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1.
We synthesized a series of cyclens substituted with mixed stilbene and poly(ethylene glycol) dendritic arms. All dendrimers terminated with different peripheral groups had good solubility in common organic solvents, and dendrimers terminated with ? CO2H groups (CO2H‐dendrimers) were also soluble in alkaline solutions. The nickel coordination properties of these dendrimers were investigated in organic solvents. Dendrimers terminated with ? CN groups (CN‐dendrimers) and the second‐generation CO2H‐dendrimer [(CO2H)8L2] could produce pentacoordinated nickel complexes; the third‐generation CO2H‐dendrimer [(CO2H)16L3] could form tetra‐ and pentacoordinated nickel complexes, and the nickel complex of the fourth‐generation CO2H‐dendrimer [(CO2H)32L4] could not be obtained. This result was due to the fact that the globular surface of (CO2H)16L3 formed a hydrogen‐bond network that selectively penetrated cations and inhibited the access of anions to the core. The formation of the hydrogen‐bond network was confirmed by Fourier transform infrared, 1H NMR, and fluorescence data. The CN‐dendrimers could not form hydrogen bonds on the surface, and the first‐ and second‐generation CO2H‐dendrimers could not form intramolecular hydrogen‐bond networks. Therefore, they had no selectivity for positive nickel ions and negative chloride ions. (CO2H)32L4 could not produce a nickel complex because it had a crammed backbone structure that could not penetrate nickel and chloride ions. Therefore, it was possible to control the ion access of cations and anions with the hydrogen‐bond network of (CO2H)16L3. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5414–5428, 2005  相似文献   

2.
Adsorption is one of the main mechanisms involved in the ECBM process, a technology where CO2 (or flue gas, i.e. a CO2/N2 mixture) is injected into a deep coal bed, with the aim of storing CO2 by simultaneously recovering CH4. A detailed understanding of the microscopic adsorption process is therefore needed, as the latter controls the displacement process. A lattice DFT model, previously extended to mixtures, has been applied to predict the competitive adsorption behavior of CO2, CH4 and N2 and of their mixtures in slit-shaped pores of 1.2 and 8 nm width. In particular, the effect of temperature, bulk composition and density on the resulting lattice pore profiles and on the lattice excess adsorption isotherms has been investigated. Important insights could be obtained; when approaching near critical conditions in the mesopores, a characteristic peak in the excess adsorption isotherm of CO2 appears. The same effect could be observed neither for the other gases nor in the micropores. Moreover, in the case of mixtures, a depletion of the less adsorbed species close to the adsorbent surface is observed, which eventually results in negative lattice excess adsorption at high bulk densities.  相似文献   

3.
Viscosities of microcrystalline cellulose + 1-butyl-3-methylimidazolium acetate ([bmIm][Ac]) solutions (0.6–1.2 wt%) in contact with CO2 were measured at 312 K with a resonant vibrational viscometer. At 4 MPa and 312 K, the CO2 could reduce the viscosity of 1.2 wt% cellulose + [bmIm][Ac] solution by about 80 %, whereas N2 at the same conditions gave less than a 10 % reduction in viscosity. The viscosity-averaged degree of polymerization and IR spectrum showed that cellulose did not decompose during experiments and that [bmIm][Ac] acted as a non-derivatizing solvent during the dissolution and viscosity reduction process. Further, although CO2 does react with [bmIm][Ac] to form 1-butyl-3-methylimidazolium-2-carboxylate, the reaction seems to be reversible and it does not affect the cellulose. Thus, [bmIm][Ac] with CO2 provides an effective solvent for cellulose and the solvent system can probably be recycled or reused.  相似文献   

