多孔石墨烯气体分离膜分子渗透机理

通过分子动力学方法模拟了4种不同气体分子(He,H2,N2和CH4)在多孔石墨烯气体分离膜中的穿透过程,揭示了气体分子穿透石墨烯纳米孔的渗透机理,指出分子的渗透不仅与其动力学参数有关,如分子直径和质量,还与分子在石墨烯表面的吸附有关。石墨烯表面的吸附层给气体分子的渗透提供了一个额外的路径,因此分子在石墨烯表面的吸附越强,分子的渗透通量越大。同时,不同大小的纳米孔下H2分子的渗透通量都随着压力的增加而线性增加。     

多孔石墨烯气体分离膜分子渗透机理

通过分子动力学方法模拟了4种不同气体分子（He,H₂,N₂和CH₄）在多孔石墨烯气体分离膜中的穿透过程,揭示了气体分子穿透石墨烯纳米孔的渗透机理,指出分子的渗透不仅与其动力学参数有关,如分子直径和质量,还与分子在石墨烯表面的吸附有关。石墨烯表面的吸附层给气体分子的渗透提供了一个额外的路径,因此分子在石墨烯表面的吸附越强,分子的渗透通量越大。同时,不同大小的纳米孔下H₂分子的渗透通量都随着压力的增加而线性增加。     

新型氧化石墨烯膜的制备及去除天然有机物研究

采用压力过滤自组装法以聚醚砜超滤膜为基体制备了氧化石墨烯膜,并通过分别与乙二胺、丙二胺、间苯二胺交联来控制不同的层间距。运用扫描电子显微镜、傅里叶变换红外光谱、接触角、X射线光电子能谱、X射线衍射等多种手段研究了不同层间距氧化石墨烯膜的结构和性质;选择天然水作为原水,进一步研究了氧化石墨烯膜的水通量、抗污染性和对天然有机物的去除情况。结果表明,氧化石墨烯膜有良好的叠层结构,并且二胺单体在层间交联形成了稳定的共价键;二胺与氧化石墨烯层间的交联反应能有效控制层间距,从而改变氧化石墨烯膜的性能。     

水分子在多孔炭材料上的吸附行为研究进展

多孔炭材料具有较大的比表面积和发达的孔隙结构,是吸附有毒有害气体的关键材料,备受环境、化工、军事化学等领域的关注。多孔炭材料对有毒有害气体的吸附性能受气氛中水分子竞争吸附的影响,研究多孔炭材料对水分子的吸附行为是复杂环境下吸附分离有毒有害气体的基础,对改进多孔炭材料的表面官能团组成和孔结构具有重要的指导意义。基于此,本文综述了国内外关于水分子在多孔炭材料上吸附的机理、过程和影响因素,探讨了水分子作为示踪分子用于多孔炭材料结构表征的潜在可能,并对未来吸附理论的研究方向和指导新型吸附材料设计的应用前景进行展望。     

石墨烯层间距调控抑制锂枝晶生长的第一性原理研究

抑制锂枝晶生长是锂金属电池中亟需解决的关键问题之一。电极表面涂覆石墨烯可以有效抑制锂枝晶生长。然而,目前对石墨烯层间距影响锂枝晶生长的机制尚不明晰。采用第一性原理计算方法从吸附和扩散两个角度考察了石墨烯层间距对锂枝晶生长的影响。结果表明,石墨烯的层间距为0.45 ~ 0.55 nm时,电极表面对锂原子的吸附较弱,锂原子扩散性能最好,有利于抑制锂枝晶的生长。若小于该层间距,锂原子在层间的扩散较难。反之,锂原子则会在石墨烯层上吸附聚集,导致锂枝晶的快速生长。此外,在最佳层间距下,B掺杂和N掺杂改性的石墨烯,能促进锂原子在石墨烯层间的扩散,避免锂的不均匀沉积,从而抑制锂枝晶的形成。     

