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1.
Sulfonic cation exchangers with two ion exchange group concentrations (0.5 and 2.4 mmol/g, samples A and B, respectively) were obtained by sulfonation of a porous styrene (S) and divinylbenzene (DVB) copolymer with chlorosulfonic acid. Strong thermal decomposition of the sulfonated copolymer A, accompanied by significant changes in its porous structure, starts at ca. 400°C. The char has no sulfonic groups. After heat treatment at 400°C in steam, a sorbent was obtained (yield 65%) that shows higher phenol sorption than the untreated sample when related to the bed volume. The chlorosulfonic derivatives of the initial copolymer were less thermally resistant than the sulfonic ones obtained by hydrolysis. Pyrolysis of the cation exchanger B, in its H+ and Ca2+ forms, was carried out at 900°C (yield of both chars close to 30%). By subsequent steam activation at 800°C to a 50% burn-off of the char, sorbents with well-developed, but distinctly different, porous structures were obtained. The activated char from the sulfonated copolymer in its hydrogen form was highly microporous and indicated an effective surface area of 1180 m2/g. However, because of a low contribution of mesopores, its ability to adsorb phenol from the liquid phase was not very high. The activated char from the calcium-doped copolymer, indicating a smaller surface area (580 m2/g) but characterized by a well-developed mesoporosity, was a better sorbent for phenol. © 1994 John Wiley & Sons, Inc.  相似文献   

2.
Summary The solvation parameter model is used to characterize the sorption properties of the porous polymer Oasis? HLB for solid-phase extraction with water and water-methanol mixtures as a sample solvent. Increasing solute size and electron lone pair interactions favor retention from water. Oasis? HLB is not competitive with water for dipole-type and hydrogen-bond interactions, which result in lower analyte retention. The selectivity of Oasis? HLB is different to porous graphic carbon (Hypercarb?), a conventional poly (styrene-divinylbenzene) porous polymer sorbent (PLRP-S 100) and two silica-based, octadecylsiloxane-bonded sorbents with a high and a low carbon loading, respectively. Because of selectivity differences no single sorbent is ideal for the extraction of analytes possessing a wide range of polar interactions. Oasis? HLB is preferred for the extraction of low molecular mass and polar compounds, PLRP-S 100 for the extraction of higher molecular mass compounds of moderate polarity, and the silica-based octadecylsiloxane sorbent with a high carbon loading is the best compromise for the extraction of compounds that cover a wide polarity range. For methanol-water mixtures as a sample solvent PLRP-S 100 is the best general choice with Oasis? HLB preferred for the extraction of strong hydrogen-bond acids. Hypercarb? is shown to have favorable retention properties for solid-phase extraction with the except for its low surface area.  相似文献   

3.
Silica microspheres have been synthesized by phase separation and sol–gel transition coupled with emulsion method. The as-obtained material is characterized by scanning electron microscopy, nitrogen sorption, elemental analysis and particle size distribution measurements. The results demonstrated that the material featured with hierarchically porous structure, possessing both mesopores and penetrable macropores. The mesopores provide large surface area while the macropores traverse the silica particles, which may facilitate fast mass transfer as well as guarantee low backpressure when such materials are used for packed high-performance liquid chromatography (HPLC) column. Therefore, their preliminary applications as HPLC packings in fast separation and low-pressure separation have been attempted in the present study. Benzene, benzaldehyde and benzyl alcohol were separated within two minutes on the silica column at a flow rate of 7 mL min−1. Vitamin E mixtures can also be baseline separated at a high flow rate of 8 mL min−1. In addition, thirteen aromatic hydrocarbons were well separated on the octadecyl-bonded silica (ODS) column. In comparison with a commercial Kromasil ODS column, the pressure of the proposed column is much lower (<1/2) under the same chromatographic conditions, while comparable separation efficiency can be achieved.  相似文献   

