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1.
A facile synthesis of micro- and mesoporous carbons has been proposed using colloidal silica nanoparticles with diameter of ∼24 nm and poly(vinylidene chloride-co-vinyl chloride) (Saran) as a carbon precursor. The resulting carbons possessed large specific surface area, ∼800 m2/g, and approximately the same volume of micro- and mesopores, each about 50% of the total pore volume. While the size of micropores was around 1 nm, the large and uniform spherical mesopores (about 24 nm) resemble the diameters of silica colloids used. Nitrogen adsorption measurements proved that these mesopores were interconnected and accessible. The well-developed microporosity was created mainly by decomposition of Saran copolymer during carbonization.  相似文献   

2.
A facile hydrothermal strategy was first proposed to synthesize flower-like Co(OH)2 hierarchical microspheres. Further physical characterizations revealed that the flower-like Co(OH)2 microspherical superstructures were self-assembled by one-dimension nanobelts with rich mesopores. Electrochemical performance of the flower-like Co(OH)2 hierarchical superstructures were investigated by cyclic voltammgoram, galvanostatic charge–discharge and electrochemical impedance spectroscopy in 3 M KOH aqueous electrolyte. Electrochemical data indicated that the flower-like Co(OH)2 superstructures delivered a specific capacitance of 434 F g−1 at 10 mA cm−2 (about 1.33 A g−1), and even kept it as high as 365 F g−1 at about 5.33 A g−1. Furthermore, the SC degradation of about 8% after 1,500 continuous charge–discharge cycles at 5.33 A g−1 demonstrates their good electrochemical stability at large current densities.  相似文献   

3.
The influence of micelle morphology transformation on the structure of mesoporous materials is fundamental in designing optimal, well-ordered, mesoporous materials. Firstly, the steady-state fluorescence technique was adopted to determine the first and second critical micelle concentrations of cetyltrimethylammonium chloride (CTAC) as 125 and 210 mmol L−1 in an equimolar mixture of water and ethanol at 25°C. Using tetraethylorthosilicate (TEOS) as the precursor, mesoporous silicas (with a surface area of 545.7–1210.5 m 545.7 ∼ 1210.5 m2 g−1 and a pore volume of 0.26 ∼ 0.80 cm3 g−1) were synthesized with the CTAC templates in the equimolar mixture of water and ethanol. Characterization by small-angle X-ray diffraction and N 2 adsorption/desorption techniques revealed that the surface area and pore volume of silica increased with the content of CTAC, whereas there existed a transition point at the CTAC/TEOS ratio of 0.15 corresponding to the fade-away of well-ordered mesoporous structure. The negative effect of the much higher content CTAC on the periodic structure of mesoporous silica is attributed to micelle transformation from spheres to cylinders related to the second critical micelle concentration of CTAC. The text was submitted by the authors in English.  相似文献   

4.
Activated carbons (ACs) are prepared from vine shoots (VS) by the method of physical activation in air, CO2 and steam atmospheres and by the method of chemical activation with H3PO4, ZnCl2 and KOH aqueous solutions. The ACs were characterized texturally by N2 adsorption at −196 °C, mercury porosimetry, and density measurements. The method of chemical activation has been proved to be more effective than the method of physical activation to prepare ACs with a well-developed porosity. ACs with high micro- and mesopore volumes are prepared with ZnCl2 and H3PO4. Using ZnCl2, the volume of micropores is 0.62 cm3 g−1 and the volume of mesopores is 0.81 cm3 g−1. A greater development of macroporosity is obtained by KOH activation. The volume of macropores is as high as 1.13 cm3 g−1 for the resulting AC. Yield of the process of preparation of the ACs is low for the method of chemical activation. Some insights into the performance of the activating agents in the activation process are provided.  相似文献   

