Stability of Fibrous Carbon Materials in Cathodic Polarization in Nitric Acid Solutions

Stability and electrical conductivity of graphitized and carbonized fibrous carbon materials are studied in cathodic polarization in nitric acid solutions.     

Dissolution Mechanism of UO2 in Nitric Acid Solution by Photochemical Reaction

Photodissolution tests of UO₂ sintered pellets were carried out in 3M nitric acid solution and at about 50 °C under UV irradiation. The light source was a Hg-lamp emitting a light of 254nm wavelength. In the products, chemicals such as H₂O₂ and NO₂ ^– ion were detected during photodissolution of the UO₂ sintered pellets. Based on this result, a new dissolution mechanism of UO₂ in nitric acid solution by photochemical reaction was suggested in this study.     

Anodic Dissolution of Palladium in Sulfuric Acid: An Electrochemical Quartz Crystal Microbalance Study

Regularities of formation of a palladium oxide layer and its cathodic reduction in 0.5 M H₂SO₄ at 0.5–1.3 V (SHE) are studied by cyclic voltammetry, x-ray photoelectron spectroscopy, and electrochemical quartz crystal microbalance. A pure Pd plate and a 0.5-m-thick Pd coating on gold-sputtered quartz crystal is used for electrochemical and microgravimetric studies. It is shown that a Pd electrode dissolves electrochemically in 0.5 M H₂SO₄ when its potential is cycled between 0.5 and 1.3 V. In the case of 0.5-m-thick Pd coating on the gold substrate, the decrease in the electrode weight during one anodic–cathodic cycle is 1.0–1.5 g/cm². It is suggested that anodic process at 0.5–1.3 V (SHE) represents electrochemical oxidation of palladium, yielding a surface layer of poorly soluble Pd(OH)₂ and/or PdO phases, as expressed by the equation Pd + 2H₂O (Pd(OH)₂/PdO)_s + 2H⁺ + 2e. This surface layer, (Pd(OH)₂/PdO)_s, undergoes reduction during the cathodic process. About 5% of the total amount of ionized palladium dissolve in electrolyte.     

An Electrochemical Puzzle: The Catalyzed Anodic Dissolution of I-coated Palladium in Halide-Free Acid Solutions

Iodine adsorbed on a Pd electrode has been shown to catalyze the anodic dissolution of Pd in halide-free acidic solutions. An undergraduate instrumental analysis laboratory experiment has been developed that enables students to use basic electrochemical techniques (cyclic voltammetry and chronocoulometry) to detect and confirm this phenomenon. Cyclic voltammograms of clean Pd and I-coated Pd were done in 0.5 M sulfuric acid solutions containing iodide and iodine as well as halide free 0.5 M sulfuric acid. The large currents noted in the halide-free solution indicate an anodic process that is not related to the oxidation process in solutions containing iodine species. Chronocoulometry was used to determine the total charge that was passed in the 0.5 M sulfuric acid solutions for clean and I-coated Pd electrodes. The results of these experiments point to a unique catalyzed corrosion process for this otherwise inert metal.     

Formation of Surface Oxides in Electrode Polarization of Fibrous Carbon Materials in a Sulfuric Acid Solution and Their Influence on Ion-Exchange and Electrochemical Properties of These Materials

Formation of surface oxides in the course of cathodic and anodic polarization of fibrous carbon materials in a 0.25 M sulfuric acid solution and their influence on the cation- and anion-exchange properties of fibrous carbon materials, steady-state electrode potential in a 0.1 M sodium sulfate solution, and electrodeposition of copper from a sulfuric acid solution were studied.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 433–437.Original Russian Text Copyright © 2005 by Varentsova, Varentsov.     

Electroosmotic Flow of a General Electrolyte Solution through a Fibrous Medium

Although hydrotropy is extensively used in industry, the molecular mechanism of hydrotropic solubilization has not been completely elucidated yet. In this paper the interaction between a nonionic surfactant (ethoxylated fatty alcohol containing between five and six oxyethylenic units) and sodium p-toluene sulfonate is examined. Surface tension measurements confirm that the hydrotropic effect occurs at a concentration in which the hydrotropes self-associate. Photon correlation spectroscopy studies show that for this concentration of hydrotropes a drastic reduction in the surfactant micellar radius occurs. Furthermore the luminescence of the hydrotrope used as a fluorescence probe indicates that at low concentrations p-toluene sulfonate dissolves in the surfactant micelles but beyond the minimum concentration for hydrotropic solubilization the hydrotrope is present in the aqueous phase. These results suggest that the hydrotropic effect is related to alterations in the water structure induced by the hydrotrope molecules and to the presence of hydrotrope aggregates that furnish an appropriate niche for the surfactant amphiphile.     

