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1.
Dai Y Meier C Ziener U Landfester K Täubert C Kolb DM 《Langmuir : the ACS journal of surfaces and colloids》2007,23(22):11058-11062
The structure of a bisterpyridine-like oligopyridine (abbreviated as 2,4'-BTP) monolayer on Au(111), adsorbed from an acetone solution, was studied by in situ scanning tunneling microscopy and cyclic voltammetry in aqueous 0.1 M H2SO4. Short-range ordered adsorption with an average distance between the individual molecules of about 2 nm was observed only at electrode potentials positive of +0.4 V vs SCE, whereas at more negative potentials, no order could be found. With the help of Cu underpotential deposition, a potential-induced, fast, and fully reversible structure transition within the organic monolayer was identified at about +0.4 V vs SCE. At negative potentials the molecules apparently cluster together and consequently current-potential curves resemble those for a bare gold surface, whereas for E>+0.4 V vs SCE the molecules are spread over the entire surface in a hexagonal, close-packed fashion. This may have interesting consequences for switching between different template structures. 相似文献
2.
K. Wohnrath C.A. Pessoa P.M. dos Santos J.R. Garcia A.A. Batista O.N. Oliveira Jr. 《Progress in Solid State Chemistry》2005,33(2-4):243-252
The electrochemical properties of mer-[RuCl3(dppb)(4-pic)] (dppb = Ph2P(CH2)4PPh2, 4-pic = CH3C5H4N), Rupic, in CHCl3 are governed by the formation of species such as [Ru2Cl5(dppb)2], [Ru2(dppb)2Cl4(4-pic)] and trans-[RuCl2(dppb)(4-pic)2] upon the reduction of “[RuCl2(dppb)]”. The overall behavior depends on whether Rupic is immobilized in cast or Langmuir–Blodgett (LB) films, or incorporated into a carbon paste electrode (CPE). In cyclic voltammograms, one redox process appears for LB/Rupic films and CPE/Rupic, at Epa = 0.35 V, Epc = 0.25 V vs SCE, and Epa = 0.32 V, Epc = 0.24 V vs Ag/AgCl, respectively. This redox process was ascribed to the RuIII/RuII charge transfer. For cast films the redox pair was poorly defined, with Epa = 0.27 V and Epc = 0.20 V. The reason for the difference lies in the phase separation and formation of aggregates onto ITO for the cast film, in contrast to the LB film. With aggregation, the formation of species occurring in solution is impaired for Rupic in cast films. The electrochemical properties for Rupic in LB films and incorporated into CPE allowed the electrocatalytic activity of Rupic to be exploited in sensors for dopamine and ascorbic acid. 相似文献
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Sandor Barany Vladimir Shilov Ferenc Madai 《Colloids and surfaces. A, Physicochemical and engineering aspects》2007,300(3):353-358
In this study, the effect of adsorbed non-ionic polyethylenoxides (PEO) and polyvinil-pyrrolidones (PVP) of different molecular mass on the electrophoresis of polystyrene, graphite and aluminum oxide particles both in weak (5–20 V/cm) and strong (50–400 V/cm) electric fields has been studied. The measurements in strong fields have been performed in short electric pulses using image analyzing equipment in which we have determined the deviation of particles from their normal sedimentation trajectory. We have shown that the adsorption of PEO and PVP strongly decreases the electrophoretic velocity (Vef) of particles in weak electric fields, and this decrease is bigger the adsorbed amount is higher. This is explained by the shift of the shear plane toward solution due to polymer adsorption. At the same time the polymer adsorption only slightly changes the Vef of particles in strong fields. It means that the non-linear (“cubic”) electrophoresis is independent of the position of the shear plane, i.e. the zeta-potential value. It proves our idea that the electrophoretic velocity in strong electric fields is determined mainly by the surface conductivity of particles, i.e. it is not a function of the electrokinetic potential but rather the Dukhin number that characterizes the polarization of the electric double layer. 相似文献
4.
