硝基苯与离子液体的相互作用对硝基苯电还原传递系数的影响

应用紫外光谱研究了离子液体和硝基苯的相互作用, 硝基苯的紫外光谱受离子液体的影响, 硝基的吸收峰红移, 末端吸收消失. 用循环伏安法研究硝基苯电还原过程中第2个电子转移的传递系数(α)随外界条件变化所呈现复杂的变化规律. 硝基苯和水的介电性质、硝基苯和水与离子液体的相互作用对α产生复杂影响. 硝基苯浓度增加使α减小, 离子液体的咪唑侧链增长也使α减小. 相同硝基苯浓度时, 水的浓度较低时, α随水的浓度增加变小; 水的浓度较高时, α随水的浓度增加稍微变大. 温度升高α值增大.     

硝基苯在离子液体EMimBF4中的选择性电还原

采用循环伏安法和恒电位电解法研究了离子液体EMimBF4中硝基苯在微铂电极上的选择性电还原特性. 研究结果表明, 硝基苯在铂电极上的电还原反应为双分子八电子三步骤电化学过程: 第一步反应为准可逆单电子转移步骤, 产生阴离子自由基; 第二步为二电子转移步骤, 并伴有随后的双分子不可逆自由基偶合反应和快速质子化及脱水反应, 主要产物为氧化偶氮苯; 第三步是二电子转移产生偶氮苯的过程. 通过控制电位, 可以选择性地合成氧化偶氮苯和偶氮苯; 在EMimBF4中, 硝基苯和水的浓度变化对电化学行为产生较大影响.     

纳米氧化锡在锌-硝基苯电池反应中的电催化

以氯化锡为原料,四丙基溴化铵为表面活性剂水热法制备纳米二氧化锡（SnO₂）催化剂,并以钛网为基材,制备催化电极. 应用SEM,XRD等手段对催化剂进行表征. 考察了反应物浓度、反应温度和反应时间对催化剂形貌的影响. 研究了纳米SnO₂催化剂对锌还原硝基苯原电池反应的电催化性能. 结果表明,当 NaOH浓度为0. 5 mol•L^-1、水热反应温度160 ℃、水热反应时间15 h时,得到的SnO₂催化剂是由纳米片构成的刺球状颗粒,粒径最小,约17 nm. 与平板铂电极相比,制备的催化电极对硝基苯电还原具有更高的催化活性,硝基苯转化率为74%,最大放电功率为21.9 mW•cm^-2,远大于平板铂电极. 硝基苯的主要还原产物为苯胺、对乙氧基苯胺和对氯苯胺.     

Electrochemical Reduction of Nitrobenzene in Ionic Liquid BMImAc

Ionic liquid,1-butyl-3-methylimidazolium acetate（BMImAc）,was used in the electrochemical reduction of nitrobenzene.The electro-reduction of nitrobenzene on platinum electrode was studied by cyclic voltammetry（CV）,in situ Fourier transform infrared（FTIR） spectroscopy and constant-potential electrolysis.The experimental results show that electrochemical reduction process of nitrobenzene was controlled by diffusion,the main reduction product was azobenzen at-1.45 V,and the influences of scan rate and temperature on the electrochemical behaviors were obviously.A reduction mechanism of nitrobenzene in an ionic liquid was a probable ‘nitrobenzene→nitrosobenzene→azobenzene→aniline＇ main reductive reaction route.     

Novel electrochemical heterogeneous catalytic reactor for organic pollutant abatement

Taking nitrobenzene as a model, electrochemical heterogeneous catalytic degradation of organic pollutant is investigated using a novel electrochemical heterogeneous catalytic reactor coupled by three-dimensional electrode with heterogeneous catalytic reactor. The nitrobenzene removal efficiencies considerably depend on the applied potential, initial pH, and the concentration of the supporting electrolyte. The results show that, with catalyst the nitrobenzene removal efficiencies are higher than that of control (without catalyst). The efficiency of ferrous catalyst is the best for nitrobenzene removal especially. It is clear that the reaction of electro-oxidation is promoted by the catalyst. A possible mechanism of nitrobenzene degradation is deduced based on products. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 3, pp. 313–318. The text was submitted by the authors in English.     

铜-镍合金电极表面组成及状态的变化对硝基苯电还原的影响

铜-镍合金电极表面组成及状态的变化对硝基苯电还原的影响;Monel合金电极;表面状态;硝基苯;对氨基苯酚;电还原     

去甲肾上腺素电极过程的圆二色谱电化学研究

现场圆二色薄层光谱电化学研究去甲肾上腺素的电化学氧化还原过程 .研究表明去甲肾上腺素 ( pH =7.0磷酸缓冲溶液中 )在玻碳电极上经历了不可逆的电化学氧化 ,且遵从后行化学反应 (EC)机理 ,去甲肾上腺素醌和去甲肾上腺素红的再还原遵从简单电子转移 (E)机理 .由双对数法获得去甲肾上腺素电化学氧化的式电位为E10’=0 .2 0V ,电子转移系数和电子转移数之积为αn =0 .38,标准复相电极反应常数k10 =1 .2× 1 0 -4 cm·s-1.去甲肾上腺素醌和去甲肾上腺素红的电化学还原反应参数分别为E2 0’=0 .2 5V ,αn =0 .37,k2 0 =4.4× 1 0 -5 cm·s-1和E3 0’=- 0 .2 5V ,αn =0 .33,k3 0 =1 .1× 1 0 -4 cm·s-1.     

