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1.
TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyl) is electrochemically oxidized to a stable form of the cation (TEMPO+) in acetonitrile (CH3CN) or 1-butyl-3-methyl-imidazolium hexafluorophosphate ([BMIm][PF6]) media. Cyclic voltammograms were characterized by a well-defined one-electron reversible redox couple in both media at low scan rates. The reduced form of TEMPO+ is catalytically regenerated in a follow-up chemical reaction with benzyl alcohol (BA) in the presence of 2,6-lutidine. It was observed that in [BMIm][PF6], the redox currents are largely suppressed compared to that in CH3CN. The apparent heterogeneous electron-transfer rate constant () of the quasi-reversible redox reaction of TEMPO was determined at a Pt electrode and found to be 1.9 × 10−3 cm s−1 and 4.5 × 10−2 cm s−1 in [BMIm][PF6] and CH3CN, respectively. With the aid of chronoamperometry (CA), the homogeneous rate constant for the catalytic oxidation of benzyl alcohol by TEMPO, in the presence of 2,6-lutidine in CH3CN was estimated to be 5.53 × 101 M−1 s−1 which is approximately double, relative to the value of 2.91 × 101 M−1 s−1 determined in [BMIm][PF6].  相似文献   

2.
S. Zhang  C. Deng  B.L. Fu  L. Ma 《Powder Technology》2010,198(3):373-400
A carbonate co-precipitation method was employed to prepare spherical Li[Ni1/3Co1/3Mn1/3]O2 cathode material. The precursor, [Ni1/3Co1/3Mn1/3]CO3, was prepared using ammonia as chelating agent under CO2 atmosphere. The spherical Li[Ni1/3Co1/3Mn1/3]O2 was prepared by mixing the precalcined [Ni1/3Co1/3Mn1/3]CO3 with LiOH followed by high temperature calcination. The preparation conditions such as ammonia concentration, co-precipitation temperature, calcination temperature and Li/[Ni1/3Co1/3Mn1/3] ratio were varied to optimize the physical and electrochemical properties of the prepared Li[Ni1/3Co1/3Mn1/3]O2. The structural, morphological, and electrochemical properties of the prepared LiNi1/3Co1/3Mn1/3O2 were characterized by XRD, SEM, and galvanostatic charge-discharge cycling. The optimized material has a spherical particle shape and a well ordered layered structure, and it also has an initial discharge capacity of 162.7 mAh g− 1 in a voltage range of 2.8-4.3 V and a capacity retention of 94.8% after a hundred cycles. The optimized ammonia concentration, co-precipitation temperature, calcination temperature, and Li/[Ni1/3Co1/3Mn1/3] ratio are 0.3 mol L− 1, 60 °C, 850 °C, and 1.10, respectively.  相似文献   

3.
Ni modified K2CO3/MoS2 catalyst was prepared and the performance of higher alcohol synthesis catalyst was investigated under the conditions: T = 280–340 °C, H2/CO (molar radio) = 2.0, GHSV = 3000 h 1, and P = 10.0 MPa. Compared with conventional K2CO3/MoS2 catalyst, Ni/K2CO3/MoS2 catalyst showed higher activity and higher selectivity to C2+OH. The optimum temperature range was 320–340 °C and the maximum space-time yield (STY) of alcohol 0.30 g/ml h was obtained at 320 °C. The selectivity to hydrocarbons over Ni/K2CO3/MoS2 was higher, however, it was close to that of K2CO3/MoS2 catalyst as the temperature increased. The results indicated that nickel was an efficient promoter to improve the activity and selectivity of K2CO3/MoS2 catalyst.  相似文献   

4.
Calcium-carbonate powders were coprecipitated with Al3+ and then decomposed in air and/or under a CO2 flux between 590 °C and 1150 °C. The data were analysed using a consecutive-decomposition-dilatometer method and the kinetic results were discussed according to the microstructure analysis done by N2 adsorption isotherms (78 K), SEM and FT-IR measurements. Below 1000 °C, CaCO3 particle thermal-decomposition was pseudomorphic, resulting in the formation of a CaO grain porous network. When the CaO grains were formed, the Al3+ diffused among them, producing AlO4 groups that promoted the CaO grain coarsening and reduced O2− surface sites available to CO2 adsorbed molecules to form CO32−. In pure CaO, CO32− diffused through the grain boundary, enhancing Ca2+ and O2− mobility; AlO4 groups reduced CO32− penetration and CaO sintering rate. Above 1000 °C, the sintering rate of the doped samples exceeded that of the undoped, likely because of Al3+ diffusion in CaO and viscous flow.  相似文献   

