利用STM针尖诱导铜表面刻蚀人工构筑表面电化学活性位

在电极电位稍负于其Nernst电位时 ,较正的探针电位可以诱导铜表面的局域刻蚀 ;同时 ,利用这一诱导刻蚀可以方便地人工构筑电极表面电化学活性位或特定的纳米结构 ,如现场构筑坑 (pit)、螺旋岛 (spiralisland)和岛 (island)等电化学活性位 ;并现场研究它们相关的 (电 )

有关电极电位概念的一些问题

有关电极电位概念的一些问题李爱昌（廊坊师专化学系廊访１０２８４９）关键词电极电位，化学位，电化学位电极电位（势）是电化学中最基本的概念，此概念具有一定的复杂性。近期出版的一些物理化学教科书、文献甚至某些专著在此概念及其相关问题上说法不一，这在一定程度...

In situ electrochemical synthesis of MOF-5 and its application in improving photocatalytic activity of BiOBr

Metal-organic frameworks（MOFs） are important functional materials. MOF-5（IL）（Zn4O（BDC）3（BDC=1,4-benzenedicarboxylate） was in situ synthesized by the electrochemical method using a tunable ionic liquid（IL）, 1-butyl-3-methylimidazolium chloride, as template. The crystallization of distinctly spherical MOF-5（IL） synthsized in ionic liquid by the electrochemical method is attributed to π-π stacking effect, ionic bond, and coordination bond. The analysis results show that the product MOF-5（IL） exhibits better crystallinity and higher thermal stability than MOF-5 generated using the solvothermal method. The cyclic voltammetry reveals that the electrosynthesis reaction is irreversible and controlled by the diffusion. The experiments on methylorange degradation show that the unique structure characteristics of MOF-5（IL） can enhance the photocatalytic ability of Bi OBr. Therefore, MOFs can replace noble metals to improve the photocatalytic properties of bismuth oxyhalide.

确定平衡体系独立自变量方法的应用(Ⅰ)

对于一个平衡体系,要规定其状态,需要确定几个独立变量成为关键问题。论述对于一个给定的多相平衡体系,由相律和广度量的一次齐函数性质可直接给出描述该平衡体系状态的独立变量,并由此推导出该体系的能斯特方程。

Anodic behavior and microstructure of Al/Pb-Ag anode during zinc electrowinning

Anodic behaviors and oxygen evolution kinetics of Pb-0.8%Ag and Al/Pb-0.8%Ag anodes during the initial 24 h zinc electrowinning were investigated with cyclic voltammetry （CV） curves and electrochemical impedance spectroscopy （EIS）. The results reveal that the anodic behaviors and reaction kinetics of the two anodes vary a lot during the anodic polarization which indicate the formation and stabilization of anodic layer. Compared with conventional Pb-0.8%Ag anode, A1/Pb-0.8%Ag anode has longer time of anodic polarization. At the very beginning of anodic polarization, the two anodes all exhibit higher potential of oxygen evolution reaction （OER） since the reaction is controlled by the transformation step of intermediates. Then, its OER potential is largely diminished and OER rate is deduced from the formation and adsorption of the first intermediate （S-OHms）. In the prolonged anodie polarization, the anodie potential of A1/Pb-0.8%Ag gradually decreases and the final value is more stable than that of conventional Pb-0.8%Ag anode. On the anodic layer after 24 h of anodic polarization, the OER potential is controlled by the formation and adsorption of intermediate. The microstructures of A1/Pb-0.8%Ag and Pb-0.8%Ag anodes after 24 h of anodie polarization were analyzed by scanning electron microscope （SEM）.

In-situ investigation of atmospheric corrosion behavior of bronze under thin electrolyte layers using electrochemical technique

The atmospheric corrosion behavior of bronze under thin electrolyte layer （TEL） with different thicknesses was monitored using cathodic polarization curves, open circuit potential （OCP） and electrochemical impedance spectroscopy （EIS）. Cathodic polarization result indicates that the cathodic limiting current density increases with decreasing the TEL thickness. EIS result shows that the corrosion rate increases with decreasing the TEL thickness at the initial stage because the corrosion is dominated by the cathodic process, whereas after long immersion time, the corrosion degree with the TEL thickness is in the sequence of 150 μm 〉 310 μm〉 10μm ≈ bulk solution 〉 57 μm. The measurements of OCP and EIS present in-situ electrochemical corrosion information and their results are in good agreement with that of physical characterizations.

