基于杂环有机锡化合物的水杨酸根离子选择电极研究

A novel heterocyclic haxacoordinated organotin(Ⅳ) complex, bis (o-vanillin)-semi-ethylenediamine dibenzyltin (VEDBT) was synthesized and used as anion ionophore for PVC membrane electrode; the novel electrode exhibits a linear response towards salicylate and an anti-Hofmeister selectivity pattern with high specificity for salicylate over many common anions, the selective pattern is: Sal^- > SCN^- > ClO₄^- > I^- > NO₂^- > NO₃^- > Cl^- ≈ Br^- > SO₄^2-. The behaviour of the electrode is influenced by the experimental conditions. The response mechanism was also investigated by UV spectroscopy. The electrode was applied to the determination of salicylate in pharmaceutical samples with satisfactory results.     

Rapid—In—situ Determination of Chromium （VI） in Water Using Modified Diphenylcarbazine with Citrate

In recent years, the determination of Cr (VI) has attracted great attention because of its toxicity to human, plants and animals1-5. Usually, in the industrial waste water, the concentration of Cr (VI) is relatively high and should be determined frequently. So, an accurate, quick, and convenient method for the measurement of Cr (VI) in environmental water, as well as in river, lake, sea and tap water, is of great importance. The method for determination of Cr (VI) by diphenylcarbazine …     

Determination of chromium(VI) and total chromium in water by in-electrode coulometric titration in a porous glassy carbon electrode

Chromium(VI) is determined through its direct electrochemical reduction in the bulk of a porous glassy carbon electrode. An electrode filled with the acidified sample and Cr(VI) is reduced by means of a constant current whereas the potential of the electrode is monitored. The limits of detection and quantification were found to be 1.9 and 6.0 μg · L⁻¹, resp. The linear range, repeatability and reproducibility were found to be 5–500 μg · L⁻¹, 1.2, and 1.8%, resp. The influence of Fe(III), Ca(II), Mg(II), sulphates, nitrates, humic acids and surfactants was investigated. Total chromium was measured after chemical oxidation of Cr(III) to chromate by permanganate. The method was applied to analyses of water samples.     

A Novel Composite Electrode of Photocatalyst—TiO2／C Loading on the Surface of the Air （Oxygen） Electrode

The methods for preparing the H2O2 generating air (oxygen) electrode and the composite electrode of photocatalyst-TiO2/C loading on the surface of the air (oxygen) electrode were introduced.In the case of the composite electrode,the current efficiency of electro-generated H2O2 is higher than 80%(J≤15mA/cm^2).The degradation of aniline was used as an example to measure the influence of the composite electrode and compared with the system in which the air (oxygen) electrode and the photocatalyst-TiO2 were sqparated.The results confirmed that the composite electrode played an active role on accelerating the degradation rate of aniline.According to the measurement of the polarization curves of composite electrode and TiO2 photo anode,and of the adsorbing amount of aniline on the surface of the composite electrode,the principle of descending the recombination reta of photo-generated electron and hole and of enhancing the oxidation rate of organic molecule was described.The mechanism about the degradation of aniline was also discussed.     

铁氰化锰修饰玻碳电极的制备及其电化学性能

A thin film of manganese hexacyanoferrate （MnHCF） was electrochemically formed on a glassy carbon （GC） electrode to prepare a chemically modified electrode （CME）. The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ（CN）6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy （SEM）, which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes.     

多臂碳纳米管/Nafion复合材料修饰玻碳电极测定痕量的铅离子

A composite material of nitric acid oxidized multiwalled carbon nanotube （MWNT） and Nation was prepared. Such composite was modified on a glassy carbon electrode to determine trace of lead by differential pulsed voltammetry. In pH=6.47 NaNO3 solution, Pb^2＋ ions were accumulated on the modified electrode at -0.4 V. Compared with a bare and a Nation film coated electrode, the composite coated GC electrode can reduce the accumulating potential and eliminate the toxic character of mercury. The calibration plots were linear at low concentration of 5.0× 10^-9-2.0× 10^-8 mol/L and high concentration of 2.5× 10^-8-5.0× 10^-6 mol/L. The performances characteristics indicate that the electrode can be used to determine trace Pb^2＋ ions.     

