MgCl2-KCI—NaCI—CaCl2熔盐电解镁机理

在725℃温度下,对MgCl2-KCl-NaCl-CaCl2熔盐体系进行电解。研究结果表明,镁电解过程中阴极过电压ηc只有12～51mV,电解过程的过电压主要是由阳极引起的;阴极还原过程的极限扩散电流密度id为1．56A／cm^2;镁离子阴极放电反应的电子转移数为1．98：2个电子转移步骤之前存在着前置转化步骤MgCl^＋→Mg^2＋ ＋Cl^-。应用循环伏安法对4种不同配比下的镁离子行为进行的研究结果表明,CaCl2质量分数从10％增加到40％,维持MgCl2质量分数为10％以及NaCl与KCl的质量比为6：1不变,随着CaCl2质量分数的增加,镁离子结合成不易移动的络合阴离子,镁离子迁移的电流分数减小,镁离子的析出电位从-1．595V逐渐负移至与钙、钠共同沉积,阴极峰值电流Ipc值逐渐增大,阳极峰值电位与阴极峰值电位之差的绝对值｜φpa-φpc｜逐渐增大,阴极放电反应的可逆性逐渐降低。     

镁电解槽中制备镁稀土合金的电解工艺及机制研究

在模拟镁电解槽中,采用电解法制备出稀土含量<10%的镁稀土合金;研究了熔盐中RECl3和CaCl2的含量、电解温度和阴极电流密度对合金中RE含量和电流效率的影响。并采用循环伏安实验和还原实验研究电解制备镁稀土合金的机制。研究结果表明,电解制备镁稀土合金最佳的工艺条件为:熔盐中RECl3和CaCl2的含量分别为3%和10%(质量分数),电解温度为948 K,阴极电流密度约为8 A.cm-2。其电解过程机制为:阴极上只电解出金属镁,而后金属镁把稀土元素还原出来,形成镁稀土合金。     

固定床电解槽变电流成对电解合成乙醛酸

对电解氧化乙二醛合成乙醛酸过程 ,固定床电解槽和变电流电解效果明显优于平板型电解槽和恒电流电解效果 .当阳极液中乙二醛和盐酸初始质量分数 (WCHOCHO 和WHCI)分别等于7.0 %和 8.0 %、阴极液为始终饱和的草酸溶液和微量的添加剂时 ,采用平均电流密度 (i)为 15 35A/m2 的变电流方式电解 ,阳极电流效率 (CEa)为 85 .3%、乙醛酸选择性 (RSa)为 93.9% ;阴极电流效率 (CEc)为 86 .7% ,乙醛酸选择性 (RSc)为 94 .0 % .阳极初产品中WCHOCOOH∶WCHOCHO≥ 4 0∶3,克服了阳极产品中乙二醛难以除去的困难     

移动阴极式掩膜电解加工微沟槽阵列均匀性研究

掩膜电解加工是一种高效率、大规模加工微结构的特种加工方法。然而,由于电流分布的边缘效应,在微结构的掩膜电解加工过程中往往存在着严重的加工尺寸不一致问题。针对这一问题,本文提出了一种移动阴极式掩膜电解加工方法。首先,利用COMSOL有限元分析软件对微沟槽阵列掩膜电解加工过程中的电流分布和阳极轮廓形状进行了数值仿真。仿真结果表明,相对于常规阴极结构的掩膜电解加工,采用移动阴极结构的掩膜电解加工方法能够获得尺寸更加均匀的微沟槽阵列结构。其次,在数值仿真的基础上,开展了掩膜电解加工实验研究。实验结果表明,移动阴极式掩膜电解加工方法能够有效地改善微沟槽阵列加工的尺寸均匀性。相对于常规阴极结构的掩膜电解加工过程,移动阴极式掩膜电解加工微沟槽阵列的均匀性提高了68.3%,并且随着阴阳极间距的增大,微沟槽深度不均匀度呈现出先减小后增大的趋势。随着阴极宽度的增大,微沟槽深度不均匀度逐渐增大;随着阴极移动速度的增大,微沟槽深度不均匀度逐渐减小,仿真与实验结果趋势一致。     

尿素-NaBr低温熔盐中Fe2+和Sm3+的电化学行为及其诱导共沉积

利用循环伏安法、计时电位法和计时电流法 ,研究了尿素$CNaBr熔盐中Fe2 +在Pt,Cu ,Ag及Ti电极上的电化学行为 ,获知Fe2 +电还原为金属铁是一步不可逆过程 ,扩散系数为 2 74× 10 - 6cm2 ·s- 1 ,交换电流密度为 2 6 8× 10 - 5A·cm- 2 。使用循环伏安曲线和断电后的放电曲线研究熔体中Sm3 +的电化学行为 ,表明Sm3 +难以单独沉积 ,但通过加入Fe2 +可以诱导其共沉积。在Cu基体上进行恒电位和恒电流电解 ,得到Sm含量高于 90 % (质量分数 )的Sm Fe合金膜 ;发现Sm含量与阴极电位、电流密度以及SmCl3 /FeCl2 的摩尔比有关。用电镜研究了不同电解方法及钐含量对Sm$CFe合金表面的影响     