Electrolysis of Nitric Acid by Using a Glassy Carbon Fiber Column Electrode System

The electrochemical redox behavior of nitric acid was studied using a glassy carbon fiber column electrode system, and its reaction mechanism was suggested and confirmed in several ways. Electrochemical reactions in less than 2.0M nitric acid was not observed. However, in more than 2.0M nitric acid, the reduction of nitric acid to nitrous acid occurred and the reduction rate was slow so that the nitric acid solution had to be in contact with an electrode for a period of time long enough for an apparent reduction current of nitric acid to nitrous acid to be observed. The nitrous acid generated in more than 2.0M nitric acid was rapidly and easily reduced to nitric oxide by an autocatalytic reaction. Sulfamic acid was confirmed to be effective to destroy the nitrous acid. At least 0.05M sulfamic acid was necessary to scavenge the nitrous acid generated in 3.5M nitric acid.     

非水体系中电解镍中间产物制备纳米NiO

采用纯镍为阳极，乙酰丙酮和乙醇的混合溶液中加入少量有机胺导电盐为电解液，施加一定电流使镍溶解，然后将电解液直接水解，控制一定的水解条件，制备得到纳米NiO粉体. 采用拉曼光谱、红外光谱、元素分析、XRD 和TEM 分别对电解得到的纳米NiO前驱体和纳米NiO进行了分析与表征, 并探讨了电化学溶解镍金属法制备纳米NiO反应的影响因素.电化学溶解镍金属得到的前驱体为Ni(OEt)2(acac)2,这种不溶性镍醇盐配合物升温至40～50℃即可溶解于乙醇溶液中,可直接应用于溶胶 凝胶(Sol gel)过程.水解后的纳米NiO呈无定形结构, 350 ℃煅烧后形成立方晶型NaCl结构, 纳米NiO经600 ℃煅烧后粒径分布在5～10 nm. 该方法理论上为二价不溶性金属醇盐经溶胶 凝胶工艺制备纳米氧化物材料提供了一条新的途径.     

阴极冷却固定床电合成乙醛酸的连续过程模拟

联用反应动力学、电荷衡算和物料衡算建立阴极冷却固定床草酸电合成乙醛酸反应器模型方程.针对反应器连续化操作过程,用正交配置法数值求解该模型方程.结果表明,在连续化操作的反应初期,反应液中的乙醛酸能够较快地达到预定浓度,但继续增加反应器的长度,反应的效果不明显.该模型还模拟了分段温控和部分回流对反应的影响.结果表明,分段温控和部分回流均可较好地提高乙醛酸在阴极液中的浓度.计算结果与试验操作基本相符.该结果对阴极冷却固定床草酸电合成乙醛酸的连续化操作工艺和反应器的优化具有重要的参考意义.     

探究铁和铝在浓硫酸和浓硝酸中的电化学行为

铁和铝在冷的浓硫酸和浓硝酸中都因被钝化而阻止其进一步被腐蚀,通过用Fe、Al做原电池的电极材料,考察其在浓硫酸、浓硝酸中的钝化情况：Fe、Al的钝化快慢、钝化后金属表面氧化膜的致密程度、酸液温度等对钝化的影响等均有所不同。     

铬酸及硝酸混合液处理以增强碳纳米管场发射

为了修饰碳纳米管(CNTs)的表面型态及改变碳纳米管的表面结构, 进一步增强碳纳米管的场发射特性, 使用铬酸及硝酸的混合溶液对碳纳米管进行后处理. 采用SEM、TEM、Raman 和EDS测试手段对样品的形貌、表面成份组成和微观结构特征进行了表征. 场发射(FE)的数据显示, 经过铬酸及硝酸的混合溶液处理20 min的碳纳米管场发射电流比未经任何处理的碳纳米管场发射电流明显增加一个数量级以上, 场发射电流增强的主要原因为样品上的碳纳米管的表面型态的改变, 造成碳纳米管场发射增强因子茁的增大. 与单独使用硝酸溶液后处理比较, 使用铬酸及硝酸的混合溶液对碳纳米管进行后处理可以得到较高的场发射电流及较低的起始电场. 铬酸及硝酸的混合溶液处理方法能经济且有效增强碳纳米管的场发射特性.     

恒容吸收系统中水和稀硝酸对NO2的吸收过程研究

采用恒容吸收系统研究了水和稀硝酸对二氧化氮气体的吸收行为,通过测量吸收液的组成和气相压力来考察吸收剂浓度、吸收剂的量和吸收压力对NO2吸收效率和产物的影响。增加水的质量,则吸收效率增加,而所得硝酸的浓度先增加后减小。随着NO2初始压强的增加,水对NO2的吸收效率和所得硝酸浓度均增加。结果表明二氧化氮在稀硝酸中的吸收速度比在水中快,较高的气相初始压力(>90 kPa)或较高的硝酸浓度(>7wt%)都有利于吸收效率的提高。从反应关系分析计算,可获得气相组成、N2O4的转化率和HNO2的分解率等参数,发现随着水的量的增加,N2O4的转化率逐渐增大,而HNO2的分解率先增大后减小,在NO2和水的物质的量的比为0.024时达到最大值。     

Enhancement of Field Emission Characteristics for Multi-Walled Carbon Nanotubes Treated with a Mixed Solution of Chromic Trioxide and Nitric Acid

