半导体催化膜上泵氧甲烷氧化偶联反应的研究 Ⅰ.传递体系的反应

在常压及６５０℃下,考察了ＣａＯ,ＳｒＯ,Ｌａ２Ｏ３,ＺｎＯ,ＴｉＯ２,ＣｅＯ２和ＭｎＯ２膜上外加电流为１６～９０ｍＡ时传递物系的甲烷氧化偶联反应结果,结果发现,在ｎ型ｐ型半导体催化膜上,ＣＯ２,Ｃ２Ｈ４和Ｃ２Ｈ６的生成速率都随泵氧量的增加而增大,而Ｃ２烃选择性随泵氧量的增加而下降,但ｐ型半导体膜上的Ｃ２烃选择性比ｎ型半导体膜上的要高：ｑ型半导体膜上Ｃ２烃选择性与其电导率大小顺序相一致,增强因子的     

甲烷与二氧化碳在Na2WO4—Mn／SiO2催化剂上反应制C2烃及其反应机理的 …

考察了Ｎａ２ＷＯ４－Ｍｎ／ＳｉＯ２催化剂上甲烷与二氧化碳反应制Ｃ２烃及其反应机理，８２０℃时，Ｃ２烃选择性可达９４．５％，随着着温度继续升高，虽然甲烷的转化增加，但Ｃ２烃选择性逐渐降低。Ｏ２－ＴＰＤ，ＣＨ４及脉冲实验表明，８００℃脱附的表面昌格氧为活性氧物种，在催化甲烷活化的同时，ＣＯ２可在该催化剂上活化分解为活性氧物种。     

甲烷与二氧化碳在Na_2WO_4-Mn/SiO_2催化剂上反应制C_2烃及其反应机理的研究

考察了Ｎａ２ＷＯ４－Ｍｎ／ＳｉＯ２催化剂上甲烷与二氧化碳反应制Ｃ２烃及其反应机理，８２０℃时，Ｃ２烃选择性可达９４．５％．随着温度的继续升高，虽然甲烷的转化增加，但Ｃ２烃选择性逐渐降低．Ｏ２－ＴＰＤ、ＣＨ４及脉冲实验表明，８００℃脱附的表面晶格氧为活性氧物种，在催化甲烷活化的同时，ＣＯ２可在该催化剂上活化分解为活性氧物种（ＣＯ２→ＣＯ＋Ｏ＊）．     

甲烷部分氧化制合成气Ⅱ．镍系催化剂的反应性能

主要用第四周期金属元素的氧化物与Ａｌ２Ｏ３的复合氧化物催化剂上甲烷氧化的结果证实了催化剂设计中的预测：（１）催化剂首先应能解离活化甲烷，（２）催化剂要能较快地活化Ｏ２分子．只有同时满足这两个条件，催化剂才可能有较好的甲烷部分氧化活性．第四周期元素中只有镍具有这样的性质．Ｃｕ，Ｍｎ，Ｃｒ，Ｌａ，Ｃａ，Ｚｎ等氧化物的添加可明显提高Ｎｉ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能，其中Ｃｕ的助催化性能最好．催化剂ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３，ＮｉＯ－ＭｎＯ－Ａｌ２Ｏ３，ＮｉＯ－Ｃｒ２Ｏ３－Ａｌ２Ｏ３的反应活性和选择性顺序，与金属Ｃｕ，Ｍｎ，Ｃｒ上ＣＯ和Ｈ２脱附的顺序是一致的     

2%Mn2O3-5%Na2WO4/SiO2催化剂上的甲烷氧化偶联反应动力学

在Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ２催化剂上的甲烷氧化偶联反应可用Ｒｉｄｅａｌ－ｒｅｄｏｘ机理描述，它包括均相及多相两个步骤。甲基自由基的生成是一个多相过程，Ｃ２烃的生成是一个均相过程。催化剂的活性同氧化速率和ＣＨ４与表面氧种的反应速率有关，Ｃ２烃的选择性与甲基自由基氧化速率常数和甲基自由基偶联速率常数的比值有关，这些常数均可从实验中求得。     

