疏水石墨烯水相分散液的制备及电化学性能

通过未添加表面活性剂和稳定剂而得到均匀的石墨烯水相分散液的方法,近来来成为研究的一大热点.本工作通过提高水合肼的用量,来替代表面活性剂或者其它稳定剂的作用,得到了良好的均匀的水相石墨烯分散液,可长期稳定存放,6个月内未发生团聚现象.其Zeta电位低于-32.5 mV(pH值为5.89),原子力显微镜和透射电子显微镜图像表明产物为具有褶皱结构的、六方晶系的单层石墨烯结构,厚度为0.38 nm.XPS分析显示这种方法对于除去羟基和环氧基团起到了有效的作用.利用这种分散液所制备的石墨烯-玻碳电极(GE-GCE)在检测抗坏血酸(AA)和尿酸(UA)时,比普通玻碳电极(GCE)显示出更良好的电化学响应.     

Aqueous dispersion of graphene sheets stabilized by ionic liquid-based polyether

Graphene sheets can be effectively dispersed by a novel ionic liquid-based polyether, poly(1-glycidyl-3-methylimidazolium chloride) (PGMIC), in aqueous solution. The reduction of graphene oxide to graphene is confirmed by UV–Vis and Raman spectrum in aqueous solution of PGMIC. TEM image showed that the stable and uniform dispersion of graphene sheets were obtained. Both the TGA and AFM analysis indicated that the graphene sheet was covered by PGMIC. FTIR spectra demonstrated that n–π, cation–π interactions and electrostatic repulsions played important roles in the dispersion of graphene sheets.     

Dispersion of Graphene Sheets in Aqueous Solution by Oligodeoxynucleotides

Applications of graphene sheets in the fields of biosensors and biomedical devices are limited by their insolubility in water. Consequently, understanding the dispersion mechanism of graphene in water and exploring an effective way to prepare stable dispersions of graphene sheets in water is of vital importance for their application in biomaterials, biosensors, biomedical devices, and drug delivery. Herein, a method for stable dispersion of graphene sheets in water by single‐stranded oligodeoxynucleotides (ssODNs) is studied. Owing to van der Waals interactions between graphene sheets, they undergo layer‐to‐layer (LtL) aggregation in water. Molecular dynamics simulations show that, by disrupting van der Waals interaction of graphene sheets with ssODNs, LtL aggregation of graphene sheets is prevented, and water molecules can be distributed stably between graphene sheets. Thus, graphene sheets are dispersed stably in water in the presence of ssODNs. The effects of size and molarity of ssODNs and noncovalent modification of graphene sheets are also discussed.     

A dense graphene monolith with poloxamer prefunctionalization enabling aqueous redispersion to obtain solubilized graphene sheets

The realization of good aqueous dispersibility of commercial graphene products composed of exfoliated graphene sheets is of significance for downstream applications. However, the tap density of commercial graphene powder is quite low (0.03–0.1 kg/m³), meaning that 1 kg graphene powder occupies about 10–30 m³ in volume during transportation. And, the available content of commercial graphene dispersion/slurry in aqueous medium cannot exceed 5 wt%, although the density is high (≈ 1050 kg/m³). In this work, a graphene monolith was prepared by oven-drying of graphene sheets prefunctionalized with poloxamer surfactants. Our graphene monoliths not only have a high density (1500 kg/m³) and high graphene content (≈ 10 wt%), but also a full capability to be completely redispersed (≈ 100%) in water by bath sonication to obtain solubilized graphene sheets, whose lateral size and thickness are unchanged compared to as-exfoliated ones. Moreover, a simple empirical method was proposed to predict the redispersion capability of graphene monoliths using different poloxamers by contact angle measurements. Our results provide a universal approach to make exfoliated graphene-based products with better downstream availability and lower transportation cost.     

Aqueous Dispersions of Graphene from Electrochemically Exfoliated Graphite

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH₄)₂SO₄, 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5–1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively.     

Determination of sulfonamides in livers using matrix solid-phase dispersion extraction high-performance liquid chromatography

The matrix solid-phase dispersion (MSPD) was applied for extracting seven sulfonamides (SAs) in liver samples. The separation and determination were carried out by high-performance liquid chromatography. The analytes were derivated with fluorescamine and detected with fluorescence detector. The types of dispersion adsorbents for MSPD were examined and the highest recovery was obtained when the diatomaceous earth was used as the dispersion adsorbent and the mass ratio of dispersion adsorbent to sample was 3:1. The acetone was used as the elution solvent. Under the optimal conditions, the linear range for determining the SAs in liver samples was 5.0-1000.0 ng/g. The porcine, chicken and cattle liver samples were analyzed and the average recoveries of seven SAs were higher than 84.6%.     

