Single Oil Drop Electrochemistry on a Screen‐Printed Electrode Surface

The use of a contaminated single oil drop on a screen‐printed carbon electrode is described for the first time here. The simple methodology developed herein opens the possibility of conducting such measurements. R‐(+)‐limonene oil, some samples of which were contaminated with 4‐nitrophenol (4‐NP), was used as the oil phase, and Britton? Robinson (BR) buffer was used as the aqueous phase. An oxidation peak at approximately 0.8 V vs. Ag was obtained when the system comprised an oil/water interface. The charge transfer resistance decreased by a factor of approximately 7.1 when an interfacial system composed of two immiscible liquids was used as an electrochemical tool.     

The Use of Diamond Electrodes in the Interface Biodiesel/Water

A boron‐doped diamond electrode was used at the interface of biodiesel and water in conjunction with square‐wave voltammetry to promote the detection of a model molecule (ferrocene). The addition of LiClO₄ to the oil phase increased the detection of ferrocene five‐fold as compared with an unsupported oil phase. A cathodic surface pretreatment of the BDD electrode caused no oscillation of currents and promoted a high stability within the system. Our successful use of this system suggests the possibility for its application in the analysis of other contaminants within biodiesel including liposoluble pesticides and glycerol.     

多菌灵在羧甲基纤维素钠/蒙脱土修饰电极上的电化学行为及测定

制备了羧甲基纤维素钠/蒙脱土修饰电极,研究了多菌灵在该修饰电极上的电化学行为并用方波伏安法对其进行测定。实验结果表明,多菌灵在修饰电极上出现了一个不可逆氧化峰,该氧化过程受扩散控制,多菌灵浓度在2.0×10-6～6.0×10-5mol/L范围内,方波伏安法的氧化峰电流与多菌灵浓度呈现良好的线性关系,检出限为8.5×10-7mol/L,可用于检测溶液中多菌灵含量。     

Electrically driven motion of an air bubble on hemispherical oil/water interface by three-phase boundary reactions

Our electrochemical cell consisted of a ferrocene-included hemispherical nitrobenzene (NB) droplet on the glassy carbon (GC) electrode which was immersed in the aqueous solution including sodium sulfate and sodium dodecyl sulfate (SDS). When an air bubble was injected near the boundary between the oil and the aqueous phase, it stayed at the top of the hemisphere on the boundary so that the lower half of the bubble was put in oil and the other half was in water. From the force balance of surface tension and buoyancy of the bubble, the bubble took an energetic minimum at the interface. It sank into the oil phase when ferrocene in the oil was electrochemically oxidized through the GC electrode by the three-phase boundary reaction. The electrochemical reduction caused the bubble to move back toward the aqueous phase. The motion of the bubble was synchronized with the redox reaction of ferrocene. The potential step oxidation showed such a rapid response that the motion could not be attributed to diffusion of ferricenium ion from the three-phase boundary to the bubble. Our idea of explaining the rapidity was the translational motion of the SDS layer along the boundary, which was driven by the difference in the surface concentration of SDS caused by the electrochemical generation of the ferricenium ion. The motion of the SDS layer was demonstrated by the shrinkage of the oil layer spread on the water surface when SDS solution was dropped on the oil layer. The spreading velocity was close to the velocity of propagating the oxidation of ferrocene to the bubble.     

Electrocatalytic Determination of Sulfite at Immobilized Microdroplet Liquid|Liquid Interfaces: The EIC′ Mechanism

Liquid|liquid interfaces provide a natural boundary and a reactive interface where an organic phase is in contact with an aqueous analyte. The selectivity of ion transfer processes at liquid|liquid interfaces can help to provide sensitivity, introduce reactive reagents, or allow analyte accumulation at the electrode surface. In this study, microdroplet deposits of the organic liquid 4‐(3‐phenylpropyl)‐pyridine (PPP) with the ferrocenylmethyl‐dodecyldimethylammonium⁺ (FDA⁺) redox system are deposited onto a basal plane pyrolytic graphite electrode and employed to transfer anions from the aqueous into the organic phase. A clear trend of more hydrophobic anions transferring more readily (at more negative potentials) is observed and an ESI‐mass spectrometry method is developed to confirm the transfer. Subsequently, the electrocatalytic oxidation of sulfite, SO₃^2?, within the organic phase and in the presence of different electrolyte anions is investigated. Competition between sulfite transfer and inert anion transfer occurs. The electrocatalytic sulfite oxidation is suppressed in the presence of PF₆^? and occurs most readily in the presence of the hydrophilic nitrate anion. The resulting process can be classified as an electrocatalytic EIC′‐process (E: electron transfer; I: ion transfer; C: chemical reaction step). The effectiveness of the electrocatalytic process is limited by i) competition during anion transfer and ii) the liquid|liquid interface acting as a diffusion barrier. The analytical sensitivity of the method is limited to ca. 100 μM SO₃^2? (or ca. 8 ppm) and potential approaches for improvement of this limit are discussed.     