硝基苯的电还原特性研究

采用准稳态极化、循环伏安、线性扫描和恒电位阶跃等测试方法,对Ｈ２ＳＯ４溶液中硝基苯的电还原特性进行研究,评价了硝基苯在Ｃｕ、Ｃｕ－Ｈｇ和Ｃｕ－Ｎｉ电极的电还原反应活性,研究了硝基苯电还原为ＰＡＰ的中间步骤,并对反应机理进行了探讨。结果表明,硝基苯在酸性介质中的电还原反应存在中间步骤,并伴有反应物吸附现象,硝基苯电还原反应受硝基苯及其还原产物在溶液中的液相传质步骤控制．     

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识. 本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱. 结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程. 结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种. 本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向.     

硝基苯在铜电极上的电还原特性研究

应用循环伏安法和线性扫描伏安法研究水溶液中硝基苯在铜电极上的电还原特性及其电还原为苯胺的中间步骤和反应机理.结果表明:铜电极上硝基苯的还原电位在-0.58V和-1.32V左右(vs.SCE),溶液的酸性和碱性均有益于该还原反应的发生;还原过程伴有反应物吸附现象,当硝基苯浓度较大时,还原过程受传质过程控制;随着厌氧程度的提高,还原速率加快.     

Electrocatalytic activity of nanoporous Pd and Pt: effect of structural features

The electrocatalytic activities of nanoporous palladium (npPd) and platinum (npPt) for oxygen reduction reaction (ORR) under alkaline conditions and hydrogen peroxide electrochemical reactions under neutral conditions were examined. npPd and npPt were prepared by the electrochemical deposition of each metal from the corresponding metal precursor in the presence of reverse micelles of Triton X-100, directing highly porous microstructures. The nanoporous catalysts showed excellent electrocatalytic activity for both the ORR and hydrogen peroxide electrochemical oxidation/reduction due to the increased active surface area. In particular, the npPd exhibited superior ORR activity (i.e., more positive onset and half-wave potentials, higher current density and greater number of electrons transferred) despite the smaller roughness factor than the npPt and commercial Pt. The catalytic activity for the hydrogen peroxide electrochemical reactions was also higher while using npPd (i.e., faster electrode reaction kinetics, increased current densities, etc.) compared to npPt. The higher catalytic activity of npPd than that of npPt suggests an advantage of the unique npPd structure, composed of nano- as well as micro-porosity, in facilitating mass transport through the porous metal layer. The npPd exhibited amperometric current responses, induced by the oxidation as well as reduction of hydrogen peroxide, linearly proportional to the hydrogen peroxide concentration with a rapid response time (<~2 s), high sensitivity, and low detection limit (<1.8 μM).     

α-蒎烯和间戊二烯共聚工艺

研究了共聚反应条件对α-蒎烯（α-P）和间戊二烯(PD)共聚产物的影响,确定最佳反应条件为：反应时间2 h,原料比例n(α-P)∶n(PD)=1∶2,反应温度15 ℃,溶剂甲苯,催化剂AlCl3用量为单体总质量1%,获得产物树脂的收率为72.3%,软化点为121.3 ℃,色度为4,相对分子质量为1549,相对分子质量分布为1.92。 其热稳定性和粘结相容性好。     

Free radicals of electrochemical reduction of derivatives of 3-nitro-1,4-dihydropyridines

By means of ESR, under conditions of eletrochemical generation of particles, the formation of four types of secondary free radicals has been confirmed in the process of electrochemical reduction of molecules of N-unsubstituted derivatives of 3-nitro-1,4-dihydropyridine in dimthylformamide — specifically, a dianion radical of the molecule of the original compound; an anion radical of the corresponding isomeric 4,5-dihydropyridine; a radical of the nitroalkane type; and in addition, for the compound substituted with a nitrobenzene group; a free radical with the nitrobenzene structure. Methods for synthesis of the individual compounds are described, and a scheme is presented for the mechanism of their electrochemical conversion.Latvian Institute of Organic Synthesis, Riga LV-1006. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 355–364, March, 1995. Original article submitted February 21, 1995.     

质子惰性介质中硝基苯在铂微盘电极上的电化学行为

采用循环伏安法, 以铂微盘电极为工作电极, 铂片为辅助电极, 饱和甘汞电极为参比电极, 研究了硝基苯在含有四丁基高氯酸铵(TBAP)电解质的N,N-二甲基甲酰胺(DMF)有机溶液中的电化学行为, 并探讨了扫描速度和底物浓度等因素对硝基苯电化学特性的影响. 结果表明,该反应属扩散控制的准可逆反应.     

