中性溶液中抗坏血酸在六氰合亚铁酸钴铜膜修饰铂电极上现场红外光谱电化学研究

抗坏血酸 ( AA)是生物化学和生物医学中的一种重要生理物质 ,因而在电催化和电化学传感器领域得到了广泛的研究 .对抗坏血酸的研究主要集中在两个方面 :一方面是研究 AA在各种电极上的电氧化机理、动力学参数及电催化机理 [1,2 ] ;另一方面是为了监测各种生物化学和生物医学中 AA的浓度发展起来的 AA传感器 .利用碳电极的各种预处理方法 [3,4 ]以及利用各种化学修饰电极 [5,6 ]来促进AA的电氧化动力学过程及解决 AA与各种共存物如多巴胺及脲酸等之间的相互干扰问题 .六氰合亚铁酸钴铜修饰电极 ( Co Cu HCF/Pt) [7] 在中性溶液中十分…     

对氨基苯甲酸BZ反应体系分区振荡行为的研究

分区振荡（也被称为双振荡，dual－frequencyoscillation）现象是封闭反应体系中发现的一种较为特殊的振荡现象，FKN机理[1]和OKN机理[2]都不能很好地解释这种振荡行为，Forsterling等曾提出了自由基控制机制[3,4]；Srivastava等则认为高、低频区均为溴控机制[5]．目前，这一问题还没有确切结论．本文报导了对氨基苯甲酸BZ反应体系中的分区振荡行为，并对分区振荡的机理作了一些探讨．1实验以对氨基苯甲酸－KBrO3－H2SO4的振荡反应作为研究体系，反应在带夹会的封闭玻璃反应器中进行，由恒温措恒温；自制Pt电极和216型Ag电极作x作电…     

电极/溶液界面pH值的现场测量

一般认为阴极表面功能陶瓷电沉积层的形成是由于基底 /溶液界面化学环境变化造成的 [1,2 ] ,但目前还没有直接的实验数据加以证明 .原位测量电极 /溶液界面 p H的变化存在两方面的困难 :(1 )传统方法是采用玻璃 p H计 ,由于其体积较大、强度脆弱等原因 ,使其在测量固 /液界面化学环境变化的应用方面受到一定限制 [3 ] ;(2 )将 p H微探针置于电极表面 ,将会影响功能陶瓷在电极表面的沉积 ,从而使测定的界面 p H值不能真实反映电沉积过程中固 /液界面化学环境的变化 .本文基于功能陶瓷电沉积过程不受影响的情况下现场直接测量电极 /溶液界面…     

邻菲罗啉对KBrO_3-Na_2SO_3-K_4[Fe(CN)_6]-H_2SO_4 pH振荡体系的扰动

本文研究了邻菲罗啉对KBrO3-Na2SO3-K4[Fe(CN)6]-H2SO4振荡体系的扰动。结果表明,当加入邻菲罗啉的浓度在0.0005~0.0035mol·L-1范围内时,导致KBrO3-Na2SO3-K4[Fe(CN)6]-H2SO4pH振荡体系的Pt电极电位、溴离子选择电极电位和pH振荡的周期和振幅均明显放大,而加入邻菲罗啉的浓度在0.004~0.013mol·L-1范围内时,该体系的振幅缩小。另外,本文就邻菲罗啉对KBrO3-Na2SO3-K4[Fe(CN)6]-H2SO4pH振荡体系的影响机理进行了讨论。     

非缓冲介质中硫脲氧化的非线性动力学

研究了在非缓冲介质中高碘酸盐氧化硫脲的复杂反应动力学。实验结果表明：高碘酸盐氧化硫脲的非线性反应不但呈现多种不同的化学计量方程式,而且体系的pH、[I-]、[I2]及Pt电极电位呈现封闭条件下的准振荡和单峰振荡以及开放条件下的双稳态和衰减振荡行为。综合考虑硫价态与碘价态变化的各自非线性过程及相互耦合,提出了包含质子快速预平衡反应、碘化合物自身反应、碘化合物-硫化合物反应以及硫－硫反应的12步反应机理,模拟出了封闭体系中pH、[I-]以及[I2]的准振荡和单峰振荡以及开放体系中的双稳态行为。     