基于离子液体的分散液液微萃取-柱前荧光衍生高效液相色谱法测定水样中8种磺胺类药物

建立了一种基于离子液体的分散液液微萃取技术结合柱前荧光衍生高效液相色谱(IL-DLLME-HPLC-FL)对8种磺胺类药物进行检测的方法,并成功应用于实际环境水样的分析。实验考察了萃取参数对磺胺萃取效率的影响及衍生产物的稳定性。最佳实验条件:以40 μL [C₆MIM]PF₆]为萃取剂,0.1 mL丙酮为分散剂,对pH=4且不含NaCl的水溶液进行不超声的分散液液微萃取,并衍生化反应6 h。结果表明:在最佳实验条件下,该法在0.2~10 μg/L和10~500 μg/L两个浓度范围内线性良好,线性相关系数r ≥0.9989;检出限为0.08~0.5 μg/L (S/N=3)。对实验室自来水、湖水、珠江水、池塘水分别加标5、50、200 μg/L的回收率为87.2%~101.4%,相对标准偏差为3.7%~6.2%。该法环保、简便,可用于测定实际水样中磺胺类药物。     

Matrix solid-phase dispersion extraction and high-performance liquid chromatographic determination of residual sulfonamides in chicken.

Simultaneous determination of the six sulfonamides (SAs) sulfadiazine, sulfadimidine, sulfamonomethoxine, sulfamethoxazole, sulfadimethoxine and sulfaquinoxaline in chicken using matrix solid-phase dispersion (MSPD) with neutral aluminium oxide as an MSPD sorbent and high-performance liquid chromatography (HPLC) is presented. In the present MSPD, six SAs could be isolated by only one step, elution with a 70% (v/v) aqueous ethanol solution, without the sorbent conditioning and the sorbent-tissue matrix washing. For the HPLC determination, a LiChrospher 100 RP-8 and a mixture of 1% acetic acid solution (pH 3.0, in water)-acetonitrile-N,N-dimethylformamide (78:22:5, v/v/v) as the mobile phase with a photodiode array detector were used. Average recoveries were greater than 87.6% with relative standard deviations between 0.5 and 8.6%. The total time and amount of solvent required for the analysis of one sample were <1.5 h and <12 ml, respectively.     

Molecular insights into the surface morphology, layering structure, and aggregation kinetics of surfactant-stabilized graphene dispersions

The production of graphene with open band gaps for the manufacturing of graphene-based electronic and optical devices requires synthesis methods to either control the number of layers to enrich AB-stacked bilayer or trilayer graphene or control the extent of functionalization of monolayer graphene. Solution-phase dispersion of graphene is promising for both methods to create printable electronics and nanocomposites. However, both methods face common challenges, including controlling the surface morphology, reducing the turbostratic layering, and enhancing the dispersion stability. To address these challenges at the molecular level, we successfully combined molecular simulations, theoretical modeling, and experimental measurements. First, we probed the surface structure and electrostatic potential of monolayer graphene dispersed in a sodium cholate (SC) surfactant aqueous solution, which exhibits 2D sheets partially covered with a monolayer of negatively charged cholate ions. Similar to the case of carbon nanotube functionalization, one may regulate the binding affinity of charged reactants for graphene functionalization by manipulating the surface morphology. Subsequently, we quantified the interactions between two graphene-surfactant assemblies by calculating the potential of mean force (PMF) between two surfactant-covered graphene sheets, which confirmed the existence of a metastable bilayer graphene structure due to the steric hindrance of the confined surfactant molecules. The traditional Derjaguin-Landau-Verwey-Overbeek (DLVO) theory was found to be adequate to explain the long-range electrostatic repulsions between the ionic surfactant-covered graphene sheets but was unable to account for the dominant, short-range steric hindrance imparted by the confined surfactant molecules. Interestingly, one faces a dilemma when using surfactants to disperse and stabilize graphene in aqueous solution: on the one hand, surfactants can stabilize graphene aqueous dispersions, but on the other hand, they prevent the formation of new AB-stacked bilayer and trilayer graphene resulting from the reaggregation process. Finally, the lifetime and time-dependent distribution of various graphene layer types were predicted using a kinetic model of colloid aggregation, and each graphene layer type was further decomposed into subtypes, including the AB-stacked species and various turbostratic species. The kinetic model of colloid aggregation developed here can serve as a useful tool to evaluate the quality of graphene dispersions for subsequent substrate-transferring or functionalization processes.     

