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.     

L-半胱氨酸功能化三维石墨烯的制备及其对亚甲基蓝的吸附行为研究

在常压下制备了L-半胱氨酸功能化三维石墨烯(L-3DRGO),研究了L-3DRGO对MB分子的吸附机理。氧化石墨烯(GO)在常压水浴中与L-半胱氨酸(L-cys)反应后,结构中的含氧官能团被大量去除,L-cys被氧化为胱氨酸,实现了GO的还原和接枝改性,并通过酰胺反应将还原后的GO片-片相连,构建成三维网络结构。L-3DRGO对MB的吸附符合Langmuir等温吸附模型,为单层吸附,通过Langmuir等温吸附模型计算得到的相关系数(RL)在0～1之间,增大MB初始浓度可以有效克服固液两相之间的传质阻力,有利于吸附的进行。拟二级动力学模型能更好地描述MB在L-3DRGO上的吸附,当MB的初始浓度为500mg/L时,L-3DRGO对MB的最大吸附量为446.43mg/g。吸附过程的焓变与熵变均为正值,说明L-3DRGO对MB的吸附是一个吸热和熵增的过程。在298～338K范围内,ΔG~0为负值并随温度的升高而减小,说明MB在L-3DRGO上的吸附可自发进行,适当升温利于吸附过程。整个吸附过程均伴随有液膜扩散和颗粒内扩散,吸附速度的主控步骤由液膜扩散转化为颗粒内扩散。     

功能化的石墨烯和磁铁掺杂的还原氧化石墨烯对亚甲基蓝的吸附作用

用简单可行的方法合成了功能化的石墨烯(GNSPF6)和磁铁掺杂的还原氧化石墨烯(RGO-Fe3O4),并进一步研究了pH值、接触的时间和温度对它们吸附亚甲基蓝(MB)的影响.结果表明,随着pH值和温度的增加其吸附量也随之变大,从而说明该吸附过程是自发吸热的.因为GNSPF6的吸附过程只用了不到20min的时间,所以它的吸附是高效的.用经典的准一级反应、准二级反应和粒内扩散模型对其吸附过程进行动态分析,从结果可以发现,准二级动力学模型比准一级动力学模型更适用于描述吸附过程.采用传统的Langmuir,Freundlich和L-F吸附等温线模型来模拟分析数据,在20℃时,由Langmuir吸附等温线模型模拟分析得知GNSPF6和RGO-Fe3O4对MB的最大吸附量分别为374.4和118.4mg/g.     

TiO2/氧化石墨烯光催化降解亚甲基蓝性能研究

理想的石墨烯具有二维平面结构,其具有良好的机械性能、热导率、高电子迁移率和量子霍尔效应。本文以改进的Hummers法制得氧化石墨烯(Graphene Oxide),超声处理和水热法制备了氧化石墨烯(GO)负载量分别为1.0 wt%、1.5 wt%,2.0 wt%,2.5 wt%的TiO_2/GO复合材料,并通过XRD、TEM等表征手段观察了复合材料的晶相和结构,探讨光催化降解亚甲基蓝性能。结果表明:较之TiO_2,复合材料均具有更大的表面积、更好的亲水性和更强的光催化性能;反应浓度均为2 g·L~(-1)的复合材料,光催化降解10 ppm亚甲基蓝,氧化石墨烯负载量为1.5 wt%的TiO_2/GO复合材料,1 h光催化降解率可达86%,效果最佳。TiO_2/GO复合材料吸附容量大,稳定性良好,能够高效光催化降解偶氮型染料,有望在进一步改良性能后广泛应用于降解工业废水领域。     

改性埃洛石材料的制备及其对亚甲基蓝吸附行为的研究

使用硅烷偶联剂KH550改性埃洛石纳米管获得改性材料HNTs-APTS,并对其吸附亚甲基蓝的行为进行研究。利用傅立叶变换红外光谱仪(FTIR)、X-衍射仪(XRD)对改性前后的埃洛石进行表征。考察了吸附时间和温度对吸附过程的影响,并采用Lagrange准二级动力学方程、Langmuir等温线方程及Freundlich等温线方程对实验数据进行拟合。结果表明,KH550成功负载到埃洛石表面;改性后材料的吸附能力大大提高。改性埃洛石对亚甲基蓝的吸附约在60 min达平衡,最大吸附容量为21.66 mg/g。其吸附过程符合准二级动力学方程,热力学较好地符合Langmuir等温线方程,且吸附过程为自发吸热,升高温度有利于吸附的进行。改性材料可重复再生6次,具有良好的再生性能,可在工业处理亚甲基蓝废水中使用。     