硝基苯在离子液体BMimBF4-H2O中的电还原

采用循环伏安法和恒电位电解法研究了离子液体BMimBF4-H2O 中硝基苯在微铂电极上的电还原特性. 实验表明, 在BMimBF4中, 随着硝基苯和水的浓度变化, 循环伏安曲线的峰电位和峰电流呈现复杂的变化规律; 硝基苯在铂电极上的电还原反应为双分子8 电子3 步骤电化学过程, 第一步反应为准可逆单分子单电子转移步骤, 产生阴离子自由基, 第二步为2 电子转移步骤, 并伴有随后的双分子不可逆自由基偶合化学反应, 主要产物为氧化偶氮苯, 第三步是2 电子转移产生偶氮苯的过程.     

有机电合成中活性镁的产生及其反应

通过低还原电位的含活泼氢的烃类化合物及苯腈在消耗性镁阳极存在下的有机电解反应证实了阴极上高分散活性镁的存在, 且其活性比以往方法所得的活性镁的活性更高。     

有机电合成中活性镁的产生及其反应

通过低还原电位的含活泼氢的烃类化合物及苯腈在消耗性镁阳极存在下的有机电解反应证实了阴极上高分散活性镁的存在,且其活性比以往方法所得的活性镁的活性更高。     

Mo,W电极在MgCl2-KCl-NaCl-CaCl2熔盐中电解镁的钝化行为

应用循环伏安法和计时电流法研究了Mg(Ⅱ)在MgCl2-KCl-NaCl-CaCl2四元熔盐体系中于(Mo、W)阴极上的放电过程及其钝化行为.结果表明,W电极放电反应的可逆性比Mo电极的好.后者的计时电流曲线偏离线性特征,且其阴极钝化比W严重.     

H型电解池中CO2电化学还原的阳极电解液问题

采用自制的H型电解池开展了KHCO₃溶液中电化学还原CO₂制甲酸的研究. 研究发现,在电解池中长时间电解时阴阳两极间的电压（槽电压）会持续升高,导致电解过程不可持续. 经过恒电位电解、恒电流电解、pH测试以及电解前后阳极室KHCO₃浓度分析等实验研究,作者发现,这是由以下过程引起的：阳极上的析氧反应产生的H⁺与电解液中的HCO₃^-反应生成水和CO₂,导致阳极室的HCO₃^-的消耗,之后阳极室的K⁺被迫扩散进入阴极室而导致阳极室电解质浓度下降. 因此,阳极室电解液导电性下降,进而引起阳极电位的升高. 研究发现,阳极电解液具有碱性时,都可能发生此种现象,因此,为了保证电解过程可持续且保持高的能量转换效率,阳极液的电解质不能是任何具有碱性的物质.     

Syntheses of 2-hydroperoxy-and 2-hydroxy-2H-imidazoles

Oxidation of fully substituted imidazoles 1 by singlet oxygen gives in good yield fully substituted 2-hydroperoxy-2H-imidazoles 2 . Reduction of 2 by triphenylphosphine leads to 2-hydroxy-2H-irnidazoles 3 . Limitations of the methods are reported.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Photocycloaddition of 2-Cyanocycloalk-2-Enones to 2, 3-Dimethylbut-2-Ene

Irradiation of 5,5-dimethyl-6-oxocyclohex- l-ene- l-carbonitrile ( 1 ) in the presence of 2,3-dimethylbut-2-ene afforded 3,3,4,4,7,7-hexamethyl-3,4,4a,5,6,7-hexahydroindeno[1,7-c,d]-],2-oxazole (3) in nearly quantitative yield. In contrast, 4,4-dimethyl-5-oxo-cyclopent-l-ene-l-carbonitrile ( 2 ) under the same conditions reacted not to a tricyclic isoxazole but to a 2:1 mixture of 3,3,6,6,7,7-hexamethyl-2-oxo-bicyclo[3.2.0]heptane-l-carbonitrile ( 4 ) and trans-3,3-dimethyl-2-oxo-5-(2,3-dimethylbut-3-en-2-yl)cyclopentane-l-carbonitrile ( 5 ), respectively.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.     

Efficient C2 functionalisation of 2H-2-imidazolines

Alkylation and oxidation of 2H-2-imidazolines, followed by regioselective deprotection, thionation and microwave-assisted Liebeskind-Srogl reaction, efficiently led to 2-aryl-2-imidazolines as new analogues of p53-hdm2 interaction inhibitors (Nutlins).