Electrosynthesis of lactic acid on copper and lead cathodes in aqueous media

The present study concerns the electrochemical reduction of pyruvic acid in different aqueous media on lead and copper electrodes. Some parameters such as electrode material, nature of the electrolyte, reduction potential and concentration of the organic substrate were systematically studied. The cathodic behavior of pyruvic acid was studied by cyclic voltammetry and suitable conditions were found in order to optimize the conversion of pyruvic acid during prolonged electrolyses. The results obtained showed that the pH of the solution (pH 10), the electrode material (Pb) and potential of electrode (−2.0 V (MSE)) allowed to enhance the selectivity of lactic acid which reached 90% with a conversion yield of 92%.     

间硝基苯甲酸在硫酸介质中的电还原特性

采用循环伏安法研究了硫酸介质中电极材料、扫描速度、反应温度和添加剂等对间硝基苯甲酸(mNBA)电解还原的影响。结果表明：在该体系中最合适的阴极材料为铜电极;在电还原过程中,随着扫描速度和温度增大,mNBA电还原反应的峰电流不断增大,其电极过程受扩散控制,电还原反应伴有不可逆随后化学反应;在溶液中加入无机盐SnCl2对mNBA的电解还原有明显的助催化作用。     

Electrosynthesis of 2,3-dimethyltartaric acid from pyruvic acid in acid medium

This study reports the electrohydrodimerization of pyruvic acid to 2,3-dimethyltartaric acid in sulphuric acid medium (0.5 M H₂SO₄) on a lead cathode. The main products detected were lactic acid and 2,3-dimethyltartaric acid. The selectivity towards the formation of 2,3-dimethyltartaric acid was studied vs. pyruvic acid concentration in sulphuric acid solution, at −1.1 V vs. MSE. The best selectivity of 2,3-dimethyltartaric acid reached 69% for an initial concentration of 1.7 M pyruvic acid. The yield of pyruvic acid was 84%.     

聚天冬氨酸对硫酸介质中碳钢的缓蚀性能研究

采用常规的失重法对聚天冬氨酸(PASP)在硫酸介质中对碳钢的缓蚀性能进行了研究。研究了聚天冬氨酸的用量、温度、硫酸的浓度等因素对其缓蚀性能的影响。得出聚天冬氨酸用量为0.2%,温度为30℃,硫酸浓度小于15%时对碳钢都有较好的缓蚀性能。用线性扫描伏安法和电化学阻抗谱对聚天冬氨酸的缓蚀机理进行了电化学研究,发现随着PASP浓度增加,金属的自腐蚀电位有变大的趋势,表明聚天冬氨酸应属于阳极型缓蚀剂;同时阻抗谱在高频区出现了半圆容抗弧,加入聚天冬氨酸的体系半圆半径变大,进一步验证了聚天冬氨酸对碳钢的缓蚀性能。     

间接电催化氧化法合成丙酮酸

采用电位扫描和旋转电极等方法对酸性介质中Ｂｒ－间接电催化乳酸合成丙酮酸的机理进行了研究，证实随后的化学反应为速度控制步骤，其反应的速率常数为３．２ｍｏｌ·Ｌ·ｓ－１。对电极材料、电流密度、溶液组成等影响因素的研究表明：铂电极较ＤＳＡ具有更好的催化活性，当电流密度为１２．５ｍＡ·ｃｍ－２，乳酸与溴化钾的摩尔比为５∶１时，得到的电流效率较高     

Silver nucleation on mercaptoacetic acid covered gold electrodes

Silver nucleation on the mercaptoacetic acid coated gold electrode under potentiodynamic and potentiostatic conditions was investigated using cyclic voltammetry, chronoamperometry, scanning electron microscopy, and mathematical simulations. Silver was easily adsorbed on the modified electrode surface due to the complexation and electrostatic interaction of silver with the carboxyl groups of mercaptoacetic acid. The rate constants for the electrochemical reduction and oxidation of silver on the mercaptoacetic acid coated gold electrode were evaluated. The variation of the site density of silver nucleus with the deposition potential, the dependences of the nucleation rate on the deposition potential and on the driving force (the concentration of silver) were investigated. The deposition potential affected the activity of the nucleation sites but the driving force did not. These variations were explained by the existence of a distribution of site energies (mercaptoacetic acid molecules) on the electrode surface.     