石墨烯层间距调控抑制锂枝晶生长的第一性原理研究

抑制锂枝晶生长是锂金属电池中亟需解决的关键问题之一。电极表面涂覆石墨烯可以有效抑制锂枝晶生长。然而,目前对石墨烯层间距影响锂枝晶生长的机制尚不明晰。采用第一性原理计算方法从吸附和扩散两个角度考察了石墨烯层间距对锂枝晶生长的影响。结果表明,石墨烯的层间距为0.45 ~ 0.55 nm时,电极表面对锂原子的吸附较弱,锂原子扩散性能最好,有利于抑制锂枝晶的生长。若小于该层间距,锂原子在层间的扩散较难。反之,锂原子则会在石墨烯层上吸附聚集,导致锂枝晶的快速生长。此外,在最佳层间距下,B掺杂和N掺杂改性的石墨烯,能促进锂原子在石墨烯层间的扩散,避免锂的不均匀沉积,从而抑制锂枝晶的形成。     

聚醚砜膜接枝氧化石墨烯改性膜吸附铅离子的研究

聚醚砜膜和氧化石墨烯都是良好的吸附材料,通过改性、接枝将二者组合,制备一种新型吸附材料聚醚砜膜接枝氧化石墨烯改性膜用于吸附Pb^2+。通过IR对膜进行了表征,考察了该膜对Pb^2+的吸附性能。研究了吸附时间、温度、溶液pH、溶液浓度、氧化石墨烯含量和氨基化剂量对吸附量的影响,检验了膜的重复使用性能。实验结果表明,在最佳吸附条件为温度55℃、pH=6.18、氧化石墨烯含量3.3%、3 mL氨基化试剂;膜重复使用4次后吸附量仍能达到初次吸附量的72.75%,表明聚醚砜膜接枝改性氧化石墨烯氨基羧酸是一种优良的吸附材料。     

半胱氨酸/石墨烯复合凝胶的制备及对Hg~(2+)吸附性质

三维石墨烯材料整合二维石墨烯片层形成三维互联的多孔贯通网状结构,具有多孔性、高活性比表面积和优良传质性能等特点。利用L-半胱氨酸做还原剂,制备了还原氧化石墨烯并构建了石墨烯三维网状结构水凝胶,作为汞离子吸附剂。实验结果表明,氧化石墨烯在L-半胱氨酸作用下得到还原,通过分子间π-π堆积以及半胱氨酸之间的交联作用形成水凝胶,同时半胱氨酸的存在增加了对重金属Hg~(2+)的吸附位点,对Hg~(2+)饱和吸附量可达到98 mg/g。     

高稳定性氧化石墨烯净水分离膜的制备和应用进展

利用氧化石墨烯特殊的纳米片层结构,可以实现对有机物分子、无机盐离子等污染物的截留,达到净水的目的.从提高稳定性和改善性能的角度出发,综述了层间支撑型氧化石墨烯净水分离膜、交联型氧化石墨烯净水分离膜、还原型氧化石墨烯净水分离膜及多手段协同作用型氧化石墨烯净水分离膜的制备及应用,为获得具有高稳定性、优异截留选择性的氧化石墨烯净水分离膜提供了思路.     

氧化石墨烯膜的制备方法研究进展

氧化石墨烯(GO)作为一种新型二维材料,在能源、环境、石油化工、生物医药、光电材料、催化等领域有巨大的应用潜能。当氧化石墨烯膜用于分离时,有着与传统膜过程不同的分离机理。氧化石墨烯膜的层间距可以通过制备方法进行调节以实现离子、分子等物质的精确筛分。总结了由氧化石墨烯溶液制备氧化石墨烯膜的主要制备方法,如真空过滤法、旋涂法、浸涂法、静电自组装法等。     

Research progress of graphene oxide membrane for water purification

Graphene oxide membranes have ultra-high water flux, controllable interlayer spacing and excellent separation properties. These outstanding characteristics make graphene oxide membranes promising to be a new generation of membrane materials and used for the precise separation of substances in the water environment. At present, researchers have performed numerous studies on graphene oxide membranes and achieved breakthrough results, including the transfer behavior of water in the membrane, the separation mechanism of the membrane and the preparation methods of the membrane, etc. However, there is still a lack of comprehensive understanding of graphene oxide membranes. This review systematically described the structural properties and structure-effect relationships of graphene oxide membrane, and summarized the typical preparation methods. In terms of the challenges faced by graphene oxide membrane in practical application, we focused on the existing modification methods of graphene oxide membrane. The applications of graphene oxide membrane in various water environments were also discussed. Finally, the future development of graphene oxide membrane was summarized and prospected. The aim of this paper is to provide novel ideas for the design and synthesis of high-performance graphene oxide membranes for water purification.     

