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1.
The electrolyses of solutions of bismuth oxide and tellurium oxide in nitric acid with molar ratios of Bi:Te=3:3–4:3 lead to cathodic deposits of films of bismuth telluride (Bi2Te3), an n-type semiconductor. Current densities of 2–5 mA/cm2 were applied. Voltammetric investigations showed that Bi2Te3 deposition occurred at potentials more negative than −0.125 V (Ag/AgCl, 3 M KCl). The deposit was identified as bismuth telluride (γ-phase) by X-ray analysis. Hall-effect measurements verified the n-type semiconducting behaviour. The films can be deposited in microstructures for thermoelectric microdevices like thermoelectric batteries or thermoelectric sensors.  相似文献   

2.
An investigation was conducted into the electrochromic properties of organotungsten oxide WO x C y films synthesized onto 60 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates using low temperature, plasma-enhanced chemical vapor deposition (PECVD) at varying oxygen concentrations. The PECVD-synthesized WO x C y films were proven to offer remarkable electrochromic performance. Cyclic voltammetry switching measurements revealed that only low driving voltages from −1 to 1 V are needed to provide reversible Li+ ion intercalation and de-intercalation in a 0.1 M LiClO4–PC electrolyte. Light modulation with transmittance variation of up to 72.9% and coloration efficiency of 62.5 cm2/C at a wavelength of 650 nm was obtained.  相似文献   

3.
1. Results of thermodynamic and kinetic investigations for the different crystalline calcium carbonate phases and their phase transition data are reported and summarized (vaterite: V; aragonite: A; calcite: C). A→C: T tr=455±10°C, Δtr H=403±8 J mol–1 at T tr, V→C: T tr=320–460°C, depending on the way of preparation,Δtr H=–3.2±0.1 kJ mol–1 at T trtr H=–3.4±0.9 kJ mol–1 at 40°C, S V Θ= 93.6±0.5 J (K mol)–1, A→C: E A=370±10 kJ mol–1; XRD only, V→C: E A=250±10 kJ mol–1; thermally activated, iso- and non-isothermal, XRD 2. Preliminary results on the preparation and investigation of inhibitor-free non-crystalline calcium carbonate (NCC) are presented. NCC→C: T tr=276±10°C,Δtr H=–15.0±3 kJ mol–1 at T tr, T tr – transition temperature, Δtr H – transition enthalpy, S Θ – standard entropy, E A – activation energy. 3. Biologically formed internal shell of Sepia officinalis seems to be composed of ca 96% aragonite and 4% non-crystalline calcium carbonate. This revised version was published online in July 2006 with corrections to the Cover Date.  相似文献   

4.
A simple method was used to fabricate flavin adenine dinucleotide (FAD)/NiOx nanocomposite on the surface of glassy carbon (GC) electrode. Cyclic voltammetry technique was applied for deposition nickel oxide nanostructures onto GC surface. Owing to its high biocompatibility and large surface area of nickel oxide nanomaterials with immersing the GC/NiOx-modified electrode into FAD solution for a short period of time, 10–140 s, a stable thin layer of the FAD molecules immobilized onto electrode surface. The FAD/NiOx films exhibited a pair of well-defined, stable, and nearly reversible CV peaks at wide pH range (2–10). The formal potential of adsorbed FAD onto nickel oxide nanoparticles film, E o′ vs. Ag/AgCl reference electrode is −0.44 V in pH 7 buffer solutions was similar to dissolved FAD and changed linearly with a slope of 58.6 mV/pH in the pH range 2–10. The surface coverage and heterogeneous electron transfer rate constant (k s ) of FAD immobilized on NiOx film glassy carbon electrode are 4.66 × 10−11 mol cm−2 and 63 ± 0.1 s−1, indicating the high loading ability of the nickel oxide nanoparticles and great facilitation of the electron transfer between FAD and nickel oxide nanoparticles. FAD/NiOx nanocomposite-modified GC electrode shows excellent electrocatalytic activity toward S2O82− reduction at reduced overpotential. Furthermore, rotated modified electrode illustrates good analytical performance for amperometric detection of S2O82−. Under optimized condition, the concentration calibration range, detection limit, and sensitivity were 3 μM–1.5 mM, 0.38 μM and 16.6 nA/μM, respectively.  相似文献   

