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1.
We observed the Raman spectra of carriers, positive polarons and bipolarons, generated in a poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT-C14) film by FeCl3 vapor doping. Electrical conductivity and Raman measurements indicate that the dominant carriers in the conducting state were bipolarons. We identified positive polarons and bipolarons generated in an ionic-liquid-gated transistor (ILGT) fabricated with PBTTT-C14 as an active semiconductor and an ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [BMIM][TFSI] as a gate dielectric using Raman spectroscopy. The relationship between the source−drain current (ID) at a constant source−drain voltage (VD) and the gate voltage (VG) was measured. ID increased above −VG = 1.1 V and showed a maximum at −VG = 2.0 V. Positive polarons were formed at the initial stage of electrochemical doping (−VG = 0.8 V). As ID increased, positive bipolarons were formed. Above VG = −2.0 V, bipolarons were dominant. The charge density (n), the doping level (x), and the mobility of the bipolarons were calculated from the electrochemical measurements. The highest mobility (μ) of bipolarons was 0.72 cm2 V−1 s−1 at x = 110 mol%/repeating unit (−VG = 2.0 V), whereas the highest μ of polarons was 4.6 × 10−4 cm2 V−1 s−1 at x = 10 mol%.  相似文献   

2.
Catalytic reduction of CO2 (saturated in organic polar solvents, e.g. N,N-dimethylfomamide, containing Me4NX or NaBF4) was achieved at smooth gold electrodes and at glassy carbon electrodes galvanostatically capped with a thin layer of gold. Under these quite explicit conditions, very sharp reduction steps were observed near − 1.5 V vs. Ag/AgCl. With small cations listed above, an unexpected behavior was observed, a progressive electrode inhibition occurring upon several scans or after a fixed-potential electrolysis at E <  1.7 V. This phenomenon could be attributed to the insertion of CO2 into gold, leading to the formation of a thick iono-metallic multi-strata layer (less conducting than pure metal) that grows with the electrode charge. The formation of this new interface is due to the concur of three elements: transient CO2 anion radical, the metal, and rather small-sized cations (M+ = Na+ or TMA+), the three possibly associated in a form {Au-CO2,M+} apparently very reactive with oxygen, moisture, and with some organic π-acceptors. Upon multi-scans up to − 2.2 V, the thickness of formed layer progressively increases reaching more than 10 7 to 10 6 mol cm 2. Such multi-layers undergo decomposition in the anodic domain at about + 1.7 V liberating CO2 beforehand trapped in Au. Coulometric analyses demonstrated that insertion (cathodic) and release (anodic) steps are quite equivalent, which permits to consider this process as chemically reversible sequestration of carbon dioxide.  相似文献   

3.
A sensitive electrochemical method for H2O2 determination was proposed with carboxyl functionalized graphene oxide (GO-COOH) as mimetic peroxidase and 3,3′,5,5′-tetramethylbenzidine (TMB) as substrate. GO-COOH exhibited intrinsic peroxidase-like activity that could catalyze the oxidation of TMB with H2O2. The generated product exhibited a sensitive second order derivative linear sweep voltammetric reduction peak at − 0.93 V (vs. Ag/AgCl) in Britton–Robinson buffer. Under the optimal conditions the reduction peak current was proportional to H2O2 concentration in the linear range from 0.006 to 0.8 μmol L 1 with the detection limit of 1.0 nmol L 1 (3σ). This proposed method was further applied to determine H2O2 content in fresh milk samples with satisfactory results.  相似文献   

4.
This study demonstrates a new kind of single-walled carbon nanotubes (SWNT)-based compartment-less glucose/O2 biofuel cell (BFC) with glucose dehydrogenase (GDH) and bilirubin oxidase (BOD) as the anodic and cathodic biocatalysts, respectively, and with poly(brilliant creysl blue) (BCB) adsorbed onto SWNT nanocomposite as the electrocatalyst for the oxidation of NADH. The prepared GDH-polyBCB-SWNT bioanode exhibits an excellent electrocatalytic activity toward the oxidation of glucose biofuel; in 0.10 M phosphate buffer containing 20 mM NAD+ and 100 mM glucose, the oxidation of glucose commences at −0.25 V and the current reaches its maximum of 310 μA/cm2 at −0.05 V vs. Ag/AgCl. At the BOD-SWNT biocathode, a high potential output is achieved for the reduction of O2 due to the direct electron transfer property of BOD at the SWNTs. In 0.10 M phosphate buffer, the electrocatalytic reduction of O2 is observed at a high potential of 0.53 V vs. Ag/AgCl with an electrocatalytic current plateau of ca. 28 μA/cm2 at 0.45 V under ambient air and ca. 102 μA/cm2 under O2-saturated atmosphere. In 0.10 M phosphate buffer containing 10 mM NAD+ and 40 mM glucose under O2-saturated atmosphere, the power density of the assembled SWNT-based glucose/O2 BFC reaches 53.9 μW/cm2 at 0.50 V. The performance and the stability of the glucose/O2 BFC are also evaluated in serum. This study could offer a new route to the development of new kinds of enzymatic BFCs with a high performance and provide useful information on future studies on the enzymatic BFCs as in vivo power sources.  相似文献   