4.
Three different aminosilanes ((3-aminopropyl)trimethoxysilane (1NS), N-[3-(trimethoxysilyl) propyl]ethylenediamine (2NS), N1-(3-trimethoxysilylpropyl)diethylenetriamine (3NS)) were grafted covalently inside nanoporous silica (NPS-1) with a large surface area to prepare CO2 adsorbents. The prepared CO2 sorbents were evaluated for their CO2 sorption capacity, kinetic behavior, temperature programmed desorption (TPD) and textural properties. Grafting efficiency of 1NS was better due to the smaller molecular size compared to 2NS and 3NS, which are difficult to react with the hydroxyl group of the silica surface due to steric hindrance. The highest adsorption capacity of 7.0 wt% was observed for the 2NS/NPS-1 adsorbent, followed by 5.2 wt% for 1NS/NPS-1, then 5.0 wt% for 3NS/NPS-1. The adsorption capacity of 2NS/NPS-1 was highest at 30 °C, and it gradually decreased as the adsorption temperature increased. TPD analysis showed that the reaction of primary amine of 2NS with CO2 inside the nanoporous silica could form less thermally stable carbamic acid and carbamate compared to 1NS and 3NS.  相似文献   

5.
The adsorption of CO2 on pore-expanded SBA-15 mesostructured silica functionalized with amino groups was studied. The synthesis of conventional SBA-15 was modified to obtain pore-expanded materials, with pore diameters from 11 to 15 nm. Post-synthesis functionalization treatments were carried out by grafting with diethylenetriamine (DT) and by impregnation with tetraethylenepentamine (TEPA) and polyethyleneimine (PEI). The adsorbents were characterized by X-ray diffraction, N2 adsorption–desorption at 77 K, elemental analysis and Transmission Electron Microscopy. CO2 capture was studied by using a volumetric adsorption technique at 45 °C. Consecutive adsorption–desorption experiments were also conducted to check the cyclic behaviour of adsorbents in CO2 capture. An improvement in CO2 adsorption capacity and efficiency of amino groups was found for pore-expanded SBA-15 impregnated materials in comparison with their counterparts prepared from conventional SBA-15 with smaller pore size. PEI and TEPA-based adsorbents reached significant CO2 uptakes at 45 °C and 1 bar (138 and 164 mg CO2/g, respectively), with high amine efficiencies (0.33 and 0.37 mol CO2/mol N), due to the positive effect of the larger pore diameter in the diffusion and accessibility of organic groups. Pore-expanded SBA-15 samples grafted with DT and impregnated with PEI showed a good stability after several adsorption–desorption cycles of pure CO2. PEI-impregnated adsorbent was tested in a fixed bed reactor with a diluted gas mixture containing 15 % CO2, 5 % O2, 80 % Ar and water (45 °C, 1 bar). A noteworthy adsorption capacity of 171 mg CO2/g was obtained in these conditions, which simulate flue gas after the desulphurization step in a thermal power plant.  相似文献   

6.
Effective K and Al incorporation in Li4SiO4 leads to the broadened adsorption temperature range and enhanced carbon dioxide adsorption performance.  相似文献   

7.
Highly crystalline ZnO–SiO2 films obtained by a sol–gel method at different ZnO contents were deposited on silicon substrate (P(100)) using spin coating process. The XRD results revealed that the strong ZnO(100) peak is grown with highly c-axis oriented film and the crystallinity is progressively improved with increasing ZnO contents. SEM micrographs of the films deposited on silicon substrate show a homogeneous and uniformity structure at different ZnO content. The prepared ZnO–SiO2 films are compared with either a film prepared from a commercial photocatalysts Hombikat UV-100 or Pilkington Glass Activ? by the determination of their photonic efficiencies for degradation of methylene blue. The photocatalytic efficiency of the 10 wt% ZnO–SiO2 film was found to be about four times higher than film prepared from UV-100 or Pilkington Glass Activ?. The photocatalytic efficiencies of ZnO–SiO2 films are increased with increasing ZnO content from 1 wt% to 10 wt% ZnO and then decreased at 15 wt% ZnO. The order of photocatalytic efficiencies of ZnO–SiO2 films at different ZnO content and commercial photocatalysts after 6 h illumination were as following: 10 wt% ZnO > 15 wt% ZnO > 1 wt% ZnO > as-prepared 10 wt% ZnO–SiO2 film > UV-100 > Pilkington Glass Activ?, which suggested that the ZnO–SiO2 films are photoactive than commercial photocatalysts. The improved efficiency and potentially the low-cost synthesis suggest that this material might be practically useful as a photocatalyst film.  相似文献   