5.
Layered metastable lithium manganese oxides, Li2/3[Ni1/3−xMn2/3−yMx+y]O2 (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na2/3[Ni1/3−xMn2/3−yMx+y]O2 precursors. The Al and Co doping produced the T#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni1/3−xMn2/3−yMx+yO2 slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T#2-Li2/3[Ni1/3Mn2/3]O2 were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g−1 in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g−1 along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T#2 into the O2 structure was observed during the initial lithium deintercalation.  相似文献   

6.
Carbon coated Li3V2(PO4)3 cathode material was prepared by a poly(vinyl alcohol) (PVA) assisted sol-gel method. PVA was used both as the gelating agent and the carbon source. XRD analysis showed that the material was well crystallized. The particle size of the material was ranged between 200 and 500 nm. HRTEM revealed that the material was covered by a uniform surface carbon layer with a thickness of 80 Å. The existence of surface carbon layer was further confirmed by Raman scattering. The electrochemical properties of the material were investigated by charge-discharge cycling, CV and EIS techniques. The material showed good cycling performance, which had a reversible discharge capacity of 100 mAh g−1 when cycled at 1 C rate. The apparent Li+ diffusion coefficients of the material ranged between 9.5 × 10−10 and 0.9 × 10−10 cm2 s−1, which were larger than those of olivine LiFePO4. The large lithium diffusion coefficient of Li3V2(PO4)3 has been attributed to its special NASICON-type structure.  相似文献   

7.
Spherical (Ni0.5Mn0.5)(OH)2 with different secondary particle size (3 μm, 10 μm in diameter) was synthesized by co-precipitation method. Mixture of the prepared hydroxide and lithium hydroxide was calcined at 950 °C for 20 h in air. X-ray diffraction patterns revealed that the prepared material had a typical layered structure with space group. Spherical morphologies with mono-dispersed powders were observed by scanning electron microscopy. It was found that the layered Li[Ni0.5Mn0.5]O2 delivered an initial discharge capacity of 148 mAh g−1 (3.0-4.3 V) though the particle sizes were different. Li[Ni0.5Mn0.5]O2 having smaller particle size (3 μm) showed improved area specific impedance due to the reduced Li+ diffusion path, compared with that of Li[Ni0.5Mn0.5]O2 possessing larger particle size (10 μm). Although the Li[Ni0.5Mn0.5]O2 (3 μm) was electrochemically delithiated to Li0.39[Ni0.5Mn0.5]O2, the resulting exothermic onset temperature was around 295 °C, of which the value is significantly higher than that of highly delithiated Li1−δCoO2 (∼180 °C).  相似文献   

8.
Anhydrous proton-conducting inorganic-organic hybrid membranes were prepared by sol-gel process with tetramethoxysilane/methyl-trimethoxysilane/trimethylphosphate and 1-ethyl-3-methylimidazolium-bis (trifluoromethanesulfonyl) imide [EMI][TFSI] ionic liquid as precursors. These hybrid membranes were studied with respect to their structural, thermal, proton conductivity, and hydrogen permeability properties. The Fourier transform infrared spectroscopy (FT-IR) and 31P, 1H, and 13C nuclear magnetic resonance (NMR) measurements have shown good chemical stability, and complexation of PO(OCH3)3 with [EMI][TFSI] ionic liquid in the studied hybrid membranes. Thermal analysis including TG and DTA confirmed that the membranes were thermally stable up to 330 °C. Thermal stability of the hybrid membranes was significantly enhanced by the presence of inorganic SiO2 framework and high stability of [TFSI] anion. The effect of [EMI][TFSI] ionic liquid addition on the microstructure of the membranes was studied by scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) micrographs and no phase separation at the surfaces of the prepared membranes was observed and also homogeneous distribution of all elements was confirmed. Proton conductivity of all the prepared membranes was measured from −20 °C to 150 °C, and high conductivity of 5.4 × 10−3 S/cm was obtained for 40 wt% [EMI][TFSI] doped 40TMOS-50MTMOS-10PO(OCH3)3 (mol%) hybrid membrane, at 150 °C under anhydrous conditions. The hydrogen permeability was found to decrease from 1.61 × 10−11 to 1.39 × 10−12 mol/cm s Pa for 40 wt% [EMI][TFSI] doped hybrid membrane as the temperature increases from 20 °C to 150 °C. For 40 wt% [EMI][TFSI] doped hybrid membrane, membrane electrode assemblies were prepared and a maximum power density value of 0.22 mW/cm2 at 0.47 mA/cm2 as well as a current density of 0.76 mA/cm2 were obtained at 150 °C under non-humidified conditions when utilized in a H2/O2 fuel cell.  相似文献   