5.
The electrochemical reduction of CO2 is strongly influenced by both the applied potential and the surface adsorption status of the catalyst. In this work a gas diffusion electrode (GDE) coated with Pd nanoparticles/carbon black (Pd/XC72) was used to study the electrochemical reduction of CO2. Cyclic voltammetric (CV) analysis of Pd/XC72 between 1.5 V and − 0.6 V (vs. RHE) shows the formation of intermediates and the blocking of hydrogen absorption on the Pd nanoparticles (NPs) under a CO2 atmosphere. The relationships between the Faradaic efficiency/current density and the applied potential reveal that the onset potential of CO formation is around − 0.4 V. Moreover, the presence of adsorbed CO was confirmed through CV analysis of Pd/XC72 under CO2 and CO/He atmospheres. This demonstrates that H atoms and CO intermediates co-adsorb on the surface of the Pd NPs at an applied potential of around − 0.4 V. When the applied potential is more negative than − 0.6 V, adsorption of CO intermediates on the surface of the Pd NPs becomes dominant.  相似文献   

6.
Cyclic voltammetry of the CuCl powder in a cavity microelectrode revealed direct electro-reduction in solid state in 1-butyl-3-methylimidazolium hexafluorophosphate. Potentiostatic electrolysis of the salt powder (attached to a current collector) in the ionic liquid produced Cu nanoparticles as confirmed by X-ray diffraction, energy dispersive X-ray analysis, scanning and transmission electron microscopy. The particle size decreased down to 10 nm when the electrode potential was shifted from −0.9 V to −1.8 V (versus Ag/Ag+). The electro-reduction and the nanoparticle formation mechanisms were investigated in the ionic liquid and also in aqueous 0.1 mol L−1 KClO4 in which larger Cu particles were obtained.  相似文献   

7.
Oxygen permeation through dense ceramic membranes of perovskite-like SrCo0.9−xFe0.1CrxO3−δ (x = 0.01–0.05), Sr1−xyLnxCoO3−δ(Ln = La, Nd, Sm, Gd; x = 0.30–0.35; y = 0–0.10), SrCo1−xTixO3−δ (x = 0.05–0.20) and LaM1−xNixO3−δ (M = Ga, Co, Fe; x = 0–0.6) was studied. The SrCoO3−δ-based solid solutions with cubic perovskite structure were found to exhibit highest permeation fluxes compared to other membranes. However, high thermal expansion coefficients and interaction with gas species such as carbon dioxide may complicate the employment of SrCoO3−δ membranes for oxygen separation membranes. Alternatively, the LaGa1−xNixO3−δ (x = 0.2–0.5) perovskites, having significant permeation fluxes as well as thermal expansion coefficients in the range of (10.8–11.6) × 10−6 K−1, were demonstrated to be suitable as membrane materials at oxygen pressures from 1 × 10−2 to 2 × 104 Pa. Testing oxygen permeation at oxygen partial pressures of 1–60 atm showed that only oxides with a high oxygen deficiency such as SrCo0.85Ti0.15F3−δ possess sufficient oxygen permeation fluxes. The oxygen permeability of perovskites on the basis of LaGaO3 and LaCoO3−δ was found to be negligible at oxygen pressures above 15 atm, caused by low oxygen vacancy concentration and ionic conductivity of such ceramic materials.  相似文献   

8.
《Solid State Sciences》2007,9(6):521-526
Members of the spinel solid solution between Li4/3Ti5/3O4 and LiCrTiO4, i.e., Li(4−x)/3Ti(5−2x)/3CrxO4 (0  x  0.9), have been investigated as possible negative electrodes for future lithium-ion batteries. Electrochemical behaviour have been studied over the potential range 1–3.5 V vs Li+/Li. Results are promising with anodic capacities between 129 and 163 mA h/g with a flat operating voltage at about 1.5 V, which is attributed to the pair Ti4+/Ti3+. The inclusion of Cr3+ in the spinel structure enhances the specific capacity. In-situ X-ray diffraction experiments confirm that the reaction proceeds in a topotactic manner.  相似文献   