4.
Mg-, Al and Mg-, Cu-, Al-layered double hydroxides well-known synthetic hydrotalcite-like sorbents, were used for the first time as carriers for indicators in the sorption catalytic determination of copper(II) and L-α-alanine. Mg-, Al and Mg-, Cu-, Al-layered double hydroxides were synthesized by coprecipitation and characterized using infrared spectroscopy, X-ray diffraction, and scanning electron microscopy. The adsorption of 0.50?mg?L?1 copper(II) solution by Mg-, Al-layered double hydroxides followed a pseudo-second-order model with an equilibrium sorption capacity of 24.2?×?10?3?mg?g?1 (3.8?×?10?4?mmol g?1) and a reaction rate constant of 4.2?g mg?1?min?1. Mg-, Al-layered double hydroxide tablets were prepared and used for sorption concentration and subsequent sensitive and selective sorption catalytic determination of 5.5?×?10?3 to 1.0?mg?L?1 copper(II) at the sorbent phase. The method was used for the analysis of natural water. A method was developed for the determination of α-alanine in Mg-, Cu-, Al-layered double hydroxide tablets with a limit of detection of 4.0?×?10?3 mol?L?1. In addition, thin layers of Mg-, Cu-, Al-layered double hydroxide were used to separate α-alanine and determine α-amino acids by thin-layer chromatography.  相似文献   

5.

From this study it was evident that outer peristaltic parts of waste tire granules gave the highest removal. Film and pore diffusions are the major factors controlling rates of sorption from solution by porous adsorbents. For sorption of 2,4‐D on waste tire rubber granules, the sorption rate coefficient of second‐order kinetic equation was utilized indirectly to determine the rate‐limiting step. The diffusion coefficient lies in the scale of 10?8 cm2/s, and the pore diffusion coefficient is in the range of 10?9–10?10 cm2/s. So both film and pore diffusion are rate limiting. Considering external mass transfer from fluid to particle, using the effect of initial concentration, and using the effect of adsorbent size, no conclusion was reached regarding rate‐controlling steps. It is apparent from the study that external mass transfer (film diffusion) as well as intra‐particle diffusion (pore diffusion) play significant roles in the sorption process for 2,4‐D removal from water onto rubber granules.  相似文献   

6.
A comprehensive evaluation of Cs ions sorption to and diffusion in crushed granite was conducted in this study. The sorption capacity of crushed granite suggested by the Langmuir model was 5.48 × 10?6 mol‐Cs/g‐granite. The distribution coefficient (Kd) was around 7.5 mL/g and pH independent. By using an in‐diffusion method with a modified capillary column, some diffusion relevant parameters of Cs ions in crushed granite were derived. The apparent diffusion coefficient (Da) seemed unaffected by Cs concentration (1.15 × 10?10 to 2.82 × 10?10 m2/s, at 10?7 and 10?3 M, respectively). The determined effective diffusion coefficients (De) were located in the window from 8.59 × 10?10 (10?7 M) to 1.69 × 10?9 (10?3 M) m2/s. Under various pH environments, pH independent Da (9.0 × 10?9 m2/s) and De (1.0 × 10?9 m2/s) values were observed. Under current systems, consistently higher De than Da implied the diffusion of Cs ions was governed by surface diffusion phenomenon. Whereas the pH insensitive feature indicated the Cs sorption to crushed granite was mainly through ion‐exchange reaction. Moreover, further SEM/EDS mapping clearly showed the adsorbed Cs ions were highly concentrated on the fracture surface of biotite.  相似文献   

7.
《Soft Materials》2013,11(2-3):195-212
Abstract

Hydrogels with various compositions of polyvinyl alcohol (PVA) and poly(1‐vinyl‐2‐ pyrrolidinone) (PVP) were prepared by irradiating mixtures of PVA and PVP in aqueous solutions with gamma‐rays from 60Co sources at room temperature. The states of water in the hydrogels were characterized using DSC and NMR T2 relaxation measurements and the kinetics of water diffusion in the hydrogels were studied by sorption experiments and NMR imaging. The DSC endothermic peaks in the temperature range ?10 to +10°C implied that there are at least two kinds of freezable water present in the matrix. The difference between the total water content and the freezable water content was referred to as bound water, which is not freezable. The weight fraction of water at which only nonfreezable water is present in a hydrogel with FVP=0.19 has been estimated to be gH2O/gPolymer=0.375. From water sorption experiments, it was demonstrated that the early stage of the diffusion of water into the hydrogels was Fickian. A curve‐fit of the early‐stage experimental data to the Fickian model allowed determination of the water diffusion coefficient, which was found to lie between 1.5×10?11 m2 s?1 and 4.5×10?11 m2 s?1, depending on the polymer composition, the cross‐link density, and the temperature. It was also found that the energy barrier for diffusion of water molecules into PVA/PVP hydrogels was ≈24 kJ mol?1. Additionally, the diffusion coefficients determined from NMR imaging of the volumetric swelling of the gels agreed well with the results obtained by the mass sorption method.  相似文献   