5.
A modified preparation of silica nanoparticles via sol–gel process was described. The ability to control the particle size and distribution was found highly dependent on mixing modes of the reactants and drying techniques. The mixture of tetraethoxysilane and ethanol followed by addition of water (Mode-A) produced monodispersed powder with an average particle size of 10.6 ± 1.40 nm with a narrow size distribution. The freeze drying technique (FD) further improved the quality of powder. In addition, the freeze dried samples have shown unique TGA decomposition steps which might be related to the well-defined structure of silica nanoparticles as compared to the heat dried samples. DSC analysis showed that FD preserved the silica surface with low shrinkage and generated remarkably well-order, narrow and bigger pore size and pore volume and also large endothermic enthalpies (ΔH FD = −688 J g−1 vs. ΔH HD = −617 J g−1) that lead to easy escape of physically adsorbed water from the pore at lower temperature.  相似文献   

6.
This paper reports the synthesis, structure, and hydrogen adsorption property of Li-doped mesoporous silica (MPS) with a 2D hexagonal structure. The Li-doping is achieved by impregnation of the cylindrical mesopores with an ethanol solution of lithium chloride followed by heat treatment. Detailed characterization by solid-state NMR, TG-MS, and FT-IR suggests that, during the heat treatment, lithium chloride reacts with surface ethoxy groups (≡Si-OEt) to form ≡SiOLi groups, while ethyl chloride is released into the gas phase. The hydrogen uptake at 77 K and 1 atm increases from 0.68 wt% for the undoped MPS to 0.81 wt% for Li-doped MPS (Li-MPS). The isosteric heat of adsorption is 4.8 kJ mol−1, which is consistent with the quantum chemistry calculation result (5.12 kJ mol−1). The specific hydrogen adsorption on Li-MPS would be explained by the frontier orbital interaction between HOMO of hydrogen molecules and LUMO of ≡SiOLi. These findings provide an important insight into the development of hydrogen storage materials with specific adsorption sites.  相似文献   

7.
Molecular imprinting techniques are becoming an increasingly important domain of porous polymers generally, to achieve molecule specific recognition through morphology or stereochemistry of cavities. Imprinting is sought to increase both selectivity and sensitivity where the polymer may be present as particulate, membrane or thin film forms. Here, we detail mechanisms involved in the formation, stability and adsorption of binding sites, through the influence of polymerisation conditions and templates on the porosity of highly crosslinked molecularly imprinted polymers (MIPs). Environmental control represents an important area for porous polymers, here we focus on two template fungicides, iprodione and pyrimethanil, for ethylene glycol dimethacrylate (EGDMA) based polymers. In general, control of the pre-polymerisation interactions were able to vary the surface areas of polymers from 40–60 m2 g−1 to 300–436 m2 g−1 while pore sizes fell into distributions (a) close to the micropore region at ∼3.8 nm, (b) in the 10 to 20 nm mesopore region and (c) in the 20 to 50 nm mesopore region. The importance of intermolecular interactions and aggregation in the pre-polymerisation solution to the Brunauer, Emmett, Teller (BET) surface areas and pore size distribution of final polymers has been demonstrated by systematic variation of chemical functionality. These effects confirm recent molecular dynamic simulation studies of MIP formation and cavity stability.  相似文献   

8.
Mesoporous carbide-derived carbons (CDC) with hierarchical pore structure were fabricated by chlorine etching of mesoporous titanium carbides. Their capacitive behaviors for electrochemical capacitor were investigated in comparison to those of purely microporous CDC. The as-prepared mesoporous CDC exhibited not only uniform micropores formed by leaching out titanium atoms but a 3-D mesoporous network inherited from their parent carbides. These mesoporous CDC could deliver a high specific capacitance of 120 F g−1 in 1 M tetraethylammonium tetrafluoroborate dissolved in propylene carbonate. Moreover, they owned excellent frequency response and superior rate capability with capacitance retention ratio of 91% at current density of 10 A g−1. A high energy density of 16.3 Wh kg−1 was obtained even though power density was raised up to 4,300 W kg−1. The distinctive capacitive performance of mesoporous CDC would be attributed to their superior microstructure, in which the uniform micropores contributed to high charge storage while the 3-D mesoporous network and nanometer-scaled dimension of particles facilitated ions transfer as well as shortened electrolyte diffusion distance.  相似文献   

