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1.
The gasification of a very high purity natural graphite was studied at temperatures between 960 and 1120°C and at CO2 pressures below 108 millitorr. For CO2 depletion up to at least 90%, gasification rates were first order in CO2 pressure, that is with no inhibition by CO observed. The activation energy for the rate constant for the oxygen transfer step (103.5 ± 5.8 kcal/mole) agreed within experimental error with that found from kinetic studies at intermediate CO2 pressures where CO does inhibit the reaction. The rate of the oxygen transfer reaction is markedly inhibited by the presence of low pressures of H2. As H2 pressure is increased up to 3 millitorr, the gasification rate in CO2 at 1100°C monotonically decreases. Further increase in H2 pressure, has a negligible effect on rate. From measurements of hydrogen uptake at reaction temperature, it is clear that inhibition is caused by dissociative chemisorption of hydrogen on to active sites. Inhibition by hydrogen is even more marked for the Graphon-CO2 reaction and is attributed not only to its chemisorbing on carbon sites but also on to impurity catalyst sites. It is doubtful if true rate constants for the C-CO2 reaction, uninhibited by hydrogen, have ever been reported.  相似文献   

2.
A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with nickel oxide (NiOx) nanoparticles and water-soluble dyes. By immersing the GC/NiOx modified electrode into thionine (TH) or celestine blue (CB) solutions for a short period of time (5–120 s), a thin film of the proposed molecules was immobilized onto the electrode surface. The modified electrodes showed stable and a well-defined redox couples at a wide pH range (2–12), with surface confined characteristics. In comparison to usual methods for the immobilization of dye molecules, such as electropolymerization or adsorption on the surface of preanodized electrodes, the electrochemical reversibility and stability of these modified electrodes have been improved. The surface coverage and heterogeneous electron transfer rate constants (ks) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 × 10−10 mol cm−2, 6.12 s−1, 5.9 × 10−10 mol cm−2 and 6.58 s−1, respectively. The results clearly show the high loading ability of the NiOx nanoparticles and great facilitation of the electron transfer between the immobilized TH, CB and NiOx nanoparticles. The modified electrodes show excellent electrocatalytic activity toward hydrogen peroxide reduction at a reduced overpotential. The catalytic rate constants for hydrogen peroxide reduction at GC/NiOx/CB and GC/NiOx/TH were 7.96 (±0.2) × 103 M−1 s−1 and 5.5 (±0.2) × 103 M−1 s−1, respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 μM, 4.14 nA μM−1 nA μM−1 and 5 μM to 20 mM, and 0.36 μM, 7.62 nA μM−1, and 1 μM to 10 mM for the GC/NiOx/TH and GC/NiOx/CB modified electrodes, respectively. Compared to other modified electrodes, these modified electrodes have many advantages, such as remarkable catalytic activity, good reproducibility, simple preparation procedures and long-term stabilities of signal responses during hydrogen peroxide reduction.  相似文献   

3.
Supercritical CO2 (SC-CO2) extraction technology and ultrasonic technology were used to extract two active sex hormones, estradiol and progesterone, and insulin-like growth factor-1 (IGF-1) from antler velvet. The effects of SC-CO2 extraction condition on the extraction yield and content of sex hormones, the ultrasonic extraction condition on the content of IGF-1 and the SC-CO2 extraction condition on the activity remaining of IGF-1 were studied. The optimal conditions were obtained. The experimental results showed that, in presence of 75% ethanol as the co-solvent, the mean yield and content of estradiol and progesterone were 87.67 pg•g-1 and 1224.10 pg•g-1, 12.38 ng•g-1 and 354.06 ng•g-1, respectively, with extraction pressure of 30 MPa, temperature of 35°C, extraction time of 30 min and CO2 consumption of 15 L•g-1 at the flow rate of 2.0 L•min-1. The highest content of IGF-1 was 7425.75 ng•g-1 antler velvet residue, when the pH10 ammonia-ammonium chloride buffer solution was used as the solvent, the ratio of solvent to sample was 20/1 (volume/mass), the extraction temperature was 0-35°C, and the ex-traction time was 4×15 min. Under these conditions, 93.68% activity remaining of IGF-1 in the residue was ob-tained, while little IGF-1 activity exists in traditional residue. The experimental results indicate that the technology of SC-CO2 with co-solvent is of advantage for getting high content sexual hormones and keeping high activity of IGF-1 in the residue, which can not be achieved by traditional extraction methods.  相似文献   

