共查询到20条相似文献,搜索用时 31 毫秒
1.
Magnetic field effects in electrochemical reactions 总被引:1,自引:0,他引:1
The influence of an external magnetic field B on the electrochemical behaviour of the systems Cu2+/Cu, Ni2+/Ni, and [IrCl6]2−/[IrCl6]3− has been studied. In the case of Cu depositions in an electrochemical cell with a large ratio of the electrode area and the cell volume the increase of the limiting current density with B can be explained with the interplay of natural convection and the Lorentz force acting on the resulting flow profile (magneto hydrodynamic or MHD effect). Ni depositions also show an MHD effect as well as a tendency to form more fine grained material in the presence of a magnetic field. The results on the homogeneous redox system [IrCl6]2−/[IrCl6]3− at 50 μm diameter micro electrodes are in qualitative agreement with recently proposed relationships to describe the influence of a B field on the limiting current density. 相似文献
2.
The α- and γ-phases of MnO2 prepared by electrolysis of MnSO4 and MxSO4 (where M = Li+, Na+, K+, Rb+, Cs+ or Mg2+) in aqueous solutions at various pH and voltage Ev values under ambient conditions have been systematically studied. The structures of powdery MnO2 produced are found to depend on the radius of the Mz+ counter cation in addition to the pH and Ev conditions. In order to achieve the α-phase for MnO2 formation under neutral pH condition, the radius of counter cation must be equal to or greater than 1.41 Å, the size of the K+ cation. The relative concentration ratio of [MnO4−]transient/[Mn2+], which is related to the pH-Ev conditions, also affects the structure of MnO2 produced with counter ions smaller than K+. For samples prepared in acidified solution with the counter ions of Li+, Na+ or Mg2+ at 2.2 V, the electrolysis products display the γ-MnO2 phase while those prepared at 2.8 V electrolysis produce a mixture of γ-MnO2 and α-MnO2 phases. Single phase of α-MnO2 is identified in the 5 V electrolysis products. Furthermore, the valence state of manganese was found to decrease as the applied voltage was reduced from 5.0 to 2.2 V. This implies that the lower [MnO4−]transient/[Mn2+] ratio or the less oxidative condition is responsible for the non-stoichiometric MnO2 structure with oxygen deficiency. 相似文献
3.
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
4.
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
5.
6.
Local dissolution/deposition processes under in situ scanning tunneling microscopy (STM) imaging conditions are studied in the systems Ag(111)/Ag+, ClO4− and Ag(111)/Ag+, SO42−. The results show that in both systems the local kinetics of these processes strongly depend on the polarization conditions. At STM-tip potentials more positive than the Ag/Ag+ equilibrium potential, a local dissolution of the Ag(111) substrate is observed even at cathodic substrate overpotentials at which the overall substrate current density is cathodic. This tip-induced Ag dissolution is in agreement with results obtained recently in the system Cu(111)/Cu2+. The enhanced local Ag dissolution is explained by a reduced Ag+ concentration underneath the STM tip promoted by both an electrostatic repulsion of Ag+ and a reduction of the mass transport due to the shielding effect of the tip. The possibility for a preparation of negative Ag nanostructures by STM tip-induced electrochemical dissolution is demonstrated. 相似文献
7.
Improvement in both sensor's characteristics and antifouling resistance has been achieved by utilising Cu2O as a dopant to the sub-micron-sized RuO2 sensing electrode (SE) of the water quality sensors. 20 mol% Cu2O-doped RuO2-SE has exhibited a linear response to dissolved oxygen (DO) between 0.5 and 8.0 ppm at various temperatures with the sensitivity slope of −46 mV/decade. This paper describes the structural properties and characteristics of thin-film Cu2O-doped RuO2-SE subjected to a field trial in sewerage environment for three months. Selectivity measurements revealed that the presence of PO43−, SO42−, Ca2+, Mg2+, Li+, NO3−, F−, Na+, K+ and Cl− in the test solution had no significant effect on the sensor's emf. Long-term stability test in harsh sewerage environment demonstrated that the Cu2O-doped RuO2-SE possesses improved antifouling resistance compared to RuO2-SE. Morphology and crystalline structure of Cu2O-doped RuO2-SE were studied by scanning electron microscopy (SEM), X-ray diffraction (XRD) technique and Raman spectroscopy. 相似文献
8.