5.
Multilayer oxide films were grown on silver in base by repetitive potential cycling; however, the type of oxide obtained, as assessed on the basis of its reduction behaviour, was dependent on the lower limit of the oxide growth cycles. Using limits of 1.03–2.60 V (RHE) the oxide film produced was assumed to be predominantly Ag2O; reduction of the latter yielded a cathodic peak at ca. 0.8 V and a surface layer of silver microparticles of diameter ranging from ca. 100 to 227 nm which, although relatively stable, were prone to rapid, extensive reoxidation. Altering the oxide growth limits to 0.7–2.60 V resulted in the growth of a different type of oxide deposit which is assumed to be AgOH; reduction of the latter occurred in a negative sweep in a random manner, i.e. in the form of cathodic spikes extending to potentials as low as ca. –0.5 V. Both types of silver oxide species are assumed to be involved in premonolayer oxidation and electrocatalysis at silver in base and the nature of the former process is discussed in some detail. Electronic Publication  相似文献   

6.
Two groups of techniques have been devised for the electrodeposition of new electroactive oxide films from [P2Mo18O62]6−. In the first group, two adsorption procedures were used: simple immersion of the electrode in a solution containing 10−4 M [P2Mo18O62]6− in a pH 3.50 medium or cycling of the electrode in this solution in the potential domain of the first three two-electron waves of the heteropolyanion results in surfaces which retain the oxometalate by mere adsorption. Strikingly, during the cycling, it was found that a fourth wave appears in the potential domain of the first three two-electron waves of [P2Mo18O62]6−, indicating an evolution of the heteropolyanion in the solution. Such an evolution was also observed with aged solutions. Then, the potential program for the actual modification step was run by cycling either of these electrodes from −0.2 V to −0.87 V vs. SCE in pure supporting electrolyte. Analysis of the STM images of the surfaces show essentially monomers 1.2–1.5 nm in diameter just after adsorption and a sizeable increase of the dimensions of the patterns after modification. The predominant sizes of these aggregates after modification remain in the range 10–12 nm. The second group of techniques consists in a modification of the electrode surface directly in the solution containing the heteropolyanion. A fixed potential as well as cycling prove efficient. Thick films are obtained readily, which are better imaged by tapping mode AFM. An increase of the pH to 4.50, in appropriate conditions, seems to be favourable to the deposition kinetics. The aggregates in the topmost layers are up to 40 nm in diameter and are assembled in interconnected islands. As a whole, these two groups of techniques appear to exert an important influence on the aggregate sizes. The paper demonstrates that these sizes might be relatively well controlled by the choice of experimental conditions. Received: 4 January 2000 / Accepted: 15 February 2000  相似文献   

7.
Electrochromic hydrated Ni-oxide films were prepared using a dip-coating technique from a nickel sulphate heptahydrate precursor in combination with glycerol, formamide and polyvinyalcohol. In-situ monochromatic (λ=400 nm) spectroelectrochemical measurements using a potential of −0.4 V to 0.8 V in 0.1M LiOH electrolyte revealed that the electrochromic efficiency was 23.5 cm2/C. The observed colouring/bleaching transmittance of a 100 nm thick film changed during potential cycling (20 cycles) by 45%. Ex-situ FT-IR absorption/reflection measurements performed at near-grazing incidence angle conditions (80°) confirmed transformation of as-deposited α-Ni(OH)2 phase to β-Ni(OH)2 at cathodic (bleached state) and β-NiOOH at anodic (coloured state) potentials during extended cycling (200 cycles). Clear evidence of the OH ions insertion and release of SO 4 2− ions from the as-deposited films when soaked (0.5 hour) in 0.1M LiOH are given. These processes are accompanied by the transformation of the residual COO groups originating from the peptisation with glacial acetic acid into CO 3 2− species residing in the films during extensive potential cycling.  相似文献   

8.
Electrochromic titanium oxide (TiO2) films were deposited on ITO/glass substrates by chemical solution deposition (CSD). The stock solutions were spin-coated onto substrates and then heated at various temperatures (200–500 °C) in various oxygen concentrations (0–80%) for 10 min. The effects of the processing parameters on the electrochromic properties of TiO2 films were investigated. X-ray diffraction measurements demonstrated that the amorphous TiO2 films were crystallized to form anatase films above 400 °C. The electrochromic properties and transmittance of TiO2 films were measured in 1 M LiClO4–propylene carbonate (PC) non-aqueous electrolyte. An amorphous 350 nm-thick TiO2 film that was heated at 300°C in 60% ambient oxygen exhibited the maximum transmittance variation (ΔT%), 14.2%, between the bleached state and the colored state, with a ΔOD of 0.087, Q of 10.9 mC/cm2, η of 7.98 cm2/C and x in Li x ClO4 of 0.076 at a wavelength (λ) of 550 nm.  相似文献   