Study on Methanol Oxidation at Pt and PtRu Electrodes by Combining in situ Infrared Spectroscopy and Differential Electrochemical Mass Spectrometry

Methanol oxidation reaction （MOR） at Pt and Pt electrode surface deposited with various amounts of Ru （denoted as PtxRuy, nominal coverage y is 0.17, 0.27, and 0.44 ML） in 0.1 mol/L HClO4＋0.5 mol/L MeOH has been studied under potentiostatic conditions by in situ FTIR spectroscopy in attenuated-total-reflection con guration and di erential electro-chemical mass spectrometry under controlled flow conditions. Results reveal that （i） CO is the only methanol-related adsorbate observed by IR spectroscopy at all the Pt and PtRu electrodes examined at potentials from 0.3 V to 0.6 V （vs. RHE）; （ii） at Pt0.56Ru0.44, two IR bands, one from CO adsorbed at Ru islands and the other from COL at Pt substrate are detected, while at other electrodes, only a single band for COL adsorbed at Pt is observed; （iii） MOR activity decreases in the order of Pt0.73Ru0.27〉Pt0.56Ru0.44〉Pt0.83Ru0.17〉Pt; （iv） at 0.5 V, MOR at Pt0.73Ru0.27 reaches a current e ciency of 50% for CO2 production, the turn-over frequency from CH3OH to CO2 is ca. 0.1 molecule/（site sec）. Suggestions for further improving of PtRu catalysts for MOR are provided.

DFT Study on Electronic Structures and Spectroscopic Properties of Oligo（silanylenediethynylanthracene）

Poly（silanylenediethynylanthracene） （PSDEA） exhibits a hole-transporting ability experimentally. In order to simulate the property of PSDEA, a series of silanylenediethynylanthracene oligomers were designed. The structures of these oligomers were optimized by using density function theory at B3LYP/6-31G（d） level. The energy gaps of the oligomers decrease with the increase in the chain length. The energy gaps of the oligomers also decrease in the presence of the electron-withdrawing group on the anthracene ring. The 13C chemical shifts and nucleus independent chemical shifts （NICS） at the anthracene ring center in the oligomers were calculated at B3LYP/6-31G level. The chemical shifts of the carbon atoms connected with the nitryl group changed upfield, compared with those of the carbon atoms without the nitryl group. The aromaticity at the anthracene ring center decreases in the presence of the electron-withdrawing group, whereas increases with the increase in the number of the silanylene units. The most sensitive location for calculating the NICS values is 0.1 nm above the anthracene plane.

Kinetics and Modeling of Chemical Leaching of Sphalerite Concentrate Using Ferric Iron in a Redox-controlled Reactor

This work presents a study for chemical leaching of sphalerite concentrate under various constant Fe3+ concentrations and redox potential conditions. The effects of Fe3+ concentration and redox potential on chemical leaching of sphalerite were investigated. The shrinking core model was applied to analyze the experimental results. It was found that both the Fe3+ concentration and the redox potential controlled the chemical leaching rate of sphalerite. A new kinetic model was developed, in which the chemical leaching rate of sphalerite was proportional to Fe3+ concentration and Fe3+ /Fe2+ ratio. All the model parameters were evaluated from the experimental data. The model predictions fit well with the experimental observed values.

Corrosion behavior of 2024 Al-Cu-Mg alloy of various tempers

Corrosion behavior of 2024 Al-Cu-Mg alloy of different tempers was assessed by potentiodynamic polarization studies in 3.5% NaCl solution, 3.5% NaCI＋I.0% H2O2 solution and 3.5% NaCl solution at pH 12. Polarization curves showed shifting of corrosion potential （φPcor） towards more negative potential with increasing ageing time and shifting of φcorr in the positive direction with the addition of H2O2 in NaCl solution. Polarization curves in 3.5% NaCl solution at pH 12 exhibited distinct passivity phenomenon. Optical micrographs of the corroded surfaces showed general corrosion, extensive pitting and intergranular corrosion as well. Cyclic potentiodynamic polarization curves exhibited wide hysteresis loop and the mode of corrosion attack confirmed that the alloy states are susceptible to pit growth damage. Attempts were made to explain the observed corrosion behavior of the alloy of various tempers in different electrolytes with the help of microstructural features.