Evolution of the local structure and electrochemical properties of spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5)
A series of Ni substituted spinel LiNixMn2−xO4 (0 ≤ x ≤ 0.5) have been synthesized to study the evolution of the local structure and their electrochemical properties. X-ray diffraction showed a few Ni cations moved to the 8a sites in heavily substituted LiNixMn2−xO4 (x ≥ 0.3). X-ray photoelectron spectroscopy confirmed Ni2+ cations were partially oxidized to Ni3+. The local structures of LiNixMn2−xO4 were studied by analyzing the and A1g Raman bands. The most compact [Mn(Ni)O6] octahedron with the highest bond energy of Mn(Ni)O was found for LiNi0.2Mn1.8O4, which showed a Mn(Ni)O average bond length of 1.790 Å, and a force constant of 2.966 N cm−1. Electrolyte decomposition during the electrochemical charging processes increased with Ni substitution. The discharge capacities at the 4.1 and 4.7 V plateaus obeyed the linear relationships with respect to the Ni substitution with the slopes of −1.9 and +1.9, which were smaller than the theoretical values of −2 and +2, respectively. The smaller slopes could be attributed to the electrochemical hysteresis and the presence of Ni3+ in the materials. 相似文献
9.
Separation performance of a nanofiltration membrane influenced by species and concentration of ions 总被引:1,自引:0,他引:1
Nanofiltration (NF), which has been largely developed over the past decade, is a promising technology for the treatment of organic and inorganic pollutants in surface and ground waters. The ESNA 1 membrane from the Nitto Denko Corporation of Japan is made of aromatic polyamide, which provides salt rejection from 50% to 90%. In this paper permeation experiments of aqueous solutions of five chlorides (NH4Cl, NaCl, KCl, MgCl2 and CaCl2), three nitrates (NaNO3, Mg(NO3)2 and Ca(NO3)2), and three sulfates (NH4)2SO4, Na2SO4 and MgSO4) were carried out. The effects of species and concentration of salts on the separation performance of the ESNA 1 membrane were investigated. The experimental results showed that the rejection to most salts by the ESNA 1 membrane decreased with the growth of the concentration. Then, the reflection coefficient and solute permeability of ESNA 1 membrane were calculated by the Spiegler-Kedem equation from experimental data. The reflection coefficients of the ESNA 1 membrane to salts are all above 0.95. The salt permeabilities, except for magnesium and calcium salts, increased with the growth of concentration. The sequence of rejection to anions by the ESNA 1 membrane is R(SO2−4) > R(Cl−) > R(NO−3) at the same concentration which ranges from 10 mol/m3 to 100 mol/m3. The sequence of rejection to anions by the ESNA 1 membrane can be written as follows: R(Na+) > R(K+) > R(Mg2+) > R(Ca2+) at 10 mol/m3 concentration and R(Mg2+) > R(Ca2+) > R(Na+) > R(K+) at 100 mol/m3 concentration. 相似文献
10.
Cubic and orthorhombic crystals of tricalcium aluminate doped with Na2O, Fe2O3 and SiO2 were prepared and examined using an electron probe microanalyzer. The cationic ratios based on six oxygen atoms were derived from the oxide compositions. These data, together with those in previous studies for clinker aluminates containing Mg2+ and K+, provided excellent correlations between Al+Fe and Si (Al+Fe=2.001−1.03Si) and Ca+Mg and Na+K+Si [Ca+Mg=3.006−0.51(Na+K+Si)]. The chemical variation that is constrained by these equations is well accounted for by the general formula (Na,K)2x(Ca,Mg)3−x−y[(Al,Fe)1−ySiy]2O6, where x is the amount of Ca substituted by Na and K (0≤x<0.158), and y is the amount of Al substituted by Si (0≤y<0.136). The crystal system changed from cubic to orthorhombic with increasing x value. The substitution of Si and Fe for Al extended the solid solution range of the orthorhombic phase to lower values of x, while its effect on the solid solution range of the cubic phase was reversed. 相似文献
11.