4.
A novel gadolinium selective coated graphite electrode based on 2,6-bis-[1-{N-cyanopropyl,N-(2-methylpridyl)}aminoethyl]pyridine [P] is described. The best performance was exhibited by the electrode having membrane composition P:NaTPB:PVC:NPOE as 8:4:30:58 (%, w/w). The electrode demonstrates excellent potentiometric characteristics towards gadolinium ion over several interfering ions. The electrode exhibited a Nernstian response to Gd3+ ion over a wide concentration range 2.8 × 10−7 to 5.0 × 10−2 M with a detection limit (6.3 ± 0.1) × 10−8 M and slope 19.6 ± 0.1 mV decade−1 of aGd3+. Furthermore, it showed a fast response time (12 s) and can be used for 2.5 months without significant divergence in its characteristics. Noticeably, the electrode can tolerate the concentration of different surfactants up to 1.0 × 10−4 M and can be used successfully in 30% (v/v) ethanol media and 10% (v/v) methanol and acetonitrile water mixture. The useful pH range of this sensor is 2.0 to 8.0. It is sufficiently selective and can be used for the determination of Gd3+ ions in waste water and rock samples. It also serves as a good indicator in the potentiometric titration of GdCl3 with EDTA.  相似文献   

5.
The oxidative coupling of methane (OCM) was investigated with a specifically designed multi-channel device operating fixed-bed reactors at high temperature and atmospheric pressure. The device allows precise temperature measurement in each channel selected for analysis and possesses a quench cooling unit right after the reaction zone. Analysis is based on a mass spectrometer allowing a time resolution of only 3 s per analysis and 30 s per reactor channel. Successful screening is demonstrated using a reactant feed of O2 and CH4 diluted in Ar at flows between 100 and 166 mL/min per reactor channel. As expected, Li/MgO-based catalysts showed good initial performance, but rapid deactivation at 800 °C excludes their use in high-temperature applications. Good C2 selectivity up to 80% and high yields up to 20% were observed for La/Sr/CaO catalysts. Even more interesting, no decline in performance was observed for those formulations identifying 10% La/20% Sr/CaO as best catalyst in an initial library. Screening of various La and Sr loadings at different operating conditions identified a optimal content of 5–10% for La and 20% for Sr. The exploration of operating conditions showed increasing C2 productivities with increasing reactant partial pressure, reaching at 800 °C values up to 1.3 × 10−5 mol (C2) s−1 g(cat)−1.  相似文献   

6.
A silica-supported Ag system made by the incipient wetness impregnation method was investigated in the reaction of heterogeneous catalytic decomposition of ozone. It was established that the catalytic ozone decomposition on Ag/SiO2 proceeded in the temperature interval −40 °C to 25 °C as a first order reaction with activation energy of 65 kJ/mol (pre-exponential factor 5.0 × 1014 s−1). Based on the results from the instrumental methods (SEM, XRD, XPS, EPR, TPD) it can be concluded that in presence of ozone the silver is oxidized to a complicated mixture of Ag2O3 and AgO. Due to the high activity and stability of the Ag/SiO2 catalyst, it is promising for neutralization of waste gases containing ozone.  相似文献   