助剂MgO对Pd／γ—Al2O3催化剂上CO氧化反应的作用

以ＣＯ氧化为模型反应,考察了Ｐｄ／γ－ Ａｌ２Ｏ３ 体系中以不同方式加入ＭｇＯ 对催化剂性能的影响,结果证实助剂ＭｇＯ能较大幅度提高Ｐｄ／γ－ Ａｌ２Ｏ３ 对ＣＯ 氧化反应的催化活性。ＭｇＯ能均匀地分散于γ－ Ａｌ２Ｏ３ 上,使ＣＯ的起燃温度降低达４４℃。对样品的ＸＲＤ、ＴＰＲ、ＸＰＳ及氧吸附等表征结果表明,共浸型的Ｐｄ－ ＭｇＯ／Ａｌ２Ｏ３ 体系具有最高的Ｐｄ 分散度;分浸型的Ｐｄ－ ＭｇＯ／Ａｌ２Ｏ３ 体系Ｐｄ 分散度亦高于Ｐｄ／Ａｌ２Ｏ３ ,且能提高催化剂表面活性Ｐｄ 的含量。表面ＭｇＯ对氧的浓缩作用有利于ＣＯ 的氧化。并讨论了助剂ＭｇＯ与Ｐｄ 的协同作用对其活性的影响     

2％Mn_2O_3－5％Na_2WO_4／SiO_2催化剂上的甲烷氧化偶联反应动力学

在Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ４催化剂上的甲烷氧化偶联反应可用Ｒｉｄｅａｌ－ｒｅｄｏｘ机理描述，它包括均相及多相两个步骤．甲基自由基的生成是一个多相过程（表面反应），Ｃ２烃的生成是一个均相过程（气相反应）．催化剂的活性同氧化速率（ｋ１）和ＣＨ４与表面氧种的反应速率（ｋ２）有关，Ｃ２烃的选择性与甲基自由基氧化速率常数和甲基自由基偶联速率常数的比值（ｋ／ｋ４）有关，这些常数均可从实验中求得．     

CuZSM-5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量、反应温度、反应时间及ｎ（ＰｈＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响．     

Fe－P－O系催化剂上的甲烷氧化偶联

研究了Ｆｅ－Ｐ－Ｏ催化剂对甲烷氧化偶联（ＯＣＭ）的低温催化活性，考察了催化剂组分的优化，最适宜的反应温区，反应过程参数，助催化剂组分，催化剂的晶型结构和活性相以及Ｆ：元素键合状态的ＸＰＳ谱．确定了８％ＬｉＮＯ３－０．８Ｆｅ／Ｐ催化剂在６５０℃，ＣＨ４：Ｏ２：Ａｒ＝２：１：２及ＧＨＳＶ＝３０００ｈ－１条件下，可获得甲烷转化率为１１．９０％和Ｃ２烃选择性为６９．８１％的结果．添加ＬｉＮＯ３为助催成分，可有效改善催化剂表面酸活性中心的分布，防止ＯＣＭ中深度氧化和表面积炭，提高Ｃ２和Ｃ２烃选择性．该催化剂为可变价型，是六方形和料方形两种晶型结构的复合磷酸铁，活性相为斜方形ＦｅＰＯ４物相．     

CuZSM—5分子筛上苯酚羟化制苯二酚

在Ｎａ２Ｏ－ＳｉＯ２－ＣｕＯ－Ｈ２Ｏ体系中以１５％ＴＰＡＢｒ－８５％ＨＭＤＡ为模板剂合成了ＣｕＺＳＭ－５分子筛，并用ＸＲＤ，ＩＲ及ＳＥＭ等方法进行了表征，考察了ＣｕＺＳＭ－５分子筛催化苯酚与过氧化氢的羟化活性，研究了催化剂用量，反应温度，反应时间及ｎ（ＰｂＯＨ）／ｎ（Ｈ２Ｏ２）等对羟化活性的影响。     