A simple acid treatment method was applied to functionalize the surface and to modify the structures of multi-walled carbon nanotubes (CNTs) grown on silicon substrates using a mixed solution of chromic trioxide (CrO₃) and nitric acid (HNO₃). Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and energy dispersive spectrometer (EDS) were employed to investigate the mechanism causing the modified field emission (FE) properties of the CNT films. After 20 min of CrO₃+HNO₃ treatment, the emitted currents were enhanced by more than one order of magnitude compared with those of the untreated CNTs. This large increase in emitted current can be attributed to the favorable surface morphologies, open-ended structures, and highly curved CNT surfaces in the CNT films. These factors altogether caused an increase in the field enhancement factors of CNTs. We also demonstrated that using a mixed solution of CrO₃+HNO₃ post-treatment exhibited a higher emission current and a lower turn-on electric field than in the CNTs treated with HNO₃. The method provides a simple, economical, and effective way to enhance the CNT field emission properties.     

水溶液中噻吩的电化学聚合成膜

本文研究水溶液中噻吩的电化学聚合。高酸度水溶液中噻吩先经历化学低聚反应,低聚合物可在较负的电位阳极氧化成膜。     

酸性溶液中离子注入钯的玻璃碳电极上硝基苯的电化学还原

用循环伏安法在离子注入钯的玻璃碳电极上，研究了硝基苯在０．５ｍｏｌ／Ｌ硫酸溶液中的电还原过程，通过ＡＥＳ测量了离子注入电极的表面组成和各元素的浓度－深度分布，在４０ｋｅＶ下，注入剂量为１×ｌ０￣（１７）离子／ｃｍ＿２的钯注入到玻璃碳（ＧＣ）中可产生钯原子最大百分含量为２０％的近表面区。原基体注入钯后比未注入的ＧＣ对硝基苯（ＮＢ）的电还原有更高的活性，用气相色谱法检测到ＮＢ的还原产物苯胺，讨论了硝基苯在酸性溶液中电化学还原机理。     

Carbon Nanostructures Derived through Hypergolic Reaction of Conductive Polymers with Fuming Nitric Acid at Ambient Conditions

Hypergolic systems rely on organic fuel and a powerful oxidizer that spontaneously ignites upon contact without any external ignition source. Although their main utilization pertains to rocket fuels and propellants, it is only recently that hypergolics has been established from our group as a new general method for the synthesis of different morphologies of carbon nanostructures depending on the hypergolic pair (organic fuel-oxidizer). In search of new pairs, the hypergolic mixture described here contains polyaniline as the organic source of carbon and fuming nitric acid as strong oxidizer. Specifically, the two reagents react rapidly and spontaneously upon contact at ambient conditions to afford carbon nanosheets. Further liquid-phase exfoliation of the nanosheets in dimethylformamide results in dispersed single layers exhibiting strong Tyndall effect. The method can be extended to other conductive polymers, such as polythiophene and polypyrrole, leading to the formation of different type carbon nanostructures (e.g., photolumincent carbon dots). Apart from being a new synthesis pathway towards carbon nanomaterials and a new type of reaction for conductive polymers, the present hypergolic pairs also provide a novel set of rocket bipropellants based on conductive polymers.     

Effect of Ethanedioic Acid Additives on the Dissolution of Manganese Oxides in Sulfuric Acid Solution

The effect of ethanedioic acid additives on the rate of manganese(IV) oxide dissolution in sulfuric acid solutions was studied by kinetic and electrochemical methods. Interaction modes were established, and some details of the studied process mechanism were elucidated. Interaction schemes corresponding to the observed kinetic dependences were proposed.     

The Chemistry of (U,Pu)O2 Dissolution in Nitric Acid

The focus of this paper is the chemistry of mixed uranium plutonium oxide (MOx,) in nitric acid. An overview of dissolution chemistry is discussed by comparing the differences in the dissolution characteristics of uranium and plutonium oxides. An overview of batch dissolution experiments, studying the dissolution chemistry of high surface area MOx powders and low surface area MOx pellets with reference to the effects of nitrous acid, nitric acid and temperature are described. The results are discussed in terms of the autocatalytic mechanism and mass transfer limited dissolution.     

Electrodeposition of Copper Selenide onto Mo Electrode in Tartaric Acid Solution

Results are presented of a study of the electrochemical behavior of copper(II) and selenium(IV) ions and their joint reduction on a molybdenum electrode by cyclic voltammetry in a tartaric acid electrolyte. The potentiostatic deposition was used to obtain copper selenide deposits on Mo plates. The diffraction and energydispersive analyses demonstrated that a Cu_2?xSe compound is formed with an admixture of the CuSe phase. A suggestion is made that the process of underpotential reduction affects the formation of copper selenide. Copper selenide films were deposited at a potential of ?0.6 V in the course of 30 min with a thickness of 0.43 μm and high adhesion to the substrate. At potentials in this range, an additional amount of the deposit may be formed due to the chemical reaction between Cu⁺ and Se^2? ions. The p-type conduction was determined for films electrodeposited at various potentials.