用于水质净化的氧化石墨烯膜研究进展

氧化石墨烯膜具有超高的水通量、可控的层间距以及卓越的分离性能，这些优异的特性使氧化石墨烯膜有望成为新一代膜材料并用于水环境中物质的精确分离。对氧化石墨烯膜的研究已经取得了许多重要的成果，本文系统地阐述了用于水质净化的氧化石墨烯膜的结构特性和构效关系，总结了氧化石墨烯膜典型的制备方法，重点介绍了氧化石墨烯膜的改性方式，概述了氧化石墨烯膜在多种水环境中的应用，总结并展望了氧化石墨烯膜的发展方向，为设计和合成高性能氧化石墨烯膜用于水质净化提供新的思路。     

Preparation and characterization of layered carbon hybrid framework materials pillared with titanocene

Novel graphene oxide layered hybrid framework materials pillared titanocene organometallic complex were prepared through a facile ultrasound intercalation approach. The products exhibited periodic layered structures with expanded interlayer spacing as characterized by XRD. Raman spectroscopy demonstrated that the skeleton structure of layered carbon still remained after titanocene treatment. Nitrogen sorption analysis indicated that the building blocks of graphene oxide sheets were cross-linked with titanocene molecules to form lamellar porous structures.     

还原温度对氧化石墨烯的湿度-甲醛交叉敏感性能的影响

以氧化石墨烯溶胶为前体,通过旋涂工艺制备薄膜型气敏元件,在低温80～180℃下进行热处理,获得系列不同还原程度的还原氧化石墨烯气敏元件,采用XRD、AFM、FT-IR、XPS对样品的层结构、薄膜厚度及含氧官能团变化属性进行表征,将气敏薄膜元件在相对湿度为11.3%～93.6%的范围内进行预湿处理,并测定元件对甲醛气氛的敏感性能。结果表明：随热还原处理温度的升高,氧化石墨烯的结构逐渐向类石墨结构转变,含氧官能团逐渐脱失,缺陷增多,薄膜的方块电阻呈数量级地减小,从41 MΩ减小至928 Ω;经不同湿度预处理的气敏元件置于甲醛气氛中产生了水分子与甲醛分子的竞争吸附,从而导致电阻的明显变化;在10^?4甲醛气氛下,未还原或热还原温度较低的气敏元件适用于低、高湿环境下甲醛气氛的气敏测试,最大灵敏度为69.1%,而还原温度适中的元件则适用于中湿环境的甲醛测试,最大灵敏度为80.3%。     

Cyclic Operation of Forced Flow Electrokinetic Separation for Simultaneous Separation and Concentration of Charged Molecules

Abstract

A new cyclic operation of membrane separation in the presence of an electric field is developed. The microporous membrane/filter acts as a barrier between two adjacent solutions (i.e., the solution in the membrane cell and in the permeate). An electric field is applied across the membrane to induce electromigration of charged molecules whose molecular weights are much smaller than the molecular weight cutoff of the membrane used. The charged molecules move freely through pores of the membrane without hindrance. In the presence of an electric field, the concentration of charged molecules in the permeate stream is determined by the electromigration velocity and the permeation flow rate through the membrane. The permeation rate is controlled by the applied pressure drop, and the electro-migration velocity can be controlled by the electric field strength applied. By applying a high electric field and a low pressure drop, the concentration in the permeate stream can be increased, thus resulting in enrichment of the charged molecules in the permeate. By applying an electric field such that the electromigration is in the opposite direction to the permeation flow, the permeate is depleted of the charged molecules. A continuously supplied feed stream to the membrane cell can be processed into a concentrated solution and a depleted solution by alternating the polarity of an electric field. This paper presents the experimental results of a cyclic operation for the simultaneous separation/recovery and concentration of acetate, phenylalanine, glycine, and aspartic acid.     