活性碳/CoFe_2O_4复合物的制备及其对亚甲基蓝的吸附性能

通过低温回流法制备了具有磁分离响应的活性碳(AC)与CoFe2O4的复合物AC/CoFe2O4(MAC)。采用批式吸附实验法对MAC吸附溶液中偶氮染料亚甲基蓝(MB)的吸附动力学过程及吸附平衡进行了研究,考察了溶液初始pH值对MAC吸附MB的影响。结果表明,MAC吸附MB的过程很快,20min几乎达到平衡。MAC吸附MB过程可以用准二级动力学方程描述。等温吸附过程服从Langmuir方程,MAC对MB的饱和吸附容量为120.48mg/g。在较低pH值时,MB吸附量较小。随着pH值的升高,MAC对MB的吸附量增大。     

Ni-MOFs@GO复合材料吸附亚甲基蓝工艺优化及其性能研究

为了提高氧化石墨烯(GO)对阳离子染料的吸附效果,采用溶液共混法制备Ni-MOFs@GO复合材料。采用X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)和扫描电子显微镜(SEM)对其结构和形貌进行了表征。采用响应曲面法(RSM)优化Ni-MOFs@GO对亚甲基蓝(MB)的吸附工艺。以Ni-MOFs@GO浓度、MB质量浓度和吸附温度3因素为变量,以MB吸附量为响应值,建立了二项式回归模型方程,确定最佳吸附条件,并进行动力学和热力学分析。结果表明：3因素的一次项和二次项对MB的吸附效果影响显著,交互项影响不明显。Ni-MOFs@GO对MB最佳吸附条件为Ni-MOFs@GO浓度为0.6 g·L^-1,MB质量浓度为30 mg·L^-1,吸附温度为26℃,MB吸附量为259.83 mg/g;吸附过程符合准二级动力学方程,吸附模型符合Freundlich等温线方程。     

CoTPP-GO纳米光敏剂的制备及对亚甲基蓝的降解性能研究

本文采用超声一锅DMF溶剂回流法制备了一种新型的未见报道的CoTPP-GO纳米复合光敏剂.该光敏剂利用紫外、红外、拉曼、XRD等手段进行了表征.0.1 g TiO2与5％的光敏剂在水中超声2h后制成的纳米光催化剂加入到100 mL pH=4.0的30 mg·L-1的亚甲基蓝溶液中,加入0.5 mL 30％双氧水氧化剂,...     

超细粉煤灰吸附亚甲基蓝的机理研究

以西安西郊热电厂粉煤灰(XFA),西安灞桥热电厂粉煤灰(BFA)和陕西渭河电厂粉煤灰(WFA)为原料,球磨后经旋风分级再用布袋收集逸出物分别得到超细粉煤灰XUFA、BUFA和WUFA。研究了超细粉煤灰对亚甲基蓝的吸附动力学、热力学以及pH值对吸附的影响。结果表明,超细粉煤灰对亚甲基蓝的吸附性能明显好于原粉煤灰。超细粉煤灰对亚甲基蓝的吸附性能按顺序为WUFA>XUFA>BUFA。粉煤灰颗粒粒度、比表面积和活性组分(SiO2 Al2O3)含量是影响粉煤灰吸附性能的主要因素。WUFA对亚甲基蓝的吸附符合Langmuir吸附等温式,而XUFA和BUFA对亚甲基蓝的吸附符合Freundlich吸附等温式。超细粉煤灰对亚甲基蓝的吸附均符合二级吸附动力学模型,吸附过程由颗粒内扩散过程控制。当溶液pH由2增加到8时,超细粉煤灰吸附量增加,后随pH值增加,吸附量略有下降。     

果胶改性硅胶复合材料的制备及其对亚甲基蓝的吸附性能

以废弃柚子皮中提取的果胶改性硅胶表面,制备出新型的果胶改性硅胶复合材料——P-硅胶,研究了P-硅胶对水中亚甲基蓝染料的吸附性能。利用红外光谱对材料进行表征,并通过分光光度法考察了用量、p H值、吸附时间、温度及实际水样对P-硅胶吸附亚甲基蓝性能的影响。硅胶经果胶改性后,其对亚甲基蓝的吸附容量由31.6 mg·g-1增至41.7 mg·g-1,吸附性能明显提高;P-硅胶对亚甲基蓝的吸附容量随着p H值、温度的升高而增大,碱性条件有利于吸附。结果显示:当p H 7.0,P-硅胶用量为5 mg,吸附时间为2 h,吸附温度为50℃时,制备出的P-硅胶对亚甲基蓝染料溶液的吸附容量最大可达59.2 mg·g-1。动力学研究显示,P-硅胶对亚甲基蓝的吸附能够在120 min内迅速达平衡,吸附行为符合准二级动力学方程,表明该吸附过程以化学吸附为主。吸附等温线研究表明,与Freundlich模型相比,实验数据拟合更符合Langmuir吸附等温模型。P-硅胶对环境水样中亚甲基蓝的去除率可达90%以上。     

Ionic polyacrylamide hydrogel improved by graphene oxide for efficient adsorption of methylene blue

Research on Chemical Intermediates - The ionic polyacrylamide/graphene oxide (PAM/GO) hydrogel as an excellent methylene blue (MB) adsorbent was prepared by an improved one-step radical...     