7.
A type of Pd–ZnO catalysts supported on multi-walled carbon nanotubes (MWCNTs) were developed, with excellent performance for CO2 hydrogenation to methanol. Under reaction conditions of 3.0 MPa and 523 K, the observed turnover-frequency of CO2 hydrogenation reached 1.15 × 10−2 s−1 over the 16%Pd0.1Zn1/CNTs(h-type). This value was 1.17 and 1.18 times that (0.98 × 10−2 and 0.97 × 10−2 s−1) of the 35%Pd0.1Zn1/AC and 20%Pd0.1Zn1/γ-Al2O3 catalysts with the respective optimal Pd0.1Zn1-loading. Using the MWCNTs in place of AC or γ-Al2O3 as the catalyst support displayed little change in the apparent activation energy for the CO2 hydrogenation, but led to an increase of surface concentration of the Pd0-species in the form of PdZn alloys, a kind of catalytically active Pd0-species closely associated with the methanol generation. On the other hand, the MWCNT-supported Pd–ZnO catalyst could reversibly adsorb a greater amount of hydrogen at temperatures ranging from room temperature to 623 K. This unique feature would help to generate a micro-environment with higher concentration of active H-adspecies at the surface of the functioning catalyst, thus increasing the rate of surface hydrogenation reactions. In comparison with the “Parallel-type (p-type)” MWCNTs, the “Herringbone-type (h-type)” MWCNTs possess more active surface (with more dangling bonds), and thus, higher capacity for adsorbing H2, which make their promoting action more remarkable.  相似文献   

8.
ZnBO-doped (Ba, Sr)TiO3 ceramics were investigated for low-temperature co-fired ceramics (LTCCs) applications. Until now, B2O3 and Li2CO3 dopants have been commonly employed as the low-temperature sintering aids. In this paper, we suggest ZnBO as an alternative dopant to the B2O3 and Li2CO3. To reduce the sintering temperature of (Ba, Sr)TiO3, we have added 1–5 wt.% of ZnBO to (Ba, Sr)TiO3. ZnBO-doped (Ba, Sr)TiO3 ceramics were respectively sintered from 750 to 1350 °C by 50 °C to confirm the sintering temperature with different dopant contents. By adding 5 wt.% of ZnBO to the (Ba, Sr)TiO3 ceramics, the sintering temperature of (Ba, Sr)TiO3 ceramics can be reduced to 1100 °C. From the XRD analysis, ZnBO-doped (Ba, Sr)TiO3 has no pyro phase. By adding ZnBO dopants to (Ba, Sr)TiO3 ceramics, both of relative dielectric permittivity and loss tangent were decreased. From the frequency dispersion of dielectric properties, the relative dielectric permittivity and loss tangent of 5 wt.% ZnBO-doped (Ba, Sr)TiO3 were 1180 and 3.3 × 10−3, while those of BST were 1585 and 4.8 × 10−3, respectively.  相似文献   

9.
The two novel ion-pairs (PB-TPB and NB-TPB) of quaternary ammonium drugs; propantheline bromide (PB), N,N-Diisopropyl-N-methyl-N-[2-(xanthen-9ylcarbonyloxy)ethyl] ammonium bromide and neostigmine bromide (NB), 3-(dimethylcarbamoyloxy) phenyl]-trimethylazanium have been synthesized, respectively and incorporated in poly (vinyl chloride)-based membrane electrodes for the quantification of propantheline bromide and neostigmine bromide in different pharmaceutical preparations. The influences of membrane compositions on the potentiometric responses of membrane electrodes have been found to substantially improve the performance characteristics. The best performance was reported with membranes having composition (w/w) of PB-TPB or NB-TPB (6%): PVC (34%): o-NPOE (60%). The proposed electrodes exhibit nernstian response in the concentration ranges of 2.1 × 10−7 M to 1.0 × 10−2 M and 4.4 × 10−7 M to 1.0 × 10−2 M with detection limit of 1.5 × 10−7 M and 3.3 × 10−7 M, respectively. Both the membrane electrodes perform satisfactorily over pH ranges of (3.5–7.5 and 4.0–7.0) with fast response times (11 s and 13 s), respectively. These drugs (PB and NB) were further utilized as different ion-pairs of Prostaglandin E1 (PGE1) and Deoxycholate (DOC) in poly (vinyl chloride)-based membrane electrodes for the determination of bioavailability of Prostaglandin E1 and Deoxycholate in plasma of different patients.  相似文献   