8.
A three‐dimensional (3D) hierarchical carbon–sulfur nanocomposite that is useful as a high‐performance cathode for rechargeable lithium–sulfur batteries is reported. The 3D hierarchically ordered porous carbon (HOPC) with mesoporous walls and interconnected macropores was prepared by in situ self‐assembly of colloidal polymer and silica spheres with sucrose as the carbon source. The obtained porous carbon possesses a large specific surface area and pore volume with narrow mesopore size distribution, and acts as a host and conducting framework to contain highly dispersed elemental sulfur. Electrochemical tests reveal that the HOPC/S nanocomposite with well‐defined nanostructure delivers a high initial specific capacity up to 1193 mAh g?1 and a stable capacity of 884 mAh g?1 after 50 cycles at 0.1 C. In addition, the HOPC/S nanocomposite exhibits high reversible capacity at high rates. The excellent electrochemical performance is attributed exclusively to the beneficial integration of the mesopores for the electrochemical reaction and macropores for ion transport. The mesoporous walls of the HOPC act as solvent‐restricted reactors for the redox reaction of sulfur and aid in suppressing the diffusion of polysulfide species into the electrolyte. The “open” ordered interconnected macropores and windows facilitate transportation of electrolyte and solvated lithium ions during the charge/discharge process. These results show that nanostructured carbon with hierarchical pore distribution could be a promising scaffold for encapsulating sulfur to approach high specific capacity and energy density with long cycling performance.  相似文献   

9.
This study investigates sorption and diffusion of Cs in two potential host rocks (granite from Kinmen Island and basalt from Penghu Island) by using batch and through-diffusion methods in order to establish a reliable safety assessment methodology. These methods were applied to crushed and intact rock samples to investigate the actual geological environment. According to solid-phase analysis, including X-ray diffraction, elemental analysis, auto radiography, and polar microscopy, the sorption component primarily contained iron?Cmagnesium (Fe?CMg) minerals in basalt and granite. Moreover, the distribution coefficient (K d) of Cs in various concentrations (~10?2?C10?7?M) obtained from batch tests indicated a higher sorption capacity in basalt than that in granite because of the 10% Fe?CMg mineral content. The diffusion of Cs in both crushed granite and basalt reached steady state after 110?days, and the apparent diffusion coefficients (D a) were 2.86?×?10?11 and 1.82?×?10?12?m2/s, respectively. However, the value of D a for Cs in intact rocks was estimated to be 1.45?×?10?12?m2/s in granite and 0.56?×?10?12?m2/s in basalt, lower than the values obtained using crushed rocks. In addition to the microporous structure (major sorption minerals), it showed that the major retardation of Cs depended on the porosity (??) of compacted media, according to through-diffusion tests. In fact, the solid/liquid (S/L) ratio decreased as is the case when switching from batch to column experiments and the sorption effect on minerals became even more negligible in retardation of radionuclide migration.  相似文献   

10.
A unique hybrid, TiO2–B nanosheets/anatase nanocrystals co‐anchored on nanoporous graphene sheets, can be synthesized by a facile microwave‐induced in situ reduction–hydrolysis route. The as‐formed nanohybrid has a hierarchically porous structure, involving both mesopores of approximately 4 nm and meso‐/macropores of 30–60 nm in the graphene sheets, and a large surface area. Importantly, electrodes composed of the nanohybrid exhibit superior rate capability (160 mA h g?1 at ca. 36 C; 154 mA h g?1 at ca. 72 C) and excellent cyclability. The synergistic effects of conductive graphene with numerous nanopores and the pseudocapacitive effect of ultrafine TiO2–B nanosheets and anatase nanocrystals endow the hybrid a superior rate capability.  相似文献   