Glycine‐functionalized reduced graphene oxide for methylene blue removal

Glycine‐functionalized reduced graphene oxide (GRGO) was prepared through the reaction of glycine and chlorine‐functionalized reduced graphene oxide. The product was characterized by SEM, HRTEM, IR, Raman, and XPS. The nitrogen content (8.28%) was high in product, peak at 285.8 eV was assigned to the C–N bond, which implied that the chlorine residues in raw material were substituted by amine group of glycine. The intensity ratio of D and G peak was about 1.5, which also implied that more saturated carbon atoms were present in the product. Results of SEM, IR, and XPS confirmed that glycine molecules were attached to graphene sheets. Compared with reduced graphene oxide (61.5 mg/g) and active carbon (45.2 mg/g), GRGO had a good adsorption capacity (98.9 mg/g) for methylene blue. The adsorption process was fitted to three kinetic models and three adsorption isotherm models. The adsorption process complied with pseudo‐second order kinetic model and Langmuir model.     

Porous graphene oxide-based carbon artefact with high capacity for methylene blue adsorption

A three-dimensional porous graphene oxide (PGO) material prepared by hydrothermal method was selected to adsorb methylene blue (MB), which demonstrates a high MB adsorption capacity, up to 1100 mg g^?1 in alkaline solution at room temperature. The influences of different pore structures and different contents of oxygen-containing functional groups on MB adsorption behaviors were studied in detail, which indicated that the high MB adsorption capacity is mainly ascribed to the synergistic effect of the large number of oxygen-containing functional groups and the interconnected 3D porous network. Moreover, based on the investigation on the adsorption kinetics and the effect of pH value on MB adsorption, we propose a two-step adsorption kinetics for PGO, which involved in two interactions between MB molecular and porous graphene oxide-based carbon: electrostatic force and π-π stacking. Besides, the calculation of the activation energies indicates that chemisorption dominates the adsorption for PGO in comparison with physisorption for three-dimensional porous graphene materials which has low adsorption capacity because of the removal of functional groups. The results are of great significance for the design and environmental applications of PGO as a promising adsorbent material for water purification.     

Removal of methylene blue from aqueous solution by graphene oxide

Graphene oxide (GO) is a highly effective absorbent of methylene blue (MB) and can be used to remove MB from aqueous solution. A huge absorption capacity of 714 mg/g is observed. At initial MB concentrations lower than 250 mg/L, the removal efficiency is higher than 99% and the solution can be decolorized to nearly colorless. The removal process is fast and more efficient at lower temperatures and higher pH values. The increase of ionic strength and the presence of dissolved organic matter would further enhance the removal process when MB concentration is high. The results indicate that GO can be applied in treating industrial effluent and contaminated natural water. The implications to graphene-based environmental technologies are discussed.     

Preparation of different graphene nanostructures for hydrogen adsorption

In this study, different types of graphene were synthesized to investigate hydrogen adsorption capacity at different pressures (0–34 bar) at room temperature (298 K). Graphene and nanoporous graphene were prepared by Chemical Vapor Deposition (CVD) method, using methane as a carbon source at a temperature of 900 °C over copper plates and nickel oxide nanocatalyst. The nickel oxide nanocatalyst was prepared by sol–gel method, whereas graphene oxide was prepared through modified Hummer's method. The products were characterized by X‐ray diffraction, field emission‐scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller and Raman spectroscopy. The adsorption of hydrogen was done by volumetric method. High adsorption capacity was achieved in nanoporous graphene because of its high pore volume (2.11 cm³/g) and large specific surface area (850 m²/g). Hydrogen adsorption values for nanoporous graphene, graphene and graphene oxide were determined as 2.56, 1.70 and 0.74 wt%, respectively. In addition, the hydrogen adsorption of graphene nanostructures fitted nicely to the selected two‐parameter and three‐parameter adsorption isotherm models. The adsorption isotherm model coefficients have been found for a 0–34 bar pressure range. The parameter values for all adsorbents showed proper conformity to the model and experimental data. Copyright © 2016 John Wiley & Sons, Ltd.     

