Au电极上CO_2电还原过程中电极失活原因

在水溶液中,电还原CO_2制取CO时,电极易中毒失活,采用扫描电子显微镜(SEM)、X射线光电子能谱(XPS)对反应前后的电极材料进行检测,研究CO_2在KHCO_3水溶液中发生电化学还原反应时,Au电极失活原因及电极材料活性降低对反应过程的影响。结果表明,电极表面吸附了一层黑色有害物质。这层黑色有害物质大部分是石墨碳,并有微量的铁和锌。采用塔菲尔曲线、电化学阻抗(EIS)、线性扫描曲线、恒电位电解和气相色谱法等研究了有害物质对CO_2电还原反应动力学过程的影响,发现随着反应的进行,生成CO的平衡电位负移,电荷转移电阻增大,交换电流密度变小,产物CO的电流效率迅速降低。说明电极表面附着的有害物质使电极材料活性降低,阻碍了CO_2电还原反应的进行。     

硫化黑2BR 200%在石墨镀银电极上的电催化还原

采用涂附法制备了石墨镀银电极。用配有EDS的扫描电子显微镜(FE-SEM)对石墨镀银电极表面结构进行了表征,以石墨镀银电极和石墨电极为工作电极,采用线性扫描法研究了硫化黑在NaOH溶液中的电化学还原行为,探讨了溶液pH值对硫化黑2BR 200%电还原反应的影响。实验结果表明：用涂附法制备得到的石墨镀银电极表面分布了大量金属银颗粒,该石墨镀银电极对硫化黑2BR 200%的还原反应显示了很高的电催化活性,其电催化活性高于石墨电极;电解液的pH值越大,硫化黑的电还原反应就越容易。在恒电流电解中,以镀银石墨电极为阴极,电流密度为6.25 mA•cm^-2,反应温度为(27±2)℃时,硫化黑的电解实验的电流效率可达92.2%。     

二氧化碳在银电极上发生电还原反应时的电极失活原因

在KHCO3水溶液中,利用线性扫描、塔菲尔曲线、恒电位电解、电化学阻抗谱方法,研究了CO2在银电极上发生电还原反应的动力学特征,发现当电解反应进行一段时间后,阴极表面生成了一层棕黑色物质附着在电极表面,导致生成CO的平衡电位负移,交换电流密度变小,电荷转移电阻增大,电流效率和电流密度迅速降低。用X射线光电子能谱(XPS)分析了有害物质的主要成分,证明阴极表面附着物主要为石墨碳和微量Zn,这些物质附着在阴极表面,导致电极失活,阻碍CO2电还原反应继续进行。     

电合成法制备纳米材料及纳米材料电极上的电催化合成

通过电化学合成前驱体直接水解法制备纳米TiO2 粉体和纳米TiO2 膜电极。用循环伏安法、循环方波伏安法和电解合成法研究了纳米TiO2 膜电极对有机合成反应的电催化活性。发现纳米TiO2 膜电极在 0 2～ - 1 2V扫描电位区间有两对氧化还原峰 (峰电位Epc1=- 0 5 6V ,峰电位Epc2 =- 0 95V ,扫描速度 10 0mV·s-1) ,具有异相氧化还原催化行为。电解结果表明 ,纳米TiO2 膜中的Ti(Ⅳ ) /Ti(Ⅲ )氧化还原电对作为媒质 ,异相间接电还原硝基苯为对氨基苯酚 (收率91 6 % ,电流效率 95 2 % )和草酸为乙醛酸 (收率 96 5 % ,电流效率 90 % )。     

高铁酸盐电合成的研究

本文采用循环伏安法,通过重复扫描,保持阴极电位不变,逐步增大阳极电位;变动扫描速度;变动电介液温度等手段,对铁电极在浓碱溶液中的电化学行为进行了较为详细的研究探讨,得出了电解合成FeO_4~(2-)的机理及影响电合成FeO_4~(2-)的因素。同时本文讨论了在电介液中加入氯化钠后,氯离子对电解合成FeO_4~(2-)的影响和作用机制。为电解法合成高铁酸盐得出了一些极为有益的理论依据。     

丙烯腈在离子液体[BMim]PF6中的电还原行为

己二腈是生产尼龙66最主要的原料,其生产技术被国外垄断,大力发展我国的己二腈工业有着重大的现实意义。本文利用循环伏安法探讨了离子液体中玻碳电极上丙烯腈浓度和扫描速度对丙烯腈电还原行为的影响,结果表明,随着扫描速度加快、丙烯腈浓度增大,反应电流变大,电极过程受扩散控制。     

