Impedance spectrum measurement in liquid/liquid interface electrochemistry .2. Study on the ion transfer at L/L interface by impedance spectrum technique

In this paper we study the ion transfer across the liquid/liquid interface by impedance spectrum technique in the four - electrode system. We present a method of getting the real interfacial impedance curve from the apparent impedance curve obtained in the four - electrode system. A practical kinetics investigation on the transfer of tetramethylammonium ion at the water/nitrobenzene interface was done with the method to verify the validity of the method. The transfer of tetramethylammonium ion at the W/O interface is really a reversible transfer.

In situ electrochemical scanning tunnelling microscopy investigation of structure for horseradish peroxidase and its electrocatalytic property

Immobilization of protein molecules is a fundamental problem for scanning tunnelling microscopy (STM) measurements with high resolution. In this paper, an electrochemical method has been proved to be an effective way to fix native horseradish peroxidase (HRP) as well as inactivated HRP from electrolyte onto a highly oriented pyrolytic graphite (HOPG) surface. This preparation is suitable for both ex situ and in situ electrochemical STM (ECSTM) measurements. In situ STM has been successfully employed to observe totally different structures of HRP in three typical cases: (1) in situ ECSTM reveals an oval-shaped pattern for a single molecule in neutral buffer solution, which is in good agreement with the dimension determined as 6.2 x 4.3 x 1.2. nm(3) by ex situ STM for native HRP; (2) in situ ECSTM shows that the adsorbed HRP molecules on HOPG in a denatured environment exhibit swelling globes at the beginning and then change into a V-shaped pattern after 30 min; (3) in situ ECSTM reveals a black hole in every ellipsoidal sphere for inactivated HRP in strong alkali solution. The cyclic voltammetry results indicate that the adsorbed native HRP can directly catalyse the reduction of hydrogen peroxide, demonstrating that a direct electron transfer reduction occurred between the enzyme and HOPG electrode, whereas the corresponding cyclic voltammograms for denatured HRP and inactivated HRP adsorbed on HOPG electrodes indicate a lack of ability to catalyse H2O2 reduction, which confirms that the HRP molecules lost their biological activity. Obviously, electrochemical results powerfully support in situ STM observations.

Impedance spectrum measurement in liquid liquid interface electrochemistry .1. Analysis of various kinds of interfacial impedance in the four-electrode system

Applying impedance spectrum technique to liquid/liquid interfacial electrochemistry, we present the theoretical expression of the liquid/liquid interfacial impedance in the four - electrode electrolytic cell measured by alternating current impedance method. The influence of the electrolytic cell parameters and input passage parameters of the impedance apparatus on impedance spectrum curves are theoretically studied.

EFFECTS OF ANODIC-OXIDATION ON THE SURFACE-STRUCTURE OF HIGHLY ORIENTED PYROLYTIC-GRAPHITE REVEALED BY IN-SITU ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY IN H2SO4 SOLUTION

Effects of the potential of anodic oxidation and of potential cycling on the surface structure of a highly oriented pyrolytic graphite (HOPG) electrode were observed by in situ electrochemical scanning tunnelling microscopy (ECSTM) in dilute H2SO4 solution with atomic resolution. With potential cycling between -0.1 V and 1.8 V vs. Ag/AgCl (sat. KCI), some atoms on the top layer of HOPG protrude out of the base plane, and the graphite lattice of these protrusions is still intact but is strained and expanded. With further potential cycling, some protrusions coalesced and some grew larger, and an anomalous superperiodic feature was observed (spacing 90 Angstrom with a rotation 30 degrees relative to atomic corrugations) which superimposed on the atomic corrugation of HOPG. On the topmost of these protrusions, some atoms form oxides and others are still resolved by the ECSTM image. With potential cycling between -0.1 V and + 2.0 V vs. Ag/AgCl (sat. KCl), damage to freshly cleaved HOPG surface is more serious and fast, some ridges are observed, the atomic structure of the HOPG surface is partially and then completely damaged due to the formation of oxide. We also found that anodic oxidation occurred nonuniformly on the surface of HOPG near defects during potential cycling.