9.
The copolymer of acrylamide and octylphenylpoly(oxyethylene) acrylate macromonomer (AM-C8PhEO7Ac) was synthesized and characterized by IR and NMR spectroscopy. The molecular weight of the copolymer was determined to be 1.21 × 105 by static light scattering. The weight contents of AM and macromonomer were determined to be 67.8 and 32.2%, respectively, by elemental analysis. The micellar behavior of the copolymer in aqueous solution was studied by UV spectroscopy and atomic force microscopy (AFM). The molecules of AM-C8PhEO7Ac copolymer form monomolecular micelles in the concentration range 4 × 10−6 – 3 × 10−5 g/ml and polymolecular micelles at concentrations above 3 × 10−5 g/ml according to the UV analysis. The AFM images indicate that the monomolecular micelles are globular with diameters of 70 nm and have a narrow size distribution. The polymolecular micelles can be globular or cylindrical depending on the concentration, and have a wide size distribution. Received: 10 February 1999 Accepted in revised form: 28 June 1999  相似文献   

10.
The metal anions of vanadium (V) and chromium (VI) in aqueous solution can be effectively adsorbed by Zr(IV)-impregnated collagen fiber (ZrICF). The maximum adsorption capacity of V(V) takes place within the pH range of 5.0 to 8.0, while that of Cr(VI) is within the pH range of 6.0 to 9.0. When the initial concentration of metal ions was 2.00 mmol L−1 and the temperature was 303 K, the adsorption capacity of V(V) on Zr-ICF was 1.92 mmol g−1 at pH 5.0, and the adsorption capacity of Cr(VI) was 0.53 mmol g−1 at pH 7.0. As temperature increased, the adsorption capacity of V(V) increased, while that of Cr(VI) was almost unchanged. The adsorption isotherms of the anionic species of V(V) and Cr(VI) can be fit by the Langmuir equation. The adsorption rate of V(V) follows the pseudo-first-order rate model, while the adsorption rate of Cr(VI) follows the pseudo-second-order rate model. Furthermore, ZrICF shows high adsorption selectivity to V(V) in the mixture solution of V(V) and Cr(VI). Practical applications of ZrICF could be expected in consideration of its performance in adsorption of V(V) and Cr(VI).  相似文献   

11.
The analysis of the porosity of materials is an important and challenging field in analytical chemistry. The gas adsorption and mercury intrusion methods are the most established techniques for quantification of specific surface areas, but unfortunately, dry materials are mandatory for their applicability. All porous materials that contain water and other solvents in their functional state must be dried before analysis. In this process, care has to be taken since the removal of solvent bears the risk of an incalculable alteration of the pore structure, especially for soft materials. In the present paper, we report on the use of small-angle X-ray scattering (SAXS) as an alternative analysis method for the investigation of the micro and mesopores within cellulose beads in their native, i.e., water-swollen state; in this context, they represent a typical soft material. We show that even gentle removal of the bound water reduces the specific surface area dramatically from 161 to 109 m2 g−1 in cellulose bead sample type MT50 and from 417 to 220 m2 g−1 in MT100. Simulation of the SAXS curves with a bimodal pore size distribution model reveals that the smallest pores with radii up to 10 nm are greatly affected by drying, whereas pores with sizes in the range of 10 to 70 nm are barely affected. The SAXS results were compared with Brunauer–Emmett–Teller results from nitrogen sorption measurements and with mercury intrusion experiments.  相似文献   