电化学还原合成N-甲基羟胺研究

N-甲基羟胺及其盐酸盐广泛应用于医药和农药中间体的合成,以及核废料处理与回收等领域.采用线性扫描和循环伏安方法,研究了硝基甲烷电还原一步制备N-甲基羟胺及其盐酸盐的反应特性.在盐酸溶液中,硝基甲烷在铜、铜汞齐和镍电极上均具有明显的还原活性,其活性大小依次为铜＞铜汞齐＞镍＞石墨,其中硝基甲烷在铜电极上的还原电位为-0.65～-0.75V(vs.SCE).电解合成试验结果表明,采用铜和铜汞齐作为阴极材料,电合成N-甲基羟胺盐酸盐的电流效率均超过90%,产品收率超过86%;采用镍和石墨作阴极,电流效率和产品收率均较低.其中铜电极在1200～2500A·m-2的电流密度范围内,电解时间为理论电解时间的80%时,具有最好的电流效率.与传统的催化氢化法合成N-甲基羟胺比较,电化学还原硝基甲烷制备N-甲基羟胺盐反应条件温和、污染少、成本低,是一种非常有效的合成新方法.     

肉桂醛电解还原制备肉桂醇的研究

研究了电化学法还原肉桂醛制备肉桂醇的反应条件,分析了电解电压、三维电极因素对电还原反应的影响,产物通过红外光谱、元素分析进行定性。反应的电解电压为4 V,活性炭作为三维电极。提出了制备天然肉桂醇的新方法。     

纳米TiO_2膜电极上乙醛酸的电催化合成研究

运用电化学循环伏安法 (CV)对纳米TiO2 膜电极 (Ti/nano TiO2 )在硫酸和草酸溶液中的电化学行为进行了研究。在c(H2 SO4 ) =1mol/L溶液中的循环伏安图上Epac1=- 0 .5 6V(vs.SCE)和Epac2 =- 0 96V(vs.SCE)处 ,出现两对可逆氧化还原峰 ,而在相同扫描速度下草酸溶液中的循环伏安曲线上 ,这两对电极反应氧化峰基本消失 ,还原峰电流增大 ,表明Ti/nano TiO2 膜电极对电还原草酸成为乙醛酸的反应具有较高的电催化活性和选择性。常温常压下 ,控制电位Epc=- 1 0V左右电解合成乙醛酸 ,乙醛酸的产率和电流效率分别达到 96 5 %和 90 %。     

2，3－二甲基－2，3－丁二醇的电化学合成

介绍用丙酮电解还原合成频那醇的方法。电解合成反应可以在碱性介质或酸性介质条件下进行。并对不同电极、温度和电流密度对反应电流效率影响进行了研究。     

Electrodeposition of palladium on the copper lead frame: Electrode reaction characteristics and the effects of primary additives

This study is mainly concerned with the electrodeposition of palladium on the copper alloy lead frame used for semiconductor assembly process. The role and effect of additives on palladium electrodeposition were studied by using various electrochemical methods. Ortho-formylbenzenesulfonic acid as a primary additive was used in palladium plating on the lead frame in this study. The electrochemical characteristics of electrode reaction were measured by the hanging mercury drop electrode for electrochemical system and the qualities of the plated surface of lead frames were also examined. The additive agent in Pd solution could have been classified as the grain refiner. It acted as the electroactive species, which increased the polarization and decreased the roughness, by adsorption on the electrode in palladium pre-plated process. The reduction of palladium ion was identified to be an irreversible reaction and the diffusion coefficient of palladium ion and the reaction rate constant were obtained from chronopotentiometry experiment.     

纳米氧化镍的低温固相合成及电容性能研究

通过低热固相反应法合成了纳米氧化镍,在不同温度热处理条件下研究氧化镍的结构、形貌及其作为超级电容器电极材料的电化学性能。采用XRD和SEM表征产物的结构特点,采用循环伏安和恒流充放电等方法表征其电化学性能。XRD测试结果表明,所制备的氧化镍为立方相,且随着热处理温度升高,晶型趋于完整。SEM和电化学测试结果表明,高温热处理（>400 ℃）使样品团聚更为严重,导致电极材料利用率降低,质子传递阻力加大,比电容急剧下降;低温处理颗粒分布均匀,粒子间存在孔道,使电极具有较大的比容量（228 F/g）和良好的化学稳定性,在20 mV/s快速扫描速率下,电极显示出良好的倍率特性。     

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%.     

Selective electroreduction of pyruvic acid on lead electrode in acid medium

This work reports the electrochemical reduction of pyruvic acid, which contains a carbonyl group more reducible than its carboxylic entity. The electrode potential and the concentration of the starting substrate seemed to be the factors that control the electrochemical production of the competitive reaction products. In fact, lactic acid was mainly obtained on a lead electrode in sulfuric acid for low concentrations of pyruvic acid while 2,3-dimethyl tartaric acid was selectively formed by electrohydrodimerization of a high amount of pyruvic acid. During the cathodic reduction of pyruvic acid in sulfuric acid solution, the effects of electrode potential and pyruvic acid concentration on the selectivity towards the formation of lactic acid were systematically studied.     