9.
Titanium dissolution and passivation were studied in NaOH aqueous solution using open-circuit potential, potentiodynamic and potentiostatic techniques. Potentiodynamic data showed that the active-passive transition involves active metal dissolution followed by formation of a poorly conducting passive oxide film that passivates the electrode. The critical current density varied with pH as d log<I> j</I><SUB>m</SUB>/d pH=-0.098 in the pH range 11.00–14.00, while the passivation potential is changed according to the following two features: at pH 10.55–13.00, d<I>E</I><SUB>m</SUB>/d pH=-0.06 V; and at pH 13.50–14.00, d<I>E</I><SUB>m</SUB>/d pH=-0.40 V. The apparent activation energy, E*, was calculated from the slope of the Arrhenius plot and was found to be 12.6 kJ mol–1. Current-time transients showed that the growth of titanium oxide passive film is a diffusion-controlled process. XPS measurements indicated that the passive oxide film consists mainly of TiO2 and a mixture of suboxides of Ti2O3 and TiO. Electronic Publication  相似文献   

10.
The standard (p0=0.1 MPa) molar enthalpies of formation, ΔfHm0, for crystalline phthalimides: phthalimide, N-ethylphthalimide and N-propylphthalimide were derived from the standard molar enthalpies of combustion, in oxygen, at the temperature 298.15 K, measured by static bomb-combustion calorimetry, as, respectively, – (318.0±1.7), – (350.1±2.7) and – (377.3±2.2) kJ mol–1. The standard molar enthalpies of sublimation, ΔcrgHm0, at T=298.15 K were derived by the Clausius-Clapeyron equation, from the temperature dependence of the vapour pressures for phthalimide, as (106.9±1.2) kJ mol–1 and from high temperature Calvet microcalorimetry for phthalimide, N-ethylphthalimide and N-propylphthalimide as, respectively, (106.3±1.3), (91.0±1.2) and (98.2±1.4) kJ mol–1. The derived standard molar enthalpies of formation, in the gaseous state, are analysed in terms of enthalpic increments and interpreted in terms of molecular structure.  相似文献   

11.
Radiation-chemical reduction of Ni2+ ions in aqueous solutions of Ni(ClO4)2 containing sodium formate or isopropyl alcohol was studied, γ-Irradiation of deaerated solutions in the presence of polyethyleneimine, polyacrylate, or polyvinyl sulfate gives stable metal sols containing spherical particles 2–4 nm in diameter. The optical absorption spectra of nickel nanoparticles exhibit a band with a maximum at 215±5 nm (ε215=4.7·103 L mol−1 cm−1) and a shoulder at 350 nm. A mechanism for the radiation-chemical reduction of Ni2+ ions by hydrated electrons and organic radicals (CO2- radical anions in the case of HCOONa and Me2C·OH radicals in the case of PriOH). The redox potentials of the Ni2+/Ni0 and Ni+/Ni0 pairs (Ni0 is a nickel atom) are approximately −2.2 and −1.7 V, respectively. The nanoparticles are readily oxidized by O2, H2O2, and other oxidants. The reactions of these species with silver ions yield relatively stable nanoaggregates containing both nickel and silver in addition to silver nanoparticles. Published inIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 10, pp. 1733–1739, October, 2000.  相似文献   

12.
The characterisation of electrochemical behaviour of electrochromic (EC) devices based on solution thermolysed (ST) tungsten oxide (WO3) thin films was carried out using the step potential excitation method. The method, based on generating plots of current density (J) as a function of passed charge (ΔQ), has been applied for the characterisation of EC-WO3 thin films in proton-containing aqueous electrolyte. EC devices have been fabricated by employing WO3 thin films with variable thickness (T) ranging from 0.04 to 0.52 μm. The J vs time (t) responses (chronoamperometry) of these devices were recorded at a fixed applied potential (±0.7 V vs S.C.E.) and values of total passed H+ charges (ΔQ) into the WO3 host lattice during the coloration process are calculated. The J-ΔQ curves corresponding to films of different thickness were plotted as a function of the passed charge volume density, ΔQ /T, and an intercalatable film thickness is calculated to be 0.13 μm. The modulation in optical transmittance after coloration and bleaching was studied in the wavelength range between 350 and 850 nm and an optical efficiency (ξλ) is calculated at λ=700 nm. It is found that the ξλ wanes with increasing intercalation. Electronic Publication  相似文献   