9.
In this study, trimetal Mg/Ce/Mn oxide-modified diatomaceous earth (DE) was synthesized at optimal conditions. Comparison of the SEM images and the results of EDX analyses of the raw and the modified DE confirmed the surface modification of the raw DE with the trimetal oxide. Groundwater fluoride removal capacity of the sorbent was evaluated by batch method at various defluoridation conditions. At a sorbent dosage of 0.6 g/100 mL (contact time: 60 min, mixing speed of 200 rpm and temperature: 297 K), the fluoride removal was >93% for solutions containing initial fluoride concentration of 10–60 mg/L. Sorbent’s optimum fluoride uptake capacity was 12.63 mg/g at the initial fluoride concentration of 100 mg/L. Fluoride removal was >91% for solutions with initial pH range of ∼4–11 (initial fluoride concentration: 9 mg/L, sorbent dosage: 0.6 g/100 mL). Appraisal of the effect of co-existing anions on fluoride removal showed that CO32− would reduce the amount of fluoride removed from solution, while other anions such as PO43−, NO3 and SO42− had no observable effect. K2SO4 solution was found to be most suitable for regeneration of spent Mg/Ce/Mn oxide-modified DE compared to Na2CO3 and NaOH. The mechanism of fluoride removal at pH > 5.45 (pHpzc = 5.45) occurred by exchange of hydroxyl groups on surface of sorbent with fluoride ions from solution. Sorption data fitted better to Langmuir isotherm and pseudo-second-order model. External diffusion was observed to be the sorption rate limiting factor.  相似文献   

10.
This work reports on a novel chitosan–hematite nanotubes composite film on a gold foil by a simple one-step electrodeposition method. The hybrid chitosan–hematite nanotubes (Chi–HeNTs) film exhibits strong electrocatalytic reduction activity for H2O2. Interestingly, two electrocatalytic reduction peaks are observed at −0.24 and −0.56 V (vs SCE), respectively, one controlled by surface wave and the other controlled by diffusion process. The Chi–HeNTs/Au electrode shows a linear response to H2O2 concentration ranging from 1 × 10−6 to 1.6 × 10−5 mol L−1 with a detection limit of 5 × 10−8 mol L−1 and a sensitivity as high as 1859 μA μM−1 cm−2.  相似文献   

11.
Micro-tubular solid-oxide fuel cell consisting of a 10-μm thick (ZrO2)0.89(Sc2O3)0.1(CeO2)0.01 (ScSZ) electrolyte on a support NiO/(ScSZ) anode (1.8 mm diameter, 200 μm wall thickness) with a Ce0.8Gd0.2O1.9 (GDC) buffer-layer and a La0.6Sr0.4Co0.2Fe0.8O3−δ (LSCF)/GDC functional cathode has been developed for intermediate temperature operation. The functional cathode was in situ formed by impregnating the well-dispersed nano-Ag particles into the porous LSCF/GDC layer using a citrate method. The cells yielded maximum power densities of 1.06 W cm−2 (1.43 A cm−2, 0.74 V), 0.98 W cm−2 (1.78 A cm−2, 0.55 V) and 0.49 W cm−2 (1.44 A cm−2, 0.34 V), at 650, 600 and 550 °C, respectively.  相似文献   

12.
A glassy carbon electrode (GCE) modified with internal-electrolysis deposited gold nanoparticles (AuNPsied) was applied to sensitively and selectively detect As(III) by anodic stripping linear sweep voltammetry (ASLSV). The AuNPsied/GCE was prepared based on the redox replacement reaction between a supporting-electrolyte-free aqueous HAuCl4 and a copper sheet in saturated KCl separated by a salt bridge. Under optimum conditions (0.5 M aqueous H2SO4, 300-s preconcentration at − 0.4 V), the ASLSV peak current for the As(0)–As(III) oxidation responded linearly to As(III) concentration from 0.02 to 3 μM with a limit of detection (LOD) of 0.9 nM (0.07 μg L 1) (S/N = 3), while that for the As(III)–As(V) oxidation was linear with As(III) concentration from 0.02 to 1 μM with a LOD of 4 nM (0.3 μg L 1) (S/N = 3). An appropriate high-scan-rate for ASLSV can enhance both the sensitivity and signal-to-noise ratio. This method was applied for analyses of As(III) in real water samples.  相似文献   

