电合成乙醛酸的研究

以过饱和草酸水溶液为阴极液 ,盐酸溶液为阳极液 ,在隔膜式平行板电解池内草酸电还原得到乙醛酸。考察改变阳极液盐酸溶液的浓度、电解液的电流密度和电解液的流速对生成乙醛酸电流效率的影响。考察催化电极对电合成的影响。结果表明 ,用碳板做电极材料 ,电流密度为 6 6 .7A·m-2 ,电解液流速为 2 6 1mL·min-1,电解温度为 2 0℃时 ,乙醛酸的电流效率可高达80 %以上。     

阴极冷却固定床反应器电合成乙醛酸

以过饱和草酸水溶液为阴极液,盐酸溶液为阳极液,在阴极冷却固定床电化学反应器内草酸电解合成乙醛酸。考察了电流密度、电极和电解液温度、阴极材料对合成乙醛酸时空产率和电流效率的影响。结果表明,阴极冷却固定床反应器是一种较理想的反应器,用石墨板作阳极,铅作阴极,电流密度为400.5A/m2,阴极空速u0=0.505m/s,电解温度为20℃左右时,电解1.5h,在阴极可得到质量分数为5.45%的乙醛酸溶液,平均时空产率可达0.12kg/dm3·h以上。     

葡萄糖电化学还原研究

本研究测定了阴极材料，电流密度，溶液ｐＨ以及温度等电解参数对葡萄糖电化学还原的电流效率的影响，为选择合适的电解条件提供依据。通过极化曲线的测定，进一步从理论上分析了电极材料对电流效率影响的原因。     

草酸电解过程中阴极失活影响因素研究

考察了草酸电解还原制乙醛酸过程中铅阴极失活的因素。实验表明,电解产物乙醛酸在电极表面的吸附量ΓR随着反应的进行不断增大,电流效率也随之大幅下降。尽管电解过后的铅电极表面可能形成草酸铅及氧化铅颗粒,导致反应物与电极表面接触区域减小,从而使得反应速率下降,但仍没有电解液组成变化对电流效率的影响大。而低析氢过电位金属在浓度较低时,电极表面的沉积对电流效率降低的影响并不显著。     

草酸电解还原制乙醛酸反应中添加剂的结构

以铅电极上草酸电解还原合成乙醛酸的反应为研究对象,考察了电解合成添加剂的结构对反应的影响。结果表明,添加剂的阴离子对电流效率和反应选择性影响显著。阴离子基团越对称,最长的烷基链越短,则电流效率越高,反应选择性越好。     

工艺参数对高速镀锡电流效率及镀锡层表面形貌的影响

采用自制旋转阴极装置模拟带钢的高速运动,并研究了电流密度、阴极转速及Sn~(2+)的质量浓度对甲基磺酸盐高速镀锡电流效率和镀锡层表面形貌的影响。结果表明:提高阴极转速和Sn~(2+)的质量浓度及降低外电流密度,可以提高电流效率;提高阴极转速和降低外电流密度,有利于镀锡层形成多晶态的形貌。电流效率与镀锡层结晶状态有良好的对应关系,电流效率越高,结晶越细致。另外,增大阴极转速能减小扩散层厚度,提高电流密度上限和电流效率,降低Sn2+的质量浓度下限,从而提高生产效率并降低生产成本。     

氨基磺酸盐镀镍的沉积速率与电流效率的研究

采用测厚法和恒电流沉积法,分别研究了镀液温度、阴极电流密度和添加剂对氨基磺酸盐镀镍的沉积速率与电流效率的影响。结果显示:在镀液中不含任何添加剂的前提下,镀镍的沉积速率和电流效率均随镀液温度的升高及阴极电流密度的增大明显提高,最高分别达到0.027 3μm/s和73.4%;而在电镀工艺参数相同的条件下,向镀液中加入适量的添加剂,镀镍的沉积速率和电流效率均略有提高。     

