers on the creep and recovery properties of composite rubber. The long-term creep of composites forecasted by the time-temperature superposition principle (TTSP). The results show that graphene doping can improve the creep resistance of the rubber. Besides, graphene oxide and surface-modified graphene oxide had better creep resistance than reduced graphene oxide filled natural rubber. It can see that the interfacial properties between the graphene sheet and the natural rubber matrix play an essential role in the creep and recovery properties of graphene/natural rubber composites.