电化学氟化的新进展

电化学氟化是利用电极反应将氟直接引入有机或无机物的一种重要方法。有机物的电化学氟化方法有两种: 一是Simons于1941年发明的, 用镍作阳极, 在无水氟化氢溶液中, 电解制备全氟化合物的方法。此方法在近年来有不少改进。另一是1970年Rozhkov提出的, 以有机溶剂(如含Et3N.3HF的MeCN)为介质, 在铂阳极上,氧化得到单氟化产物的方法。本文全面地综述了这两种方法, 并着重于最新民发展。     

(NH_4)_(42)[Mo_(132)O_(372)(CH_3COO)_(30)(H_2O)_(72)]膜修饰电极的构筑和电化学性质的研究

由于过渡金属替代的多金属氧酸盐(polyoxometalates)的催化、磁性、电化学等性质,越来越受到人们的关注~([1-7]). 目前世界上约有10亿人生活在缺碘地区,碘的缺乏严重影响人类健康.对食物、生物临床、环境及工业中碘含量检测很有实际意义.     

The Electrochemical Behavior of PPV/PEO Blend

Light-emittingelectrochemicalcellisanewpromisingdeviceforlarge-areadisplay'.Theelectrochemicaldopinginthepolymerblendofpoly(ethyleneoxide)(PEO)andpoly(l,4-phenylenevinylene)(PPV)usedintheLECplaysaveryimpo~roleinitselectroluminescence.TheaimofthisinvestigationistounderstandiftheadditionofPEOaffectstheelectrochemicalbehaviorofPPVandtheeffectsofdopantsonsuchablendsystem.Accordingtotheprocessesreportedintheliteramresl',wepreparedthepolymerblendonaPtelectrodewhichwasusedastheworkingelectrode…     

Electrochemical machining of metals: Fundamentals of electrochemical shaping

Basic problems of metal electrochemical shaping theory are considered. Exact and approxi1mate (quasi-steady-state, locally one-dimensional) methods for solving direct and inverse problems are analyzed. Experimental methods for improving the electrochemical shaping accuracy are considered.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1438–1480.Original Russian Text Copyright © 2004 by Davydov, Volgin, Lyubimov.     

Disposable and Flexible Electrochemical Paper-based Analytical Devices Using Low-cost Conductive Ink

In this work, a simple procedure for construction of disposable electrochemical paper-based analytical devices (ePADs) by screen-printing using low-cost materials and a home craft electronic printer is proposed. The devices were constructed using liner paper as a substrate and carbon ink prepared with graphite powder and wood glue. The ePAD was evaluated as an electrochemical sensor and biosensor. The proposed conductive carbon-based ink can be easily prepared and is an eco-friendly and non-toxic material. The developed ePAD was simple to produce and can be used as a low-cost electrochemical sensor, at less than US $0.20 per device.     

纳米材料电化学与生物传感器——有机微污染物检测新途径

本文介绍了近年来纳米材料电化学与生物传感器在有机微污染物检测中的研究现状,分析了这些传感器中纳米材料修饰电极的特点,重点阐述了纳米材料在有机微污染物检测中的重要作用,列举了一些纳米材料电化学与生物传感器在有机微污染物检测中的应用。最后对纳米材料电化学与生物传感器用于有机微污染物的检测研究进行了简要评述和展望。     

Sub-millivolt amplitude potential oscillations observed in the noise of hydrogen evolution on Ag and Cu microelectrodes

A strange effect was observed while using the method of quasi-simultaneous determination of electrochemical voltage noise and impedance to obtain information on the kinetics of the hydrogen evolution reaction on Ag and Cu microelectrodes. Beyond a certain polarizing current density we found microvolt-amplitude potential oscillations on both electrodes with a frequency in the 5 Hz–5 kHz range. The oscillations were observed in every single experiment with Ag and Cu, while no oscillatory behavior was observed during the control experiments with the Pt microelectrode. The presence of the oscillations indicates that the mechanism of hydrogen evolution is more complex compared to the original assumption.      