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
12.
Hong-Bo Han Shao-Wei Feng Wen-Fang Feng Jin Nie Hong Li Hajime Matsumoto Zhi-Bin Zhou 《Electrochimica acta》2010,55(23):7134-10666
New functionalized ionic liquids (ILs), comprised of multi-methoxyethyl substituted quaternary ammonium cations (i.e. [N(CH2CH2OCH3)4−n(R)n]+; n = 1, R = CH3OCH2CH2; n = 1, R = CH3, CH2CH3; n = 2, R = CH3CH2), and two representative perfluorinated sulfonimide anions (i.e. bis(fluorosulfonyl)imide (FSI−) and bis(trifluoromethanesulfonyl)imide (TFSI−)), were prepared. Their fundamental properties, including phase transition, thermal stability, viscosity, density, specific conductivity and electrochemical window, were extensively characterized. These multi-ether functionalized ionic liquids exhibit good capability of dissolving lithium salts. Their binary electrolytes containing high concentration of the corresponding lithium salt ([Li+] >1.6 mol kg−1) show Li+ ion transference number (tLi+) as high as 0.6-0.7. Their electrochemical stability allows Li deposition/stripping realized at room temperature. The desired properties of these multi-ether functionalized ionic liquids make them potential electrolytes for Li (or Li-ion) batteries. 相似文献
13.
FTIR spectroscopy was used to identify the oxochloride species of tantalum(V) in ionic liquids and to confirm the correlations between their presence in electrolytes and the changes in the route of electrochemical reduction of tantalum(V). Electrochemical behaviour of the mixtures (x)1-butyl-1-methyl-pyrrolidinium chloride-(1 − x)TaCl5 at x = 0.80, 0.65, and 0.40 was investigated over the temperature range 90-160 °C with respect to the electrochemical deposition of tantalum and was discussed in terms of spectroscopic data. The mechanism of electrochemical reduction of tantalum(V) in the basic and acidic electrolytes depends strongly on the structure and composition of the electro active species of tantalum(V) defined by the molar composition of ionic liquids and on the competition between tantalum(V) chloride and oxochloride species. In the basic mixture at x = 0.80, with octahedral [TaCl6]− ions as the electrochemically active species only the first reduction step Ta5+ → Ta4+ at −0.31 V was observed. The competitive reduction of tantalum(V) oxochloride species occurs at more anodic potential (−0.01 V) than the reduction of the chloride complexes and can restrict the further reduction of tantalum(IV). In the basic ionic liquid at x = 0.65, the cyclic voltammograms exhibit reduction peaks at −0.31 V and −0.51 V attributed to the diffusion controlled process as [TaCl6]− + e− → [TaCl6]2− and [TaCl6]2− + e− → [TaCl6]3−. The further irreversible reduction of tantalum(III) to metallic state may occur at −2.1 V. In the acidic ionic liquids, at x = 0.40 the electrochemical reduction of two species occurs, TaCl6− and Ta2Cl11− and it is limited by two electron transfer for both of them at −0.3 V and −1.5 V, respectively. 相似文献
14.