SCANNING-TUNNELING-MICROSCOPY (STM) AND LATERAL FORCE MICROSCOPY (LFM) INVESTIGATION OF THE STRUCTURE AND CHARACTER OF CONDUCTIVE POLYPYRROLE FILM

Polypyrrole doped with p-toluenesulfonate was electropolymerized onto highly oriented pyrolytic graphite (HOPG), glassy carbon (GC) and Pt electrode surfaces under the same experimental conditions. The resulting films were studied by scanning tunneling m

FABRICATION AND CHARACTERIZATION OF TIPS FOR ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY

We report a new technique for preparing tips for electrochemical scanning tunneling microscopy (ECSTM) with particular consideration of its simplicity and reproducibility. In preparing scanning tunneling microscopy (STM) tips by electrochemical etching, w

INVESTIGATION OF METALLOPORPHYRIN MODIFIED HOPG AND GC ELECTRODES BY SCANNING TUNNELING MICROSCOPE

HOPG and GC electrode surface feature modified with Cobaltmethyltetraphenylorphyrins (CoTPP) was investigated by scanning tunneling microscope combined with cyclic voltammograms. The effect of electrode surface morphologie

THEORETICAL-ANALYSIS OF NERNSTIAN PLOTS IN THE THIN-LAYER SPECTROPOTENTIOSTATIC TECHNIQUE

The Nernstian plots in a spectropotentiostatic experiment for complex electrode processes were studied theoretically. The plots are linear for an electron transfer process coupled with a preceding or succeeding chemical reaction, and the electron stoichio

AMPEROMETRIC DETECTION OF AMINO-ACIDS IN A FLOW-INJECTION SYSTEM WITH A NICKEL(II)-MODIFIED ELECTRODE WITH AN EASTMAN-AQ POLYMER FILM

Amperometic flow measurements were made at +0.55 V (vs. Ag/AgCl) in 0.1 mol l-1 KOH electrolyte with an Ni(II) chemically modified electrode (CME) with an Eastman-AQ polymer film. The use and characteristics of a Ni(II)-containing crystalline and polymer-modified electrode obtained by a double coating step as a detector for amino acids in a flow-injection system using reversed-phase liquid chromatography are described. The detection of these analytes is based on the higher oxidation state of nickel (NiOOH) controlled by the applied potential. The electroanalytical parameters and the detection current for a series of amines and amino acids were investigated. The use of such a CME in the flow-injection technique was found to be suitable in a solution at low pH. The linear range for glycine is 5 X 10(-6)-0.1 mol 1-1 with a detection limit of 1.0 X 10(-6) mol l-1. A 1 X 10(-4) mol 1-1 mixture of serine and tyrosine was also detected after separation on an Nucleosil C18 column.

STUDY OF A 1/12 PHOSPHOMOLYBDIC ANION DOPED POLYPYRROLE FILM ELECTRODE AND ITS CATALYSIS

A phosphomolybdic anion doped polypyrrole (PMo12O403- + PPy) film electrode has been prepared by electrochemical polymerization of pyrrole in an aqueous solution of 0.5 mol l-1 H2SO4 or 0.5 mol l-1 KNO3 containing PMo12O403- anions, and characterized by scanning electron microscopy and in-situ UV-visible spectroelectrochemical methods. The film electrode obtained is very stable upon potential cycling in acidic solution, but not in neutral solution. The catalytic effect of the film electrode on the reduction of ClO3- and BrO3- was studied.

SENSITIVE AMPEROMETRIC DETECTION OF GLUCOSE BY REVERSED PHASE LIQUID-CHROMATOGRAPHY AT A PRUSSIAN BLUE CHEMICALLY MODIFIED ELECTRODE OF NOVEL CONSTRUCTION

A new liquid chromatography electrochemical (LCEC) scheme for glucose sensing has been developed on the basis of a Prussian Blue chemically modified electrode (CME) of novel construction and characterized in terms of various experimental parameters by the flow injection analysis (FIA) technique. Unique hydrodynamic voltammograms were obtained for the first time at the CME in the flow-through amperometric detection of glucose, and subsequently both anodic and cathodic peaks could be expected on monitoring the operating potential in the modest positive or negative region. The unique pH dependence on the CME response towards glucose makes it perfectly compatible with conventional reversed phase liquid chromatography systems. On the basis of these features, practical application in glucose LCEC detection has been effectively performed; a linear response range over three orders of magnitude and a detection limit of subpicomole level were readily obtained. The capability of the established LCEC mode in the direct sensing of urinary glucose has been demonstrated.