Electrochemical behavior of single crystals of nonstoichiometric cerium(III) fluorides

The electrochemical properties of single crystals of cerium fluoride alloyed with bivalent cations Sr²⁺, Ca²⁺, Ba²⁺, Sr²⁺ + Ca²⁺, Sr²⁺ + Ba²⁺, Ba²⁺ + Ca²⁺ and also with La³⁺ and La³⁺ + Ba²⁺ cations are studied using the dynamic voltammetry and impedance spectroscopy. The conductivity of symmetrical cells with Ag electrodes is determined using the method of impedance spectroscopy in the frequency range from 450 to 5 kHz at the temperatures from 20 to 100°C: for CeF₃: Sr²⁺ (0.5 mol %) + Ba²⁺ (0.5 mol %), σ = σ₀ exp[(?0.284 ± 0.005/kT]; for CeF₃:Ca²⁺ (0.5 mol %) + Sr²⁺ (0.5 mol %), σ = σ₀ exp[(?0.292 ± 0.017/kT]. The steady-state and dynamic voltammogams of symmetrical electrochemical cells with nonpolarizable reference electrodes and CeF₃ single crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺ bivalent cations exhibited ohmic polarization. For cells with CeF₃ containing La³⁺ as an admixture, a hysteresis was observed, which could not be eliminated by chemical and electrochemical treatment of crystals. In the dynamic voltammetric curves of asymmetric cells with nonpolarizable and silver electrode and CeF₃ crystals alloyed with Sr²⁺, Ca²⁺, and Ba²⁺, a range of ideal polarizability (from 0 to ～?2.7 V), and also cerium redox processes and silver fluorination-boundary regeneration were observed. In the dynamic voltammetric curves of asymmetric cells with CeF₃ containing La³⁺ admixture, no range of ideal polarizability was observed; however, the reactions of silver fluorination and reduction of solid-electrolyte cerium were well pronounced at the corresponding potentials.     

Miniaturized electrochemical sensors and their point-of-care applications

Most of the current analytical methods depend largely on laboratory-based analytical techniques that require expensive and bullky equipment,potentially incur costly testing,and involve lengthy detection processes.With increasing requirements for point-of-care testing(POCT),more attention has been paid to miniaturized analytical devices.Miniaturized electrochemical(MEC)sensors,including different material-based MEC sensors(such as DNA-,paper-,and screen electrode-based),have been in strong demand in analytical science due to their easy operation,portability,high sensitivity,as well as their short analysis time.They have been applied for the detection of trace amounts of target through measuring changes in electrochemical signal,such as current,voltage,potential,or impedance,due to the oxidation/reduction of chemical/biological molecules with the help of electrodes and electrochemical units.MEC sensors present great potential for the detection of targets including small organic molecules,metal ions,and biomolecules.In recent years,MEC sensors have been broadly applied to POCT in various fields,including health care,food safety,and environmental monitoring,owing to the excellent advantages of electrochemical(EC)technologies.This review summarized the state-of-the-art advancements on various types of MEC sensors and their applications in POCT.Furthermore,the future perspectives,opportunities,and challenges in this field are also discussed.     

纤维蛋白原在Pt电极上的界面电化学研究

应用电化学方法和电化学原位红外反射光谱(electrochemical in-situ FTIR)等研究了纤维蛋白原在Pt电极上的界面电化学行为.结果表明:纤维蛋白原在Pt电极上的吸附使电极的析氢与氧脱附过程减弱,影响程度随扫速的增加而增强;同样纤维蛋白原的吸附会降低亚铁氰化钾-铁氰化钾电对的氧化还原反应可逆性和电流;在-0.1~0.6V(vs.SCE)扫描范围内没有出现纤维蛋白原的特征"氧化还原"峰.电化学原位红外反射光谱测试表明纤维蛋白原在0.3~0.5V(vs.SCE)间发生化学反应,有新的产物生成.