Formation of intermacromolecular complexes containing viologen and electron-transfer reaction occurred on the electrode modified by the complex films were studied. Compositions and morphology of the complexes depend on the properties of polyanion and chemical environment of complexation. The analytical results of cyclic voltammetry (CV) and rotating disk voltammetry(RDV) indicated: (1) active sites of viologen in network of complexes transferred single electron reversibly; (2) the redox peak currents showed excellent symmetry and stability; (3) redox potentials were related to properties of polyanions, varying from —0.4 to-0.6V (vs. SCE). Electrochromic materials with different displaying colors could be obtained by changing the structure of polyviologen. 相似文献
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The cathodic stripping voltammetry of six thiols by deposition at a hanging mercury drop electrode (+0.05 V vs. SCE) from acetate-buffered solution (pH 4.76) and scanning to —0.8 V is described. Peak potentials are reported. The peak height—concentration relationships are reasonably linear in the range 0.4–1.2 μM. The compounds tested are 2-mercaptopyridine, 2-mercapto-3-pyridinol, 2-mercaptopyridine-N-oxide, mercaptosuccinic acid, 2-mercaptopyrimidine and cysteine hydrochloride. 相似文献
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The self-assembly of 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) on Au(111) electrodes was investigated. The adlayer structure was found to depend on the electrode potential. At positive potentials (>0.5V(SCE)), a disordered layer of TPyP is formed on the Au(111) electrode. STM images showed that the disordered molecules are immobile. At negative potentials (-0.2V(SCE)), however, the molecules are highly mobile and can no longer be imaged by STM, though they remain on the surface. At intermediate potentials (-0.2 to +0.2V(SCE)), the TPyP formed a highly ordered adlayer. Once the ordered adlayer is formed, it persists even after the potential is stepped to higher values (0.5-0.8 V(SCE)). These results can be explained by the role of potential modulated adsorbate-substrate interaction and surface mobility. This suggests the intriguing prospect of using electrode potential to tune surface interactions and to drive surface processes, e.g., molecular self-assembly, in electrochemical systems. 相似文献
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Santos VO Alves MB Carvalho MS Suarez PA Rubim JC 《The journal of physical chemistry. B》2006,110(41):20379-20385
This is the first report of in situ SER spectra of chemical species adsorbed on a Ag/room temperature ionic liquid (RTIL) interface. We have investigated the dependence of the SERS intensity of the RTIL derived from 1-n-butyl-3-methylimidazolium hexafluorophosfate (BMIPF6) adsorbed on a silver electrode. It has been shown that the BMI+ adsorbs on the silver electrode for potentials more negative than -0.4 V vs a Pt quasireference electrode (PQRE). In the -0.4 to -1.0 V potential range the SER spectra are similar to the Raman spectrum of the RTIL BMIPF6. At potentials more negative than -1.0 V some imidazolium ring vibrational modes and N-CH3 vibrations are enhanced, suggesting that the imidazolium ring is parallel to the surface and for potentials <-2.8 V the BMI+ is reduced to the BMI carbene. The potential dependence of the SERS intensities of Py adsorbed on a silver electrode in BMIPF6 has also been investigated. The results have shown that at potentials less negative than -0.8 V (vs PQRE) Py adsorbs at an end-on configuration forming an Ag-N bond. In the -0.9 to -1.4 V potential range Py molecules lie flat on the electrode surface and at potentials <-1.4 V Py is replaced by the BMI+. The electrochemical and SERS results have shown that Py has the effect of changing the oxidation of silver in that medium as well as the reduction of BMI+ to the BMI carbene. In the presence of Py the BMI+ reduction is observed at potentials near -2.4 V. The Ag electrode has presented SERS activity from 0.0 to -3.0 V. 相似文献
9.