DIRECT ELECTRON-TRANSFER REACTION OF HEMEPROTEINS PROMOTED BY METHYLENE-BLUE MODIFIED ELECTRODE

The heterogeneous electron transfer reaction of hemeproteins including hemoglobin, myoglobin and cytochrome C at Pt mesh electrode adsorbed methylene blue has been investigated. Thin-layer spectroelectrochemical technique was used for observing the electron transfer processes of three kinds of proteins, and the corresponding electrode rate constants were measured.

ELECTROCATALYSIS ON ELECTROCHEMICALLY PRETREATED GLASSY-CARBON ELECTRODE

The surface structure of glassy carbon electrode subjected to "galvanostat" pretreat- ment and its electrocatalytic behaviour in the presence of ascorbic acid, catechol and hydroquinone were studied by means of cyclic voltammetry, chronoamperometry, chronocoulometry and scanning electron microscopy. The electrocatalytic mechanism was discussed, which was due to the adsorption and the catalysis of functional groups at the electrode surface. Three separated peaks from the mixture of catecnol, hydroq...

Ionophore Based Bismuth Film Electrode for Lead

A Nafion/ionophore, 4-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide) composite coated and bismuth film modified glassy carbon electrode. (GC/NA-IONO/BiFE) was described to determine trace lead sensitively and selectively. The characteristics of such modified GC/NA-IONO/BiFE were studied by scanning electron microscopy and cyclic voltammetry. The influence of various experimental parameters upon the stripping lead signal at the GC/NA-IONO/BiFE was explored. Under the optimized conditions, the differential pulse voltammetric stripping response is highly linear over the 0.1-8.0 nM lead range examined (180s preconcentration at -1.2V), with a detection limit of 0.044nM and good precision (RSD=5.4% at 0.5nM). Also applicability to seawater samples was demonstrated at such modified electrode. The high selectivity of ionophore coupled with the excellent electrochemical characteristics of bismuth endow the GC/NA-IONO/BiFE a promising and robust tool for monitoring of trace lead rapidly and precisely.