Spectroelectrochemical study of trichloroacetic acid reduction at copper electrodes in an aqueous sodium sulfate medium

The electrochemical reduction of trichloroacetic acid (TCAA) in water has been analyzed through voltammetric studies with a copper rotating disc electrode supported by controlled-potential bulk electrolysis and electrochemical surface-enhanced Raman spectroscopy (SERS) experiments. The influences of the mass-transport conditions and concentration were studied. It has been pointed out that the electrochemical reduction of trichloroacetic acid takes place prior to the massive hydrogen evolution. Strong adsorption was observed on the electrode surface, and dichloroacetic acid (DCAA), monochloroacetic acid (MCAA), and chloride anions were detected as reduction products. The SERS experiments point to a secondary mechanism in which dissociative adsorption of the trichloroacetic acid gives rise to the adsorption of CO, and therefore, to the production of 1C molecules as by-products of the electrochemical reduction.     

几种芳香化合物电化学性质的研究

采用循环伏安法考察了苯胺在铂电极上不同浓度、pH值和不同扫描速率等条件下的电化学反应特性。结果表明:在中性条件下,苯胺未出现明显的氧化还原峰,氯苯、苯甲酸分别出现了2个氧化峰和1个还原峰;随着硫酸浓度的增大,氯苯和苯甲酸峰电流密度呈减小趋势,而苯胺峰电流密度增大,这可能与氨基、氯、羧基的Hammet常数和溶液的pH值有关,Hammet常数越小易于发生亲电攻击;苯胺的氧化峰和还原峰相比大约为1,接近于可逆反应,苯胺的可逆性最强。     

酯化水解法提取L-乳酸工艺研究

L-乳酸是一种重要的发酵有机酸,又是生产生物可降解材料聚乳酸的原料。采用酯化水解法精制提取L-乳酸,得出成熟的工艺条件：乳酸与甲醇用量比为1∶3.5,乳酸浓度为85%左右,硫酸加入量为总投料量的2.5%左右,酯化时间为2.5 h。在最佳工艺条件下,酯化水解工序总收率由70%提高到85%,且产品质量稳定,经济效益明显提高。     

Voltammetric behavior study of folic acid at phosphomolybdic-polypyrrole film modified electrode

The electrochemical behavior of folic acid at the Keggin-type phosphomolybdate (PMo₁₂) doped polypyrrole (PPy) film modified glassy carbon electrode (PMo₁₂-PPy/GCE) was studied. PMo₁₂ doped PPy modified electrodes were achieved during the electrochemical preparation of the polymer films in aqueous solution. The redox behavior of the modified electrode was described by cyclic voltammetry. The electrochemical behavior of folic acid at PMo₁₂-PPy/GCE was studied by 0.5 order differential voltammetry. Numerous factors affecting the reduction peak currents of folic acid at PMo₁₂-PPy/GCE were optimized to maximize the sensitivity. The results showed that folic acid had high inhibitory activity toward the reduction of modified electrode in 0.01 M H₂SO₄. The reduction peak currents were directly proportional to the concentration of folic acid from 1.0 × 10⁻⁸ to 1 × 10⁻⁷ M with correlation coefficient of 0.9976, a detection limit of 1.0 × 10⁻¹⁰ M of folic acid was estimated. From the inhibitory effect of folic acid on PMo₁₂-PPy/GCE, the apparent formation constant of folic acid with the modified film was estimated. This modified electrode showed excellent sensitivity and stability for the determination of folic acid. The response mechanism of folic acid at PMo₁₂-PPy/GCE was discussed in detail.     

Preparation of modified electrode with molybdophosphate anion and its electrocatalysis for bromate reduction

A molybdophosphate anion modified electrode has been prepared in 2 M sulfuric acid solution containing PMo₁₂O₄₀³⁻ by electrochemical cycling scan or simple adsorption on a glassy carbon electrode anodized before modification. The film electrode obtained is very stable upon potential cycling in acid solution. The catalytic effect of the film for reduction of bromate was investigated in detail.     

