Sorption and desorption behavior of water and organic solvents from graphite oxide

The sorption-desorption of water and different organic solvents (methanol, 1-propanol, benzene, chloroform and carbon tetrachloride) from the vapor phase in graphite oxide (GO) was studied. Changes observed in the GO interlayer distance, initially due to solvent uptake, were subsequently monitored during desorption by means of time-resolved X-ray diffraction so providing desorption kinetics. A limiting geometric stability in the GO interlayer distance was envisaged, corresponding to an expansion of about 60%, with an intercalation of about 45 mL of solvent/100 g of GO. Specific desorption kinetics behavior was found for each solvent to be related to their chemical nature and geometry. Finally, from this study it was also found that the layer distortions of GO, when exposed to water and organic solvent vapors, occurred in a lesser extent than that found when the intercalation occurred from the liquid solvents.     

Graphene oxide/polybenzimidazole composites fabricated by a solvent-exchange method

Homogenous organic dispersion of graphene oxide (GO) sheets was prepared by a solvent-exchange method. This method enabled the simultaneous achievement of full exfoliation and high concentration of GO in several organic solvents such as dimethyl sulfoxide, which would facilitate the fabrication of individual graphene reinforced polymer composites through a solution-based process. To this end, poly [2,2′-(p-oxydiphenylene)-5,5′-bibenzimidazole] (OPBI)/GO composites were fabricated. X-ray diffraction characterization showed that the GO sheets were individually incorporated into the OPBI matrix. Scanning electron microscope images that taken of the fracture surface of the composites revealed that the GO sheets were spontaneous aligned parallel to the surface of the composite films as the content of GO exceeded 0.3 wt.%. The incorporation of GO also showed profound effects on the macroscopic properties of OPBI. Compared to pure OPBI, the composites showed a 17% increase in Young’s modulus, 33% increase in tensile strength and 88% improvement in toughness by the addition of only 0.3 wt.% of GO. Moreover, although the thermal stability of GO is far inferior to OPBI, it is found the thermal stability of OPBI is still improved by the addition of GO.     

Formation of self-organized graphene honeycomb films on substrates

Mixing graphene oxide (GO) aqueous solution with tridodecylmethylammonium chloride (TDMAC) aqueous solution has gradually produced a precipitate of a complex of GO and TDMAC. The complex is soluble in many polar and nonpolar organic solvents, including low dielectric nonpolar organic solvents such as toluene and hexane. In addition, thin films cast the complex specified organic solutions under high humidity conditions have honeycomb-like structures with ordered self-organized macropores. Such insulating honeycomb films have become well conductive, when they were treated by the p-toluenesulfonicacid and then reduced by chemicals such as hydrazine or HI acid.     

Phase inversion and mass transfer during liquid–liquid dispersed flow through mini-channel

The present study aims to identify means of process intensification during liquid–liquid flow through a mini-channel. During liquid–liquid flow, depending on the flow conditions either the organic or the aqueous phase can be dispersed and with increase in flow velocity the dispersed phase can spontaneously invert to form the continuous phase or vice-versa. The present study aims to investigate the phenomena of phase inversion and its influence on mass transfer during toluene/acetic acid-water flow in a 1.98 mm glass mini-channel. It is observed that for organic phase as dispersed regime, higher mass transfer efficiency is achieved when the liquid–liquid mixture is in the phase inversion zone which marks the transition from organic to aqueous phase dispersion. The mixture velocities as well as the inlet concentration of diffusing species influence mass transfer characteristics in this zone. The results have indicated some interesting observations which can be exploited for process intensification in monolith and micro-reactor.     

Membrane contactor for reactive extraction of succinic acid from aqueous solution by tertiary amine

A hollow fibre membrane contactor (HFMC) made of microporous, hydrophobic, polypropylene (PP) fibres was used for removing dissolved succinic acid (SA) from aqueous streams. The Liquicel^® HFMC module was operated in the liquid–liquid extraction (LLE) mode with aqueous SA as the feed solution. The aqueous feed was prepared by dissolving measured amounts of SA in deionised water, with concentrations varying from 5000 to 59 000 ppm. Two different types of organic extractant solutions were chosen to extract SA from aqueous streams: (a) 30% tripropylamine (TPA) dissolved in 1-octanol and (b) 30% trioctylamine (TOA)–TPA mixture in a 2:8 weight ratio and dissolved in 1-octanol. The aqueous feed was circulated through the lumens of the hollow fibres, and the extractant solution was passed through the shell side (i.e., inside the shell) of the HFMC module. Both liquids flowed counter-currently within the HFMC module and were recirculated continuously. Conditions such as SA-water flow rate, organic phase flow rate, and initial SA-water concentration were selected as the operating variables. The complexation reaction of SA with the amine was assumed at the aqueous–organic interface on the lumen side. The complex thus formed first diffused through the membrane pores filled with the organic phase (hereafter “organic-filled membrane pores”) and was subsequently swept by the organic liquid flowing through the shell side of the module. The HFMC was observed to be highly efficient in removing SA from water, and a removal efficiency of more than 95% was obtained. A mathematical analysis was performed by considering the transport of SA molecules through the bulk aqueous phase and within the organic-filled membrane pores. The results of the model simulation were shown to be in agreement with the experimental data.     