13.
Thin solid films of mixed Fe/Ti oxide composition (Fe/Ti molar ratios: 0.5∶1, 1∶1, 1.5∶1) have been made from Fe(NO3)3 alcoholic solution to which Ti(OiPr)4 was added. Films have been deposited by the dip-coating technique and heat-treated at 300°C and 500°C. Powders of Fe/Ti oxide heat-treated at 300°C are amorphous, while powders annealed at 500°C for 40 hours transformed to mixed rutile, pseudobrookite and hematite phases. The structure of the XRD amorphous films was identified with the help of near-normal reflection absorption (6°) (IRRA) and near-grazing incidence angle (NGIA) spectroscopy. NGIA FT-IR spectra of films are characterised with a single phonon mode appearing in the spectral range 600–950 cm−1 which shifts with increasing Ti concentration from 675 cm−1 (Fe2O3) to 904 cm−1 (TiO2) thus exhibiting one-mode behavior. Electrochemical investigations made with the help of cyclic voltammetry (CV) and chronocoulometry (CPC) performed in 0.01M LiOH and in 1M LiClO4/propylene carbonate electrolytes revealed that films are able to uptake reversibly Li+ ions with a charge capacity (Q) per film thickness (d) in the range 0.1–0.26 mC/cm2nm and 0.06 mC/cm2nm, respectively. The temperature at which the films were prepared alters the rate of Li+ insertion which is faster for less compact films obtained at 300°C. In situ UV-VIS spectroelectrochemical measurements revealed that Fe/Ti oxide films bleached in the UV spectral region (300 nm<λ<450 nm) and colored in the VIS spectral region (450 nm<λ<800 nm), thus exhibiting mixed anodic and cathodic electrochromism.  相似文献   

14.
This paper presents the characterization of TiO2 nanostructures obtained by low-voltage anodization using alternate current electrochemical microscopy (AC-SECM) and photoelectrochemical (PEC) measurements. TiO2 nanostructures were obtained from the exposure of titanium foils to several aqueous acidic solutions of hydrofluoric acid + phosphoric acid at potentials of 1 to 3 V. Scanning electron microscopy, X ray diffraction, and atomic force microscopy studies evidence the formation of a thin porous amorphous layer (<600 nm) with pore size in the range of 200–1,000 nm. By AC-SECM studies at different bias, we were able to confirm the unambiguous semiconducting properties of as-obtained porous titania films, as well as differences in surface roughness and conductivity in specimens obtained at both potentials. The difference in conductivity persists in air annealed samples, as demonstrated by electrochemical impedance spectroscopy and PEC measurements. Specimens obtained at 3 V show lower photocurrent and dark current than those obtained at 1 V, regardless of their larger conductivity, and we proposed it is due to differences on the oxide layer formed at the pore bottom.  相似文献   

15.
The gravimetric and optical spectroscopic methods reveals that light irradiation with λ = 300–750 nm and intensity I = 6.9 × 1014–1.1 × 1016 quanta cm−2 s−1 for τ = 1–160 min in atmospheric conditions significantly changes the absorption and reflection spectra and mass of aluminum films (d = 2–200 nm). The kinetic curves of the degree of conversion versus aluminum film thickness are satisfactorily described in the inverse logarithmic and parabolic terms. The contact potential difference is measured for Al and Al2O3 films along with the photo-EMF of Al-Al2O3 systems. The suggested model includes the stages of generation and redistribution of nonequilibrium charge carriers in the contact field of Al-Al2O3 systems, oxygen adsorption, Al3+ diffusion, and Al2O3 formation.  相似文献   

16.
Using experimental potential values for a vitreous carbon electrode in contact with the RbCu4Cl3I2 solid electrolyte, the concentration of Cu2+ ions in the electrolyte was determined. At 0.5 V, the concentration of Cu2+ was 1.25×1018 cm–3. The estimated values of the Cu2+ ion concentration in RbCu4Cl3I2 (0.8%) and the potential of the vitreous carbon electrode after electrochemical decomposition of RbCu4Cl3I2 (0.606 V) correspond to experimental values of 2% and 0.58 V, respectively. This demonstrates the adequacy of the model describing the electrode potential of Cu2+ as a function of the concentration in RbCu4Cl3I2. When the C/RbCu4Cl3I2 interface was polarized, the diffusion coefficient of Cu2+ was 1.5×10–8 cms–1. Investigations of the interface between the copper electrode and RbCu4Cl3I2 were carried out by galvanostatic and potentiostatic methods. A 1-μm layer of cuprous oxide, Cu2O, was discovered on the interface of the copper electrode with RbCu4Cl3I2. This layer blocks the course of the electrochemical reaction Cu0–e⇌Cu+ with participation of copper metal. The copper electrode behaves as an inert redox electrode at low overvoltages. In this case, at the Cu2O/RbCu4Cl3I2 interface an electrochemical reaction with Cu2+ ion participation, Cu+–e⇌Cu2+, takes place. The results suggest that the reaction rate is limited by slowing the Cu2+ diffusion in RbCu4Cl3I2. The initial Cu2+ ion concentration in the electrolyte near this interface is about 1.4×1017 cm–3. The exchange current density is about (4±2)×10–6 A cm–2. At potentials ϕ>8–10 mV, an electrical breakdown of the Cu2O layer takes place, allowing copper metal to ionize to Cu+. We suggest that at 10 mV<ϕ<100 mV the rate of this reaction is limited by the formation and growth of copper nuclei and at ϕ>120 mV the reaction rate is limited by charge transfer. Electronic Publication  相似文献   