MTsPc催化H2S还原硝基苯反应性能的研究

就工业气休中有害物质Ｈ２Ｓ的综合利用开发进行了有益的探索,采用ＭＴｓＰｃ（Ｍ＝Ｆｅ,Ｃｏ,Ｎｉ,Ｃｕ）做催化剂,水做溶剂,研究了催化剂物种及浓度、碱浓度反应温度对Ｈ２Ｓ还原硝基苯制备苯胺反应性能的影响。结果表明,在诸多催化剂中双核磺化酞菁钴（ＣｏＰｃ－ＰｃＣｏ）催化活性最高,且得到最佳反应条件为：氨水浓度０．６ｍｏｌ／Ｌ,反应温度４０℃,催化剂质量浓度１ｇ／Ｌ,在此条件下苯胺的产率达３５．９％,表明在传统的脱硫工艺上加以技术改造不仅是可行的,而且是有效的。     

α -羟基-α -氨甲酰基酰胺类化合物的合成新方法

N, N-二甲氨酰基三甲基硅烷与一系列α -羰基酰胺在无水无氧、105 ℃的条件下反应, 较高产率地合成了α -羟基-α -氨甲酰基酰胺类化合物或α -三甲基硅氧基-α -氨甲酰基酰胺衍生物。 其结构用元素分析、¹H NMR、¹³C NMR和IR等技术手段进行了表征。 通过研究反应机理和影响反应的因素发现, 在α -羰基上连的烃基的空间位阻是该加成反应的重要影响因素, 而电子效应则影响反应的速率。 提出了可能的反应机理。     

三维花状结构α-FeOOH纳米材料的制备与表征

以硫酸亚铁、尿素及乙醇为原料,采用低温常压一步回流法制备了具有三维花状结构的α-FeOOH纳米材料.考察了反应时间、反应温度、尿素浓度和乙醇用量对其结构和形貌的影响及α-FeOOH纳米材料对双氯芬酸钠的吸附性能.实验结果表明,当反应温度为90℃、反应时间为6 h、尿素浓度为0.1 mol/L、乙醇的体积分数为20%时,所得α-FeOOH纳米材料具有规整的三维花状结构,对双氯芬酸钠的吸附量达199.2mg/g.基于扫描电子显微镜(SEM)和X射线衍射(XRD)分析,推断三维花状结构α-FeOOH的生长机制包括定向聚集和外延生长2个过程,反应初期生成的高活性晶核快速形成不规则橄榄状颗粒并定向聚集成短簇状结构,再沿z轴方向外延生长,形成长簇的三维花状结构.     

对硝基苯酚在质子惰性溶剂中的氧化还原机理

利用现场红外光谱电化学法、红外光谱循环伏吸法(CVA)和导数循环伏吸法(DCVA)研究了对硝基苯酚(PNP)在乙腈中的氧化还原机理,并结合B3LYP方法在6-311++G*水平上计算得出反应中自由基阴离子和二聚体可能的结构.通过循环伏安曲线(CV)和快速扫描红外光谱验证了在电化学还原过程中PNP在乙腈溶剂中发生较复杂的自质子化反应,并且PNP的电化学行为受其浓度的影响.当PNP浓度较高时,PNP在还原成自由基阴离子后发生自质子化作用,然后自由基阴离子与质子化产物得到电子发生二聚反应,随后PNP阴离子还原成二价阴离子;当PNP浓度较低时,电化学还原机理会发生改变,二聚现象消失,阴离子自由基继续还原.     

Electrochemical sensor for nitrobenzene based on carbon paste electrode modified with a poly(3,4-ethylenedioxythiophene) and carbon nanotube nanocomposite

A sensitive and selective electrochemical sensor for the determination of nitrobenzene (NB) was developed based on a carbon paste electrode (CPE) modified with a nanocomposite prepared from the conducting polymer poly(3,4-ethylenedioxythiophene) and carbon nanotubes. The modified CPE exhibits good conductivity, a large surface area, and excellent catalytic activity towards the electrochemical reduction of NB. Under optimal conditions, the modified CPE is capable of detecting NB in the 0.25 to 43 μM concentration range and with a detection limit at 83 nM. Moreover, the sensor is highly stable and reusable, and free of interferences by other commonly present nitro compounds. It was used to determine NB in wastewater samples.

阿霉素的光谱电化学研究

利用循环伏安、紫外可见光谱电化学、荧光光谱电化学、圆二色光谱电化学等方法研究了阿霉素(ADM)在石墨电极上的电化学行为.结果发现,阿霉素在+0.2～+0.7V和-0.2～-0.7V范围内分别出现一对氧化还原峰.正电位下,蒽环上的酚羟基发生单电子氧化,并伴随后续化学反应.负电位范围内,阿霉素经历ECE电极反应过程,即蒽醌经单电子还原生成半醌自由基,半醌可发生不可逆的化学反应,脱去配氧糖基,转变为7-去氧柔毛霉醌(7-deoxyadriamycinone),后者在更负的电位下形成一对可逆的新的氧化还原峰.