膜法组合工艺在电解锰产品中的影响因素分析

探究双膜三室工艺中不同影响因素对阴阳格室电解锰和二氧化锰产量及电流效率的影响。分别从溶液浓度、电解温度、pH、电流密度、添加剂含量及极板材质方面进行了考察。实验表明,双膜三室工艺中,控制溶液中Mn2+质量浓度35～41g/L、电解温度35～37℃、阴极pH=7.0～7.2、阳极酸浓度2.5mol/L、阴极电流密度350～400 A/m2、阳极电流密度800 A/m2、阴极添加剂SeO2质量浓度0.03～0.04 g/L、阴极板采用不锈钢板、阳极板采用钛涂二氧化铅板条件下,阴极电流效率高于70%,阳极1 L电解液中二氧化锰产量高于40 g。     

膜法组合工艺在电解锰产品中的影响因素分析

双膜三室工艺中，探究不同影响因素对阴阳格室电解锰和二氧化锰产量及电流效率的影响。分别从溶液浓度、电解温度、pH、电流密度、添加剂含量及极板材质方面进行了考察。实验表明：双膜三室工艺中，控制溶液中Mn2+质量浓度 35~41g/L、电解温度35~37℃、阴极pH=7~7.2；阳极酸浓度2.5mol/L、阴极电流密度350~400A/m2；阳极800A/m2、阴极添加剂SeO2浓度0.03~0.04g/L、阴极板采用不锈钢板阳极板采用钛涂二氧化铅板条件下，阴极电流效率高于70%，阳极1L电解液中二氧化锰产量高于40g。     

草酸电解还原制备乙醛酸的研究

研究连续草酸电解还原制备乙醛酸的过程和工艺。采用一膜两室电解面积为10cm×10cm的离子膜电解槽进行连续电解实验,比较了电极材料、阳离子交换膜材料、研究了电解液流量对电流效率的影响以及电流密度、电解温度和电解时间对电解过程的影响。结果表明以铅极板作阴极、钽-铱作阳极板、NF-1型含氟磺酸阳离子交换膜时电解的效果较好,得到的优化电解条件为:电流密度1000A.m-2,电解温度25℃,电解时间4.5h,阴极液和阳极液流量均为2L.min-1。在此条件下的电耗为3038.9kWh.t-1产品,研究结果可为工业化设计提供参考数据。     

Electrochemical degradation of clofibric acid in water by anodic oxidation: Comparative study with platinum and boron-doped diamond electrodes

Aqueous solutions containing the metabolite clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid) up to close to saturation in the pH range 2.0-12.0 have been degraded by anodic oxidation with Pt and boron-doped diamond (BDD) as anodes. The use of BDD leads to total mineralization in all media due to the efficient production of oxidant hydroxyl radical (OH). This procedure is then viable for the treatment of wastewaters containing this compound. The effect of pH, apparent current density, temperature and metabolite concentration on the degradation rate, consumed specific charge and mineralization current efficiency has been investigated. Comparative treatment with Pt yields poor decontamination with complete release of stable chloride ion. When BDD is used, this ion is oxidized to Cl₂. Clofibric acid is more rapidly destroyed on Pt than on BDD, indicating that it is more strongly adsorbed on the Pt surface enhancing its reaction with OH. Its decay kinetics always follows a pseudo-first-order reaction and the rate constant for each anode increases with increasing apparent current density, being practically independent of pH and metabolite concentration. Aromatic products such as 4-chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol are detected by gas chromatography-mass spectrometry (GC-MS) and reversed-phase chromatography. Tartronic, maleic, fumaric, formic, 2-hydroxyisobutyric, pyruvic and oxalic acids are identified as generated carboxylic acids by ion-exclusion chromatography. These acids remain stable in solution using Pt, but they are completely converted into CO₂ with BDD. A reaction pathway for clofibric acid degradation involving all these intermediates is proposed.     

Anodic oxidation of mecoprop herbicide at lead dioxide

The electrochemical oxidation of an aqueous solution containing mecoprop (2-(2-methyl-4-chlorophenoxy)propionic acid) has been studied at PbO₂ anodes by cyclic voltammetry and bulk electrolysis. The influence of current density, hydrodynamic conditions, temperature and pH on the degradation rate and current efficiency is reported. The results obtained show that the use of PbO₂ leads to total mineralization of mecoprop due to the production of oxidant hydroxyl radical electrogenerated from water discharge. The current efficiency for the electro-oxidation of mecoprop is enhanced by low current density, high recycle flow-rates and high temperature. In contrast, the pH effect was not significant. It has also been observed that mecoprop decay kinetics follows a pseudo-first-order reaction and the rate constant increases with rising current density.     