溶胀对膜萃取传质性能的影响

溶剂对膜的溶胀,使膜的物理结构发生变化,进而对膜萃取传质性能产生一定的影响。本文以３０％ＴＢＰ（煤油）－醋酸－水,正丁醇－醋酸－水和２０％７３０１（煤油）－醋酸－水为实验体系在聚砜和聚四氟乙烯微孔平板膜器中系统地了溶胀地膜萃取总传质系数的影响。结果表明,微孔膜发生溶胀后孔隙率发生明显的变化,其总传质系数有较大的下降。     

Covalently intercalated graphene oxide for oil–water separation

We report the transformation of hydrophilic graphene oxide (GO) sheets into superhydrophobic nanomaterial by direct esterification with epoxy-functionalized polyhedral oligomeric silsesquioxane (ePOSS). The covalently functionalized GO–ePOSS composite shows superhydrophobicity with a water/air contact angle of ∼145°. The highest dispersion limits for GO in selected organic solvents are obtained in the literature. The dispersion of GO–ePOSS can be extended to solvents with Hansen solubility parameters as low as 3.4. Efficient oil–water separation is also demonstrated by using a GO–ePOSS membrane.     

Photoelectrochemical and electrochromic properties of polyimide/graphene oxide composites

A series of novel multicolored near-infrared electrochromic polyimide (PI)-based composites with graphene oxide (GO) were prepared by using in situ polymerization. The prepared PI/GO composites are readily soluble in many organic solvents, and display outstanding thermal resistance, stably electrochromic characteristics, high coloration efficiency, short switching time, and anodic electrochromic behavior. Scanning electron microscope and transmission electron microscopy showed a good and uniform dispersion of the GO sheets in the PI matrix. The surface of the composites contains hydrophilic functional groups such as C–O and CO, which have been characterized by X-ray photoelectron spectroscopy. The typical, stable photoelectrical response showed that there was electron transfer in the interior of composites film under illumination, and the electrochemical impedance spectra result was consistent with the photoelectrical response. The different content of GO played a pivotal role in the electron transfer and regulated the conductivity of the composites. The work functions were obtained by KPFM measurements, and the work function is increasing with the contents increasing of GO in the composites. The properties prove that the composite is multipurpose material which will cater for photoelectric conversion and electrochromic application.     

Extraction of penicillin G from aqueous solutions: Analysis of reaction equilibrium and mass transfer

Analysis of the reaction equilibrium and mass transfer in the extraction of penicillin G (Pen G) into an organic phase is an important research area to develop a cost-effective process for its separation from an aqueous fermentation media. In order to evaluate this, equilibrium experiments were first carried out to select the organic phase (composed of the carrier and solvent) that gives good values for the distribution of penicillin G between the aqueous and organic phases. An organic phase of Amberlite LA-2 in any of the solvents (Shellsol TK/butyl acetate/tributyl phosphate) gave high distribution coefficient and the stoichiometry of the reaction has been shown to follow a simple ratio of 2:2. The performance of the organic phases was evaluated in a membrane contactor and very high percentage extraction was achieved. The extraction was performed by contacting a “feed” solution containing penicillin G (flowing in the fiber side) with an “organic phase” of Amberlite LA-2 in one of the solvents (flowing on the shell side) of the contactor. The antibiotic solutes formed complex with the Amberlite LA-2 molecules which were transported across the fiber wall to the shell side and extracted in the organic phase. The extraction in once-through mode was low and the feed/organic solutions need to be recycled to increase the percentage extraction. In the recycle mode operated at flow rates of 3.6–4.4 mL/s, an extraction of 90–98% was achieved. A simple mathematical model and its semi-analytical solution presented here can be used to determine the overall mass transfer coefficient using the experimental values of the distribution coefficient, operating parameters and the dimensions of the membrane module.     