Simultaneous detection of ascorbic acid, uric acid and homovanillic acid at copper modified electrode

The copper was deposited on glassy carbon (GC) and indium tin oxide (ITO) electrodes by electrochemical method. The copper structures on electrode were characterized by atomic force microscope, X-ray diffractometeric pattern and differential pulse voltammetric studies. Optimal conditions for uniform growth of copper structures on the electrode were established. Voltammetric sensor was fabricated using the copper deposited GC electrode for the simultaneous detection and determination of uric acid (UA) and homovanillic acid (HVA) in the presence of excess concentrations of ascorbic acid (AA). The voltammetric signals due to AA and UA oxidation were well separated with a potential difference of 400 mV and AA did not interfere with the measurement of UA and HVA at the GC/Cu electrode. Linear calibration curves were obtained in the concentration range 1-40 μM for AA and 20-50 μM for UA at physiological pH and a detection limit of 10 nM of UA in the presence of 10-fold excess concentrations of AA was achieved. The simultaneous detection of submicromolar concentrations of AA, UA and HVA was achieved at the GC/Cu electrode. The practical utility of the present GC/Cu modified electrode was demonstrated by measuring the AA content in Vitamin C tablet, UA content in human urine and blood serum samples with satisfactory results.     

Electrolytic oxidation of Ce(III) in nitric acid and sulfuric acid media using a flow type cell

The electrochemical oxidation behavior of Ce(III) in nitric acid and sulfuric acid media with various concentrations and compositions were investigated by cyclic voltammetry (CV) and potentiostatic electrolysis. In nitric acid media, the peak potential separation for the redox reactions of the Ce(III)/Ce(IV) couple shifted to base side with the increasing concentration of nitric acid from 1 to 6 M. The kinetics of the Ce(III)/Ce(IV) couple is rapid in high concentration nitric acid. The formal potential is independent of both proton and nitrate concentrations while the standard rate constant increases with added protons but is independent of nitrate concentration. Constant-potential electrolysis also shows that a high proton concentration is electrochemically favorable for the electron transfer of the Ce(III)/Ce(IV) couple and for a high Ce(IV) yield in nitric acid media. The current efficiency was ca. 75% for the oxidation process of Ce(III) at 298 K. A Ce(IV) yield of ca. 80% was achieved for the electrolysis of 100 mM Ce(III) in 6 M HNO₃ solution. In sulfuric acid media, the peak potential separation for the redox reactions of the Ce(III)/Ce(IV) couple shifted to noble side with rising concentration of sulfuric acid from 0.1 to 2 M and then shifted to base side with further increase in the concentration. A Ce(IV) yield of ca. 95% was achieved for the potentiostatic electrolysis of 100 mM Ce(III) in 3 M H₂SO₄ solution.     

Observed electrochemical oscillations during the oxidation of aqueous sulfur dioxide on a sulfur modified platinum electrode

The electrochemical oxidation of aqueous sulfur dioxide has been investigated on a sulfur modified polycrystalline platinum electrode. It has been found that time and potential-based current oscillations occur on a modified electrode in the oxidation region >0.7 V vs. SHE. The oscillation is specific to catalytic oxidation on sulfur modified platinum and is not observed on an unmodified electrode. Using i–R compensation techniques, the oscillation has been found to stem from electrochemical origins; the interfacial potential being an essential variable. The influence of other controllable variables including holding potential, sulfur dioxide concentration and sulfuric acid concentration have also been investigated for their effects on the oscillation. The electrochemical oscillation is explained here in part by the intermediate formation of dithionate. Two possible mechanisms, including a dual pathway mechanism, are explored.     

The electrocatalytic oxidation of ascorbic acid on polyaniline film synthesized in the presence of β-naphthalenesulfonic acid

Polyaniline-β-naphthalenesulfonic acid composite film on platinum electrode surface has been synthesized via the electrochemical polymerization of aniline in the presence of β-naphthalenesulfonic acid (NSA). FT-IR, UV-vis and electrochemical characterization indicate the formation of the doped polyaniline. Further investigations found that the polyaniline (PAN) doped with NSA extended the electroactivity of PAN in neutral and even in alkaline media. The PAN-NSA composite film coated platinum electrodes are shown to be good electrocatalytic surfaces for the oxidation of ascorbic acid (AA) in phosphate buffer solution (PBS) of pH 7.0. The anode peak potential of AA shifts from 0.62 V at bare platinum electrode to 0.34 V at the PAN-NSA composite modified platinum electrode with greatly enhanced current response. A linear calibration graph is obtained over the AA concentration range of 5-60 mM using cyclic voltammetry. The kinetics of the catalytic reaction is investigated using rotating disk electrode (RDE) voltammetry, cyclic voltammetry and chronoamperometry. The results are explained using the theory of electrocatalytic reactions at chemically modified electrodes. The PAN-NSA composite film on the electrode surface shows good reproducibility and stability.     