Comparison on corrosion resistance and surface film of pure Mg and Mg−14Li alloy

To study different corrosion resistances and surface film types of hexagonal close-packed(HCP)pure Mg and body-centered cubic(BCC)Mg−14wt.%Li alloy in 0.1 mol/L NaCl,a series of experiments were conducted,including hydrogen evolution,mass loss,in-situ electrochemical testing combined with Raman spectroscopy and microstructural observation.The results indicate that the corrosion resistance of pure Mg is superior to that of Mg−14Li,and the protective function of the surface films on both magnesium systems is elevated within 16 h of immersion in 0.1 mol/L NaCl.An articulated,thick,and needle-like surface film containing Li2CO3 on Mg−14Li,different from the typically thin,flaky Mg(OH)2 film on pure Mg,is confirmed via scanning electron microscopy(SEM).However,both surface films can be broken down at a high anodic over-potential.Thus,different corrosion resistances of the two Mg systems are ascribed to various protective films forming on their surfaces.

Electrochemical behaviour of Ti alloys containing Mo and Ta as β-stabilizer elements for dental application

Corrosion behaviour of the studied Ti12Mo and Ti60Ta alloys with the same Mo equivalent values （12%, mass fraction） together with the currently used metallic biomaterials Cp-Ti were investigated for dental applications. The electrochemical properties of the samples were examined using electrochemical techniques： such as open-circuit potential, potentiodynamic polarization curves and electrochemical impedance spectroscopy （EIS）, in two electrochemical media of artificial saliva and fluoridated artificial saliva （0.1%fluoride ions, F-） at 37 °C. Fluoride is commonly included in toothpastes, odontological gels and dental rinses to prevent dental caries and relieve dental sensitivity. The passive behaviour for all the titanium samples is observed for both solutions. The Ti60Ta alloy appears to possess superior corrosion resistance than the Ti12Mo and Cp-Ti in both electrochemical media.

Flotation behavior and adsorption mechanism of fine wolframite with octyl hydroxamic acid

Flotation behavior and adsorption mechanism of octyl hydroxamic acid(OHA)on wolframite were investigated through flotation experiments,adsorption tests,zeta-potential measurements,infrared spectroscopy and solution chemistry calculations.Results of flotation and adsorption experiments show that the maximum values of flotation recovery and adsorption capacity occur around p H 9.In term of the solution chemistry calculations,the concentration of metal hydroxamate is greater than that of metal tungstate and metal hydroxyl,and metal hydroxamate compounds are identified to be the main species on wolframite surface at p H region of 8-10,contributing to the increase of OHA adsorption and flotation performance.Results of zeta-potential and IR spectra demonstrate that OHA adsorbs onto wolframite surface by chemisorptions.Hydroxamate ions can bond with Mn_2+/Fe_2+cations of wolframite surface,forming metal hydroxamate compounds,which is a key factor in inducing the hydrophobicity of wolframite under the conditions of maximum flotation.

Cyclic voltammetry and potentiodynamic polarization studies of chalcopyrite concentrate in glycine medium

Cyclic voltammetry and potentiodynamic polarization analyses were utilized to investigate the mechanism and kinetics of glycine leaching reactions for chalcopyrite.The effects of pH(9−12),temperature(30−90℃)and glycine concentration(0−2 mol/L)on corrosion current density,corrosion potential and cyclic voltammograms were investigated using chalcopyrite concentrate−carbon paste electrodes.Results showed that an increase in the glycine concentration from 0 to 2 mol/L led to an increased oxidation peak current density.Under the same conditions,corrosion current density was found to change from approximately 28 to 89μA/cm2,whereas corrosion potential was decreased from−80 to−130 mV.Elevated temperatures enhanced the measured current densities up to 60℃;however,above this level,current density was observed to decrease.A similar current density behavior was determined with pH.A pH change from 9 to 10.5 resulted in an increase in current density and pH higher than 10.5 gave rise to a reduced current density.In addition,the thermodynamic stability of copper and iron oxides was found to increase at higher temperatures.

Redox behavior and chemical species of arsenic in acidic aqueous system

Arsenic(As)removal from smelting acidic wastewater is an urgent task.The most common method is oxidation of trivalent As(III)to pentavalent As(V)subsequently precipitated by ferric(Fe(III))salts.Foundations of redox behavior and chemical species are of great importance for understanding As removal.In this work,cyclic voltammetry(CV)and UV?Vis spectroscopy were used for laboratory observation;meanwhile HSC and MINTEQ software were employed for theoretical analyses.It is found that As(III)oxidation,a multiple electron transfer reaction,is diffusion-controlled.The oxidation over-potential is very high(about0.9V)in sulfuric acid solutions(pH1.0).In addition,Fe(III)?As(V)complexes are evidenced by UV?Vis spectra and chemical species analyses in series of Fe(III)?As(V)?H2SO4?H2O solutions.Therefore,the Fe(III)and As(V)species distribution against pH values are determined and a newφ?pH diagram with inclusion of Fe?As complexes is consequently compiled based on thermodynamic data predicted by other researchers.