线状铜电极在磷酸溶液中电流混沌振荡的同步行为

研究了恒电位下两个铜线电极在磷酸溶液中的电流混沌振荡行为,通过恒定不同的电位数值,改变单个电极的电流振荡混沌行为,研究了不同混沌间的相互作用.调整线电极间的距离,研究了电极间距对电流振荡行为的影响.实验中两电极的振荡间呈现了复杂的耦合作用,耦合后的频率与耦合前电极原有的频率不同.两电极的混沌电流振荡中呈现出同步、准周期同步和反相同步等现象.电极距离一定时,振荡波形差别很大的两电极的电流容易呈现反相同步和准周期同步,波形差别不大时容易产生同步.强的耦合导致电极间电流振荡的同步,电极距离的加大,电极间电流振荡难以产生同步.对耦合作用机制也进行了探讨.     

从铜离子的作用研究Orbán振荡体系中的动力学特征

近年来 ,化学反应的奇异现象[1～ 3] 如振荡、混沌、时空图案等激起了化学家的极大兴趣 ,非线性反应机理不仅是重要的研究方向之一 ,而且是复杂现象研究的基础 .Orbán发现的 H2 O2 -SCN- -OH- -Cu2 + 反应体系呈现闭系、开系振荡和周期性化学发光现象[4～ 6 ] .我们发现体系也呈现复杂振荡、双节律、两种不同型的 p H振荡[7,8] 和无铜催化振荡[9] ,为此提出双振荡反应机理 ;Cu2 + 在封闭体系振荡和开系复杂振荡中是必不可少的一个成分 ,它在此非线性反应体系中的地位及影响需要进一步深入研究 ,以解释出现的各类复杂动力学现象 .本文…     

Mn(Ⅱ)在铅电极上的超声电氧化

苯甲醛电合成法大多是将媒质Ｍｎ(Ⅱ )在电解槽中电氧化为Ｍｎ(Ⅲ ) ,再利用Ｍｎ(Ⅲ )在化学反应器中氧化甲苯成苯甲醛[1 ] 。其中电氧化时用的阳极材料多为铅电极或复合电极[2 ,3] 。王岚等[4] 、林祥钦等[5] 报道了复合电极具有可提高氧的过电位 ,降低界面电阻 ,阻止基体氧化 ,改善电极催化活性和反应的选择性等作用。但它也存在制备繁琐、镀层易脱落、使用寿命不长等缺点。与铅电极一样 ,为获得较高的Ｍｎ(Ⅲ )的产率 ,施加的电解电压较高[6] ,能耗较大。超声波作为一种新的能量形式已用于有机合成[7] ,考虑到铅电极价廉易得且析氧电位较…     

一种新型低噪音碳纤维纳米电极

近年来,碳纤维超微电极在生命科学领域中已取得了广泛应用,电极的超微尺寸使之能对生物微环境进行实时监测^[1],还可作为微柱分离的检测 ^[2],自Adams研究组1976年开展微电极伏安法对细胞外液中生物胺以及有关代谢物的检测研究以来,碳纤维超微电极已成为探测脑内甚至单个细胞内神经递质的一种有力的工具,人们已对单个细胞内神经递质^[3]及激素^[4]的释放进行了探索性研究。     

[Pt]—Ni（Ⅱ）电极的研究

我们首次发现Pt浸于镍、钴或铁盐溶液中,只有镍可形成[Pt]-Ni(Ⅱ)电极。在NaOH电解液中,此电极有明显的氧化还原峰,表现出Ni电极的特征。本文研究[Pt]-Ni(Ⅱ)电极的电化学性能、电极制备的影响因素。 1 实验部分 研究电极:Pt为基底,用5~#金相砂纸磨光,在王水中浸渍,二次蒸馏水冲洗(也可再进     

Application of a Zeolite-Poly(vinyl chloride) Electrode to Potentiometric Studies of Alkali Metal Ions

Potentiometric electrodes based on the incorporation of zeolite particles into poly(vinyl chloride) (PVC) membranes are described. The electrode characteristics are evaluated regarding the response towards alkali ions. PVC membranes plasticized with dibutyl phthalate and without lipophilic additives (co-exchanger) are used throughout this study. The electrode exhibits a Nernstian response over the alkali metal cation concentration range of 1.0 × 10^?4 to 1.0 × 10^?1 M with a slope of 57.0 ± 0.9 mV per decade of concentration with a working pH range 3.0–9.0 and a fast response time of ≤15 s. The selectivity coefficients for cesium ion as test species with respect to alkaline earth, ammonium, and some heavy metal ions are determined. The proposed zeolite-PVC electrode is applied to the determination of ionic surfactant.     