Mn(Ⅱ)和Ce(Ⅳ)离子对铬酸氧化乳酸的影响

The kinetics and mechanism of lactic acid oxidation in the presence of Mn(II)and Ce(IV)ions by chromic acid were studied spectrophotometrically.The oxidation of lactic acid by Cr(VI)was found to proceed in two measurable steps,both of which gave pyruvic acid as the primary product in the absence of Mn(II).2Cr(VI) 2CH3CHOHCOOH→2CH3COCOOH Cr(V) Cr(III)Cr(V) CH3CHOHCOOH→Cr(III) CH3COCOOH The observed kinetics was explained due to the catalytic and inhibitory effects of Mn(II)and Ce(IV)on the lactic acid oxidation by Cr(VI).The reactivity of lactic acid depends upon the experimental conditions.It acts as a two-or three-equivalent reducing agent in the absence or presence of Mn(II).It was examined that Cr(III)products resulting from the direct reduction of Cr(VI)by three-equivalent reducing agents.The oxidation of lactic acid follows the complex order kinetics with respect to [lactic acid].The activation parameters Ea,ΔH#,and ΔS# were calculated and discussed.     

The detection of bergenin based on the gold nanoparticles/chitosan/reduced graphene oxide modified electrodeEI北大核心CSCD

Gold nanoparticles (AuNPs)/chitosan (CS)/reduced graphene oxide (RGO) modified electrode was prepared. The electrochemical behaviors of bergenin on this modified electrode was investigated by cyclic voltammetry. The results showed that the proposed electrode exhibited an obvious electrocatalytic ability to the oxidation of bergenin. The differential pulse voltammetry was employed to detect bergenin in 0.1 mol/L phosphate buffer solution (pH 6.0). A good linear relationship between the oxidation peak current and the concentration of bergenin was found in the range of 2.0×10-7-1.2×10-6 mol/L with the detection limit of 6.0×10-8 mol/L (S/N=3).The prepared electrode had good anti-interference ability and potential application in the actual detection of bergenin. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

纳米结构Ce掺杂PbO2膜电极的电化学沉积和性质

The effect of Ce(Ⅲ) on the morphology and structure of deposited film of lead dioxide was studied by cyclic voltammetry (CV), X-ray diffractometry (XRD) and scanning tunneling microscopy (STM). The results indicated that the Ce-doped PbO2 film consisted of a mixture of α- and β-phase of PbO2. Ce doping changed the size of PbO2 crystal grains and made the crystallite size on the electrode surface in the nanometer range. Owing to the formation of nanometer-structured grains, the specific surface areas and activity sites of the electrode surface were increased, hence the catalytic activity of Ce-doped PbO2 electrode was evidently higher than that of undoped PbO2 electrode.     

Thiocyanate ion selective electrode based on bis(N-3-methylphenyl salicylidenaminato)copper(Ⅱ) ionophore

In this work a PVC membrane electrode based on bis(N-3-methyl phenyl salicylidenaminato)copper(II)as ionophore was prepared.The electrode was tested by inorganic anions and showed good selectivity for thiocyanate ion.This sensor showed Nerstian behavior with a slope of a-59.3 mV per decade at 25℃.The proposed electrode exhibited a wide linear range from 1.0 × 10~(-6) mol/L to 1.0× 10~(-1) mol/L with a detection limit of 5.0×10~(-7) mol/L.The electrode response was independent of pH in the range of 4.0-10.0.The response time is about 9-21s,and the electrode can be used for over 60 days without considerable deterioration.The prepared sensor was applied as an indicator electrode in potentiometric titration of SCN with Ag~+ ion and to determine the thiocyanate in samples of urine and saliva.     

A solid state Cr(VI) ion-selective electrode based on polypyrrole

We report on a graphite electrode onto which polypyrrole was electrodeposited and then doped with chromate ion. This electrode can serve as a Cr(VI)-selective solid-state electrode. Electropolymerization of pyrrole was performed potentiostatically at 0.80?V (vs. SCE) using battery graphite as the working electrode in a solution containing 0.10?M of pyrrole and 20?mM of chromate. A platinum wire was used as an auxiliary electrode. The new electrode displays high selectivity, a very wide dynamic range, a sufficiently fast response time and a good shelf lifetime. It shows a linear Nernstian response over 1.0?×?10^?6 to 1.0?×?10^?1?M concentration range (with a slope of 26.55?±?0.20?mV per log of concentration). The detection limit is 0.5?μM, and the pH optimum is 7.0.