Comparative investigation on copper atmospheric corrosion by electrochemical impedance and electrical resistance sensors

Electrochemical impedance(EIS)and thin electrical resistance(ER)sensors were invented for atmospheric corrosion measurement of copper(Cu)during cyclic wetting−drying/high−low temperature tests and field exposure tests.Three-month field exposure results showed that average corrosion rate of Cu measured by ER sensor was well in accordance with that by weight loss method.During cyclic wetting−drying test,EIS was proven to reflect sensitively time of wetting and drying on the surface of sensor.Although corrosion rate obtained from EIS had a similar tendency to that obtained from ER sensors,the former was more dependent on environmental humidity than the latter.When relative humidity was low than 60%,corrosion rate of Cu measured by EIS was much lower than that by weight loss method,mainly attributing to the fact that impedance sensor failed to detect corrosion current of interlaced Cu electrodes due to the breakdown of conductive passage composed of absorbed thin liquid film under low humidity condition.Promisingly,ER sensor was proven to be more suitable for atmospheric corrosion monitoring than electrochemical techniques because it could sensitively monitor thickness loss of Cu foil according to the Ohmic law,no matter how dry or wet the sensor surface is.

Mechanism of oxidation of low rank coal by nitric acid

The pretreatment of low rank coal with nitric acid oxidation can promote its bio-liquefaction. However, the detailed mechanism of which remains an unresolved problem. In the present work, the characteristics of Fushun coal before and after oxidation by nitric acid were investigated combined with elemental composition, pore volume and pore size, Zeta potential, FT-IR, and 13C solid NMR spectrum analysis. The results show that the inorganic substance inlaid in coal are dissolved by ni- tric acid, which results in the decrease of coal ash content and increase of pore volume and pore size. Furthermore, there exist obvious chemical reactions between nitric acid and the functional groups of coal including aromatic ring carboxylation, side chain alkyl of aromatic ring oxidation and aromatic ring nitration. Among these reactions, some led to the increase in content of carboxyl, aliphatic carbon connected with O and humic acid carbon, while others caused the reduction of aromaticity, methyl carbon, substituted aryl carbon and side chain.

In-situ electrochemical surface-enhanced Raman spectroscopy in metal/polyelectrolyte interfaces

Polyelectrolyte becomes more and more popular in electrocatalysis.The understanding of electrode/polyelectrolyte interfaces at the molecular level is important for guiding further the polyelectrolyte-based electrocatalysis.Herein,we demonstrate an in-situ surface-enhanced Raman spectroscopic method by using a three-electrode spectroelectrochemical cell towards characterizing the electrode/polyelectrolyte interfaces.The Ag/AgCl and Ag/Ag_(2)O electrodes are used as the reference electrode in the acidic and the alkaline systems,respectively.The working electrode is made of a transparent carbon thin film which loads the electrocatalysts.The applications of this method are demonstrated through the in-situ characterizations of the p-methylthiophenol adsorbed on the Au and Pt and the electrochemical oxidation of Au on polyelectrolyte membranes.The potential-dependent spectral features of these two systems show that this method is a powerful tool for investigating the electrode/polyelectrolyte interfaces in electrocatalysis.

Solution to reinforcement learning problems with artificial potential field

A novel method was designed to solve reinforcement learning problems with artificial potential field.Firstly a reinforcement learning problem was transferred to a path planning problem by using artificial potential field(APF),which was a very appropriate method to model a reinforcement learning problem.Secondly,a new APF algorithm was proposed to overcome the local minimum problem in the potential field methods with a virtual water-flow concept.The performance of this new method was tested by a gridworld problem named as key and door maze.The experimental results show that within 45 trials,good and deterministic policies are found in almost all simulations.In comparison with WIERING's HQ-learning system which needs 20 000 trials for stable solution,the proposed new method can obtain optimal and stable policy far more quickly than HQ-learning.Therefore,the new method is simple and effective to give an optimal solution to the reinforcement learning problem.