盐水振荡与液膜振荡耦合

为进一步增大盐水振荡产生的电势差,并使盐水振荡可逆，该文将液膜振荡与盐水振荡耦合，组成一个耦合的振荡器.实验结果发现:(1)由于两振荡器耦合形成共振，所以此耦合振荡器的振幅明显增大; (2)耦合后的化学振荡器变为可逆振荡器.耦合振荡机理如下:扩散过程中形成的缔合物存于油相，难溶于水，通电后缔合物发生解离，因此造成反扩散，形成可逆振荡，且可逆程度及逆反应产生的电势差（即振幅）大大提高，扩展了盐水振荡在二次电池开发方面的应用.     

8-hydroxyquinoline based neutral tripodal ionophore as a copper (II) selective electrode and the effect of remote substitutents on electrode properties

New PVC membrane ion selective electrodes based on 1,3,5-Tris(8-quinolinoxymethyl)-2,4,6-trimethylbenzene (MO8HQ) are reported. The basic sensing material belongs to the group of tripodal ionophores. Also their derivatives prepared by placing suitable substitutents at fifth position of 8-oxine moiety, i.e, 1,3,5-Tris(5-chloro-8-quinolinoxymethyl)-2,4,6-trimethylbenzene (5CHQ), 1,3,5-Tris(5-benzoyl-8-quinolinoxymethyl)-2,4,6-trimethylbenzene (5BHQ) and 1,3,5-Tris[(5-phenylhydroxymethylene)-8-quinolinoxymethyl]-2,4,6-trimethylbenzene (HYD-8HQ) ionophores have also been used to make copper-selective membrane electrodes. Among all the four electrodes, MO8HQ and HYD-8HQ ionophores based electrodes show excellent response towards Cu (II) ions. The electrodes having composition 33% PVC, 4% MO8HQ and 63% dibutyl phthalate (DBP) and 33% PVC, 6% HYD-8HQ, 63% dibutyl phthalate (DBP) exhibit a good Nernstian response to Cu (II) ions in the range of 1.0 × 10⁻⁶ to 1 × 10⁻¹ M. The electrode shows a reasonably fast response time of 15 s. The effect of pH and electrode response is also reported. It shows good selectivity for Cu (II) ions in comparison to heavy metal ions, transition metal ions and for alkali and alkaline earth metal ions. The electrode response and selectivity remains unchanged for at least 5 months. The electrode can be used as an indicator electrode in the potentiometric titration of Cu (II) ions with EDTA.     

Measuring quaternary ammonium cleaning agents with ion selective electrodes

Data for coated-wire, ion selective electrodes (ISEs) are presented for cationic surfactant ions found in common cleaners including benzyldimethyltetradecylammonium, benzyldimethyldodecylammonium, and benzyldimethylhexadecylammonium. The ion exchangers dinonylnaphthalene sulfonic acid, tetraphenyborate, and tetrakis(4-chlorophenyl)borate are examined, showing dinonylnaphthalene sulfonic acid to be the favored species. The ISEs exhibit approximately Nernstian behavior down to the 10⁻⁶ M limit of detection with lifetimes in excess of 50 days when used continuously, and a shelf life of over 100 days. Reaching the upper detection limit at the critical micelle concentration requires use of polymeric-membrane reference electrodes including a new membrane cocktail, which allow response measurements of an order of magnitude higher than the traditional fritted-glass reference electrode. The surfactant ISEs show excellent selectivity over the common metal ions Na⁺, K⁺, Mg²⁺, Ca²⁺, and Cu²⁺ with selectivity coefficients less than 10^−5.3. The ISEs are also selective over the lower molecular weight quaternary ammonium ions tetradecyltrimethylammonium, dodecyltrimethylammonium, benzyldimethyl(2-hydroxyethyl)ammonium, and tetrabutylammonium with selectivity coefficients ranging from 10^−1.7 to 10^−5.5. Use of a single electrode to determine accurately the total cationic surfactant concentration in common cleaning solutions is accomplished with information about concentration dependent interferences and a modified Nikolsky–Eisenman model. Finally, quaternary ammonium surfactants have a deleterious effect on the measurements of pH and common ions like K⁺, Mg²⁺ and Ca²⁺ with polymeric ISEs. This makes it critical to include surfactant electrodes in a detector array when cleaning agents are present.     

Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small-Angle Neutron Scattering

A molecular-level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double-layer capacitors. Here, in operando small-angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron-scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.     

Preparation of porous Cu-rich CuNi electrodes via electrochemically dealloying in ionic liquid

Commercial CuNi (55/45 wt%) alloy can be electrochemically dealloyed to be the porous Cu-rich CuNi electrodes, which reveals an enhanced catalytic activity toward nitrate reduction in contrast with that of the mother alloy electrodes. In comparison with the use of aqueous electrolytes, the formation of the porous structures is reproducible if ionic liquid (IL) is used as the electrolyte for the dealloying process. During the dealloying process, a relatively more quantity of Ni but both Ni and Cu were electrochemically oxidized to be Ni(II) and Cu(II) complex ions; different ions seemed to own different coordinating molecules in accordance with the NMR analysis. Cu(II) ions could be reduced to Cu metal and deposited upon the counter electrode during the dealloying process. Ni(II) ions, on the other hand, can be mostly removed from the IL phase by extraction into the immiscible water phase. A sustainable system may be developed for the preparation of nitrate-active electrodes in accordance with the study shown here.     

含嘧啶环的双冠醚——Ⅲ.用双冠醚作载体的PVC膜离子选择性电极性质的研究

合成了九种用嘧啶环桥联的新的双冠醚,其中分别含有苯并-12-冠-4、(1、47)、苯并-15-冠-5(2、5、8)和苯并-18-冠-6(3、6、9 )。用它们作为载体分别制成钠、钾和铯离子选择性电极,测定了电极的选择性系数。结果表明,电极(7)(8)(9)具有较好的性能。     

基于羧基化碳纳米管修饰电极伏安法同时测定痕量锢和铝

基于羧基化多壁碳纳米管(c-MWCNT),制备了可同时测定In3+和Al3+的新型碳材料修饰电极.利用循环伏安法(CV)和交流阻抗法(EIS)对此修饰电极进行了表征,用线性扫描伏安法(LSV)研究了In3+与Al3+共存于修饰电极上的电化学行为.与裸玻碳电极相比,新型碳材料修饰电极的电化学活性得到很大提高;In3+与A...     

Tungsten electrode for urea

Tungsten electrodes for urea were prepared via covalent linking of urease on oxidized metal surfaces in different ways. The most stable electrodes were obtained when tungsten was silanized and activated by glutaraldehyde or hexamethylene diisocyanate. The electrode with urease coupled via glutaraldehyde was tested for optimum conditions of use. The nature of the buffer and its concentration and ionic strength are particularly important.     

Observation of Ion Electrosorption in Metal–Organic Framework Micropores with In Operando Small‐Angle Neutron Scattering

A molecular‐level understanding of transport and adsorption mechanisms of electrolyte ions in nanoporous electrodes under applied potentials is essential to control the performance of double‐layer capacitors. Here, in operando small‐angle neutron scattering (SANS) is used to directly detect ion movements into the nanopores of a conductive metal–organic framework (MOF) electrode under operating conditions. Neutron‐scattering data reveals that most of the void space within the MOF is accessible to the solvent. Upon the addition of the electrolyte sodium triflate (NaOTf), the ions are adsorbed on the outer surface of the protrusions to form a 30 Å layer instead of entering the ionophobic pores in the absence of an applied charging potential. The changes in scattering intensity when potentials are applied suggests the ion rearrangement in the micropores following different mechanisms depending on the electrode polarization. These observations shed insights on ion electrosorption in electrode materials.