9.
A monolayer of Keggin-type heteropolyanion [SiNi(H2O)W11O39]6− was fabricated by electrodepositing [SiNi(H2O)W11O39]6− on cysteamine modified gold electrode. The monolayer of [SiNi(H2O)W11O39]6− modified gold electrode was characterized by atomic force microscopy (AFM) and electrochemical method. AFM results showed the [SiNi(H2O)W11O39]6− uniformly deposited on the electrode surface and formed a porous monolayer. Cyclic voltammetry exhibited one oxidation peak and two reduction peaks in 1.0 M H2SO4 in the potential range of −0.2 to 0.7 V. The constructed electrode could exist in a large pH (0-7.6) range and showed good catalytic activity towards the reduction of bromate anion (BrO3) and nitrite (NO2), and oxidation of ascorbic acid (AA) in acidic solution. The well catalytic active of the electrode was ascribed to the porous structure of the [SiNi(H2O)W11O39]6 monolayer.  相似文献   

10.
In order to get homogeneous layered oxide Li[Ni1/3Mn1/3Co1/3]O2 as a lithium insertion positive electrode material, we applied the metal acetates decomposition method. The oxide compounds were calcined at various temperatures, which results in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni1/3Mn1/3Co1/3]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry and SEM. XRD experiment revealed that the layered Li[Ni1/3Mn1/3Co1/3]O2 material can be best synthesized at temperature of 800 °C. In that synthesized temperature, the sample showed high discharge capacity of 190 mAh g−1 as well as stable cycling performance at a current density of 0.2 mA cm−2 in the voltage range 2.3-4.6 V. The reversible capacity after 100 cycles is more than 190 mAh g−1 at room temperature.  相似文献   

11.
Various ionic liquids (ILs) were prepared via metathesis reaction from two kinds of 1-(2-hydroxyethyl)-3-methyl imidazolium ([HEMIm]+) and N-(2-hydroxyethyl)-N-methyl morphorinium ([HEMMor]+) cations and three kinds of tetrafluoroborate ([BF4]), bis(trifluoromethanesulfonyl)imide ([TFSI]) and hexafluorophosphate ([PF6]) anions. All the [HEMIm]+ derivatives were in a liquid state at room temperature. In particular, [HEMIm][BF4] and [HEMIm][TFSI] showed no possible melting point from −150 °C to 200 °C by DSC analysis, and their high thermal stability until 380-400 °C was verified by TGA analysis. Also, their stable electrochemical property (electrochemical window of more than 6.0 V) and high ionic conductivity (0.002-0.004 S cm−1) further confirm that the suggested ILs are potential electrolytes for use in electrochemical devices. Simultaneously, the [HEMMor]+ derivatives have practical value in electrolyte applications because of their easy synthesis procedures, cheap morpholinium cation sources and possibilities of high Li+ mobility by oxygen group in the morpholinium cation. However, [HEMMor]+ derivatives showing high viscosity usually had lower ionic conductivities than [HEMIm]+ derivatives.  相似文献   

12.
The solubility of CO2 in saturated polyester resins at different temperatures (306 and 343 K) and pressures (0.1-30 MPa) has been measured using a magnetic suspension balance. The solubility data were used for estimating the binary diffusion coefficients. The results show a good solubility of CO2 in polymers, up to 0.64 g CO2/g polymer. The diffusion coefficients of supercritical CO2 in polymers have generally high values and are in the range from 0.156 × 10−8 to 10.38 × 10−8 cm2/s. DSC and XRD analyses of the semi-crystalline polymer samples indicate that amorphous degree of polymers after exposure to CO2 is increased. The observed structural effects are dependent on pressure, temperature and time of exposure to CO2.  相似文献   