Simultaneous Detection of Single Attoliter Droplet Collisions by Electrochemical and Electrogenerated Chemiluminescent Responses

We provide evidence of single attoliter oil droplet collisions at the surface of an ultra‐microelectrode (UME) by the observation of simultaneous electrochemical current transients (i–t curves) and electrogenerated chemiluminescent (ECL) transients in an oil/water emulsion. An emulsion system based on droplets of toluene and tri‐n‐propylamine (2:1 v/v) emulsified with an ionic liquid and suspended in an aqueous continuous phase was formed by ultrasonification. When an ECL luminophore, such as rubrene, is added to the emulsion droplet, stochastic events can be tracked by observing both the current blips from oxidation at the electrode surface and the ECL blips from the follow‐up ECL reaction, which produces light. This report provides a means of studying fundamental aspects of electrochemistry using the attoliter oil droplet and offers complementary analytical techniques for analyzing discrete collision events, size distribution of emulsion systems, and individual droplet electroactivity.     

Synthesis and assembly of ultrathin film of Ni(OH)2 nanoparticles at gas/liquid interface, its high electrocatalytical oxidation toward bio-thiols and selective determination of cysteine

A facile strategy was reported to synthesize and assemble a stable ultrathin film of Ni(OH)₂ nanoparticles at gas/liquid interface where the aqueous phase contained Ni²⁺ and the organic phase was composed of triethylamine toluene solution. The ultrathin film of Ni(OH)₂ nanoparticles that precipitated at the interface was transferred onto the electrode surface for the electrocatalysis of bio-thiols and selective electroanalysis of cysteine. The preparation of Ni(OH)₂ ultrathin film and its transfer to an electrode substrate is very simple. The obtained Ni(OH)₂ ultrathin film modified electrodes are stable, showing high electrochemical oxidation toward bio-thiols and good selectivity toward cysteine in phosphate buffered solution of pH 7.5.     

多壁碳纳米管-聚茜素红膜修饰电极测定多菌灵

制备了多壁碳纳米管-聚茜素红膜(MWNT-PAR)修饰电极,用循环伏安法和线性扫描伏安法、计时电量法等研究多菌灵在修饰电极上的电化学行为.结果表明,多菌灵在MWNT-PAR修饰电极上是扩散控制的不可逆电氧化过程.实验测定了部分电极过程参数,并发现多菌灵氧化峰电流的一阶导数值与其浓度在5.0×10~(-6)～1.0×10~(-4) mol/L范围内呈线性关系,回归方程为:I_p ′(A)=-3.112×10~(-6)-1.198c(mol/L),R=-0.9953,其检出限为2.0×10~(-7) mol/L,回收率为99.0%～105.6%.     

二甲醚燃料电池复合镍阳极的研究

制备并表征了二甲醚(DME)固体氧化物燃料电池(SOFCs)系列Ni-Fe-La0.8Sr0.2Ga0.8Mg0.115Co0.085O3(LSGMC8.5) 复合阳极, 电极中Ni与Fe的摩尔比分别为9:1、8:2、7:3、5:5, 电极中Ni-Fe的总质量分数为75%. 利用多种技术考察了电极的物相组成, 电极以及电极/电解质界面的微观结构, 电极/电解质界面上进行的DME电化学氧化反应. 结果表明, 复合阳极中Fe含量的增加促进了电极的烧结, 同时改变了电极/电解质界面的微观结构. 电极催化DME电化学氧化的活性依赖于Ni、Fe的比例, Ni、Fe的摩尔比为8:2的电极具有最高的电化学活性. Ni-Fe-LSGMC8.5电极具有较高的催化DME氧化反应的活性与稳定性, 没有观察到电极中存在明显的积碳现象.     