Lauryl sulfate@magnetic graphene oxide nanosorbent for fast methylene blue recovery from aqueous solutions

Lauryl sulfate is utilized to functionalize magnetic graphene oxide (MGOLS) for fast removal of methylene blue (MB) using batch sorption experiments. The effects of different analytical parameters including medium pH, equilibration time, MGOLS dosage, initial MB concentration and temperature on the % MB removal are investigated. Among different isotherm and kinetic models, the experimental data were best fitted to the Langmuir and pseudo-second-order rate equations. The maximum Langmuir loading capacity reaches 624.42?mg g^?1 for MGOLS under optimal conditions. Sorption kinetic of MGOLS is very fast: Approximately 96% of dye extraction was recorded within the first 2?minutes of this sorption process. The sorption mechanism is proposed and the feasibility, thermic and entropic characteristics were evaluated. Sorption and desorption performances of MGOLS are maintained almost constant over five cycles of sorption/desorption. The results concluded MGOLS as an efficient extractor for fast and feasible recovery of MB from aqueous matrices.     

Preparation of a novel Fe3O4/graphene oxide hybrid for adsorptive removal of methylene blue from water

In this work, a novel Fe₃O₄/graphene oxide (GO) hybrid was prepared and its removal ability of cationic methylene blue dye from water was investigated. To improve the dispersability of Fe₃O₄/GO hybrid in water, GO was first modified by polyethylene glycol (PEG) via a click approach before deposition of Fe₃O₄ nanoparticles onto its surface. The successful modification of GO surface and the deposition of Fe₃O₄ nanoparticles were confirmed by transmission electron microscopy directly. The saturation magnetization of the resultant Fe₃O₄/GO hybrid is 7.8 eum/g. The adsorption capacities of Fe₃O₄/GO hybrid for methylene blue at 35 and 60°C were as high as 96.05 and 120.05 mg/g, respectively. Moreover, the Langmuir, Freundlich, and Temkin models are used to investigate the isothermal adsorption behavior of Fe₃O₄/GO hybrid.     

Functionalization effect of Fe-type MOF for methylene blue adsorption

Water pollutant such as dyes had danger the water quality. Todays, porous materials are great potential for dye adsorption from water bodies. In this study, the iron-based metal–organic framework (MOF-Fe) of MIL-101 is synthesized through a facile solvothermal method. The amine-functionalization effect of the MOF-Fe (amine-MOF-Fe) is evaluated for the adsorptive removal of methylene blue (MB) from aqueous solution. The adsorption behaviour had shown a rapid MB adsorption within the first hour of the process due to the pore-filling mechanism of the porous MOF-Fe structure. The electrostatic interaction between the amino group of amine-MOF-Fe and MB had contributed to the high adsorption capacity. The amine-functionalization effect also found the amine-MOF-Fe is having two times higher adsorption capacity when used with the loading two times lower than non-functionalized MOF-Fe. The maximum equilibrium adsorption capacities were measured at 149.25 and 312.5 mg/g with optimum MOFs loading of 0.8 and 0.4 g/L for MOF-Fe and amine-MOF-Fe, respectively. The adsorption mechanism proposed includes the electrostatic interaction, pore filling, hydrogen bonding, and π–π stacking. The regeneration study showed the MOFs could be recycled without interfering with the removal efficiency. Hence, the results indicate that the MOFs had desirable reusability for the practical adsorption of cationic dyes with its features of fast adsorption and high capacity.     

Preparation of ZnS-Fluoropolymer nanocomposites and its photocatalytic degradation of methylene blue

The ZnS particles were immobilized on the surface of poly(vinylidene difluoride) (PVDF) mixing methacrylic acid (MAA)-trifluoroethyl acrylate (TFA) copolymer electrospun nanofibers. The PVDF and MAATFA copolymer nanofibers were prepared by electrospinning. Zinc ions were introduced onto the surface of nanofibers by coordinating with the carboxyls of MAA, and then sulfide ions were added to react with zinc ions to form ZnS particles under hydrothermal condition. The size and the amount of ZnS particles increased with the reaction time prolonging. The Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) results reveal that a chemical interaction exists between ZnS and fluoropolymer fibers. The degradation rate of methylene blue in ZnS-fluoropolymer nanocomposite system was considerably higher than in that of ZnS powders system under UV irradiation. There may be an adsorption-migration-photodegradation process during the degradation of methylene blue by using ZnS-fluoropolymer nanocomposites as photocatalyst. The photocatalytic activity of ZnS-fluoropolymer nanocomposites changes indistinctively after 10 times repeating tests.