12.
A new adsorbent is proposed for the solid-phase extraction of phenol and 1-naphthol from polluted water. The adsorbent (TX-SiO2) is an organosilica composite made from a bifunctional immobilized layer comprising a major fraction (91%) of hydrophilic diol groups and minor fraction (9%) of the amphiphilic long-chain nonionic surfactant Triton X-100 (polyoxyethylated isooctylphenol) (TX). Under static conditions phenol was quantitatively extracted onto TX-SiO2 in the form of a 4-nitrophenylazophenolate ion associate with cetyltrimethylammonium bromide. The capacity of TX-SiO2 for phenol is 2.4 mg g−1 with distribution coefficients up to 3.4 × 104 mL g−1; corresponding data for 1-naphthol are 1.5 mg g−1 and 3 × 103 mL g−1. The distribution coefficient does not change significantly for solution volumes of 0.025–0.5 L and adsorbent mass less than 0.03 g; 1–90 μg analyte can be easily eluted by 1–3 mL acetonitrile with an overall recovery of 98.2% and 78.3% for phenol and 1-naphthol, respectively. Linear correlation between acetonitrile solution absorbance (A 540) and phenol concentration (C) in water was found according to the equation A 540 = (6 ± 1) × 10−2 + (0.9 ± 0.1)C (μmol L−1) with a detection range from 1 × 10−8 mol L−1 (0.9 μL g−1) to 2 × 10−7 mol L−1 (19 μL g−1), a limit of quantification of 1 μL g−1 (preconcentration factor 125), correlation coefficient of 0.936, and relative standard deviation of 2.5%. A solid-phase colorimetric method was developed for quantitative determination of 1-naphthol on adsorbent phase using scanner technology and RGB numerical analysis. The detection limit of 1-naphthol with this method is 6 μL g−1 while the quantification limit is 20 μL g−1. A test system was developed for naked eye monitoring of 1-naphthol impurities in water. The proposed test kit allows one to observe changes in the adsorbent color when 1-naphthol concentration in water is 0.08–3.2 mL g−1.  相似文献   

13.
In accordance with thermodynamic analysis, cuprous oxide layers are formed spontaneously in the Cu|Cu(II), gluconic acid system at pH > 3.7 under open-circuit conditions. A current peak of Cu2O reduction is observed on cathodic voltammograms at ca −0.7 V, its height being dependent on the exposure time. The analysis of the charge transferred in this region yields the rate of Cu2O formation equal to 1.25 × 10−10 mol cm−2 s−1. The light perturbation of Cu electrode under open-circuit conditions results in the generation of a negative photopotential, which is indicative of n-type conductivity. The threshold wavelength is equal to ∼590 nm and is consistent with a band gap of ∼2.1 eV. Anodic photocurrents, which are observed near the open-circuit potential, decrease with cathodic polarization and change their sign at ∼0.05 V. Analysis of impedance data was performed, invoking the equivalent circuit that accounts for the two-step charge transfer. In the presence of Cu2O, some retardation of Cu(II) reduction was found to occur with a slight increase in the admittance of the double layer. The suggestion has been made that oxide layers formed in Cu(II) gluconate solutions cannot be compact and uniformly distributed over the entire electrode surface. Relevant investigations of surface morphology support this conclusion.  相似文献   

14.
Microwave digestion and isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-SFMS) has been applied to the determination of Pb in rice flour. In order to achieve highly precise determination of low concentrations of Pb, the digestion blank for Pb was reduced to 0.21 ng g−1 after optimization of the digestion conditions, in which 20 mL analysis solution was obtained after digestion of 0.5 g rice flour. The observed value of Pb in a non-fat milk powder certified reference material (CRM), NIST SRM 1549, was 16.8 ± 0.8 ng g−1 (mean ± expanded uncertainty, k = 2; n = 5), which agreed with the certified value of 19 ± 3 ng g−1 and indicated the effectiveness of the method. Analytical results for Pb in three brown rice flour CRMs, NIST SRM 1568a, NIES CRM 10-a, and NIES CRM 10-b, were 7.32 ± 0.24 ng g−1 (n = 5), 1010 ± 10 ng g−1 (n = 5), and 1250 ± 20 ng g−1 (n = 5), respectively. The concentration of Pb in a candidate white rice flour reference material (RM) sample prepared by the National Metrology Institute of Japan (NMIJ) was observed to be 4.36 ± 0.28 ng g−1 (n = 10 bottles). Figure Digestion blank of Pb was carefully reduced to approximately 0.2 ng g-1 which permitted the highly precise determination of Pb at low ng g-1 level in foodstuff samples by ID-SFMS  相似文献   