The effect of surface treatment on oxidation of oxalic acid at nanocrystalline diamond films

The surface investigation of undoped and boron doped nanocrystalline diamond (NCD/BDND) films associated to their electrochemical behavior of oxalic acid after four pre-treatments was studied. The films were produced using Hot Filament CVD technique on Si substrate with a gas mixture of CH₄/H₂/Ar. Surface pre-treatments were carried out to analyze the surface chemical changes induced by hydrogen and oxygen plasma and as well as cathodic and anodic treatments performed in 0.1 mol L^? 1 HClO₄. The films wetting analyzed by contact angle presented a strong dependence of their surface before and after each treatment was also confirmed by the electrochemical response from cyclic voltammograms. Independent of the surface pre-treatments, all the electrodes exhibited response for oxalic acid oxidation, but the electrode submitted to hydrogen plasma presented the lowest starting oxidation potential and the highest current density. Nonetheless, the BDND electrode presented higher oxidation current than that for NCD electrodes, after all pre-treatments studied. The use of square wave voltammetry with BDND electrode treated by hydrogen plasma for the analytical determination of oxalic acid is described. The detection limits of 0.75 μmol was obtained from the linear relationship between the peak currents of voltammograms as a function of the oxalic acid concentrations.     

Synthesis and characterization of polypyrrole/TiO2 composites on mild steel

The anodic codeposition of polypyrrole and TiO₂ on AISI 1010 steel substrates in oxalic acid medium was studied from the standpoint of their use as protective coatings against corrosion. The influence of surface treatment, pH, stirring and current density (j) on the current efficiency () and pigment concentration incorporated in the polymer (C _c) were investigated. The highest C _c values (7.5%) were found at j = 5 mA cm^–2, pH 4 and stirred baths. The composites were characterized by adherence and surface roughness tests, XPS, EDX, SEM, FTIR and cyclic voltammetry.     

Grafting vinyl monomers onto polyester fibers. III. Graft copolymerization of methyl methacrylate onto poly(ethylene terephthalate) using potassium permanganate–oxalic acid redox system

The use of the KMnO₄—oxalic acid redox system to initiate graft copolymerization of methyl methacrylate (MMA) onto poly(ethylene terephthalate) (PET) fiber has been investigated. The rate of grafting was determined by varying the concentrations of monomer, KMnO₄, oxalic acid, acidity of the medium, and temperature. The graft yield increases steadily with increasing KMnO₄ concentration. The graft yield is also influenced with concentration. The graft yield is also influenced with temperature. The effect of certain solvents on the rate of grafting has been investigated, and a suitable reaction mechanism has been proposed.     

Photocatalytic degradation of organics in water in the presence of iron oxides: Influence of carboxylic acids

The effects of four carboxylic acids: malic, citric, tartaric and oxalic acids on the leaching of iron from two commercial iron oxides (hematite, α-Fe₂O₃, and magnetite, Fe₃O₄) have been investigated. The variables studied were the doses of iron oxides and carboxylic acids used as well as aqueous pH, temperature and the presence of hydrogen peroxide and/or UV-A radiation. On the whole, Fe₃O₄ led to higher amounts of leached iron than α-Fe₂O₃, and oxalic acid was the most effective carboxylic acid used. The importance of iron leaching has been considered to explain the photodegradation of bisphenol A (BPA) by UV-A/iron oxides systems. The influence of the presence of hydrogen peroxide and/or titania on the efficiency of these oxidation systems was also investigated. At the conditions tested, advanced oxidation with the UV-A/iron oxide/oxalic acid/H₂O₂/TiO₂ system led to the lowest BPA half life (<15 min) among those processes studied.     