11.
Poly(p-phenylene biphenyltetracarboximide) films with various thicknesses were prepared from the poly(amic acid) precursor by thermal imidization at 230–400°C for 1–10 h under a nitrogen atmosphere. The water sorption in the films was measured at 25°C over 22–100% relative humidity using a Cahn microbalance as a function of film thickness and thermal imidization history. The water diffusion in all the films followed nearly Fickian process despite the morphological heterogeneity due to the ordered and less ordered phases. The diffusion coefficient and water uptake varied in 0.85 × 10?10 ? 7.50 × 10?10 cm2/s and 0.12–2.4 wt %, respectively, depending upon humidity, film thickness, and imidization history. Both diffusion coefficient and water uptake increased with increasing humidity, but decreased as imidization temperature and time increased. With increasing film thickness, the diffusion coefficient increased whereas the water uptake decreased. The water sorption behavior was interpreted with the consideration of morphological variations, such as polymer chain order, in-plane orientation, and intermolecular packing order due to the film thickness and imidization history. © 1995 John Wiley & Sons, Inc.  相似文献   

12.
We have prepared a kind of molecularly imprinted nano-porous sensing film for the adsorption of melamine. It consists of a graphite electrode impregnated with paraffin and modified with melamine, chitosan, silver nanoparticles and polyquercetin by employing an electrochemical method. The film displays excellent and highly selective sorption of melamine in the 3-dimensional porous nanomaterial, and this was applied to the determination of melamine in dairy products. The electrode responds linearly to melamine in the concentration range of 1?×?10?8 to 9?×?10?7?M, with a detection limit of 1.3?×?10?9?M (at 3??) in real samples, and with recoveries in the range of 99 to 102%. The surface structure and composition of the sensor was characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, infrared spectroscopy, and electrochemical techniques. The interaction between the porous film and melamine was also studied by using hexacyanoferrate (III) as an electrochemical indicator.
Figure
Extremely sensitive sensor for melamine used a kind of molecularly mprinted nano-porous film, which displays an excellent and highly selective sorption to melamine in the 3-dimensional porous nanomaterial. The interaction between the porous film and melamine also was studied by using hexacyanoferrate (III) as an electrochemical indicator.  相似文献   

13.
The recovery of three rare earth (RE) metals ions [Yb(III), Dy(III) and Nd(III), belonging to heavy, mild and light REs, respectively] was investigated using hybrid chitosan-magnetic nano-based particles functionalized by diethylenetriamine (DETA). The effect of pH on sorption performance was analyzed: the optimum initial pH value was found close to 5 (equilibrium pH value close to 6.5). The nanometric size of sorbent particles (30–50 nm) minimized the contribution of resistance to intraparticle diffusion on the control of uptake kinetics, which is efficiently modeled using the pseudo-second order rate equation: under selected experimental conditions the contact time required for reaching equilibrium was less than 1 h. Sorption isotherms were efficiently modeled using the Langmuir equation: maximum sorption capacities reached about 50 mg metal g?1, regardless of the RE. The temperature had a very limited effect on sorption capacity (in the range 300–320 K). The thermodynamic parameters were determined: the sorption was endothermic (positive values of ΔH°), spontaneous (negative values of ΔG°) and contributed to increasing the disorder of the system (positive values of ΔS°). The three REs have similar sorption properties on DETA-functionalized chitosan magnetic nano-based particles: the selective separation of these elements seems to be difficult. The sorbed metal ions can be removed from loaded sorbents using thiourea, and the sorbent can be recycled for at least five sorption/desorption cycles with a limited loss in sorption performance (by less than 6 %). The saturation magnetization was close to 20 emu g?1; this means that nano-based superparamagnetic particles can be readily recovered by an external magnetic field, making the processing of these materials easy.  相似文献   