东海陆架盆地西南部烟囱构造与油气运聚关系研究

In recent years, chimney structure has been proved one of important indicators and a useful guide to major petroleum fields exploration through their exploration history both at home and abroad. Chimney structure, which has been called "gas chimney" or "seismic chimney", is the special fluid-filled fracture swarm, which results from the boiling of active thermal fluid caused by abruptly decreasing of high pressure and high temperature in sedimentary layers of upper lithosphere. Chimney structure is well developed in continental shelf basin of East China Sea, which indicates the great perspectives of petroleum resources there. However, the chimney structure also complicated the petroleum accumulation. So the study of chimney structure on its formation, its effect on occurrence and distribution of petroleum fields is very important not only on theoretical, but also on its applied research. It is for the first time to make a clear definition of chimney structure in this paper, and the existence and practical meaning of chimney structure are illustrated. Firstly, on the viewpoint of exploration, this will amplify exploration area or field, not only in marine, but also on continent. Secondly, this is very important to step-by-step exploration and development of petroleum fields with overpressure. Thirdly, this will provide reference for the study on complex petroleum system with multi-sources, commingled sources and accumulation, multi-stage accumulations, and multi-suits petroleum system in the overlay basin. Fourthly, when the thermal fluid enters the oceanic shallow layer, it can help form gas hydrate under favorable low-temperature and high-pressure conditions. Meanwhile, the thermal fluid with its particular component and thermal content will affect the physical, chemical and ecological environments, which will help solving the problem of global resources and environment. Beginning from the regional tectonic evolution characteristics, this paper discussed the tectonic evolution history of the Taibei depression, then made an dynamical analysis of the tectonic-sedimentary evolution during the Mesozoic and Cenozoic for the East China Sea basin. A numerical model of the tectonic-thermal evolution of the basin via the Basin-Mod technique was carried out and the subsidence-buried history and thermal history of the Taibei depression were inverse calculated: it had undergone a early rapid rift and sag, then three times of uplift and erosion, and finally depressed and been buried. The Taibei depression contains a huge thick clastic sedimentary rock of marine facies, transitional facies and continental facies on the complex basement of ante-Jurassic. It is a part of the back-arc rifting basins occurred during the Mesozoic and Cenozoic. The author analyzed the diagenesis and thermal fluid evolution of this area via the observation of cathodoluminescence, scanning electron microscope and thin section, taking advantage of the evidences of magma activities, paleo-geothermics and structural movement, the author concluded that there were at least three tectonic-thermal events and three epochs of thermal-fluid activities; and the three epochs of thermal-fluid activities were directly relative to the first two tectonic-thermal events and were controlled by the generation and expulsion of hydrocarbon in the source rock simultaneously. Based on these, this paper established the corresponding model between the tectonic-thermal events and the thermal-fluid evolution of the Taibei Depression, which becomes the base for the study on the chimney structures. According to the analyses of the gas-isotope, LAM spectrum component of fluid inclusion, geneses of CO_2 components and geneses of hydrocarbon gases, the author preliminarily verified four sources of the thermal fluid in the Taibei Depression: ① dehydration of mud shale compaction, ② expulsion of hydrocarbon in the source rock; ③ CO_2 gas hydro-thermal decomposition of carbonatite; ④magma-derived thermal fluid including the mantle magma water and volatile components (such as H_2O, CO_2, H_2S, SO_2, N_2 and He etc.). On the basis of the vitrinite reflectance (Ro), homogenization temperature of fluid inclusion, interval transit time of major well-logging, mud density of the wells, measured pressure data and the results of previous studies, this paper analyzed the characteristics of the geothermal fields and geo-pressure fields for the various parts in this area, and discussed the transversal distribution of fluid pressure. The Taibei depression on the whole underwent a temperature-loss process from hot basin to cold basin; and locally high thermal anomalies occurred on the regional background of moderate thermal structure. The seal was primarily formed during the middle and late Paleocene. The overpressured system was formed during the middle and late Eocene. The formation of overpressured system in Lishui Sag underwent such an evolutionary process as "form-weaken-strengthen-weaken". Namely, it was formed during the middle and late Eocene, then was weakened in the Oligocene, even partly broken, then strengthened after the Miocene, and finally weakened. The existence of the thermal fluid rich in volatile gas is a physical foundation for the boiling of the fluid, and sharply pressure depletion was the major cause for the boiling of the fluid, which suggests that there exists the condition for thermal fluid to boil. According to the results of the photoelastic simulation and similarity physical experiments, the geological condition and the formation mechanism of chimnestructures are summarized: well compartment is the prerequisite for chimney formation; the boiling of active thermal fluid is the original physical condition for chimney formation; The local place with low stress by tension fault is easy for chimney formation; The way that thermal fluid migrates is one of the important factors which control the types of chimney structures. Based on where the thermal fluid come from and geometrical characteristics of the chimney structures, this paper classified the genetic types of chimney structures, and concluded that there existed three types and six subtypes chimney structures: organic chimney structures generated by the hydrocarbon-bearing thermal fluid in middle-shallow layers, inorganic and commingling-genetic chimney structures generated by thermal fluid in middle-deep layers. According to the seismic profiles interpretations, well logging response analysis and mineralogical and petrological characteristics in the study area, the author summarized the comprehensive identification marks for chimney structures. Especially the horizon velocity analysis method that is established in this paper and takes advantage of interval velocity anomaly is a semi-quantitative and reliable method of chimney structure s identification. It was pointed out in this paper that the occurrence of the chimney structures in the Taibei depression made the mechanism of accumulation complicated. The author provided proof of episodic accumulation of hydrocarbon in this area: The organic component in the boiling inclusion is the trail of petroleum migration, showing the causality between the boiling of thermal fluid and the chimney structures, meanwhile showing the paroxysmal accumulation is an important petroleum accumulation model. Based on the evolutionary characteristics of various types of chimney structures, this paper discussed their relationships with the migration-accumulation of petroleum respectively. At the same time, the author summarized the accumulating-dynamical models associated with chimney structures. The author analyzed such accumulation mechanisms as the facies state, direction, power of petroleum migration, the conditions of trap, the accumulation, leakage and reservation of petroleum, and the distribution rule of petroleum. The author also provides explanation for such practical problems the existence of a lot of mantle-derived CO_2, and its heterogeneous distribution on plane. By study on and recognition for chimney structure, the existence and distribution of much mantle-derived CO_2 found in this area are explained. Caused by tectonic thermal activities, the deep magma with much CO_2-bearing thermal fluid migrate upward along deep fault and chimney structures, which makes two wells within relatively short distance different gas composition, such as in well LF-1 and well LS36-1-1. Meanwhile, the author predicted the distribution of petroleum accumulation belt in middle-shallow layer for this area, pointed out the three favorable exploration areas in future, and provided the scientific and deciding references for future study on the commingling-genetic accumulation of petroleum in middle-deep layer and the new energy-gas hydrate.