Thin‐Film Voltammetry of a Lutetium Bisphthalocyanine at Ionic Liquid|Water Interface

At room temperature, tetraoctylphosphonium bromide is a viscous ionic liquid, this gel‐like organic phase can be cast over a basal‐plane graphite electrode (BPGE). Cyclic voltammetry at such a modified electrode, in contact with an aqueous solution have revealed one reversible oxidation and five reversible reduction steps for a Lu^III bisphthalocyanine dissolved in the ionic liquid film, a proof that the highly reactive reduced species were protected from interaction with water in this highly lipophilic phase. It has also been shown that the redox properties are influenced by the ions in the aqueous phase, a property which has been attributed to ion‐pairing effects; obviously, the ion transfers at the organic|aqueous interface has been ignored. Electrochemistry of Lu(III)[(_tBu)₄Pc]₂ (cyclic voltammetry and square wave voltammetry) under similar conditions shows that the nature and concentration of the anion in the aqueous solution in contact with the ionic liquid film influences the potential of the electrode reaction. This can be attributed to variations of the interfacial potential and also because the organic phase is an anion exchanger. Moreover, SWV experiments suggest that the rate of the overall reaction varies with the nature and concentration of the anion of the aqueous electrolyte, which implies that the ion transfer through the organic|aqueous interface is slower than the electron exchange rate of the molecule at the surface of graphite.     

NADH Oxidation Catalyzed by Electropolymerized Azines on Carbon Nanotube Modified Electrodes

Electropolymerizing azines on a carbon nanotube (CNT) modified electrode yields a high‐surface area interface with excellent electrocatalytic activity towards NADH oxidation. Electrodeposition of poly(methylene green) (PMG) and poly(toluidine blue) (PTBO) on the carboxylated CNT‐modified electrodes was achieved by cyclic voltammetry. The PMG‐CNT interface demonstrates 5.0 mA cm^?2 current density for NADH oxidation at 50 mV vs. Ag|AgCl in 20 mM NADH solution. The kinetics of NADH electrocatalysis were analyzed using a quantitative mass‐transport‐corrected model with NADH bulk concentration and applied potential as independent variables. This high‐rate poly(azine)‐CNT interface is potentially applicable to high‐performance bioconversion, bioenergy and biosensors involving NADH‐dependent dehydrogenases.     

Voltammetric Antioxidant Analysis in Mineral Oil Samples Immobilized into Boron‐Doped Diamond Micropore Array Electrodes

Mineral oil microdroplets containing the model antioxidant N,N‐didodecyl‐N′,N′‐diethyl‐phenylene‐diamine (DDPD) are immobilized into a 100×100 pore‐array (ca. 10 μm individual pore diameter, 100 μm pitch) in a boron‐doped diamond electrode surface. The robust diamond surface allows pore filling, cleaning, and reuse without damage to the electrode surface. The electrode is immersed into aqueous electrolyte media, and voltammetric responses for the oxidation of DDPD are obtained. In order to further improve the current responses, 20 wt% of carbon nanofibers are co‐deposited with the oil into the pore array. Voltammetric signals are consistent with the oxidation of DDPD and the associated transfer of perchlorate anions (in aqueous 0.1 M NaClO₄) or the transfer of protons (in aqueous 0.1 M HClO₄). From the magnitude of the current response, the DDPD content in the mineral oil can be determined down to less than 1 wt% levels. Perhaps surprisingly, the reversible (or midpoint) potential for the DDPD oxidation in mineral oil (when immersed in 0.1 NaClO₄) is shown to be concentration‐dependent and to shift to more positive potential values for more dilute DDPD in mineral oil solutions. An extraction mechanism and the formation of a separate organic product phase are proposed to explain this behavior.     

Ion Transport Across Liquid|Liquid Interfacial Boundaries Monitored at Generator‐Collector Electrodes

Anion transfer processes at a liquid|liquid interface were studied with an interdigitated gold band array electrode. The organic phase, 4‐(3‐phenylpropyl)‐pyridine containing Co(II)phthalocyanine, was immobilised as random droplets at the electrode surface and then immersed into aqueous electrolyte. Oxidation of Co(II)phthalocyanine at the generator electrode was shown to be associated with anion transfer from the aqueous into the organic phase. The corresponding back reduction at the collector electrode with anion expulsion was delayed by the anion/cation diffusion time across the interelectrode gap. A working curve based on a finite difference numerical simulation model was employed to estimate the apparent diffusion coefficients for anions in the organic phase (PF₆^?4^?3^?). Potential applications in ion analysis are discussed.     

Scanning electrochemical microscopy study of ion transfer process across water/2-nitrophenyloctylether interface supported by hydrophobic carbon ceramic electrode

A carbon ceramic electrode (CCE) modified with the redox probe—decamethylferrocene solution in hydrophobic organic solvent—2-nitrophenyloctyl ether and immersed into an aqueous solution was studied by scanning electrochemical microscopy (SECM). After the electrochemical oxidation of decamethylferrocene, its cations were detected near the electrode surface in the aqueous phase. This indicates that some fraction of the redox-active cations electrochemically produced in the organic phase is transferred across the liquid/liquid interface. They are reduced at the SECM tip and form a solid deposit. The amount of deposited decamethylferrocene was estimated by the anodic reaction at the tip. It is affected by the substrate–tip distance, deposition time, and electrolyte concentration. The SECM images of unmodified and modified CCEs are consistent with their heterogeneous structure.     