用电化学循环伏安法和电化学石英晶体微天平(EQCM)技术研究了Sb在Au电极上不可逆吸附的电化学过程. 研究结果表明, 在-0.25 V到0.18 V(vs SCE)范围内, Sb可在Au电极上稳定吸附, 并且在0.15 V附近出现特征氧化还原峰. 根据EQCM实验数据, 在电位0.18 V时, Sb在Au电极上的氧化产物是Sb2O3; 同时Sb的吸附阻止了电解液中阴离子和水在Au电极上的吸附. 当电极电位超过0.20 V时, Sb2O3会被进一步氧化成Sb5+化合物, 同时逐渐从Au电极表面脱附. 相似文献
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The cysteamine (CA) was bound onto surface of the pretreated glassy carbon electrode (GC) with cyclic voltammetry (CV). Gold nanoparticles were self-assembled to the electrode binding with cysteamine via strong AuS covalent bond to fabricate the nano-Au self-assembled modified electrode (nano-Au/CA/GC). The modified electrode was characterized with cyclic voltammetric and ac impedance methods. The electrochemical behavior of dopamine (DA) on the modified electrode was investigated with cyclic voltammetry and differential pulse voltammetry (DPV). A well-defined redox peaks of DA on the nano-Au/CA/GC electrode were obtained at Epa = 0.175 V and Epc = 0.146 V (vs. SCE), respectively. The peak current of DA is linear with the concentration of DA in the range of 1.0 × 10−8 mol L−1 to 2.5 × 10−5 mol L−1, with the correlation coefficient of 0.998. The detection limit is 4.0 × 10−9 mol L−1 (S/N = 3). The modified electrode exhibited an excellent reproducibility, sensibility and stability for determination of DA in the presence of high concentration AA, and can be applied to determinate dopamine injection, with satisfied result. 相似文献
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本文研究厌氧条件下产电绿脓杆菌P. aeruginosa BTE-1的电化学催化特征。研究结果表明,P. aeruginosa BTE-1菌株在厌氧条件下,不能分泌可充当电子介体的绿脓菌素,但可通过在电极表面形成生物膜呈现了直接电催化性能。P. aeruginosa BTE-1在电极表面形成生物膜与其在特定电极电位下向电极传递电子的过程直接相关,适宜的电位为+0.2 V (vs. SCE),电位过高可能会损害P. aeruginosa BTE-1细胞。室温范围内升高温度可增强P. aeruginosa BTE-1生物膜电催化活性,但过高的温度(>60℃)会抑制生物膜电催化活性。循环伏安曲线显示,在厌氧条件下形成的P. aeruginosa BTE-1生物膜,具有与典型产电菌株G. sulfurreducens相近的氧化还原电位(-0.4 V~ -0.2 V vs. SCE)。P. aeruginosa BTE-1生物膜可电催化酵母抽取物和葡萄糖,但不能电催化醋酸盐。 相似文献
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Here was demonstrated for the first time a possible application of abrasive stripping voltammetry in the direct measurement of trace metals in anoxic, sulfidic marine sediments (peloid mud) from a small and shallow (0.2–1 m) marine lagoon in Central Dalmatia, Croatia. Trace amounts of sample compounds are transferred to the graphite electrode surface and electrochemical reduction or oxidation processes are followed by the cyclic voltammetry in seawater or 0.55 M NaCl as electrolyte. After a preelectrolysis at potentials ranging from ?1.0 to ?1.5 V (vs. SCE) a well‐defined anodic stripping peak corresponding to the oxidation of metal deposits generated at deposition potentials is obtained around ?0.74 V (vs. SCE). The same samples were studied by anodic stripping voltammetry at the Hg electrode and inductively coupled plasma‐mass spectrometer (ICP‐MS). ICP‐MS showed higher concentrations of trace metals such as Al, Fe, Mo, Mn. A relatively high concentration of reduced sulfur species (RSS) (10?3 M) is determined electrochemically in porewater of the peloid mud, indicating that the magnitude of metal enrichment in the sediments is probably controlled by precipitation with sulfide. 相似文献
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P. Velsquez H. Gmez J. R. Ramos-Barrado D. Leinen 《Colloids and surfaces. A, Physicochemical and engineering aspects》1998,140(1-3):369-375
A chalcopyrite CuFeS2 electrode obtained from the “El Teniente” mine (Chile) has been studied by cyclic voltammetry (CV) in a borax alkaline solution at pH 9.2 and by X-ray photoelectron spectroscopy (XPS) before and after the electrochemical treatment at oxidation and reduction potentials. The voltagram shows two peaks in the positive sweep direction which can be assigned to an oxidation process at the electrode surface that involve the formation of Fe2O3 and CuO giving rise to an irregular surface layer of the electrode with islands of different chemical composition. The XPS results confirm the formation of Fe2O3 and CuO at the electrode surface and their stability against decomposition at reduction potential. In addition, the formation of FEOOH, CuFeO and CuS species at the electrode surface can be deduced by XPS as well as a covering of the whole electrode surface by species due to carbon–oxygen groups. 相似文献
15.