14.
To improve the oil absorbency of caster oil‐based polyurethane foam, nano‐organic‐montmorillonite (OMMT) was used for the additives. The aim of this study is to evaluate the oil diffusion mechanism and dispersion uniformity of OMMT modified caster oil‐based polyurethane (MPU) using experiments and molecular dynamic simulation. Molecule movement and molecule trajectory of oil was investigated by molecular dynamic simulation and numerical simulation. According to the quantitative analyzing results, the diffusion model was put forward. The average diffusion coefficient of crude oil in 0, 1, 2 wt%, 4, and 6 wt% MPU is 2.4 × 10?4 cm2/s, 2.6 × 10?4 cm2/s, 3.0 × 10?4 cm2/s, 3.2 × 10?4 cm2/s, and 3.3 × 10?4 cm2/s, respectively. It indicated that crude oil appeared gradient in the MPU. The optimal diffusion direction of crude oil is (0, 0, 1) crystal face, and the small particles of crude oil are easy to be adsorbed. The two‐dimensional diffusion trajectory of crude oil is nonlinear. The diffusion model includes the diffusion of crude oil at the interface of oil and polyurethane, surface diffusion and pore diffusion, and pore adsorption. Furthermore, the diffusion model showed that the van der Waals force was the main reason for crude oil diffusion or adsorption. OMMT could improve the ability of oil/water separation of polyurethane.  相似文献   

15.
A novel polyimide-epoxy or PI-EP alloys are prepared by the modification of polyamic acid in the concentration range of 1.54×10−6 to 1.54×10−2 mol/L. The methanol sorption for these alloys at 24 hrs and at equilibrium conditions are determined and the residual solvent in fully cyclized polyimides were calculated. The presence of the residual solvent is visualized in fully imidized polymer and a structure containing partly imidized amic acid moiety is proposed and their concentration (in percentage) is calculated. The water sorption for these alloys at 24 hrs and at equilibrium conditions and the values of the water diffusion coefficient are determined from absorption isotherms. The PI-EP alloys have shown comparatively lower water sorption and higher diffusion coefficient than the unmodified polyimide. The mechanistic aspects of water sorption and diffusion are discussed.  相似文献   

16.
This study describes equilibrium and kinetic sorption studies to remove the antibiotic drug Ciprofloxacin (CF) from aqueous solutions using poly(acrylamide-co-itaconic acid) [poly(AAm-co-IA)] as polymeric cation exchanger sorbent material. The co-polymeric sorbent was prepared by free radical induced aqueous polymerization and was characterized by FTIR spectroscopy and TGA analysis. In addition, its physicochemical parameters were also determined. The various isotherm models, when applied to equilibrium sorption data at 28°C, followed the following order: Langmuir > Temkin > Freundlich, with the fair maximum sorption capacity (Q o ) of 178.5 mg g?1. The kinetic sorption data, obtained at 28°C, was applied to kinetic models such as pseudo first order equation, pseudo second order model and a simple Elovich model. Based on regression values, the order of fitness of these models was pseudo second order > pseudo first order > simple Elovich model. The second order adsorption coefficients k2adswere found to be 58 × 10?3, 52.7 × 10?3, 34.01×10?3 g/mg min for drug solutions with initial concentrations of 10, 20 and 30 mg L?1 respectively The sorption mean free energy from the Dubinin–Raduschkevich (DR) isotherm was found to be nearly 8.839 kJ mol?1 indicating an ion-exchange mechanism for drug uptake. The optimum pH value of sorbate solution for drug uptake was found to be around 6.0. Finally, the antibacterial action of drug was investigated and it was found that after adsorption there was a decrease in bacterial growth inhibition efficiency of drug solution.  相似文献   

17.
A new preconcentration method is presented for lead on TAN‐loaded polyurethane foam (PUF) and its measurement by differential pulse anodic stripping voltammetry (DPASV). The optimum sorption conditions of 1.29 × 10?5 M solution of Pb(II) ions on TAN‐loaded PUF were investigated. The maximum sorption was observed at pH 7 with 20 minutes equilibrated time on 7.25 mg mL?1 of TAN‐loaded foam. The kinetic study indicates that the overall sorption process was controlled by the intra‐particle diffusion process. The validity of Freundlich, Langmuir and Dubinin ‐ Radushkevich adsorption isotherms were tested. The Freundlich constants 1/n and KF are evaluated to be 0.45 ±0.04 and (1.03 +0.61) × 10?3 mol g?1, respectively. The monolayer sorption capacity and adsorption constant related to the Langmuir isotherm are (1.38 ± 0.08) × 10?5 mol g?1 and (1.46 ± 0.27) × 105 L mol?1, respectively. The mean free energy of Pb(II) ions sorption on‐TAN loaded PUF is 11.04 ± 0.28 kJ mol?1 indicating chemisorption phenomena. The effect of temperature on the sorption yields thermodynamics parameters of ΔH, ΔS and ΔG at 298 K that are 15.0 ± 1.4 kJ mol?1, 74 ±5 J mol?1 K?1 and ‐7.37 ± 0.28 kJ mol?1, respectively. The positive values of enthalpy (ΔH) and entropy (ΔS) indicate the endothermic sorption and stability of the sorbed complexes are entropy driven. However, the negative value of Gibb's free energy (ΔG) indicates the spontaneous nature of sorption. On the basis of these data, the sorption mechanism has been postulated. The effect of different foreign ions on the sorption and desorption studies were also carried out. The method was successfully applied for the determination of lead from different water samples at ng levels.  相似文献   