A self-assembly pipette tip graphene solid-phase extraction coupled with liquid chromatography for the determination of three sulfonamides in environmental water

A sensitive, economical, and miniaturized self-assembly pipette tip graphene solid-phase extraction (PT-G-SPE) coupled with liquid chromatography fluorescence detection (LC-FD) was developed for rapid extraction and determination of three sulfonamide antibiotics (SAs) in environmental water samples. The PT-G-SPE cartridge, assembled by packing 1.0 mg of graphene as sorbent into a 100 μL pipette tip, showed high adsorption capacity for the SAs owing to the large surface area and unique structure of graphene. The factors that affected the extraction efficiency of PT-G-SPE, including sample volume, pH, sorbent amount, washing solvent and eluent solvent were optimized. Good linearity for SAs was obtained in a range of 2–4000 pg mL⁻¹ with correlation coefficients (r²) ≥ 0.9993. The recoveries of the SAs at three spiked levels ranged from 90.4% to 108.2% with relative standard deviations (RSD) ≤ 6.3%. In comparison with other sorbents such as C₁₈, HLB, SCX, PCX, and multiwalled carbon nanotubes, one advantage of using graphene as sorbent of pipette tip solid-phase extraction (PT-SPE) was that PT-G-SPE could adsorb larger sample volume (10 mL) at a small amount of sorbent (1 mg) and low solvent consumption with good extraction efficiency, which not only increased the fraction of analytes to LC and the sensitivity of SAs determination, but also reduced the cost and pollution.     

Preparation of magnetic CoFe2O4-functionalized graphene sheets via a facile hydrothermal method and their adsorption properties

Magnetic CoFe₂O₄-functionalized graphene sheets (CoFe₂O₄-FGS) nanocomposites have been synthesized by hydrothermal treatment of inorganic salts and thermal exfoliated graphene sheets. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations show that cobalt ferrite nanoparticles with sizes of 10-40 nm are well dispersed on graphene sheets. OH⁻ was recognized as a tie to integrate the inorganic salts with the graphene sheets, which made reaction started and developed on the surface of graphene sheets and formed cobalt ferrite nanoparticles on graphene sheets. The adsorption kinetics investigation revealed that the adsorption of methyl orange from aqueous solution over the as-prepared CoFe₂O₄-FGS nanocomposites followed pseudo-second-order kinetic model and the adsorption capacity was examined as high as 71.54 mg g⁻¹. The combination of the superior adsorption of FGS and the magnetic properties of CoFe₂O₄ nanoparticles can be used as a powerful separation tool to deal with water pollution.     

Graphene oxide dispersions in organic solvents

The dispersion behavior of graphene oxide in different organic solvents has been investigated. As-prepared graphite oxide could be dispersed in N, N-dimethylformamide, N-methyl-2-pyrrolidone, tetrahydrofuran, and ethylene glycol. In all of these solvents, full exfoliation of the graphite oxide material into individual, single-layer graphene oxide sheets was achieved by sonication. The graphene oxide dispersions exhibited long-term stability and were made of sheets between a few hundred nanometers and a few micrometers large, similar to the case of graphene oxide dispersions in water. These results should facilitate the manipulation and processing of graphene-based materials for different applications.     

微波固相法快速制备氮掺杂石墨烯

以鳞片石墨为原料, 首先通过Hummers法制备氧化石墨, 再将洗涤至中性的氧化石墨分散液与乙二胺反应得到功能化石墨烯。干燥后的功能化石墨烯在微波辐照下能瞬间产生高热, 促使接枝的乙二胺分子分解并实现对石墨烯原位掺杂制备出氮掺杂石墨烯。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、X射线衍射(XRD)、X射线能谱(EDS)对样品的形貌、结构和组成进行了表征。结果表明:该合成途径能成功实现对氧化石墨烯的还原和掺杂, 所合成的氮掺杂石墨烯呈现透明绢丝状结构。     