17.
Manganese–vanadium oxide had been synthesized by a novel simple precipitation technique. Scanning electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller, thermogravimetric analysis/differential scanning calorimetry, and X-ray photoelectron spectroscopy were used to characterize Mn–V binary oxide and δ-MnO2. Electrochemical capacitive behavior of the synthesized Mn–V binary oxide and δ-MnO2 was investigated by cyclic voltammetry, galvanostic charge–discharge curve, and electrochemical impedance spectroscope methods. The results showed that, by introducing V into δ-MnO2, the specific surface area of the mixed oxide increased due to a formation of small grain size. The specific capacitance increased from 166 F g−1 estimated for MnO2 to 251 F g−1 for Mn–V binary oxide, and the applied potential window extended to −0.2–1.0 V (vs. saturated calomel electrode). Through analysis, it is suggested that the capacitance performance of Mn–V binary oxide materials may be improved by changing the following three factors: (1) small grain and particle size and large activity surface area, (2) appropriate amount of lattice water, and (3) chemical state on the surface of MnO2 material.  相似文献   

18.
Abstract  Aluminium anodization behavior in ammonium sebacate solution (w = 4%) in ethylene glycol, and in several H3PO4-containing electrolytes, has been investigated. A new mechanism is proposed for the formation of porous anodic films. The model emphasizes the close relationship between pore generation and oxygen evolution. PO4 3− ions incorporated in the anodic films behave as the primary source of avalanche electrons. It is the avalanche electronic current through the barrier film that causes oxygen evolution during anodization. When growth of anodic oxide and oxygen evolution occur simultaneously at the aluminium anode, cavities or pores are formed in the resulting films. Accordingly, the mechanisms of growth of barrier and porous films are not very different in nature. These findings are a decisive new step towards full understanding of the nature of anodic alumina films. Graphical abstract     相似文献   

19.
The transfer of the α-hydroxy-carboxylates of glycolic, lactic, mandelic and gluconic acid from the aqueous electrolyte phase into an organic 4-(3-phenylpropyl)-pyridine (PPP) phase is studied at a triple-phase boundary electrode system. The tetraphenylporphyrinato complex MnTPP dissolved in PPP is employed to drive the anion transfer reaction and naphthalene-2-boronic acid (NBA) is employed as a facilitator. In the absence of a facilitator, the ability of α-hydroxy-carboxylates to transfer into the organic phase improves, consistent with hydrophobicity considerations giving relative transfer potentials (for aqueous 0.1 M solution) of gluconate>glycolate>lactate>mandelate. In the presence of NBA, a shift of the reversible transfer potential to more negative values is indicating fast reversible binding (the mechanism for the electrode process is EICrev) and the binding constants are determined as K glycolate = 2 M−1, K mandelate = 60 M−1, K lactate = 130 M−1 and K gluconate = 2,000 M−1. The surprisingly strong interaction for gluconate is rationalised based on secondary interactions between the gluconate anion and NBA.  相似文献   

20.
Proton conducting tantalum oxide films were deposited on ITO (Indium Tin Oxide) coated glass, fused silica and soda-lime glass substrates by spin coating using a sol-gel process. The coating solutions were prepared using Ta(OC2H5)5 as a precursor. X-ray diffraction studies determined that the sol-gel films, heat treated at temperatures below 400°C, were amorphous. Films heat treated at higher temperatures were crystalline with the hexagonal δ-Ta2O5 structure. The solar transmission values (T s ) of tantala films on glass generally range from 0.8–0.9, depending on thickness. The refractive index and the extinction coefficient were evaluated from transmittance characteristics in the UV-VIS-NIR regions. The refractive index values calculated at λ=550 nm increased fromn=1.78 to 1.97 with increasing heat treatment from 150 to 450°C. The films heat treated at different temperatures showed low absorption, with extinction coefficients of smaller thank=1×10−3 in the visible range. Impedance spectroscopic investigations performed on Ta2O5 films revealed that these films have a protonic conductivity of 3.2×10−4S/m. The films are suitable for proton conducting layers in electrochromic (EC) devices.  相似文献   

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