DY-1酸洗缓蚀剂的研制与机理研究

通过正交试验设计方法研制了DY - 1新型酸洗缓蚀剂。该缓蚀剂缓蚀率高达 98.4%,加入量少 ,在 5 0℃以下的HCl溶液中对A3钢具有良好的缓蚀作用。通过化学失重法、电化学法及物理测试对DY - 1的缓蚀率、极化电阻和交流阻抗等电化学性能及缓蚀机理进行了研究 ,结果表明DY- 1是以物理吸附的方式吸附于金属表面而起作用。     

Effect of oxygen flow rate on the structural and electrochemical properties of lithium nickel oxides synthesized by the sol–gel method

The structural and electrochemical properties of LiNiO₂ powders were investigated as a function of the oxygen flow rate employed in the preparation of lithium nickel oxide. It was found that oxygen played an important role in the synthesis of highly crystallized LiNiO₂(R3¯m). In the crystallization process of LiNiO₂, a deficiency of oxygen in the calcination reactor induced the formation of impurities and cubic rock-salt structure (Fm3m) in LiNiO₂ powders. For LiNiO₂ prepared at higher oxygen flow rates, the electrode delivered high discharge capacities with relatively good retention rates. But very low electrode capacity was obtained from LiNiO₂ prepared at lower oxygen flow rates.     

Diffusion in porous silicon: effects on the reactivity of alkenes and electrochemistry of alkylated porous silicon

Alkenes are known to react with hydrogen-terminated silicon surfaces to produce robust organic monolayers that are attached to the surface via covalent SiC bonds. In this report we investigate the dependence of the rate of alkylation of porous silicon samples on the reaction time using photochemical initiation. The kinetics of the photochemical alkylation of hydrogen-terminated porous silicon by undec-1-ene in toluene were observed to be pseudo first order, however the apparent rate constant decreased as the concentration of undec-1-ene increased. This behaviour is opposite to what would be expected if the rate-limiting process was an elementary chemical reaction step involving the alkene. Instead, it suggests that transport of the alkene to reactive sites and in the correct orientation is the rate-limiting step. Comparison of the rates of alkylation of porous silicon by undec-1-ene and dimethoxytrityl (DMT)-undecenol is consistent with such an interpretation as the bulky DMT headgroup gives a lower rate of alkylation. The diffusion of some simple redox-active probe molecules in porous silicon was investigated using a scanning electrochemical microscope (SECM). The probe molecules are converted at diffusion-controlled rate at an inlaid disk ultramicroelectrode (UME) consisting of the cross-section of a microwire sealed in glass. If the microelectrode is placed a short distance above the porous silicon, the microelectrode current depends on kinetics of the electrochemical reactions at the porous silicon and the mass transport properties within the open thin layer cell formed by the microelectrode and the alkylated porous silicon. In order to differentiate the effects of finite heterogeneous kinetics at silicon from diffusion limitations, current-distance curves were fitted over a wide range of applied potentials (on the Si) and it was observed that the diffusion coefficient in the porous layer was strongly anisotropic. The measured diffusion rates are comparable to those in bulk water along the pores, but with negligible diffusion between pores. This indicates that few pore-pore interconnections exist in the porous silicon.     

Electrochemical conversion of phenolic wastewater on carbon electrodes in the presence of NaCl

The electrochemical conversion of highly concentrated synthetic phenolic wastewater was studied on carbon electrodes in a batch electrochemical reactor. The effects of reaction temperature, electrolyte concentration, current density and initial phenol concentration on phenol conversion were elucidated. The wastewater was synthetically prepared and used in reactions carried out generally at 25 °C with an initial phenol concentration of 3500 mg dm^?3. Although current density increased, phenol conversion% and initial phenol conversion rate did not increase correspondingly above 35 °C and an electrolyte concentration of 90 g dm^?3. As the voltage values applied were increased, the increasing current density resulted in fast phenol conversion. Kinetic investigations denoted that overall phenol destruction kinetics was of zero order with an activation energy of 10.9 kJ mol^?1. Under appropriate conditions, phenol was completely converted within 15 min for an initial phenol concentration of 98 mg dm^?3 while 8 h was required to gain 95% conversion using 4698 mg dm^?3. Solid polymeric materials were produced at initial phenol concentrations above 500 mg dm^?3 using the appropriate current density. In the reaction medium, only mono‐, di‐ and tri‐substituted chlorophenols were formed and 100% of all species were either oxidised or contributed to the formation of a polymeric structure. Almost all of the phenol loaded to the reactor was converted into non‐passivating polymeric products, denoting a safe and easy method for the separation of phenol. © 2001 Society of Chemical Industry     

