Silver nanoparticle decorated poly(2-aminodiphenylamine) modified carbon paste electrode as a simple and efficient electrocatalyst for oxidation of formaldehyde

This work describes the promising activity of silver nanoparticles on the surface of a poly(2-amino diphenylamine) modified carbon paste electrode (CPE) towards formaldehyde oxidation. Electrodeposition of the conducting polymer film on the CPE was carried out using consecutive cyclic voltammetry in an aqueous solution of 2-aminodiphenylamine and HCl. Nitrogen groups in the polymer backbone had a Ag ion accumulating effect, allowing Ag nanoparticles to be electrochemically deposited on the surface of the electrode. The electrochemical and morphological characteristics of the modified electrode were investigated. The electro-oxidation of formaldehyde on the surface of electrode was studied using cyclic voltammetry and chronoamperometry in aqueous solution of 0.1 mol/L NaOH. The electro-oxidation onset potential was found to be around -0.4 V, which is unique in the literature. The effect of different concentrations of formaldehyde on the electrocatalytic activity of the modified electrode was investigated. Finally, the diffusion coefficient of formaldehyde in alkaline media was calculated to be 0.47 × 10^-6 cm²/s using chronoamperometry.     

聚1,8-萘二胺修饰玻碳电极测定痕量汞

采用电化学聚合的方法制备了聚1,8-萘二胺修饰玻碳电极,建立了吸附富集-阳极溶出伏安法测定痕量Hg2+的新方法.优化了各种实验参数(如富集底液的pH,富集时间等),并考察了其它离子的干扰.在最佳实验条件下,Hg2+在0.001～0.1 mg/L及0.1～5.0 mg/L质量浓度范围内均与溶出峰电流成良好的线性关系,检出限为0.0005 mg/L.该法可用于实际工业废水中汞的测定.     

聚L-赖氨酸修饰电极对去甲肾上腺素的电催化氧化

研究了L 赖氨酸在玻碳电极上电化学聚合的条件及修饰电极的电化学特性,发现该聚合膜对去甲肾上腺素(NE)的电氧化有显著的催化作用,在磷酸盐缓冲溶液(pH7)中,恒电位-0.2V富集2.0min后,用方波溶出伏安法对NE进行了测定,线性范围为1.0×10-8～5.0×10-4mol L,检出限(信噪比=3)为8 2×10-10mol L。对1.0×10-7mol LNE平行测定8次相对标准偏差为2 4%。     

纳米分子筛LTA包裹Ni-Salen配合物为修饰碳糊电极用于电催化氧化肼反应

采用柔性配体法将Ni-salen配合物包裹在纳米分子筛LTA的超笼中,用来修饰碳糊电极制得Ni(Ⅱ)-SalenA/CPE,并采用循环伏安法、计时电流法和计时库仑法考察了该电极电催化氧化0.1 mol/L NaOH溶液中肼反应性能.首先采用无有机模板剂法合成纳米分子筛LTA,并用各种技术进行了表征.XRD和粒径分析结果分别显示LTA晶体的平均粒径为56.1和72nm.在Ni(Ⅱ)-SalenA/CPE电极氧化还原位上水合肼催化氧化反应电子转移系数为0.64,速率常数为1.03×105cm3/(mol·s).电催化反应机理研究表明,水合肼氧化反应通过它与Ni3+(Salen)O(OH)反应或直接进行电氧化反应.阳极峰电流与扫描速率的平方根呈线性关系,表明反应受扩散控制,水合肼的扩散系数为1.18×10?7cm2/s.结果表明,Ni(Ⅱ)-SalenA/CPE对水合肼氧化反应表现出高的电催化活性,这是由于纳米分子筛LTA的多孔结构以及Ni(Ⅱ)-Salen的存在.最后研究了水合肼在碱性溶液中Ni(Ⅱ)-SalenA/CPE电极上的氧化反应机理,发现其为四电子过程,第一个电子转移反应为速率控制步骤,然后是一个三电子过程,产生环境友好的最终产物氮气和水.     

Elaboration of carbon paste electrode containing pentadentate Nickel-(II) Schiff base complex: Application to electrochemical oxidation of thiosulfate in alkaline medium

A Nickel Schiff base complex, insoluble in water, was synthesized and used as modifier. A Nickel Schiff base modified carbon paste electrode MCPE was build. The electrodes were characterized by scanning electron microscopy (SEM), energy dispersive X-Ray spectroscopy (EDXS), cyclic voltammetry and chronoamperometry. The modifier is elctroactive, a well defined redox couple of Ni^III/Ni^II in alkaline medium was made in evidence. It presents a quasi-reversible system with electron transfer coefficient (0.38) and electron transfer rate of 4.5 s⁻¹. The electrogenerated Ni^III species on the surface of the electrode act as an excellent catalyst toward thiosulfate oxidation reaction with a chemical rate constant K_h equal to 23,6 M⁻¹s⁻¹. The different techniques involved in this study qualify our modified electrode as sensitive, reliable and very stable for thiosulfate analysis.     