Masoud Ghanei-Motlagh Mohammad Ali Taher Vahid Saheb Maryam Fayazi Iran Sheikhshoaie 《Electrochimica acta》2011,56(15):5376
A novel ion-selective poly(vinyl chloride) (PVC) membrane sensor for Cu2+ ions based on N,N′-(2,2-dimethylpropane-1,3-diyl)-bis(dihydroxyacetophenone) (NDHA) as a new ionophore was prepared and studied. The best performance was observed for the membrane composition, including 30:65:1:4 (wt%) = PVC:DBP:KTpClPB:NDHA. The electrode showed a good Nernstian slope of 30.0 ± 0.5 mV/decade in a wide linear range activity of 3.0 × 10−7 to 1.0 × 10−2 mol dm−3 Cu(NO3)2 with limit of detection 2.5 × 10−7. Sensor exhibited a fast response time (t95% < 10 s) and could be used for about 4 months in the pH range of 3.0–7.4. The proposed potentiometric sensor was found to work satisfactorily in partially non-aqueous media up to 30 (vol%) content of methanol, ethanol and acetone. Applications of this electrode for the determination of copper in real samples, and as an indicator electrode for potentiometric titration of Cu2+ ion using EDTA, were reported. In order to predict the extraction ability of NDHA for different metallic ions, the complexes [M(NDHA)] and [M(H2O)6] (where M = Cu2+, Co2+, Hg2+, Pb2+, Ag+, Mg2+, Ca2+, Mn2+, Zn2+, Cd2+, K+ and Al3+) were investigated using ab initio theoretical calculations. The metal binding capability was evaluated using the binding energy. Results of our study could be useful for prediction of the extraction power of this Schiff base and could play a guiding role in planning experiments. 相似文献
15.
Amorphous LiCoO2 thin films were deposited on the NASICON-type glass ceramics, Li1+x+yAlxTi2−xSiyP3−yO12 (LATSP), by radio frequency (RF) magnetron sputtering below 180 °C. The as-deposited LiCoO2 thin films were characterized by X-ray diffraction, scanning electron microscopy and atomic force microscope. All-solid-state Li/PEO18-Li (CF3SO2)2N/LATSP/LiCoO2/Au cells were fabricated using the amorphous film. The electrochemical performance of the cells was investigated by galvanostatic cycling, cyclic voltammetry, potentiostatic intermittent titration technique and electrochemical impedance spectroscopy. It was found that the amorphous LiCoO2 thin film shows a promising electrochemical performance, making it a potential application in microbatteries for microelectronic devices. 相似文献
16.
Frank Uwe Renner Gerald Andreas Eckstein Liverios Lymperakis Andrea Dakkouri-Baldauf Michael Rohwerder Jörg Neugebauer Martin Stratmann 《Electrochimica acta》2011,(4):1694
We present an electrochemical study of Au3Cu (0 0 1) single crystal surfaces in 0.1 mol dm−3 H2SO4 and 0.1 mol dm−3 H2SO4 + 0.1 mmol dm−3 HCl, and of Cu3Au (0 0 1) in 0.1 mol dm−3 H2SO4. The focus is on in situ scanning tunneling microscopy experiments. The changes of the surface morphology, which are time- and potential-dependent, have been observed, clearly resolving single atomic steps and mono-atomic islands and pits. Chloride additives enhance the surface diffusion and respective morphologies are observed earlier. All surfaces have shown considerable roughening already in the passive region far below the critical potential. 相似文献
17.
Rudolf Kiefer 《Electrochimica acta》2008,53(5):2593-2599
Free standing PEDOT [poly(3,4-ethylenedioxythiophene)] films (with surface conductivities of 200-400 S cm−1) were generated in tetrabutylammonium trifluromethanesulfonate (TBACF3SO3) electrolytes by potentiostatic (EP 1.05 V vs. Ag wire) electropolymerisation in propylene carbonate (at −27 °C) and methyl benzoate (at −4 °C). Films obtained in the TBACF3SO3 electrolytes showed a length increase of 2-3% during scans to negative potentials under isotonic (constant load 1.35 MPa) and stress of 0.3 MPa under isometric (constant length) conditions. Cation movement occurred due to immobilisation of CF3SO3− anions during electropolymerisation. The system showed good stability and low creep during square wave electrochemical cycling in the potential range from 0.0 to 1.0 V. The surface morphology (SEM) of the PEDOT films showed that the polymer structure is dependent upon the solvent used during the polymerisation process. 相似文献
18.