10.
The goal of this paper was to make the link between sintering of a 1.6% Pt/Al2O3 catalyst and its activity for CO oxidation reaction. Thermal aging of this catalyst for different durations ranging from 15 min to 16 h, at 600 and 700 °C, under 7% O2, led to a shift of the platinum particle size distributions towards larger diameters, due to sintering. These distributions were studied by transmission electron microscopy. The number and the surface average diameters of platinum particles increase from 1.3 to 8.9 nm and 2.1 to 12.8 nm, respectively, after 16 h aging at 600 °C. The catalytic activity for CO oxidation under different CO and O2 inlet concentrations decreases after aging the catalyst. The light-off temperature increased by 48 °C when the catalyst was aged for 16 h at 600 °C. The CO oxidation reaction is structure sensitive with a catalytic activity increasing with the platinum particle size. To account for this size effect, two intrinsic kinetic constants, related either to platinum atoms on planar faces or atoms on edges and corners were defined. A platinum site located on a planar face was found to be 2.5 more active than a platinum site on edges or corners, whatever the temperature. The global kinetic law {r (mol m−2 s−1) = 103 × exp(−64,500/RT)[O2]0.74[CO]−0.5)} related to a reaction occurring on a platinum atom located on planar faces allows a simulation of the CO conversion curves during a temperature ramp. Modeling of the catalytic CO conversion during a temperature ramp, using the different aged catalysts, allows prediction of the CO conversion curves over a wide range of experimental conditions.  相似文献   

11.
In the present work, nano-crystalline Ce0.9Gd0.1O1.95 (GDC) powder has been successfully prepared by a novel sol–gel thermolysis method using a unique combination of urea and PVA. The gel precursor obtained during the process was calcined at 400 and 600 °C for 2 h. A range of analyzing techniques including XRD, TGA, BET, SEM, EDS and TEM were employed to characterize the physical and chemical properties of obtained powders. GDC gel precursors calcined at 400 and 600 °C were found to have an average crystallite size of 10 and 19 nm, respectively. From the result of XRD patterns, we found that well-crystalline cubic fluorite structure GDC was obtained by calcining the precursor gel at 400 and 600 °C. It has been also found that the sintered samples with lower temperature calcined powder showed better sinterability as well as higher ionic conductivity of 2.21 × 10−2 S cm−1 at 700 °C in air.  相似文献   

12.
The rate of Fischer–Tropsch synthesis over an industrial well-characterized Co–Ru/γ-Al2O3 catalyst was studied in a laboratory well mixed, continuous flow, slurry reactor under the conditions relevant to industrial operations as follows: temperature of 200–240 °C, pressure of 20–35 bar, H2/CO feed ratio of 1.0–2.5, gas hourly space velocity of 500–1500 N cm3 gcat− 1 h− 1 and conversions of 10–84% of carbon monoxide and 13–89% of hydrogen. The ranges of partial pressures of CO and H2 have been chosen as 5–15 and 10–25 bar respectively. Five kinetic models are considered: one empirical power law model and four variations of the Langmuir–Hinshelwood–Hougen–Watson representation. All models considered incorporate a strong inhibition due to CO adsorption. The data of this study are fitted fairly well by a simple LHHW form − RH2 + CO = apH20.988pCO0.508 / (1 + bpCO0.508)2 in comparison to fits of the same data by several other representative LHHW rate forms proposed in other works. The apparent activation energy was 94–103 kJ/mol. Kinetic parameters are determined using the genetic algorithm approach (GA), followed by the Levenberg–Marquardt (LM) method to make refined optimization, and are validated by means of statistical analysis. Also, the performance of the catalyst for Fischer–Tropsch synthesis and the hydrocarbon product distributions were investigated under different reaction conditions.  相似文献   