Removal of cadmium and production of cadmium powder using a continuous undivided electrochemical reactor with a rotating cylinder electrode

The behaviour of a continuous undivided electrochemical reactor with a rotating cylinder electrode under potentiostatic control is examined for the abatement of cadmium from synthetic sodium sulfate solutions with Cd(II) concentrations lower than 500 mg dm^?3 at a reactor inlet pH ? 7. The process was designed to convert the metal ions in solution to metal powder, which settles to the conical of the reactor and may be removed at intervals as a sludge by opening a drop valve. The effect of applied potential, inlet cadmium concentration, rotation speed and hydrogen evolution as side cathodic reaction on the ‘figures of merit’ of the reactor are analysed. The best results were obtained for cathode potentials in the range from ?0.9 V to ?1.0 V against the saturated calomel electrode. Therefore, when the rotation speed was 1000 rpm the space time yield and the normalized space velocity were 0.64 ×10^?2 mol m^?3 s^?1 and 0.89 h^?1 respectively, while the fractional conversion per pass was 35% with a current efficiency higher than 74%. The surface morphology of the deposits as a function of the process variables is also reported. © 2002 Society of Chemical Industry     

环境污染物的电化学处理技术

对电化学技术在环境污染物治理中的应用进行了综述，分析了应用中可能存在的问题，提出了相应的对策。     

Direct electrochemical reduction of indigo: process optimization and scale-up in a flow cell

Reducing agents required in the dyeing process for vat and sulfur dyes cannot be recycled, and lead to problematic waste products. Therefore, modern economical and ecological requirements are not fulfilled. The industrial feasibility of the direct electrochemical reduction of indigo as a novel method has been determined and a preliminary optimization of electrolytic conditions was performed using a laboratory-scale flow-cell system. The role of current density, pH, temperature and the rate of mass transport are discussed. The influence of particle size reduction by the application of ultrasound is critically considered.     

Electrochemical studies of magnetite coating on carbon steel in ascorbic and picolinic acid

Electrochemical impedance and cyclic voltammetric measurements of magnetite coating formed on carbon steel substrates were carried out in deaerated solutions of 1.0 × 10^–2 M ascorbic acid and 3.5 × 10^–2 M picolinic acid at 28 °C. Impedance data showed that the interaction between magnetite and ascorbic acid is associated with an incubation period, after which reductive dissolution takes place accompanied by oxidation of ascorbic acid. Once the magnetite film loses its thickness and protective properties on prolonged exposure to ascorbic acid, the charge transfer resistance and the capacitance is reduced. Initial dissolution of magnetite in picolinic acid is due to congruent chemical dissolution with little contribution from reduction by the electrons arising from the corrosive attack of acid on the carbon steel. With time the contribution of the latter process increases as more and more of the substrate opens up. Cyclic voltammetric studies showed that there is an adsorption phenomenon leading to the formation of a surface ferric complex that undergoes reduction to the ferrous species and transfers to the bulk solution. The accumulation of the ferrous ion accelerates the dissolution resulting in an increase in current. Dissolution of magnetite in picolinic acid is slow. The better complexing capability of picolinic acid compared to ascorbic acid does not permit the accumulation of the ferrous ion as indicated by the absence of a peak in the voltammogram.     

Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C₄ carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.     

Influence of various parameters on the electrochemical treatment of landfill leachates

The influence of some basic parameters of an electrolytic system on the effectiveness of the treatment of landfill leachates is investigated. The controlling parameters of the system examined were: (i) the leachate input rate, (ii) pH and temperature, (iii) the amount of electrolyte (NaCl) added, (iv) the voltage applied and (v) the concentration of Fe²⁺ (added as FeSO₄ · 7H₂O). The performance of the system was assessed in terms of the COD, BOD₅ and NH₄ ⁺ reduction in the leachate samples as well as in terms of the energy consumption of the system (i.e., kWh consumed per kg of COD removed). These two parameters are referred to as the optimization parameters of the system. By implementing a 2⁶ factorial experiment, linear models, which interrelate each optimization parameter with the controlling parameters of the system, were generated. Using these models, effective treatment of landfill leachates by electrochemical oxidation can be designed.