15.
The strontium content of serum, bone, marrow, and teeth was determined by inductively-coupled plasma mass spectrometry (ICP–MS). Significant correlations were obtained after the data were subjected to quality assurance (QA) performed according to validated procedures. After four weeks of treatment with strontium malonate, strontium levels increased from 76 ± 9 μg g−1 in placebo-treated dogs to levels of 7.2 ± 1.7 mg g−1, 9.5 ± 2.7 mg g−1, and 9.8 ± 2.7 mg g−1 in groups treated with 300, 1000, and 3000 mg kg−1 day−1, respectively. Strontium induced a highly significant increase in the bone formation marker, bone-specific alkaline phosphatase (BSAP), and an excellent correlation was found with the bone-strontium content. In females, the placebo-treated group showed a decrease in BSAP of 53%, whereas the three strontium malonate-treated groups showed an increase of 60, 276, and 278% for the groups treated with 300, 1000, and 3000 mg kg−1 day−1, respectively. For males the corresponding values were −44%, +142%, +194%, and +247% increases in BSAP in the placebo, 300, 1000, and 3000 mg kg−1 day−1 groups respectively.  相似文献   

16.
This paper describes the application of TiO2 nano-particles (anatase form) for the solid-phase extraction of iron from coastal seawater samples. We investigated the adsorption processes by infra-red spectroscopy. We compared in batch and on-(mini)column extraction approaches (0.1 and 0.05 g TiO2 per sample, respectively), combined to external calibration and detection by inductively coupled plasma mass spectrometry at medium mass resolution. Globally, this titania phase was slightly more efficient with seawater than with ultra-pure water, although between pH 2 and pH 7, the Fe retention efficiency progressed more in ultra-pure water than in seawater (6.9 versus 4.8 times improvement). Different reaction schemes are proposed between Fe(III) species and the two main categories of titania sites at pH 2 (adsorption of [FeL x ](3 − x)+ via possibly the mediation of chlorides) and at pH 7 (adsorption of [Fe(OH)2]+ and precipitation of [Fe(OH)3]0). Under optimised conditions, the inlet system was pre-cleaned by pumping 6% HCl for ∼2 h, and the column was conditioned by aspirating ultra-pure water (1.7 g min−1) and 0.05% ammonia (0.6 g min−1) for 1 min. Then 3 g seawater sample was loaded at the same flow rate while being mixed on-line with 0.05% ammonia at 0.6 g min−1 to adjust the pH to 7. The iron retained on the oxide powder was then eluted with 3 g 6% HCl (<0.002% residual salinity in the separated samples). The overall procedural blank was 220 ± 46 (2 s, n = 16) ng Fe kg−1 (the titania was renewed in the column every 20 samples, with 2-min rinsing in between samples with 6% HCl at 1.5 g min−1). The recovery estimated from the Canadian certified reference material CASS-2 was 69.5 ± 7.6% (2 s, n = 4). Typically, the relative combined uncertainty (k = 2) estimated for the measurement of ∼1 μg Fe kg−1 (0.45 μm filtered and acidified to pH 1.5) of seawater was ∼12%. We applied our method to a similar sample, from the coastal region of the North Sea. The agreement well within stated uncertainties of our result with the value obtained independently by isotope dilution mass spectrometry further validated our method.  相似文献   