13.
Ag nanocubes that are 45 nm in size are synthesized and successfully used as catalysts in oxygen electroreduction. Electrochemical surface areas (ESAs) are considered to determine the effect on HO2 production, which is found to be in the following order: nanocubes < nanoparticles. Comparative data generated using Tafel analyses in 0.1 M NaOH electrolyte without and with methanol show that unchanged slopes on the prepared cubic catalysts can indicate high resistance of Ag nanocubes for methanol oxidation during oxygen reduction reaction. Among these Ag catalysts, nanocubes exhibit 9.29 × 10 2 mA cm 2 (at − 0.15 V vs. Ag/AgCl), the better activity in the oxygen reduction reaction.  相似文献   

14.
Microcalorimetry, spectrophotometry, and high-performance liquid chromatography (h.p.l.c.) have been used to conduct a thermodynamic investigation of the glutathione reductase catalyzed reaction {2 glutathionered(aq) + NADPox(aq)=glutathioneox(aq) + NADPred(aq)}. The reaction involves the breaking of a disulfide bond and is of particular importance because of the role glutathionered plays in the repair of enzymes. The measured values of the apparent equilibrium constant K for this reaction ranged from 0.5 to 69 and were measured over a range of temperature (288.15 K to 303.15 K), pH (6.58 to 8.68), and ionic strength Im (0.091 mol · kg−1 to 0.90 mol · kg−1). The results of the equilibrium and calorimetric measurements were analyzed in terms of a chemical equilibrium model that accounts for the multiplicity of ionic states of the reactants and products. These calculations led to values of thermodynamic quantities at T=298.15 K and Im=0 for a chemical reference reaction that involves specific ionic forms. Thus, for the reaction {2 glutathionered(aq) + NADPox3−(aq)=glutathioneox2−(aq) + NADPred4−(aq) + H+(aq)}, the equilibrium constant K=(6.5±4.4)·10−11, the standard molar enthalpy of reaction ΔrHom=(6.9±3.0) kJ · mol−1, the standard molar Gibbs free energy change ΔrGom=(58.1±1.7) kJ · mol−1, and the standard molar entropy change ΔrSom=−(172±12) J · K−1 · mol−1. Under approximately physiological conditions (T=311.15 K, pH=7.0, and Im=0.25 mol · kg−1 the apparent equilibrium constant K≈0.013. The results of the several studies of this reaction from the literature have also been examined and analyzed using the chemical equilibrium model. It was found that much of the literature is in agreement with the results of this study. Use of our results together with a value from the literature for the standard electromotive force Eo for the NADP redox reaction leads to Eo=0.166 V (T=298.15 K and I=0) for the glutathione redox reaction {glutathioneox2−(aq) + 2 H+(aq) + 2 e=2 glutathionered(aq)}. The thermodynamic results obtained in this study also permit the calculation of the standard apparent electromotive force E′o for the biochemical redox reaction {glutathioneox(aq) + 2 e=2 glutathionered(aq)} over a wide range of temperature, pH, and ionic strength. At T=298.15 K, I=0.25 mol · kg−1, and pH=7.0, the calculated value of E′o is −0.265 V.  相似文献   

15.
The electrochemical reversibility of magnesium was observed in an electrolyte consisting of 0.5 M Mg[TFSI]2 in tetraglyme in the presence of a small amount of Mg[BH4]2. The cyclic efficiency of the cathodic/anodic process was found to increase initially with [BH4] then plateau at about 75% beyond 6 mM in these experiments. This concentration is in the region of that indicated by Karl Fischer analysis of the electrolyte as required of [BH4] as a dehydrating agent. Cyclic voltammetry showed the reduction onset potential at approximately − 0.35 V vs. Mg and subsequent oxidation around 0 V vs. Mg. Stable cyclic efficiency of approximately 75% over 500 cycles is demonstrated on a platinum substrate. Mg cycling on magnesium, copper and aluminium substrates all show stable cycling over 500 cycles with cyclic efficiency > 73%.  相似文献   

16.
A novel selective thiocyanate PVC membrane electrode based on bis-bebzoin-semitriethylenetetraamine binuclear copper(II) [Cu(II)2–BBSTA] as neutral carrier is reported, which displays an anti-Hofmeister selectivity sequence in following order: SCN > ClO4 > I >Sal >SO32− >NO3 > H2PO4 > Cl >NO2 > SO42−. The electrode exhibits Nernstian potential linear range to thiocyanate from 1.0 × 10−1 to 9.0 × 10−7 mol/l with a detection limit 7.0 × 10−7 mol/l and a slope of −57.0 mV/decade in pH 5.0 of phosphorate buffer solution at 25 °C. The response mechanism is discussed in view of the AC impedance technique and the UV spectroscopy technique. From comparison of potentiometric response characteristics between the binuclear metallic complex copper(II) [Cu(II)2–BBSTA] and mononuclear copper(II) metallic complex [Cu(II)–BBSDA], an enhanced response towards thiocyanate from the electrode based on binuclear metallic complex copper (II) [Cu(II)2–BBSTA] was observed. The electrode based on binuclear copper(II) compound was used to determine the thiocyanate content in waste water with satisfactory results.  相似文献   