硫脲在10-甲基吩噻嗪修饰碳糊电极上的电催化氧化及电分析方法研究

研究了硫脲(Thiourea,Tu)在10-甲基吩噻嗪修饰碳糊电极(MPT/CPE)上的电催化氧化行为.结果表明,Tu在裸碳糊电极(CPE)上的直接电化学氧化过程十分迟缓,MPT/CPE对Tu的电化学氧化具有良好的催化作用.用计时电流法(CA)测定了Tu在MPT/CPE上的电极过程动力学参数,测得电荷传递系数α=0.61,电催化氧化反应的速率常数k=(1.96±0.10)×104(mol/L)-1·s-1.用方渡伏安法(SWV)测得催化氧化峰电流与Tu浓度在1.0×10-6～8.0×10-3mol/L范围内呈良好的线性关系,线性回归方程为,Ips(μA)=10.836c(10-3mol/L)+5.326,R=0.9984,检出限为2.2×10-7mol/L(S/N=3).方法可用于Tu的电化学法测定.     

Palladium nanoparticle decorated carbon ionic liquid electrode for highly efficient electrocatalytic oxidation and determination of hydrazine

In this work arrays of palladium nanoparticles were synthesized on carbon ionic liquid electrode (CILE) (Pd/CILE), and the electrocatalytic oxidation of hydrazine was investigated using this electrode. Electrochemical oxidation of hydrazine in phosphate buffer (pH 7) was performed using cyclic voltammetry and square wave voltammetric techniques (SWV). Using the proposed electrode, a highly reproducible and well-defined peak was obtained for hydrazine at a very low potential of −0.02 V versus Ag/AgCl. A linear dynamic range of 5-800 μM with an experimental detection limit of 0.82 μM was obtained. These results show that the proposed electrode displays better electrocatalytic activity compared to the previously reported palladium modified electrodes towards oxidation of hydrazine.     

Electrochemical modification of a carbon paste electrode with poly (1,5-diaminonaphthalene) and copper-cobalt nanostructures for the determination of thioctic acid in real samples

This study used square-wave voltammetry and cyclic voltammetry to investigate the electrochemical oxidation of Thioctic Acid (TA) on a Carbon Paste Electrode (CPE) modified with copper-cobalt nanostructures and poly (1,5-Diaminonaphthalene). The voltammetric sensor was sensitive to the oxidation of TA. In addition, we optimized the effects of multiple cycles of deposition of Cu-Co nanostructures, and electro-polymerization of monomer 1,5-DAN, scan rate, and pH. The sensor showed good identification capabilities for TA. The linear responses obtained ranged from 0.6 μM to 150 μM with a detection limit of 0.48 μM for the modified CPE. The adsorption process controlled the oxidation of TA. We used the proposed sensor and method to determine TA in real samples.     

铂/聚邻甲基苯胺/碳材料掺杂碳糊电极对甲醇的催化氧化

以石墨和液体石蜡油为主要原料,分别制备了掺杂不同量多壁碳纳米管(MWCNT)、石墨烯(GRA)、电容活性炭(YEC)和电池活性炭(YBC)的多种碳糊底电极Y-CPE(Y代表各种掺杂碳材料,CPE代表纯碳糊电极).采用恒电位法在-0.10 V(vs.Ag/Ag Cl)电位下将铂电沉积到这些电极上.结果表明,当电池碳的含量为14%时,Pt/YBC-CPE(14%)复合电极对甲醇具有最好的电催化氧化活性.采用恒电位方法在0.85 V(vs.Ag/Ag Cl)电位下将聚邻甲基苯胺(POT)电聚合沉积到纯碳糊电极CPE和含有电池碳的YBC-CPE(14%)电极上,得到复合电极POT/CPE和POT/YBC-CPE(14%),再通过恒电位方法将铂电沉积到这2个复合电极上.扫描电镜(SEM)观察结果表明,在Pt/CPE,Pt/YBC-CPE(14%),Pt/POT(6.5 mC)/CPE和Pt/POT(6.5 mC)/YBC-CPE(14%)4个复合电极中,在Pt/POT/YBC-CPE(14%)复合电极上的铂粒子的尺寸最小,并且Pt/POT(6.5 mC)/YBC-CPE(14%)复合电极电催化氧化甲醇活性最高.在POT(6.5 mC)/CPE和POT(6.5 mC)/YBC-CPE(14%)上Pt纳米颗粒的电沉积过程是一个近似的3D成核过程.研究还发现,复合电极Pt/POT/CPE和Pt/POT/YBC-CPE电催化氧化甲醇的活性随POT膜厚度的增加先增大后减少,存在一个最佳的膜厚度.     