Determination of Cr(VI) with Selective Sensing of Cr(VI) Anions by a PVC‐Membrane Electrode Based on Quinaldine Red

A dichromate‐selective PVC‐membrane electrode based on Quinaldine Red (an acridinium derivative) is described. The electrode exhibits rapid (< 30 s) and linear response to the activity of Cr(VI) anions in the range of 5.2 × 10^?6 ?1.0 × 10^?1 M dichromate with the limit of detection 2.5 × 10^?6 Mof Cr₂O₇^2?. The sensor is used as an indicator electrode in potentiometric determination of Cr(VI) anions and is also suitable for end‐point indication in the titrations of proper metal ions with dichromate under laboratory conditions. The proposed electrode has been applied to the direct potentiometric determination of Cr(VI) anions in water samples with satisfactory results.     

Electroanalytical Detection of Cr(VI) and Cr(III) Ions Using a Novel Microbial Sensor

A microbial sensor, namely carbon paste electrode (CPE) modified with Citrobacter freundii (Cf–CPE) has been developed for the detection of hexavalent (Cr(VI)) and trivalent (Cr(III)) chromium present in aqueous samples using voltammetry, an electroanalytical technique. The biosensor developed, demonstrated about a twofold higher performance as compared to the bare CPE for the chosen ions. Using cyclic voltammetry and by employing the fabricated Cf–CPE, the lowest limit of detection (LLOD) of 1x10⁻⁴ M and 5x10⁻⁴ M for Cr(VI) and Cr(III) ions respectively could be achieved. By adopting the Differential Pulse Cathodic Stripping Voltammetric technique, the LLOD could be further improved to 1x10⁻⁹ M and 1x10⁻⁷ M for Cr(VI) and Cr(III) ions respectively using the biomodified electrodes. The reactions occurring at the electrode surface‐chromium solution interface and the mechanisms of biosorption of chromium species onto the biosensor are discussed. The stability and utility of the developed biosensor for the analysis of Cr(VI) and Cr(III) ions in chromite mine water samples has been evaluated.     

Luminol-K2S2O8体系中金属离子化学发光行为的研究

报导了在自行设计的流动注射式化学发光分析仪上,对Luminal-K2S2O8体系中32种金属离子的化学发光行为的系统研究.确定了对金属离子的最优测定条件以及大多数金属离子的检出极限和线性范围.     

茜素S选择电极的研制和应用

本文报道了茜素S电极的研制和应用。比较了季铵盐、季鏻盐、碱性染料和邻二氮菲金属配合盐作为活性物质、各种介体溶剂以及活性物质在膜相中的含量对电极性能的影响。以三辛基甲基氯化铵制成的PVC膜型电极对茜素S在2×10~(-4)～5×10~(-7)M浓度范围内呈Nernstian响应,检测下限为2×10~(-7)M。测定了一些阴离子的选择系数,ClO_4~-,CNS~-,I~-以及能与茜素S配合的金属离子有明显干扰。报道了以茜素S电极为指示电极,用EDTA和茜素S为滴定剂滴定钪和稀土的情况。以茜素8电位滴定钪及钴-钐合金中的钐,都获得良好的结果。     

A Fluorescence Quenching Method for the Determination of Chromium(VI) with L-Tyrosine

Abstract

A fluorescence quenching method for the determination of Cr(VI) in aqueous solution is described. The fluorescence intensity of the system is linear ever the range 5×10^?6 - 1.0×10^?4 M Cr(VI). The method has been applied to the determination of Cr(VI) In cast iron and waste water.     