13.
In this work we develop a simple method to synthesize nanosized Ag colloids with the addition of urea which produce intermediates AgOCN and Ag2CO3 before the formation of silver. These intermediates are beneficial to obtaining high conversions of narrow size distributions of silver colloids from this synthesis process. At the molar ratio of [Urea]/[Ag+] = 4, [NaOH]/[Ag+] = 0.8, the weight ratio of PVP/AgNO3 = 1 g/g, using dextrose as a reducing agent and a reaction temperature of 70 °C, we obtain silver colloids of average size 22 nm with a standard deviation of 4.7 nm after separation and washing procedures. The conversion under these conditions was nearly complete at about 98%. After a thorough washing procedure, the purity of silver colloids is up to 94.4% and its dried film is electrically conductive at room temperature. The electrical resistivity reached 4.5 × 10−6 Ω cm after 250 °C heating for 30 min.  相似文献   

14.
The amidoximated macroporous membranes (AO membranes) were prepared by post irradiation grafting of acrylonitrile (AN) onto thermally bonded non-woven matrix of poly(propylene) sheet using electron beams. These precursor membranes were reacted with hydroxylamine to convert AN to AO groups, and conditioned by treating them with 2.5% KOH at 80°C for 1 h. The water uptake capacity in seawater, Na+-exchange capacity, and uranium loading capacity from seawater of AO membranes were found to be 200±10 wt.%, (3.1±0.2)×10−4 mol/g, and (1.60±0.18)×10−3 mol/g, respectively. The expected functional group density based on the degree of AN grafting (125 wt.%) and its subsequent conversion to AO groups (80%) was found to be 7.8×10−3 mol/g. The comparison of the expected functional group density and uranium uptake capacity seems to suggest that UO22+ forms a complex with AO groups in 1:4 proportion. The uranium could be quantitatively desorbed (>90%) from the AO membrane in Na2CO3 and mineral acids like HCl in the equilibration times of 60 min and 40 min, respectively. Alkaline conditioning was found to be necessary for reuse of the membrane equilibrated with acid. However, AO membranes equilibrated with Na2CO3 could be reused without any conditioning for uranium sorption.  相似文献   

15.
PTFE-F-PbO2 电极在H2SO4溶液中的析氧行为   总被引:1,自引:0,他引:1  
F-PbO2 electrode and polytetrafluoroethylene (PTFE) doped F-PbO2 electrode (PTFE-F-PbO2) were prepared on a plexiglas sheet substrate by a series of procedure including chemical and electrochemical depositions. The electrochemical activities of these two electrodes for oxygen evolution (OE) reaction were examined by electrochemical tests. In comparison with F-PbO2, PTFE-F-PbO2 electrode exhibited larger active surface area and higher oxygen vacancy deficiency, which resulted in its higher electrocatalytic activity for OE. In addition, both exchange current density and activation energy of the electrodes for OE were calculated in terms of active surface area. The values of exchange current density and activation energy in 0.5 mol·L^-1 H2SO4 aqueous solution were 1.125×10^ -3 mA·cm^-2 and 18.62 kJ·mol^-1 for PTFE-F-PbO2, and 8.384×10^-4 mA·cm^- 2 and 28.98 kJ·mol^-1 for F-PbO2, respectively. Because these values are calculated on the basis of the active surface areas of the electrodes, the enhanced activity of PTFE-F-PbO2 can be attributed to an increase in oxygen vacancy deficiency of PbO2 due to doping by PTFE. The influence of PTFE adulteration on the activity of PbO2 film electrode for OE was investigated in detail in this study.  相似文献   

16.
The electrodeposition of silver from a nitrate bath can be improved by lowering the temperature and by the addition of ethyleneglycol as anti-freeze. When the bath temperature is lowered below 0°C, the dendritic silver deposition is suppressed and a smooth surface is obtained; at −30°C a very finegrained deposit results. The dendritic growth is supposedly prohibited partly by the lowering of temperature and to a less extent by the adsorption of ethyleneglycol at the surface both of which might enhance the activation overvoltage of silver deposition. From the polarisation measurement in, 0·25 M AgNO3 electrolytes, the exchange current density of Ag deposition was evaluated as 1·70 × 10−2 A/cm2(25°C) and with 50 vol. per cent ethyleneglycol, 9·72 × 10−4 A/cm2 (25°C) and 1·22 × 10−5 A/cm2 (−32°C). Adsorption of ethyleneglycol on Ag cathode was discussed by differential capacitance change.  相似文献   