13.
Hui Xia  M.O. Lai 《Electrochimica acta》2009,54(25):5986-5991
Kinetic and transport parameters of Li ion during its extraction/insertion into thin film LiNi0.5Mn0.5O2 free of binder and conductive additive were provided in this work. LiNi0.5Mn0.5O2 thin film electrodes were grown on Au substrates by pulsed laser deposition (PLD) and post-annealed. The annealed films exhibit a pure layered phase with a high degree of crystallinity. Surface morphology and thin film thickness were investigated by field emission scanning electron microscopy (FESEM). The charge/discharge behavior and rate capability of the thin film electrodes were investigated on Li/LiNi0.5Mn0.5O2 cells at different current densities. The kinetics of Li diffusion in these thin film electrodes were investigated by cyclic voltammetry (CV) and galvanostatic intermittent titration technique (GITT). CV was measured between 2.5 and 4.5 V at different scan rates from 0.1 to 2 mV/s. The apparent chemical diffusion coefficients of Li in the thin film electrode were calculated to be 3.13 × 10−13 cm2/s for Li intercalation and 7.44 × 10−14 cm2/s for Li deintercalation. The chemical diffusion coefficients of Li in the thin film electrode were determined to be in the range of 10−12-10−16 cm2/s at different cell potentials by GITT. It is found that the Li diffusivity is highly dependent on the cell potential.  相似文献   

14.
Sen Zhang 《Electrochimica acta》2007,52(25):7337-7342
Li[Ni1/3Co1/3Mn1/3]O2 cathode material for lithium ion batteries was prepared by mixing metal hydroxide, (Ni1/3Co1/3Mn1/3)(OH)2, with 6% excess LiOH followed by calcinations. The (Ni1/3Co1/3Mn1/3)(OH)2 with secondary particle of about 12 μm was prepared by hydroxide co-precipitation. The tap density of the obtained Li[Ni1/3Co1/3Mn1/3]O2 powder was 2.56 ± 0.21 g cm−3. The powder was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), particle size distribution (PSD) and galvanostatic charge-discharge cycling. The XRD pattern of Li[Ni1/3Co1/3Mn1/3]O2 revealed a well ordered hexagonal layered structure with low cation mixing. Secondary particles with size of 13-14 μm and primary particles with size of about 1 μm can be identified from the SEM observations. In the voltage range of 2.8-4.3 V, the initial discharge capacity of the Li[Ni1/3Co1/3Mn1/3]O2 electrode was 166.6 mAh g−1, and 96.5% of the initial capacity was retained after 50 charge-discharge cycling.  相似文献   

15.
The structures, vibrational frequencies, infrared and Raman intensities of hexafluorophosphate anion (PF6) and M+PF6 (M+ = Li+, Na+, K+, Rb+ and Cs+) ion pairs have been studied by ab initio calculations. It is shown that the tridentate coordination of cation by PF6 is the most stable structure in gas phase. The vibrational spectroscopies of the most stable geometries were calculated and the changes in band position were used to probe the ion associations.  相似文献   

16.
Indium oxide (In2O3) microspheres with hollow interiors have been prepared by a facile implantation route which enables indium ions released from indium-chloride precursors to implant into nonporous polymeric templates in C2Cl4 solvent. The templates are then removed upon calcination at 500 °C in air atmosphere, forming hollow In2O3 particles. Specific surface area (0.5-260 m2 g−1) and differential pore volume (7 × 10−9 to 3.8 × 10−4 m3 g−1 Å−1) of the hollow particles can be tailored by adjusting the precursor concentration. For the hollow In2O3 particles with high surface area (260 m2 g−1), an enhanced photocatalytic efficiency (up to ∼one-fold increase) against methylene blue (MB) dye is obtained under UV exposure for the aqueous In2O3 colloids with a dilute solids concentration of 0.02 wt.%.  相似文献   