Analysis of the chemical and physical factors affecting reactive adsorption of ammonia on graphene/nanoporous carbon composites

Adsorption of ammonia was studied on composites of graphene and nanoporous carbon (5 and 20 wt.% graphene). The breakthrough curves were measured in three consequent adsorption–desorption runs in either dry or wet conditions. The mechanism of ammonia retention was evaluated from the point of view of either reactive or physical adsorption. The important finding is the insensitivity of the ammonia adsorption on the composites on the water content in the challenge gas. An about 50% decrease in the surface area and volume of micropores compared to nanoporous carbons does not affect the amount of physically adsorbed ammonia. It is governed by the volume of ultramicropores (pore width <0.7 nm), density of groups on the surface, hydrophobicity level, and the electronic conductivity. The surface acidity level and thus the amounts and strength of oxygen groups being able to react with ammonia at ambient conditions are of paramount importance for the reactive adsorption process.     

Dehydration of C2–C4 alcohol/water mixtures via electrostatically enhanced graphene oxide laminar membranes

The dehydration of alcohol/water mixtures using pervaporation membranes requires less energy than is required by conventional separation technologies. In this paper, we report electrostatically enhanced graphene oxide (GO) membranes for the highly efficient pervaporation dehydration of C₂–C₄ alcohol/water mixtures. Positively charged molecules were introduced as the interlayer of negatively charged GO layers via layer-by-layer assembly, thereby creating an electrostatic attraction that drives the assembly of GO nanosheets into ordered interlayer channels. The effects of the feed temperature, water concentration, and continuous operation on the membrane transport behavior were systematically investigated. In the dehydration of 90 wt% alcohol/water mixtures at 70°C, the membrane exhibited ethanol/water, isopropanol/water, and n-butanol/water fluxes of 2.35, 2.98, and 4.69 kg/(m² hr), respectively, as well as separation factors for the same mixtures of 3,390, 5,790, and 4,680, respectively. This excellent alcohol/water dehydration performance outperforms those of state-of-the-art polymeric membranes and GO-based membranes.     

Sonication-free dispersion of large-area graphene oxide sheets using internal pressure from release of intercalated carbon dioxide

A new concept to disperse graphene sheets without sonication, significant size reduction, and any further removal of intercalating materials, is demonstrated using ejection pressure of CO₂ gas captured by water molecules dissolved in the interlayer of graphene and the ice structure surrounding it. After graphene oxide (GO) layers are swelled with water molecules, CO₂ gas is dissolved in the swelled interlayer of GO. The CO₂ gas within the GO layers is well maintained by the transformation of excess water molecules outside of interlayer to solid ice at low temperature (around −30 °C). The resulting CO₂-incorporating GOs are well dispersed in various solvents by the ejection pressure of stored CO₂ without sonication, and without additional treatment for removal of the intercalating material as surrounding ices spontaneously melt. We show that the lateral length of these well-dispersed GO sheets is 10 times larger than that of GO sheets obtained by the conventional sonication method.     

Two-beam-laser interference mediated reduction,patterning and nanostructuring of graphene oxide for the production of a flexible humidity sensing device

Two-beam-laser interference was used for the simultaneous reduction, patterning and nanostructuring of graphene oxide on flexible polyethylene terephthalate substrates for the production of a high performance humidity sensing device. Hierarchical graphene nanostructures were formed after laser interference treatment of graphene oxide, which holds great promise for gaseous molecular adsorption, and thereby significantly increases their sensing performance. By tuning the laser power, the content of oxygen functional groups, could be changed within a certain range, which contributes not only controllable conductivity but also tunable response/recovery time of the humidity sensor due to the interaction between water molecules and oxygen functional groups on the graphene oxide sheets. The laser interference processing of graphene oxide films is a mask-free, surfactant-free and large-area approach to the production of hierarchical graphene micro-nanostructures, and thus shows great potential for fabrication of future graphene-based microdevices.