Permanent adsorption of organic solvents in graphite oxide and its effect on the thermal exfoliation

The dispersion of graphite oxide (GO) in organic solvents followed by their evaporation at relative high temperature resulted in a strong adsorption of the solvent molecules in the graphitic interlayers as confirmed by ¹³C magic-angle-spinning NMR. Three series of solvents, alcohols (1-methanol, 1-propanol, 1-pentanol, 1-heptanol), aromatics (benzene, toluene, p-xylene, chlorobenzene) and chloride compounds (dichloromethane, chloroform, carbon tetrachloride) were studied to understand the interaction of graphite oxide with solvents. The distribution of basal interlayer spacing changed due to solvent intercalation and this distribution was particularly different for each solvent series. Even though there was on average 1 solvent molecule per 100 carbon atoms of GO, they had a profound effect on the thermal properties of the resulting GO. The exfoliation temperature was drastically reduced by the presence of the solvents due to the increase of the interlayer spacing and the reducing power of the solvent.     

Kinetic and thermodynamic study of the transfer of anionic polyamidoamine dendrimers across two immiscible liquids

The kinetics and thermodynamics for the phase transfer of carboxyl-terminated polyamidoamine (PAMAM) dendrimers across the water/dichloroethane interface were analyzed by cyclic voltammetry and electrochemical impedance spectroscopy. A three phase junction was employed by inserting a cylindrical gold electrode through the liquid–liquid interface. The reversible redox species decamethylferrocene (DMFc) was used in the organic phase in order to promote dendrimer transfer. It was found that the electrochemical behaviour of DMFc at the gold/dichloroethane interface depends on the generation and concentration of the dendrimer species in the aqueous phase. In addition, it was observed that the electrochemically driven transfer of these macromolecules corresponds to a quasi-reversible process. The data obtained from thermodynamic studies indicate that dendrimers are transferred between the two phases under study by an entropy controlled process.     

Effect of swelling on mass transfer performance in membrane extraction

The membrane extraction experiments were performed with tributyl phosphate/acetic acid (HAc)/water, n-butanol/HAc/water and 20% Alamine (in kerosene); HAc; and water as working systems. HAc was transferred from the aqueous phase to the organic phase. The effect of flat membranes swelling on mass transfer was studied. The membranes were microporous polysulfone and microporous polytetrafluoroethylene. The overall mass transfer coefficients based on the water phase were calculated and compared between nonswollen and swollen membranes. The experimental results show that the physical structure of the flat membranes used in our experiments was changed if soaked by organic solvents; however, change in thickness was not found. The overall mass transfer coefficients clearly were decreased after the flat membranes were swollen. The most likely reason is that the mass transfer resistance was increased because of the change of the membrane structure. The results also show that it is better to choose a hydrophilic membrane to reach high mass transfer performance when the equilibrium constant is very low. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1555–1561, 1999     

Electrochemical reduction of graphene oxide in organic solvents

Graphene oxide (GO) cast on conductive substrates was electrochemically reduced in some organic solvents. The amount of electricity required for the almost complete reduction of GO was 2.0 C for 1 mg GO, corresponding to attaching of a one-electron reducible species to each benzene ring in graphene. The electrochemically reduced GO film gave an electrical conductivity of about 3 S cm⁻¹ and exhibited a relatively high specific capacitance of 147.2 F g⁻¹ in propylene carbonate. The electrochemical reduction of GO was feasible on Al foils as well.     

Polarity‐reversal‐producing phase transfer of hydrophilic silver nanoclusters capped by a hyperbranched polymer from water to nonpolar organic solvents

Hyperbranched poly(ethylene imine) (PEI)‐capped Ag nanoclusters, synthesized starting from an aqueous environment, dispersed well in water and most polar organic solvents. However, with the addition of 1,4‐dioxane, the PEI‐capped Ag nanoclusters could be separated completely to obtain hydrophilic and hydrophobic Ag nanoclusters. Through this facile method, the successful phase transfer of PEI‐capped Ag nanoclusters from the aqueous phase to the nonpolar organic phase, such as from water to carbon tetrachloride, chloroform, and methylene bichloride, was easily realized. The polarity reversal of Ag nanoclusters were considered to be associated with the conformational change of PEI on the basis of the hydrophobic methylene groups of polymer backbone facing the external side or internal side, and this polarity reversal was irreversible. Moreover, PEIs with higher molecular weights showed a higher efficiency of phase transfer of the Ag nanoclusters. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43206.     