18.
Silica materials (ILDEHPASGs) consisting of ionic liquids and di-(2-ethylhexyl)phosphoric acid (DEHPA) for Ce(III) extraction was prepared by a sol–gel method using the hydrophobic ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate ([C8mim]PF6) as porogen and solvent medium. The ILDEHPASGs were characterized by scanning electron microscopy, Brunauer–Emmett–Teller surface area, Fourier transform infrared, and thermogravimetric analyses. The results indicated the doping of DEHPA and [C8mim]PF6 in ILDEHPASG-3 would evidently affect the formation of porous structure of sol–gel materials. ILDEHPASG-3 also possessed more channels and macropores than the blank sorbent; the surface area and pore volume of ILDEHPASG-3 were 409 m2 g?1 and 0.444 cm3 g?1, respectively. [C8mim]PF6 and DEHPA were only physically confined or entrapped in the growing covalent silica network rather than chemically bound to the inorganic matrix. The majority of [C8mim]PF6 and DEHPA were stably immobilized in the gel. Then, the effects of contact time and pH were determined. The results showed the sorption of Ce(III) strongly depended on the contact time and pH, and ILDEHPASGs had high sorption ability for Ce(III). The results were analyzed by both Langmuir and Freundlich adsorption isotherm models, and the latter was found to give a better fit.  相似文献   

19.
Chitosan was modified by grafting 2-pyridyl-ethyl moieties on the biopolymer backbone for the synthesis of a Platinum Group Metal (PGM) sorbent. The sorbent was tested for Pd(II) and Pt(IV) sorption from HCl solutions. Stable for HCl concentrations below 0.5 M, the sorbent reached sorption capacities as high as 3.2 and 2.6 mmol metal g−1 for Pd(II) and Pt(IV), respectively. Metal sorption mainly proceeds by electrostatic attraction in acidic solutions, though a contribution of complexation mechanism cannot be totally rejected. The resistance to intraparticle diffusion is the main controlling mechanism for uptake kinetics. While agitation speed has a limited effect on kinetics, metal concentration and sorbent dosage have a greater effect on the kinetic profiles. The intraparticle diffusivity varies between 3 × 10−11 and 4.5 × 10−10 m2 min−1. Thiourea (combined with HCl solution) is used for Pd(II) and Pt(IV) desorption. The resin could be desorbed and recycled for a minimum of five cycles maintaining high efficiencies of sorption and desorption.  相似文献   

20.
Carnation‐like CuO hierarchical nanostructures assembled by ultrathin porous nanosheets were successfully fabricated via a facile solvothermal route followed with heat treatment. As‐prepared CuO nanostructures exhibited excellent catalytic activity toward glucose oxidation in the absence of any enzymes. Under the optimized conditions, the CuO‐based enzymeless glucose sensor showed high sensitivity of 3.15 mA mM?1 cm?2, low limit of detection (98 nM, S/N=3), good reproducibility, excellent selectivity and long‐time stability. The superb nonenzymatic glucose sensing performance of the CuO hierarchical nanostructures was attributed to the highly catalytically active sites at the edges and basal planes of the CuO nanosheets, facile transportation of analytes through the abundant mesopores and macropores, robust and stable hierarchical structure. Moreover, the CuO‐based enzymeless glucose sensor showed high accuracy and reliability in comparison with clinical glucometer for quantitative determination of glucose in human blood serum samples.  相似文献   

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