8.
In this work, the films of poly(ether-block-amide) (Pebax 1657) and hydrophilic/hydrophobic silica nanoparticles (0–10 wt%) were coated on a poly(vinyl chloride) (PVC) ultrafiltration membrane to form new mixed matrix composite membranes (MMCMs) for CO2/N2 separation. The membranes were characterized by SEM, FTIR, DSC and XRD. Successful formation of a non-porous defect-free dense top layer with ~4 μm of thickness and also uniform dispersion of silica nanoparticles up to 8 wt% loading in Pebax matrix were confirmed by SEM images. The gas permeation results showed an increase in the permeance of all gases and an increase in ideal CO2/N2 selectivity with the increase in silica nanoparticle contents. Comparison between the incorporation of hydrophilic and hydrophobic silica nanoparticle into Pebax matrix revealed that the great enhancement of CO2 solubility is the key factor for the performance improvement of Pebax + silica nanoparticle membranes. The best separation performance of the hydrophilic silica nanoparticle-incorporated Pebax/PVC membrane for pure gases (at 1 bar and 25 °C) was obtained with a CO2 permeability of 124 barrer and an ideal CO2/N2 selectivity of 76, i.e., 63 and 35% higher than those of neat Pebax membrane, respectively. The corresponding values for hydrophobic silica nanoparticle-incorporated Pebax/PVC membrane were 107 barrer for CO2 permeability and 61 for ideal CO2/N2 selectivity. Also the performances of MMCMs improved upon pressure increase (1–10 bar) owing to the shift in plasticizing effect of CO2 towards the higher pressures. In addition, an increase in permeabilities with a decrease in ideal selectivity was observed upon temperature increase (25–50 °C) due to the intensification of chain mobility.  相似文献   

9.
Oxidative desulfurization (ODS) of organic compounds containing sulfur element from a model oil was performed using tungsten oxide catalysts supported on mesoporous silica with cubic Ia3d mesostructure, well-defined mesopores (7.2 nm), high surface area (719 m2/g), and three-dimensional pore network (WO x /KIT-6). The prepared WO x /KIT-6 catalysts (5–20 wt% WO x ) were characterized by X-ray diffraction analysis, N2 sorption measurements, electron microscopy, H2-temperature programmed reduction, Raman spectroscopy, and thermogravimetric analysis. Among the mesoporous catalysts, 10 wt% WO x /KIT-6 exhibited the best catalytic performance. Sulfur-containing organic compounds, such as dibenzothiophene, 4,6-dimethyldibenzothiophene, and benzothiophene, were completely (100 %) removed from the model oil over 10 wt% WO x /KIT-6 catalyst in 2 h. In addition, the catalyst could be reused several times with only slight decrease in catalytic activity.  相似文献   

10.
A sol–gel based hybrid process was developed by manipulating different techniques in sol–gel process to synthesize γ-alumina and (CuO, CuO + ZnO) doped γ-alumina spherical particles. Catalysts having spherical geometry have an important advantage over powders or pellets which are impervious to fluids, when packed in a reactor. Boehmite sol was used as alumina precursor for synthesizing porous γ-alumina and doped materials. γ-alumina particles having 5 wt% CuO, 4 wt% CuO + 1 wt% ZnO, 3 wt% CuO + 2 wt% ZnO and 2 wt% CuO + 3 wt% ZnO were prepared by adding required amounts of Cu(NO3)2 and Zn(NO3)2 solutions prior to gelation of the sol. Methanol dehydration studies were carried out by employing these synthesized catalysts. Hundred percent conversion of methanol to dimethyl ether was observed with (4 wt% CuO + 1 wt% ZnO)-γ-alumina and (5 wt% CuO)-γ-alumina microspheres at 325 and 350 °C, respectively.  相似文献   