超声波促进新型席夫碱类化合物的水相合成

在超声波促进下以聚乙二醇(PEG 6000)为相转移催化剂,在水相中合成了8个席夫碱类化合物。采用1HNMR、13CNMR、IR、MS(ESI)和X-射线衍射对其结构进行了表征,结果与目标化合物一致。采用相转移催化剂水相超声波合成,与传统的加热反应或有机溶剂相超声波合成比较,水相超声波合成不但可以避免使用酸碱催化剂和乙醇等挥发性溶剂,而且使得反应时间从数小时缩短至0.5 h左右,产率高达76%~92%。经查证,其中6个席夫碱类化合物是未见文献报道的新化合物。     

Highly soluble polyetheramine-functionalized graphene oxide and reduced graphene oxide both in aqueous and non-aqueous solvents

Among many methods to synthesize graphene, solution-based processing provides many advantages owing to its low cost, high productivity, chemical versatility, and scalability. In particular, graphene oxide (GO) is one of the most promising nanocarbons that enable the incorporation of graphene and related materials into bulk materials and nanocomposites. GO has hydrophilic nature that enables straightforward dispersion in aqueous solution by sonication, but GO show poor dispersibility in common organic solvents, which prevent much wider applications such as solution-mixing polymer nanocomposites. Here we prepared highly soluble, functionalized GO in both aqueous and non-aqueous solvents. This was achieved by reacting polyetheramine consisting of amphiphilic components, e.g., polypropylene oxide and polyethylene oxide, with carboxylic acid groups at GO edges. Moreover, the reduced GO (rGO) was also highly dispersible in aqueous solution as well as non-aqueous solutions. These functionalized GO and rGO can be used for many solution-processed graphene composites.     

Preparation of polymer decorated graphene oxide by γ-ray induced graft polymerization

Herein, we report a facile approach to decorate graphene oxide (GO) sheets with poly(vinyl acetate) (PVAc) by γ-ray irradiation-induced graft polymerization. The content of PVAc in the obtained sample, i.e., PVAc grafted GO (GO-g-PVAc) is calculated by the loss weight in thermogravimetric analysis (TGA) curves. A GO-g-PVAc sample with a degree of grafting (DG) of 28.5% was well dispersed in common organic solvents and the dispersions obtained were extremely stable at room temperature without any aggregation, even after standing for 2 months. The excellent dispersibility and stability of GO-g-PVAc in common organic solvents are readily rationalized in terms of the full coverage of PVAc chains and solvated layer formation on graphene oxide sheets surface, which weakens the interlaminar attraction of GO sheets. This approach presents a facile route for the preparation of dispersible GO and shows great potential in the preparation of graphene-based composites by solution-processes.     

Investigations of mass transfer with chemical reactions in two-phase liquid–liquid systems

A new method based on experimental determination of the product distribution of a set of complex test reactions has been introduced and applied to study mass transfer in liquid–liquid systems. The test reactions consist of two parallel reactions, one of them being instantaneous and the second fast relative to mass transfer. Two reactants are transferred from the dispersed, organic phase (phase volume 1% vol) to the continuous aqueous phase, where the third reactant is present. Experiments were carried out in a batch system agitated with either a six-blade paddle impeller or a high-shear rotor–stator LR4 Silverson mixer to disperse drops and increase the mass transfer rate. The product distribution and the drop size distribution were measured using gas chromatography–mass spectroscopy and Malvern MasterSizer, respectively with pH variation recorded during the process. The results show that the focused supply of energy in the Silverson mixer is effective for the short term irreversible drop break-up process producing smaller droplets than the six-blade paddle impeller. However for the long term mass transfer process the paddle impeller is more effective due to more uniform supply of energy and better mixing throughout the tank compared to the more localized mixing of the Silverson.     

Graphite–graphite oxide composite electrode for vanadium redox flow battery

A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer–Emmett–Teller method. The redox reactions of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO₂]⁺/[VO]²⁺ and V³⁺/V²⁺ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.     

Graphene oxide membrane for liquid phase organic molecular separation

The selective permeation of organic solvents and water through graphene oxide (GO) membranes has been demonstrated. Water was found to permeate through GO membranes faster than various alcohols. The permeation rates of ethanol, 1-propanol and 2-propanol (IPA) are about 80 times lower than that of water. Taking advantage of the differences in the permeation rates, we separated water from the alcohols and obtained alcohols with high purity. For ethanol and 1-propanol, binary solutions of the alcohol and water were filtered efficiently to produce alcohols with concentration of about 97%. However, the selectivity of the filtration of methanol is significantly lower than those of the other alcohols. To understand the mechanism we followed the structural changes in the GO membranes by X-ray diffraction analysis. From the X-ray diffraction results we speculate that the selectivity of the permeation of water and alcohols is closely related to the molecular sizes of the solvents and their polarity. In order to demonstrate the potential applications of this process for the selective removal of water from aqueous organic mixtures, we performed the separation of water from a bio-oil containing 73% of water. The majority of the water was filtered out resulting in a higher purity bio-oil.