17.
Highly organized (3-mercaptopropyl)trimethoxysilane (3-MPT) films have been prepared via self-assembled coupled with sol–gel linking technology. Horseradish peroxidase (HRP) is successfully immobilized onto the densely packed three-dimensional (3D) 3-MPT network and the direct electrochemistry of HRP is achieved without any electron mediators or promoters. Redox thermodynamics of HRP on the 3-MPT films, which is obtained from the temperature dependence of the reduction potential, suggests that the positive shift of redox potentials of HRP at the interface of 3-MPT originates from the solvent reorganization effects and conformational change of the polypeptide chain of HRP. Based on the direct electrochemistry and electrocatalytic ability of HRP, a sensitive third-generation amperometric H2O2 biosensor is developed with two linear dependence ranges of 5.0 × 10−7 to 1.0 × 10−4 and 1.0 × 10−4 to 2.0 × 10−2 mol L−1.  相似文献   

18.
The solubility of highly selective and potent third-generation aromatase inhibitors includes the non-steroidal agents letrozole and anastrozole and the steroid exemestane in supercritical carbon dioxide (SC-CO2) has been investigated. The experiments were carried out using the simple and static method at pressures in the range of 12.1–35.5 MPa and temperatures ranging from 308 to 348 K. The mole fraction solubilities ranged from 0.22 × 10−5 to 1.88 × 10−4. Solubility data were correlated using six empirical models (Chrastil model, dV–A model, K–J model, Bartle model, Yu model and Gordillo model). The results showed that these models can be applied to satisfactory solubility predictions at different pressures and temperatures. A comparison among the six models revealed that the K–J, and Gordillo models gave much better correlations of the solubility data with an average absolute relative deviation (AARD%) ranging from 0.2 to 2.3 and from 1.6 to 2.5%, respectively. Using the correlation results, the heat of drug–CO2 solvation and that of drug vaporization was separately approximated in the range of −17.3 to −17.5 and 93.0–112.1 kJ mol−1.  相似文献   

19.
Catalytic gasification of waste motor oil (MO) for the generation of high purity of hydrogen and then integrated to a proton exchange membrane fuel cell (PEMFC) is economically and environmentally attractive. Thus, the objective of the present work was to investigate a MO catalytic gasification for generating high-purity hydrogen with 15 wt.% NiO/Al2O3 catalysts. In a lab-scale fixed-bed downdraft experimental approach, catalytic gasification of MO was accompanied by a substantial production of syngas at 760–900 K. From the XANES spectra, most of the Ni(II) reduced to Ni(0) was found in the MO catalytic gasification process. The EXAFS data also showed that the central Ni atoms have a Ni–O and a Ni–Ni with bond distances of 2.04 ± 0.05 Å and 2.48 ± 0.05 Å, respectively. In addition to over 85% of syngas generation, approximately 8.35 × 105 kcal h−1 of thermal energy was recovered and cold gas efficiency (CGE) was 77–84% when the catalytic gasifier was operated at O/C atomic ratios between 1.1 and 1.3. The proposed syngas production unit can be integrated in a fuel processor (e.g. PEMFC), in order to separate and purify the syngas to yield a 99.99% hydrogen stream. Moreover, cost or benefit analyses of MO catalytic gasifiers of 10- and 20-TPD (tons per day) were also performed.  相似文献   

20.
Layered double hydroxides CuxZn6 − xCr2(OH)16(CO3)·4H2O with different molar ratios of Cu/Zn/Cr were synthesized by accelerated carbonation. The products were characterized by XRD, SEM, FT-IR and TG-DTG-DSC-MS. The chemical stability was tested by the modified Toxicity Characteristic Leaching Procedure (TCLP). The results showed that the products were the mixture of CuxZn6 − xCr2(OH)16(CO3)·4H2O and (CuZn)2(CO3)(OH)2, with similar thermal behavior. All products were chemically stable with reduced leaching at pH > 6 (Cu2+, Zn2+) or > 5 (Cr3+).  相似文献   

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