11.
The effect of Rh dispersion on reforming of CH4 with CO2 over H‐Beta supported Rh catalysts has been investigated. The CH4 and CO2 conversion over the catalysts increase with increasing Rh loading from 0.5 wt% to 4.0 wt% in the reaction temperature range of 823–1123 K. The high TOF of CH4 over 0.5 wt% and 1.0 wt% Rh/H‐beta may be attributed to high dispersion of rhodium species. The catalysts before and after the reaction were characterized by XRD, TEM, and TG‐DTA and the results indicate the catalysts with Rh loading of 0.5 wt% and 1.0 wt% exhibiting high resistance to coke. Under controllable conditions, we confirm that the coke is originated from methane dissociation and can be substantially oxidized by active oxygen species dissociated from the adsorbed carbon dioxide on the catalyst with high dispersion of Rh species.  相似文献   

12.
Barium cerate doped by trivalent rare earth metal ions is a potentially huge component of materials for electrochemical industry due to its high protonic conductivity. However, the poor chemical stability especially in the presence of CO2, SO2 or H2O, resulting in decreasing the mechanical durability of obtained materials, limits their possible applications. The new approach towards stable ceramic protonic conductors with high electrical conductivity is presented. Thermal stability of yttrium doped (10 mol%) of BaCeO3 was enhanced by forming the composite material BaCe0.9Y0.1O3–BaWO4 (10 mol% of BaWO4). The synthesis was performed by solid-state reaction method. The detailed study of thermal decomposition of starting powders mixture was performed using thermogravimetry and differential thermal analysis (TG/DTA) techniques combined with Evolved Gas Analysis (EGA—mass spectrometry). Structure, phase composition and microstructure together with thermal stability of sintered materials were determined. The exposition tests were performed to characterise the stability of composites in carbon dioxide and water vapour-rich atmospheres. The samples were exposed to atmosphere containing CO2/H2O (7 % of CO2 in air, 100 % RH) at temperature of 25 °C for 300 h. Thermal analysis supplied with mass spectrometry was applied to analyse the materials after the test. The results of this experiment showed better chemical resistance of composite material—BaCe0.9Y0.1O3 with 10 mol% of BaWO4 compared to single phase material.  相似文献   

13.
Here a novel material for methane adsorption was synthesized and studied, which is a graphene-like two-dimensional (2D) carbide (Ti2C, a member of MXenes), formed by exfoliating Ti2AlC powders in a solution of lithium fluoride (LiF) and hydrochloric acid (HCl) at 40 °C for 48 h. Based on first-principles calculation, theoretically perfect Ti2C with O termination has a specific surface area (SSA) of 671 m2 g?1 and methane storage capacity is 22.9 wt%. Experimentally, 2.85 % exfoliated Ti2C with mesopores shown methane capacity of 11.58 cm3 (STP: 0 °C, 1 bar) g?1 (0.82 wt%) under 5 MPa and the SSA was 19.1 m2 g?1. For Ti2C sample intercalated with NH3·H2O, the adsorbed amount was increased to 16.81 cm3 (STP) g?1 at same temperature. At the temperature of 323 K, the adsorbed amount of as-prepared Ti2C was increased to 52.76 cm3 (STP) g?1. For fully exfoliated Ti2C, the methane capacity was supposed to be 28.8 wt% or 1148 V (STP)v?1. Ti2C theoretically has much larger volume methane capacity than current methane storage materials, though its SSA is not very high.  相似文献   