17.
Micro-spherical particle of MnCO3 has been successfully synthesized in CTAB-C8H18-C4H9OH-H2O micro-emulsion system. Mn2O3 decomposed from the MnCO3 is mixed with Li2CO3 and sintered at 800 °C for 12 h, and the pure spinel LiMn2O4 in sub-micrometer size is obtained. The LiMn2O4 has initial discharge specific capacity of 124 mAh g−1 at discharge current of 120 mA g−1 between 3 and 4.2 V, and retains 118 mAh g−1 after 110 cycles. High-rate capability test shows that even at a current density of 16 C, capacity about 103 mAh g−1 is delivered, whose power is 57 times of that at 0.2 C. The capacity loss rate at 55 °C is 0.27% per cycle.  相似文献   

18.
A composite of Sc2W3O12/Cu where Sc2W3O12, the core, is coated by the Cu shell was synthesized using simple electroless plating method. As-prepared Sc2W3O12/Cu composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and thermomechanical analyzer (TMA) techniques. The study results show that the Pd-Sn activator was successfully formed on the surface of Sc2W3O12 after the sensitization and activation. In the electroless plating process, Cu nanocrystals formed firstly, and then grew together to form a continuous coating. Sc2W3O12/Cu core-shell composites exhibit a negative linear coefficient of thermal expansion CTE = −4.47 × 10−6 °C−1 from room temperature to 200 °C.  相似文献   

19.
In this work, 3% Ru-Al2O3 and 2% Rh-CeO2 catalysts were synthesized and tested for CH4-CO2 reforming activity using either CO2-rich or CO2-lean model biogas feed. Low carbon deposition was observed on both catalysts, which negligibly influenced catalytic activity. Catalyst deactivation during temperature programmed reaction was observed only with Ru-Al2O3, which was caused by metallic cluster sintering. Both catalysts exhibited good stability during the 70 h exposure to undiluted equimolar CH4/CO2 gas stream at 750 °C. By varying residence time in the reactor during CH4-CO2 reforming, very similar quantities of H2 were consumed for water formation. Reverse water-gas shift (RWGS) reaction occurred to a very similar extent either with low or high WHSV values over both catalysts, revealing that product gas mixture contained near RWGS equilibrium composition, confirming the dominance of WGS reaction and showing that shortening the contact time would actually decrease the H2/CO ratio in the syngas produced by CH4-CO2 reforming, as long as RWGS is quasi equilibrated. H2/CO molar ratio in the produced syngas can be increased either by operating at higher temperatures, or by using a feed stream with CH4/CO2 ratio well above 1.  相似文献   

20.
Multinegatively charged metal complex, hexacyanoferrate ([Fe(CN)6]4−), was electrostatically trapped in the cationic polymer film of N,N-dimethylaniline (PDMA) which was electrochemically deposited on the boron-doped diamond (BDD) electrode by controlled-potential electro-oxidation of the monomer. This ferrocyanide-trapped PDMA film was used to catalyze the oxidation of ascorbic acid (AA). Increase in the oxidation current response with a negative shift of the anodic peak potential was observed at the cationic PDMA film-coated BDD (PDMA|BDD) electrode, compared with that at the bare BDD electrode. A more drastic enhancement in the oxidation peak current as well as more negative shift of oxidation potential was found at the ferrocyanide-trapped PDMA film-coated BDD ([Fe(CN)6]3−/4−|PDMA|BDD) electrode. This [Fe(CN)6]3−/4−|PDMA|BDD electrode can be used as an amperometric sensor of AA. Ferrocyanide, electrostatically trapped in the polymer film shows more electrocatalytic activity than that coordinatively attached to the polymer film or dissolved in the solution phase. The electrocatalytic current depends on the surface coverage of ferricyanide, ΓFe, within the polymer film. Diffusion coefficient (D) of AA in the solution was estimated by rotating disk electrode voltammetry: D = (5.8 ± 0.3) × 10−6 cm2 s−1. The second-order rate constant for the catalytic oxidation of AA by ferricyanide was also estimated to be 9.0 × 104 M−1 s−1. In the hydrodynamic amperometry using the [Fe(CN)6]3−/4−|PDMA|BDD electrode, a successive addition of 1 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.233 μA cm−2 μM−1.  相似文献   

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