17.
Effect of fumed silica dispersion on poly(vinylidene fluoride-co-hexafluoropropylene)-based magnesium ion-conducting gel polymer electrolyte has been studied using various physical and electrochemical techniques. The composite gel electrolytes are free-standing and flexible films with enough mechanical strength. The optimized composition with 3 wt.% filler offers a maximum ionic conductivity of ∼1.1 × 10−2 S cm−1 at ∼25 °C with good thermal and electrochemical stabilities. The Mg2+ ion conduction in the gel nanocomposite film is confirmed from the cyclic voltammetry, impedance spectroscopy, and transport number measurements. The space-charge layers formed between filler particles and gel electrolyte are responsible for the enhancement in ionic conductivity. The applicability of the gel nanocomposite to a rechargeable battery is examined by fabricating a prototype cell consisting of Mg [or Mg-multiwalled carbon nanotube (MWCNT) composite] and MoO3 as negative and positive electrodes, respectively. The discharge capacity and the rechargeability of the cell have been improved when Mg metal is substituted by Mg-MWCNT composite. The discharge capacity of the optimized cell has found to be ∼175 mAh g−1 of MoO3 for an initial ten charge–discharge cycles.  相似文献   

18.
Guanosine-5′-monophosphate (GMP) was investigated the electrochemical behaviors based on solid-phase extractionon (SPE) at Cu-Mg-Al hydrotalcite-like compound (HTLC) modified glass carbon electrode. Cu-Mg-Al hydrotalcite-like compound (HTLC) was proved as a new sorbent for SPE of GMP, which showed an irreversible adsorption oxidation process on the HTLC/GCE with the oxidation peak potential located at 1.15 V (vs. SCE) in a pH 5.0 acetate buffer solution. Influencing factors of the electrochemical behavior of GMP on the HLTC/GCE were optimized and kinetic parameters were calculated. Under the optimal conditions, with differential pulse voltammetry (DPV), a linear relationship was obtained between the oxidation peak current and the GMP concentration in the range from 1.0 × 10− 6 to 8.0 × 10−4 mol L−1 with the detection limit as 5.0 × 10−7 mol L−1 (signal-to-noise ratio of 3). The modified electrode surface has very good reproducibility and stability.  相似文献   

19.
The disaccharide isomaltose is produced via an enzymatic reaction and is adsorbed to BEA zeolite. This reaction integrated adsorption can be achieved as fluidized bed as well as fixed bed. We investigated isotherms, adsorption enthalpies and sorption kinetics of BEA zeolite and extrudates with a novel aluminum phosphate sintermatrix. These extrudates contain 50% (w/w) of BEA 150 zeolites (Si/Al = 75) as primary crystals. BET-surface for extrudates is 245 m2⋅g−1 and 487 m2⋅g−1 for zeolite. Extrudates show a monomodal macropore structure with a maximum at 90 nm. All isotherms show a type I shape. For lower equilibrium concentrations, which occur during the enzymatic reaction, Henry’s law is applied and compared to a Langmuir model. Adsorption equilibrium constant K i,L calculated from Langmuir for extrudates at 4 °C is 64.7 mL⋅g−1 and more than twice as high as obtained from Henry’s law with K i is 26.8 mL⋅g−1. Adsorption on extrudates at 4 °C is much stronger than on zeolite crystals where the Henry coefficient K i is 17.1 mL⋅g−1. Adsorption enthalpy Δh Ad calculated from van’t Hoff plot with the Henry equation is −44.3 kJ⋅mol−1 for extrudates and −29.6 kJ⋅mol−1 for zeolite crystals. Finally, the kinetics for ad- and desorption were calculated from the initial slope. The diffusion rate for ad- and desorption on extrudates were in the same range while adsorption on zeolites is three orders of magnitudes faster than desorption.  相似文献   

20.
The activated carbons (ACs) are prepared from mesophase pitch which is pre-carbonized by using potassium hydroxide as an activating agent. Nitrogen adsorption at 77 K is used to characterize the surface area and the porous structure of the ACs. By changing the pre-carbonization temperature from 560 to 750 °C, the arrangement of the ACs’ microcrystallines might be controllable, and the pore size could be adjusted between 1.5 and 2.4 nm. The electrochemical performance of the ACs in organic solvent (1 M Et4NBF4 in propylene carbonate) is investigated by voltage sweep cyclic voltammetry and constant current charge–discharge cycling tests. The results show that the ions can transfer rapidly and freely in the pore larger than or equal to 1.85 nm, even when the current density increases to 25 A g−1.  相似文献   

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