Rong Chen 《Research on Chemical Intermediates》2013,39(3):843-851
The primary electroreduction behavior of 6-amino-5-nitroso-1,3-dimethyluracil (ANDMU) on an active carbon fiber (ACF) electrode in acidic aqueous solution was studied by cyclic voltammetry and ultraviolet spectrophotometry for application in electrochemical synthesis and electrosorption separation in the caffeine industry. On the ACF electrode at potentials more negative than ?0.3 V versus SCE, ANDMU could be electro-reduced to 5,6-diamino-1,3-dimethyluracil. The mechanism of electroreduction of ANDMU is possibly coupling of two electron-transfer steps with electrocatalytic hydrogenation. ANDMU could also be electro-oxidized on an ACF electrode at potentials more positive than 0.8 V versus SCE. The potential window of ANDMU on the ACF electrode is deduced to be ?0.3 to 0.8 V versus SCE under these experimental conditions. The results are indicative of high feasibility of electrochemical hydrogenation of ANDMU on an ACF electrode in caffeine green synthesis. 相似文献
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运用电化学循环伏安(CV)和原位红外反射光谱(in situ FTIRS)研究了中性介质中L-丝氨酸在Pt电极上的解离吸附和氧化过程. 结果表明, 在中性溶液中, 以两性离子形式存在的丝氨酸可以在很低的电位下(-0.6 V, vs. SCE)在Pt电极表面发生解离吸附, 生成强吸物种一氧化碳(COL)、(COB)和氰负离子(CN-). 研究结果还表明, 当电位低于0.7 V(vs. SCE)时, CN-能稳定存在于电极表面, 抑制丝氨酸的进一步反应. 在更高电位时则主要为丝氨酸分子的氧化过程. 相似文献
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Molybdenum(VI) is determined by anodic stripping voltammetry using a carbon paste electrode modified in situ with cetyltrimethylammonium bromide (CTAB). The preconcentration of molybdenum is performed by adsorption and reduction of ion-pairs of cetyltrimethylammonium and molybdenum(VI) oxalate at a potential of −0.4 V vs. the saturated calomel electrode (SCE). The supporting electrolyte contains 0.01 M oxalic acid and 0.075 mM CTAB. Differential pulse anodic stripping voltammetry exploiting the reoxidation signal is used for the determination of trace levels of molybdenum(VI). Linearity between current and concentration exists for a range of 0.5–500 μg 1−1 Mo with proper preconcentration times; the limit of detection (calculated as 3σ) is 0.04 μg 1−1 with an accumulation period of 10 min. 相似文献
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A liquid chromatographic method for the selective detection of riboflavin (vitamin B2) and flavin adenine dinucleotide (FAD) utilizing a thin-layer amperometric detector with two electrodes in series is described. The upstream electrode was held at ?0.4 V (vs. SCE) with the downstream electrode at +0.1 V (vs. SCE). The linear ranges are 40 ng?10 μg for riboflavin and 200 ng?8 μg for FAD and the limits of detection are 8 and 40 ng, respectively. The interference of thirteen different vitamins on the spectrophotometric or electrochemical detection of FAD and vitamin B2 was studied and no interference was found using the two-electrode detector. The effects of light on riboflavin and FAD is discussed. The method is convenient, rapid and economic, and has high selectivity. 相似文献
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