Isotopic Labeling Reveals Active Reaction Interfaces for Electrochemical Oxidation of Lithium Peroxide

The unresolved debate on the active reaction interface of electrochemical oxidation of lithium peroxide (Li₂O₂) prevents rational electrode and catalyst design for lithium‐oxygen (Li‐O₂) batteries. The reaction interface is studied by using isotope‐labeling techniques combined with time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and on‐line electrochemical mass spectroscopy (OEMS) under practical cell operation conditions. Isotopically labelled microsized Li₂O₂ particles with an Li₂¹⁶O₂/electrode interface and an Li₂¹⁸O₂/electrolyte interface were fabricated. Upon oxidation, ¹⁸O₂ was evolved for the first quarter of the charge capacity followed by ¹⁶O₂. These observations unambiguously demonstrate that oxygen loss starts from the Li₂O₂/electrolyte interface instead of the Li₂O₂/electrode interface. The Li₂O₂ particles are in continuous contact with the catalyst/electrode, explaining why the solid catalyst is effective in oxidizing solid Li₂O₂ without losing contact.     

硬脂酸钠在油/水界面自组装膜的电化学研究

应用循环伏安法,以铜离子为探针研究硬脂酸钠在油/水界面上的自组装过程.结果表明,硬脂酸钠在蓖麻油/水界面上自组装,经4种聚集状态而达到完整的有序单层膜.Cu2+离子在涂蓖麻油电极上的氧化是完全受吸附控制,而在表面活性剂硬脂酸钠自组装膜的油/水界面上,则其电极过程受扩散和吸附两者混合控制.循环伏安测试给出,峰电流ip随扫描速率v变化的拟合方程为:ip=9.214?3.889v1/2+0.5809v,r=0.9978.     

Analysis of methyldopa in the presence of phenylephrine using electrocatalytic effect of a ferrocene derivative at a surface of feather like La3+/ZnO nano‐flowers modified carbon paste electrode

The purpose of the present study was to introduce a newly designed approach for simultaneous determination of methyldopa and phenylephrine using modified carbon paste electrode with feather like La³⁺/ZnO nano‐flowers and N‐(ferrocenylmethylidene) fluoren‐2‐amine (La³⁺/ZnONFMF2ACPE). According to the results from the electrochemical experiments, oxidation current of methyldopa on the modified electrode surface was incremented and its oxidation occurred at a potential about 110 mV less positive than that of an unmodified carbon paste electrode. A linear response was observed for the electrode at different methyldopa concentrations (0.2 to 500.0 μM). The existence of phenylephrine did not induce any change in the modified electrode sensitivity to methyldopa, indicating that they could be measured simultaneously or independently. Real human body samples were used to test our technique efficacy in detecting methyldopa and phenylephrine.     

单晶Au表面和Au/TiO2（110）模型催化剂表面CO氧化反应机理和活性位

在分子尺度上介绍了Au/TiO2(110)模型催化剂表面和单晶Au表面CO氧化反应机理和活性位、以及H2O的作用.在低温(<320 K), H2O起着促进CO氧化的作用, CO氧化的活性位位于金纳米颗粒与TiO2载体界面(Auδ+–Oδ––Ti)的周边. O2和H2O在金纳米颗粒与TiO2载体界面边缘处反应形成OOH,而形成的OOH使O–O键活化,随后OOH与CO反应生成CO2.300 K时CO2的形成速率受限于O2压力与该反应机理相印证.相反,在高温(>320 K)下,因暴露于CO中而导致催化剂表面重组,在表面形成低配位金原子.低配位的金原子吸附O2,随后O2解离,并在金属金表面氧化CO.     

Ion‐Specific Self‐Assembly of Low‐Dimension Aggregate Structures of Conjugated Polymer at Two‐Phase Interface

A novel and facile approach to manipulate the morphology of Cu²⁺‐ion‐specific assembly of conjugated polymer by coordinative interaction at an oil–water two‐phase interface is present. The application of increasing importance is the use of π‐conjugated polymers as receptors, exploiting their ability to selectively form complexes, which can obviously change the optical properties in solution and induce the formation of varied solid nano/microstructures. By this method, microtubes are formed through self‐rolling of a strained ionic bilayer film at the oil/water interface.