Electrocatalytic carboxylation of aromatic ketones with carbon dioxide in ionic liquid 1-butyl-3-methylimidazoliumtetrafluoborate to α-hydroxy-carboxylic acid methyl ester

A new electrochemical procedure for the electrocatalytic carboxylation of aromatic ketones with carbon dioxide in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoborate (BMIMBF₄), to α-hydroxycarboxylic acid methyl ester was investigated for the first time. The electrochemical behavior of acetophenone in BMIMBF₄ was studied by cyclic voltammetry with a reduction peak at −1.9 V (vs. Ag). The electrolyses experiments were carried out in an undivided cell under mild conditions without any toxic solvents, catalysts and supporting electrolytes, followed by addition of an alkylating agent, affording the α-hydroxycarboxylic acid methyl ester in a moderate yield (62%). The results showed that the yields were strongly affected by various factors: temperature, current density, charge passed, electrode material and substrate concentration. Moreover, the ionic liquid was successfully recycled for this reaction.     

Synthesis and characterization of poly(aniline) and poly(o-anisidine) films in sulphamic acid solution and their anticorrosion properties

Poly(o-anisidine) (POA) and polyaniline (PANI) coatings were synthesized on platinum (Pt) surface and stainless steel (SS) in monomer containing 0.50 M sulphamic acid (SA) solution by means of cyclic voltammetry (CV) technique. Meanwhile, poly(o-anisidine) film was also deposited with a different scan rate on SS electrode. The behaviour of PANI and POA films obtained on stainless steel examined by CV was different from the one obtained for PANI and POA on Pt electrode. The corrosion performances of PANI and POA coatings in 3.5% NaCl solution were investigated with anodic polarization technique and electrochemical impedance spectroscopy (EIS). EIS measurements verified the effect of monomers and that of scan rate on corrosion inhibition of coatings on SS electrode. The results showed that POA film synthesized at low scan rate exhibited an effective anticorrosive property on SS electrode. POA synthesized at low scan rate and PANI coatings provided a remarkable anodic protection to SS substrate for longer exposure time than the one observed for POA coating produced at high scan rate as well as that of bare SS electrode.     

Electrochemical behavior of high-pressure synthetic boron doped diamond powder electrodes

Boron doped diamond (BDD) was synthesized under high pressure and high temperature using B-doped graphite intercalation compositions (GICs) as carbon sources. The electrochemical characteristics of high-pressure synthetic BDD powder electrodes were investigated by measuring the cyclic voltammetry curves and AC impedance spectrum. For the [Fe(CN)₆]^3−/4− redox couple, the electrode reaction process is reversible or quasi-reversible at the scan rates of 0.01-1.0 V/s. At the low scan rate the linear relation between peak current and square root of scan rate indicates that the electrode process was a diffusion-controlled mass transport process. The electrochemical behavior is similar to a planar electrode. With the increasing of the scan rate the electrode process is controlled by the mass transport plus kinetic process. AC impedance spectra exhibit the porous structure characteristic of BDD powder electrode.     

酞菁铁添加剂对AB3型镍氢电池电化学性能影响

采用共沉淀还原扩散法制备了La0.67Mg0.33Ni2.5Co0.5合金.以固相法合成酞菁铁,研究了酞菁铁作为镍氢电池电解液添加剂和负极添加剂时对电池电化学性能的影响,结果表明,在电解液中,当酞菁铁添加量为0.045％时,电池的最大放电容量提高了20 mAh/g,容量衰减率降低了10.98％;在电池负极中,当酞菁铁添加量为1.0％时,电池的最大放电容量提高了40 mAh/g,容量衰减率降低了13.14％.     

2,6-萘二甲酸的合成研究

使用1,8-萘二甲酸酐为原料,采用亨克尔法,以碳酸锌做催化剂、萘和碘化钾为助剂,在二氧化碳气氛中进行反应,通过异构化反应制备2,6-萘二甲酸.探讨了反应温度、反应时间、催化剂用量、反应压力、搅拌速度、助催化剂和助剂用量对异构化转位反应的影响.结果表明:根据正交实验确定了1,8-萘二甲酸二钾盐异构化转位反应的较优工艺,各...     

碳毡负载Sn气体扩散电极CO2电化学还原性能

针对CO₂电化学还原中气体扩散电极可强化CO₂的传质,基于碳毡制备了负载锡-石墨烯催化层的新型气体扩散电极,研究了CO₂反应条件、电极厚度、催化剂载量及反应电位对CO₂电化学还原性能的影响。实验结果表明：与溶解态CO₂反应条件相比,采用气相CO₂反应条件电化学还原性能更好;一定范围内增加电极厚度和催化剂载量可以增加气-液-固三相反应界面,提升CO₂电化学还原性能;随着电解电位负移,甲酸产量增加,电流效率先增大后减小;实验中使用厚度为5 mm、载量为5 mg·cm^-2的电极,在-1.8 V（vs Ag/AgCl）条件下进行电化学还原时,平均电流密度为（12.79±1.27） mA·cm^-2,甲酸电流效率达到最佳为41.55%±2.50%。