微波固相法快速制备氮掺杂石墨烯

以鳞片石墨为原料,首先通过Hummers法制备氧化石墨,再将洗涤至中性的氧化石墨分散液与乙二胺反应得到功能化石墨烯。干燥后的功能化石墨烯在微波辐照下能瞬间产生高热,促使接枝的乙二胺分子分解并实现对石墨烯原位掺杂制备出氮掺杂石墨烯。利用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)、X射线衍射(XRD)、X射线能谱(EDS)对样品的形貌、结构和组成进行了表征。结果表明:该合成途径能成功实现对氧化石墨烯的还原和掺杂,所合成的氮掺杂石墨烯呈现透明绢丝状结构。     

磁性氧化石墨烯固相萃取/高效液相色谱-串联质谱法测定环境水样中6种三嗪类除草剂残留

采用一步合成法制备磁性氧化石墨烯材料(GO-Fe_3O_4),将其用作磁性固相吸附剂对环境水样中的6种三嗪类除草剂进行萃取和富集,并与高效液相色谱-串联质谱法相结合进行测定。以扫描电镜和傅立叶红外光谱对合成材料进行了表征,并考察了GO-Fe_3O_4用量、萃取时间、水样的pH值及离子强度和解吸条件等因素对萃取效率的影响。6种三嗪类除草剂的检出限为0.1~1.0 ng/L,富集倍数可达616~902倍。将方法应用于苏州地区太湖水、运河水和护城河水等实际水样的分析,加标回收率为85.4%~117.6%,相对标准偏差为1.2%~10.0%。该方法操作简单快速,富集倍数较高,检出限低,可用于水样中痕量三嗪类除草剂残留的检测。     

Synthesis of polydopamine‐functionalized magnetic graphene and carbon nanotubes hybrid nanocomposites as an adsorbent for the fast determination of 16 priority polycyclic aromatic hydrocarbons in aqueous samples

A novel adsorbent made of polydopamine‐functionalized magnetic graphene and carbon nanotubes hybrid nanocomposite was synthesized and applied to determine 16 priority polycyclic aromatic hydrocarbons by magnetic solid phase extraction in water samples. FTIR spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy consistently indicate that the synthesized adsorbents are made of core–shell nanoparticles well dispersed on the surface of graphene and carbon nanotubes. The major factors affecting the extraction efficiency, including the pH value of samples, the amount of adsorbent, adsorption time and desorption time, type and volume of desorption solvent, were systematically optimized. Under the optimum extraction conditions, a linear response was obtained for polycyclic aromatic hydrocarbons between concentrations of 10 and 500 ng/L with the correlation coefficients ranging from 0.9958 to 0.9989, and the limits of detection (S/N = 3) were between 0.1 and 3.0 ng/L. Satisfactory results were also obtained when applying these magnetic graphene/carbon nanotubes/polydopamine hybrid nanocomposites to detect polycyclic aromatic hydrocarbons in several environmental aqueous samples.     

Determination of sulfonamide antibiotics in fish and shrimp samples based on magnetic carbon nanotube dummy molecularly imprinted polymer extraction followed by UPLC-MS/MS

In this study, a novel purification method using magnetic solid-phase extraction (MSPE) based on magnetic carbon nanotube dummy molecularly imprinted polymer (MCNTMIP) nanocomposite was investigated for separation and enrichment of sulfonamide antibiotics (SAs) in fish and shrimp samples. The MCNTMIP nanocomposite was successfully synthesized by applying carbon nanotubes as supporting template, methacrylic acid as functional monomer, sulfabenzamide as the dummy template for SAs, and ethylene glycol dimethacrylate as crosslinking agent, then was characterized by Fourier-transform infrared spectrometry and vibrating sample magnetometry. The adsorption performance of MCNTMIP was evaluated by binding experiments, including static adsorption, kinetic adsorption, and selectivity recognition study. The results confirmed that an imprinted polymer layer was successfully constructed on the surface of the MCNTMIP and this sorbent has advantages of simple magnetic separation, specific molecular recognition, and high adsorption capacity. Combined with ultra-high performance liquid chromatography tandem mass spectrometry (UPLC-MS/MS), we developed a rapid, sensitive, efficient MSPE method for detecting SAs analytes. Under the optimal conditions, the limits of detection were low to 0.1 μg/kg, and the recoveries of SAs analytes were ranged between 90.2 and 99.9%. In addition, the precision values were ranged between 0.5 and 9.1%. This method was successfully applied to analyze SAs in fish and shrimp samples with satisfactory recoveries.     