14.
We report the use of second harmonic generation (SHG) and temperature resolved second harmonic generation (TR-SHG) for in situ probing and monitoring the structural purification of m-hydroxybenzoic acid (MHBA). Pure and mixtures of the two polymorphic forms of MHBA (metastable Pna21 and stable P21/c) and commercial MHBA were analysed by: DSC, XRPD and SHG. Results obtained with these three techniques are compared and demonstrate for that particular component, the high sensitivity and accuracy of SHG in assessing the polymorphic purity of MHBA. The SHG detection threshold for the metastable polymorph is circa 2 ppm and is several orders of magnitude better than the sensitivity of XRPD (1 wt%) and DSC (only 17 wt%). The proportion of the metastable phase in the commercial MHBA was evaluated to 1 wt% by SHG. Results of TR-SHG measurements performed on commercial MHBA at 5 K min?1 heating rate show that TR-SHG is a good technique for an in situ monitoring of the structural purity. The present study clearly demonstrates that SHG and TR-SHG are relevant and accurate techniques for probing the structural purity and for the monitoring of solid–solid phase transitions provided one of the two varieties crystallizes in a non-centrosymmetric space group.  相似文献   

15.
In this work, a 2D covalent triazine-based framework was prepared by using 1,3-dicyanobenzo[c]thiophene(DCBT) as monomer to effectively capture CO_2. The resulting CTF-DCBT was characterized by FT-IR, XPS, PXRD, elemental analysis, SEM, TEM, and N_2 adsorption-desorption.The results indicate that CTF-DCBT is partially crystalline and has ultramicropore(6.5 A?) as well as high heteroatom contents(11.24 wt% and 12.61 wt% for N and S, respectively). In addition, the BET surface area and total pore volume of CTF-DCBT are 500 m~2/g and 0.26 cm~3/g, respectively. CTF-DCBT possesses excellent thermal stability(450 °C) and chemical stability towards boiling water, 4 M HCl, and 1 M Na OH.The CO_2 adsorption capacity of CTF-DCBT is 37.8 cm~3/g at 1 bar and 25 °C. After six adsorption-desorption cycles, there is no obvious loss of CO_2 uptake observed. Due to the ultramicropore and high heteroatom contents, CTF-DCBT has high isosteric heats of adsorption for CO_2 and high selectivities of CO_2 over N_2 and CH_4. At 25 °C, the CO_2/N_2 and CO_2/CH_4 selectivities are 112.5 and 10.3, respectively, which are higher than those of most POFs. Breakthrough curves indicate that CTF-DCBT could effectively separate CO_2/N_2 and CO_2/CH_4 mixtures.  相似文献   

16.
Resolution of the cis-, trans-isomers of vitamin K1 (phylloquinone) is important in nutritional analysis since only the trans-isomer is biologically active, while artificial vitamin K1 may contain significant amounts of the inactive cis-isomer. The cis-, trans-isomers of vitamin K1 were separated, with a resolution of 3.4, using pure carbon dioxide (CO2) as the mobile phase, with a run time ≈6 min, on a 4.6 × 150 mm, 3.5 μm RX-Sil bare silica column, using supercritical fluid chromatography (SFC). With 2.5 % ethyl acetate in CO2, Rs = 2.77, with a run time <4 min. On a 3 × 100 mm, 1.8 μm RX-Sil column Rs remained at 2.69, with a run time just over 2 min. This is the first report on the apparent separation of these isomers by SFC, and is up to 3–5 times faster than separations using high performance liquid chromatography (HPLC) in the literature. Unlike most HPLC separations, no dichloromethane, acetonitrile, or hexane/heptane was used. The CO2 was beverage grade, at 1/20th to 1/50th the cost of the replaced organics, is recycled, and is considered “green”.  相似文献   

17.
CO2 biofixation was investigated using tubular bioreactors (15 and 1.5 l) either in the presence of green algae Chlorella vulgaris or Nannochloropsis gaditana. The cultivation was carried out in the following conditions: temperature of 25 °C, inlet-CO2 of 4 and 8 vol%, and artificial light enhancing photosynthesis. Higher biofixation were observed in 8 vol% CO2 concentration for both microalgae cultures than in 4 vol%. Characteristic process parameters such as productivity, CO2 fixation, and kinetic rate coefficient were determined and discussed. Simplified and advanced methods for determination of CO2 fixation were compared. In a simplified method, it is assumed that 1 kg of produced biomass equals 1.88 kg recycled CO2. Advance method is based on empirical results of the present study (formula with carbon content in biomass). It was observed that application of the simplified method can generate large errors, especially if the biomass contains a relatively low amount of carbon. N. gaditana is the recommended species for CO2 removal due to a high biofixation rate—more than 1.7 g/l/day. On day 10 of cultivation, the cell concentration was more than 1.7?×?107 cells/ml. In the case of C. vulgaris, the maximal biofixation rate and cell concentration did not exceed 1.4 g/l/day and 1.3?×?107 cells/ml, respectively.  相似文献   