Influence of variables in nickel-manganese-zinc alloy plating from a sulphate bath

An Ni-Mn-Zn alloy has been satisfactorily electrodeposited from a sulphate bath containing nickel sulphate (20–23 g dm⁻³), manganese sulphate (76–88 g dm⁻³), zinc sulphate (18–24 g dm⁻³), ammonium sulphate (30 g dm⁻³), thiourea (18g dm⁻³) and ascorbic acid (0.8 g dm⁻³) under various plating conditions, namely, current density 1.0–3.0 A dm⁻²; temperature 30–45° C; pH 2.7–4.2 and duration of electrolysis 15–30 min. Semibright, blackish-grey, thin films were generally deposited with the proportion of nickel and manganese in the deposits increasing with increasing current density, temperature and duration of electrolysis. However, the amount of zinc increased as the pH of the solution was raised. The cathode efficiency for alloy deposition increased linearly as the temperature or the pH of the solution was decreased, whereas at any particular pH and temperature it continuously rose with increasing current density or the time of deposition. The cathode polarization shifted to more negative values on increasing the current density and to less negative values at higher pH values and temperatures which consequently lowered the throwing power under the latter conditions.     

Electrochemical removal of the insecticide imidacloprid from water on a boron-doped diamond and Ta/PbO<Subscript>2</Subscript> anodes using anodic oxidation process

The removal of pesticides from water is a major environmental concern. This study investigates the electrochemical removal of the insecticide imidacloprid (IMD) from aqueous solutions on a boron-doped diamond (BDD) and Ta/PbO₂ anodes under galvanostatic electrolysis. The influence of operating parameters, such as applied current density (50–100 mA cm^?2), initial chemical oxygen demand COD (0) (281–953 mg L^?1), temperature (25–65 °C) and pH (3.0–10.0) on COD and instantaneous current efficiency (ICE), was studied using the BDD electrode. The degradation efficiency of IMD increased by increasing current density and temperature, but noticeably decreased by the increase of initial pH value and initial concentration of IMD. The COD decay follows a pseudo-first-order kinetic, and the process was under mass transport control. COD removal reaches 90% when using an apparent current density of 100 mA cm^?2, initial COD of 953 mg L^?1, pH of 3.0 and at 25 °C after 4.5 h electrolysis time. Compared with Ta/PbO₂, BDD anode has shown better performance and rapidity in the COD removal using the same electrolysis device.     

In situ degradation of formaldehyde with electrogenerated hypochlorite ion

The oxidant ClO^– was generated on an SPR (SnO₂-PdO-RuO₂-TiO₂) anode and used to degrade formaldehyde in aqueous solution. The current efficiency of the production of hypochlorite ion was significantly affected by the concentration of chloride ion, pH and stirring rate. The effect of current density and temperature on the current efficiency for electrogeneration of hypochlorite ion was slight. The maximum anodic current efficiency was 99.3% when 100 C was charged. Increasing the concentration of chloride ion, pH, temperature, stirring rate and the concentration of formaldehyde in the solution and decreasing the current density and charge passed resulted in increased current efficiency of degradation of formaldehye with electrogenerated hypochlorite ion.     

Application of Ni-doped ZnO rods for the degradation of an azo dye from aqueous solutions

Ni-doped ZnO rods were applied as a photocatalyst for the degradation of an azo dye (Reactive Black 5). Effects of solution pH, catalyst dosage, initial RB5 concentration, H₂O₂ concentration, different purging gases, and type of organic compounds on the removal efficiency of RB5 were studied. Ni-doped ZnO rods were synthesized by co-precipitation method. Neutral pH was selected as an optimal pH condition due to a photo-corrosion of ZnO in acidic and basic conditions. Photocatalytic degradation efficiency of RB5 was increased as the catalyst dosage increased up to 1 g/L, while it was decreased by increasing initial RB5 concentration. Pseudo-first-order rate constant (k _obs ) decreased from 0.122 to 0.0051 min^-1 and electrical energy per order (E _Eo ) increased from 39.34 to 941.18 (kWh/m³) by increasing RB5 concentration from 5 to 100mg/L, respectively. Photocatalytic degradation efficiency of RB5 increased by increasing H₂O₂ concentration, but this trend was not observed above 10 mM. Photocatalytic degradation efficiency of RB5 increased in the presence of folic acid and citric acid while interference was observed in the presence of humic acid, EDTA, oxalic acid, and phenol. Photocatalytic activity was maintained even after five successive cycles.