17.
A high specific capacitance was obtained for α-Co(OH)2 potentiostatically deposited onto a stainless-steel electrode in 0.1 M Co(NO3)2 electrolyte at −1.0 V vs. Ag/AgCl. The structure and surface morphology of the obtained α-Co(OH)2 were studied by using X-ray diffraction analysis and scanning electron microscopy. A network of nanolayered α-Co(OH)2 sheets was obtained; the average thickness of individual α-Co(OH)2 sheets was 10 nm, and the thickness of the deposit was several micrometers. The capacitive characteristics of the α-Co(OH)2 electrodes were investigated by means of cyclic voltammetry and constant current charge–discharge cycling in 1 M KOH electrolyte. A specific capacitance of 860 F g−1 was obtained for a 0.8 mg cm−2 α-Co(OH)2 deposit. The specific capacitance did not decrease significantly for the active mass loading range of 0.1–0.8 mg cm−2 due its layered structure, which allowed easy penetration of electrolyte and effective utilization of electrode material even at a higher mass. This opens up the possibility of using such materials in supercapacitor applications.  相似文献   

18.
Electrochemistry/mass spectrometry (EC/MS) using two different types of electrolytic cells was employed for the systematic mechanistic study of colchicine's reduction, both in aqueous and non-aqueous media. In aqueous media, at around − 1 V vs. Ag/AgCl, colchicine suffers a single-electron reduction to a transient anion radical, which after a follow-up protonation leads to a neutral free radical (ErCi mechanism). Depending on the experimental conditions, the latter undergoes some dimerization. At more negative potentials (− 1.4 V vs. Ag/AgCl) and pH < 7, the free radical is undergoing another single-electron reduction and a subsequent protonation. In the absence of protons (aprotic media), the one-electron reduction gives the anion radical. This process becomes fully reversible at high scan rates (≥ 10 V/s).  相似文献   

19.
The effects of doping the mixed-conducting (La,Sr)FeO3−δ system with Ce and Nb have been examined for the solid-solution series, La0.5−2xCexSr0.5+xFeO3−δ (x = 0–0.20) and La0.5−2ySr0.5+2yFe1−yNbyO3−δ (y = 0.05–0.10). Mössbauer spectroscopy at 4.1 and 297 K showed that Ce4+ and Nb5+ incorporation suppresses delocalization of p-type electronic charge carriers, whilst oxygen nonstoichiometry of the Ce-containing materials increases. Similar behavior was observed for La0.3Sr0.7Fe0.90Nb0.10O3−δ at 923–1223 K by coulometric titration and thermogravimetry. High-temperature transport properties were studied with Faradaic efficiency (FE), oxygen-permeation, thermopower and total-conductivity measurements in the oxygen partial pressure range 10−5–0.5 atm. The hole conductivity is lower for the Ce- and Nb-containing perovskites, primarily as a result of the lower Fe4+ concentration. Both dopants decrease oxide-ion conductivity but the effect of Nb-doping on ionic transport is moderate and ion-transference numbers are higher with respect to the Nb-free parent phase, 2.2 × 10−3 for La0.3Sr0.7Fe0.9Nb0.1O3−δ cf. 1.3 × 10−3 for La0.5Sr0.5FeO3−δ at 1223 K and atmospheric oxygen pressure. The average thermal expansion coefficients calculated from dilatometric data decrease on doping, varying in the range (19.0–21.2) × 10−6 K−1 at 780–1080 K.  相似文献   

20.
The electrochemical measurements were carried out by using thermophilic cytochrome P450 CYP119A2 (P450st) modified with poly(ethylene oxide) (PEO) in PEO200 as an electrochemical solvent. The PEO modified P450st gave clear reduction–oxidation peaks by cyclic voltammetry in oxygen-free PEO200 up to 120 °C. The midpoint potential measured for the P450st was −120 mV vs. [Fe(CN)6]4−/[Fe(CN)6]3− at 120 °C. The peak separation, ΔE, was 16 mV at 100 mV/s. The estimated electron transfer rate of PEO-P450st at 120 °C was 35.1 s−1. The faster electron transfer reaction was achieved at higher temperatures. The electrochemical reduction of dioxygen was observed at 115 °C with the PEO-modified P450st system.  相似文献   

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