酸催化水解蔗糖制取乙酰丙酸

以蔗糖为原料,在H2SO4催化下制备乙酰丙酸,主要考察了反应时间、反应温度、蔗糖浓度、H2SO4浓度对乙酰丙酸产率的影响。实验结果表明,反应时间60min,反应温度110℃,蔗糖浓度0.4mol/L,H2SO4浓度3.5mol/L条件下乙酰丙酸的产率最高。     

5-羟甲基糠醛在稀硫酸催化下的降解反应动力学

5-羟甲基糠醛脱羧生成乙酰丙酸是生物质资源出发制备乙酰丙酸过程中的关键步骤之一。为了研究低硫酸浓度下水解生物质制备乙酰丙酸工艺的可行性,系统地测定了在压力5 MPa、初始浓度1～9 mg·ml^-1、硫酸浓度0.05%～0.4%（质量分数）、温度150～190℃条件下,5-羟甲基糠醛在稀硫酸催化下的降解反应动力学数据,并以主反应生成乙酰丙酸、副反应生成腐黑质的平行反应动力学模型对数据进行了拟合,拟合结果表明,在实验范围内,主、副反应对5-羟甲基糠醛均为一级反应;主反应对H⁺浓度为1.16级,反应的活化能为78.5 kJ·mol^-1;副反应对H⁺浓度为0.722级,反应的活化能为98.0 kJ·mol^-1。研究结果表明,降低温度和提高硫酸浓度有利于提高生成乙酰丙酸的选择性。     

复合体系下磷酸和硫酸的萃取动力学

为了深入了解萃取过程的机理和动力学特征,采用了恒界面池法研究了复合体系下磷酸和硫酸的萃取动力学,分别考察了比界面积、初始水相中磷酸浓度、初始水相中硫酸浓度对磷酸、硫酸萃取速率的影响,并提出了60℃下硫酸-磷酸复合体系中萃取磷酸和硫酸的动力学方程。实验结果表明:磷酸和硫酸的萃取速率随着比界面积增大而减小,随着初始水相中磷酸浓度的升高而逐步增加;初始水相中硫酸浓度的增大也有利于提高磷酸和硫酸的萃取速率。并研究了在60℃硫酸-磷酸复合体系中,磷酸和硫酸的萃取动力学方程,并用工业原料磷酸对萃取动力学进行了验证,表明拟合所得的方程计算的磷酸和硫酸萃取速率和实际测得的值相近。     

Effects of the method of preparing iron orthophosphate catalyst on the structure and the catalytic activity

Catalytic activity of iron orthophosphate [FePO₄] was studied using oxidative dehydrogenation of lactic acid to pyruvic acid as a reaction probe. The structure and surface area are different depending on the differences in the source of starting materials as well as in the preparing methods. However, the specific activity, activity per unit surface area, is little affected with the variation in the structure. By the reduction and reoxidation, the catalytic activity clearly increases.     

Effect of operating parameters on precipitation for recovery of lactic acid from calcium lactate fermentation broth

Precipitation is a simple, efficient method for separating and recovering lactic acid in the form of calcium lactate from fermentation broth by adding sulfuric acid. Major operating parameters of the recovery step as well as the temperature of concentration of the recovered lactic acid solution and the type and amount of adsorbent used for pigment (color) removal were optimized. When the molar ratio of calcium lactate to sulfuric acid was 1: 1 and the pH was increased to a value greater than the pKa (3.86), calcium sulfate was precipitated and could be removed more effectively, allowing for more efficient separation and recovery of supernatant lactic acid. Precipitation could be facilitated by adding calcium lactate solution with mixing (up to 220 rpm) and was completed in over 18 h. The optimal temperature for the concentration of lactic acid recovered from the supernatant after removing the precipitated calcium sulfate was found to be 90 °C in terms of the time required for concentration and the stability of the product. Activated carbon (SX-PLUS, 9 g/L) was most effective as an adsorbent for color removal from the recovered lactic acid. Under the optimized precipitation conditions, an overall yield of 92% of lactic acid from fermentation broth could be achieved.