Highly sensitive and selective electrochemical detection of sub-ppb level chromium(VI) using nano-sized gold particle

Gold nanoparticle based nanostructured electrode has been developed for the amperometric detection of ultratrace amount of toxic Cr(VI). The nano-sized Au particles have been grown on a conducting substrate modified with sol-gel-derived thiol functionalized silicate network and used for the electroanalysis of Cr(VI). The nanostructured interface show well-defined voltammetric peak for the reduction of Cr(VI) at approximately 0.4 V. The voltammetric behavior of Cr(VI) strongly depends on the coverage of nanoparticle on the electrode surface. Constant potential amperometry has been used for the detection of Cr(VI) at well below the guideline value set by World Health Organization (WHO). This electrode is highly sensitive (30+/-0.2 nA/ppb) and the detection limit (S/N=9) was 0.1 ppb. Cr(III) and coexisting other metal ions and surface active agent present in water do not interfere with the amperometric measurement of Cr(VI). This nanostructured electrode is highly stable and it can be used for continuous measurement of Cr(VI) without using any pretreatment or activation procedures. The accuracy of the measurement has been validated by measuring the concentration of Cr(VI) in the certified reference material (CRM).     

A novel Au–Ag–Pt three-electrode microchip sensing platform for chromium(VI) determination

A simple, rapid and portable electrochemical microchip sensing platform has been successfully constructed for chromium(VI) determination. Gold–silver–platinum (Au–Ag–Pt) three-material electrodes (gold as working electrode, silver as reference electrode and platinum as counter electrode) were integrated on one poly(methyl methacrylate) (PMMA) substrate by polymer compatible photolithography process. The three-electrode microchip sensing platform was used for Cr(VI) determination for the first time, and exhibited high sensitivity and good reproducibility. A wide linear range from 2 to 200 μM with a good linear correlation (R² = 0.998) was obtained, and the detection limit was 0.9 μM. In addition, the practical analytical application of the sensing micro-platform was assessed by determination of Cr(VI) in real water samples with satisfactory results. Armed with the remarkable advantages, such as ease of use, low analyte consumption, inexpensive cost and fast response time, the microchip sensing platform may hold great potential for the high-throughput and in-field environmental monitoring Cr(VI) pollutant.     

Determination of Cr(VI) Using a Pulse Amperometric Method with an Ionophore‐Immobilized Membrane Electrode

A pulse amperometric method for the determination of Cr(VI) in aqueous solution has been investigated with an ionophore‐immobilized membrane electrode. The double potential step chronoamperometry was applied to measure the current for the facilitated transfer of Cr(VI) by the membrane with N,N,N′,N′‐tetrakis(3‐aminopropyl)‐1,4‐butanediamine (DABAm4) coated on a silver electrode. The current responses were stably detected by the pulse amperometry while voltage pulses, ΔE=?240 mV, of short duration of 50 ms were employed at the interval of 5 s. In the range of 1.65–81.3 μM, Cr(VI) in water could be selectively determined in the presence of various interfering anions below 100 μM without removal of Cr(VI) from the interferences using an ion exchange column.     

Potentiometric Cr(VI) selective electrode based on novel ionophore-immobilized PVC membranes

For the determination of Cr(VI) concentrations with a potentiometric ion-selective electrode (ISE), ionophore-immobilized membranes were prepared by ultraviolet (UV)-induced graft polymerization followed by chemical treatment. Novel ionophores comprising various amine structures were immobilized onto poly(vinyl chloride) (PVC) matrixes, and these were examined to determine Cr(VI) selectively. Of the three ionophores examined in this study, the membranes with N,N,N,N-tetrakis(3-aminopropyl)-1,4-butanediamine (DABAm4) exhibited the highest Cr(VI) ion selectivity in both extraction and potentiometry experiments. The plasticizer in the membrane was optimized as 1.0 ml o-nitrophenyl octyl ether (NPOE)/g PVC to form diffusible channels. The potentiometric studies revealed that the performance of DABAm4-immobilized PVC was equivalent to that of mobile ionophores in supported liquid membranes (SLMs). A reproducible response of Cr(VI) was attained within a response time of 1 s in the range of 2.16 × 10⁻⁶ to 0.1 M, using the membrane prepared in this study. The selectivity for the Cr(VI) ion against the other interfering ions was compared reasonably between a solvent extraction and potentiometry. The long-term response of the Cr(VI) ISE showed slight deterioration over a continuous operation for 6 months, while the detection limit slightly decreased due to the leaching-out of the plasticizer. The ISE along with the DABAm4 immobilized membrane showed a higher Cr(VI) ion selectivity and more stable response under long-term usage than ISEs with typical SLMs.