Jung-Min Kim 《Electrochimica acta》2004,49(6):937-944
In this research, we studied the first cycle characteristics of Li[Ni1/3Co1/3Mn1/3]O2 charged up to 4.7 V. Properties, such as valence state of the transition metals and crystallographic features, were analyzed by X-ray absorption spectroscopy and X-ray and neutron diffractions. Especially, two plateaus observed around 3.75 and 4.54 V were investigated by ex situ X-ray absorption spectroscopy. XANES studies showed that the oxidation states of transition metals in Li[Ni1/3Co1/3Mn1/3]O2 are mostly Ni2+, Co3+ and Mn4+. Based on neutron diffraction Rietveld analysis, there is about 6% of all nickel divalent (Ni2+) ions mixed with lithium ions (cation mixing). Meanwhile, it was found that the oxidation reaction of Ni2+/Ni4+ is related to the lower plateau around 3.75 V, but that of Co3+/Co4+ seems to occur entire range of x in Li1−x[Ni1/3Co1/3Mn1/3]O2. Small volume change during cycling was attributed to the opposite variation of lattice parameter “c” and “a” with charging-discharging. 相似文献
19.
Al and/or Mg-substituted Li[Ni0.8Co0.1Mn0.1−x−yAlxMgy]O2 were prepared by a co-precipitation method and characterized by X-ray diffraction with Rietveld refinement, thermogravimetric analysis, differential scanning calorimetry (DSC), and electrochemical measurements. The Rietveld refinement results show that cation mixing of Al and/or Mg-substituted Li[Ni0.8Co0.1Mn0.1−x−yAlxMgy]O2 was reduced with increased doping amounts of Al and Mg. The Al and/or Mg substitution in Li[Ni0.8Co0.1Mn0.1]O2 also resulted in improved electrochemical cycling behavior, structural stability, and thermal stability compared to pristine Li[Ni0.8Co0.1Mn0.1]O2. The improvements of electrochemical and thermal properties resulted from the stabilized host structure by Al and/or Mg incorporation into Li[Ni0.8Co0.1Mn0.1]O2. 相似文献
20.
The oxidation and reduction of carbonate, GR(CO3), and sulphate, GR(SO4), green rusts (GR) have been studied through electrochemical techniques, electrochemical quartz crystal microbalance (EQCM), FTIR, XRD and SEM. The used samples were made of thin films electrodeposited on gold substrate. The results from the present work, from our previous studies and from literature were compiled in order to establish a general scheme for the formation and transformation pathways involving carbonate or sulphate green rusts. Depending on experimental conditions, two routes of redox transformations occur. The first one corresponds to reaction via solution and leads to the formation of ferric products such as goethite or lepidocrocite (oxidation) or to the release of FeII ions into the solution (reduction) with soluble FeII-FeIII complexes acting as intermediate species. The second way is solid-state reaction that involve conversion of lattice Fe2+ into Fe3+ and deprotonation of OH groups in octahedra sheets (solid-state oxidation) or conversion of lattice Fe3+ into Fe2+ and protonation of OH groups (solid-state reduction). The solid-state oxidation implies the complete transformation of GR(CO3) or GR(SO4) to ferric oxyhydroxycarbonate exGRc-Fe(III) or ferric oxyhydroxysulphate exGRs-Fe(III), for which the following formulas can be proposed, FeIII6(OH)(12−2y)(O)(2+y)(H2O)(y)(CO3) or FeIII6(OH)(12−2z)(O)(2+z)(H2O)(6+z)(SO4) with 0 ≤ y or z ≤ 2. The solid-state reduction gives ferrous hydroxycarbonate exGRc-Fe(II) or ferrous hydroxysulphate exGRs-Fe(II), which may have the following chemical formulas, [FeII6(OH)10(H2O)2]·[CO3, 2H2O] or [FeII6(OH)10(H2O)2]·[SO4, 8H2O]. 相似文献