Trace quantification of selected sulfonamides in aqueous media by implementation of a new dispersive solid‐phase extraction method using a nanomagnetic titanium dioxide graphene‐based sorbent and HPLC‐UV

Herein, a new dispersive solid‐phase extraction method using a nano magnetic titanium dioxide graphene‐based sorbent in conjunction with high‐performance liquid chromatography and ultraviolet detection was successfully developed. The method was proved to be simple, sensitive, and highly efficient for the trace quantification of sulfacetamide, sulfathiazole, sulfamethoxazole, and sulfadiazine in relatively large volume of aqueous media. Initially, the nano magnetic titanium dioxide graphene‐based sorbent was successfully synthesized and subsequently characterized by scanning electron microscopy and X‐ray diffraction. Then, the sorbent was used for the sorption and extraction of the selected sulfonamides mainly through π–π stacking hydrophobic interactions. Under the established conditions, the calibration curves were linear over the concentration range of 1–200 μg/L. The limit of quantification (precision of 20%, and accuracy of 80–120%) for the detection of each sulfonamide by the proposed method was 1.0 μg/L. To test the extraction efficiency, the method was applied to various fortified real water samples. The average relative recoveries obtained from the fortified samples varied between 90 and 108% with the relative standard deviations of 5.3–10.7%.     

Determination of sulfonamides in soil samples based on alumina-coated magnetite nanoparticles as adsorbents

In this study, alumina-coated magnetite nanoparticles (Fe₃O₄/Al₂O₃ NPs) were synthesized, and they were applied to the analysis of sulfonamides (SAs) including sulfadiazine (SDZ), sulfamerazine (SMR), sulfamethoxazole (SMX), sulfamonomethoxine (SMM), sulfamethoxydiazine (SMD), sulfadimethoxine (SDM) and sulfaquinoxaline (SQX) in different soil samples based on magnetic solid-phase extraction (MSPE). The extraction and concentration process was carried out in a single step by mixing the extraction solvent, magnetic adsorbents and soil sample under ultrasonic action. Then, the adsorbents were isolated from the complicated matrix easily with an external magnetic field. The SAs desorbed from the adsorbents were determined by liquid chromatography-tandem mass spectrometry. Compared with traditional methods, the MSPE method simplified the operation procedure and reduced the analysis time. Under the optimum conditions, the recoveries of SDZ, SMR, SMX, SMM, SMD and SDM by analyzing the five spiked soil samples were between 71% and 93% except for SQX (42-60%). This may be due to the stronger hydrophobic property of SQX. Detection limits of SAs were between 0.37 and 6.74 ng g⁻¹. It was also found that the “aging” effect of SAs contaminated soil could cause the recoveries to decrease.     

Functionalized graphene/thermoplastic polyester elastomer nanocomposites by reactive extrusion‐based masterbatch: preparation and properties reinforcement

A reactive extrusion process was developed to fabricate polymer/graphene nanocomposites with good dispersion of graphene sheets in the polymer matrix. The functionalized graphene nanosheet (f‐GNS) activated by diphenylmethane diisocyanate was incorporated in thermoplastic polyester elastomer (TPEE) by reactive extrusion process to produce the TPEE/f‐GNS masterbatch. And then, the TPEE/f‐GNS nanocomposites in different ratios were prepared by masterbatch‐based melt blending. The structure and morphology of functionalized graphene were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, X‐ray diffraction and transmission electron microscopy (TEM). The incorporation of f‐GNS significantly improved the mechanical, thermal and crystallization properties of TPEE. With the incorporation of only 0.1 wt% f‐GNS, the tensile strength and elongation at break of nanocomposites were increased by 47.6% and 30.8%, respectively, compared with those of pristine TPEE. Moreover, the degradation temperature for 10 wt% mass loss, storage modulus at ?70°C and crystallization peak temperature (T_cp) of TPEE nanocomposites were consistently improved by 17°C, 7.5% and 36°C. The remarkable reinforcements in mechanical and thermal properties were attributed to the homogeneous dispersion and strong interfacial adhesion of f‐GNS in the TPEE matrix. The functionalization of graphene was beneficial to the improvement of mechanical properties because of the relatively well dispersion of graphene sheets in TPEE matrix, as suggested in the TEM images. This simple and effective approach consisting of chemical functionalization of graphene, reactive extrusion and masterbatch‐based melt blending process is believed to offer possibilities for broadening the graphene applications in the field of polymer processing. Copyright © 2014 John Wiley & Sons, Ltd.