18.
Two generations of poly (propylene imine) dendrimer with amino terminated groups (G2- and G5-PPI-NH2) were grafted on cotton cellulose fabric using cross linking agents (citric or glutaric acids). Fourier transform infrared (FTIR) spectroscopy identified ester groups which were formed between hydroxyl groups of the cotton fabric and carboxylic groups of the cross linking agents. Also, attenuated total reflectance-FTIR (ATR-FTIR) analysis confirmed formation of amide groups between the carboxylic groups of the cross linking agents and the amino end groups of the dendrimers. Nitrogen content (N-content) analysis revealed the presence of the dendrimers on the cotton fabric even after 5 washing cycles. In order to study the dispersion of the PPI dendrimers on the surface of the cotton fabric, field emission scanning electron microscopy (FE-SEM) was performed. The particle size distribution of the G2- and G5-PPI-NH2 aqueous solutions was also determined by dynamic light scattering (DLS) analysis. Antimicrobial activity of the PPI dendrimer aqueous solutions and the cotton cellulose fabric grafted with the dendrimers was evaluated both quantitatively and qualitatively against Gram-positive bacterium (Staphylococcus aureus), Gram-negative bacteria (Pseudomonas aeruginosa and Escherichia coli) and fungus (Candida albicans). The dendrimer grafted cotton cellulose fabric exhibited a 99 % reduction in bacterial counts against S. aureus, E. coli and C. albicans. The antimicrobial activities of the grafted cotton cellulose fabric with the PPI dendrimers were maintained even after 5 washing cycles.  相似文献   

19.
Incompatibility between filler and polymer chains accompanied by particle agglomeration has a detrimental effect on the performance of mixed matrix membranes (MMMs). To obviate intermolecular forces of different additives, functional groups (-COOH, –NCO, and –NH2) were grafted on the surface of multi-walled carbon nanotubes (MWCNTs) which were then incorporated as fillers in the poly(ether-block-amide) (PEBA) polymeric matrix in the range of 0.1–1 wt% loading. CO2 permeability and ideal CO2/N2 and CO2/CH4 selectivity of MMMs was compared with the neat membrane, and the results revealed favorable enhancement and surpassed CO2/N2 Robeson's upper bound under 4–10 bar in the range of 15–55 °C. Mixed gas separation performance of MMMs, which is of vital importance in industrial applications, was also investigated. The results indicate that MWCNT-NCO created superior grafts with the polymer chains, and MMMs with this additive had a better gas separation performance with high mechanical and thermal stability.  相似文献   

20.
The adsorption of cetyl trimethyl ammonium bromide (CTAB) and two commercial inhibitor base chemicals, an oleic imidazoline salt (OI) and a phosphate ester (PE), onto iron carbonate (FeCO3), was studied by zeta potential measurements in a 0.1 wt% sodium chloride (NaCl) solution under 1 bar CO2 at 22°C, in the absence and presence of a refined low-aromatic oil. The zeta potential of oil-in-water emulsion droplets was also determined. Surface tension of 0.1 wt% and 3 wt% brines was measured as a function of inhibitor concentration. The isoelectric point was pH 6.0 in the 0.1 wt% NaCl solution under 1 bar CO2. The results show that all three inhibitor compounds adsorbed onto the iron carbonate particles both at pH 4.0 and pH 6.0. Adsorption on both negatively charged surfaces and surfaces with no charge were thus found for all inhibitors. The addition of oil had no significant effect on the measured zeta potential on iron carbonate particles.  相似文献   

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