Improvement of an enzyme electrode by poly(vinyl alcohol) coating for amperometric measurement of phenol

A poly(vinyl alcohol) film cross-linked with glutaraldehyde (PVA-GA) was introduced to the surface of a tyrosinase-based carbon paste electrode. The coated PVA-GA film was beneficial in terms of increasing the stability and reproducibility of the enzyme electrode. The electrode showed a sensitive current response to the reduction of the o-quinone, which was the oxidation product of phenol, by the tyrosinase, in the presence of oxygen. The effects of the PVA and PVA-GA coating, the pH, and the GA:PVA ratio on the current response were investigated. The sensitivity of the PVA-GA-Tyr electrode was 130.56 μA/mM (1.8 μA/μM cm²) and the linear range of phenol was 0.5-100 μM. At a higher concentration of phenol (>100 μM), the current response showed the Michaelis-Menten behavior. Using the PVA-GA-Tyr electrode, a two-electrode system was tested as a prototype sensor for portable applications.     

A Simple and Efficient Electrochemical Sensor for Electrocatalytic Reduction of Nitrite Based on Poly(4‐aminoacetanilide) Film Using Carbon Paste Electrode

In this study, the electrochemical reduction of nitrite was investigated on poly(4‐aminoacetanilide) (PPAA) forming by cyclic voltammetry at the surface of carbon paste electrode. The electrochemical properties of the modified electrode have been studied by cyclic voltammetry and double potential step chronoamperometry. Results showed that in the optimum condition (pH = 0.00) the reduction of nitrite occurred at a potential about 667 mV more positive than that unmodified carbon paste electrode. This amount of electrocatalytic ability is high compared with other electrocatalysts. Using a chronoamperometric method, the catalytic rate constant (k) was calculated 8.4 × 10⁴ cm³ mol^‐1 s^‐1. Also, the electrocatalytic reduction peak currents was found to be linear with the nitrite concentration in the ranges of 5 × 10^‐4 M to 2.5 × 10^‐2 M and 2 × 10^‐5 M to 7 × 10^‐3 M with detection limits (2σ) were determined as 4.5 × 10^‐4 M and 1 × 10^‐5 M by cyclic voltammetry (CV) and hydrodynamic amperometry methods respectively. Recovery experiments exhibit the satisfactory results.     

Ni(II)-baicalein complex modified multi-wall carbon nanotube paste electrode toward electrocatalytic oxidation of hydrazine

A modified electrode Ni(II)-BA-MWCNT-PE has been fabricated by electrodepositing nickel(II)-baicalein [Ni(II)-BA] complex on the surface of multi-wall carbon nanotube paste electrode (MWCNT-PE) in alkaline solution. The Ni(II)-BA-MWCNT-PE exhibits the characteristic of improved reversibility and enhanced current responses of the Ni(III)/Ni(II) couple compared with Ni(II)-BA-CPE. It also shows good electrocatalytic activity toward the oxidation of hydrazine. Kinetic parameters such as the electron transfer coefficient α, rate constant k_s of the electrode reaction, the diffusion coefficient D of hydrazine and the catalytic rate constant k_cat of the catalytic reaction are determined. Moreover, the catalytic currents present linear dependence on the concentration of hydrazine from 2.5 μM to 0.2 mM by amperometry. The detection limit and sensitivity are 0.8 μM and 69.9 μA mM⁻¹, respectively. The modified electrode for hydrazine determination is of the property of simple preparation, good stability, fast response and high sensitivity.     

Modified interdigitated arrays by novel poly(1,8-diaminonaphthalene)/carbon nanotubes composite for selective detection of mercury(II)

This study describes a novel type of interdigitated arrays (IDA), microfabricated by electropolymerizing structured Poly(1,8-diaminonaphthalene)/functionalized multi-walled carbon nanotubes (PDAN/CNT) thin film onto a silicon chip for square wave voltammetry (SWV) multi-element heavy metal ion detection. The structure of PDAN/CNT was characterized by Raman, FE-SEM and AFM techniques. Analysed experiments reveal that the uptake of Hg²⁺ by PDAN/CNT is quite specific and it can be used advantageously for electrochemical sensing of Hg²⁺ thanks to original feature of (Hg²⁺/Hg₂²⁺) redox potential with the respect to that of PDAN/CNT. As-developed IDA type electrode can extend its utility in other sensing applications.     

A selective modified carbon paste electrode for determination of cyanide using tetra-3,4-pyridinoporphyrazinatocobalt(II)

A chemically modified carbon paste electrode with 3,4-tetra pyridinoporphirazinatocobalt(II) (Co(3,4 tppa) was applied to the determination of free cyanide ion. The electrode has a linear range between 1.5 × 10⁻⁵ M and 1.0 × 10⁻² M with a Nernstian slope of 60 ± 1.5 mV/decade and its detection limit is 9 × 10⁻⁶ M. The response time of electrode is 5 min. The proposed electrode was applied successfully for the determination of cyanide in commercially available spring water. Some anions, such as SCN⁻, I⁻, Cl⁻, Br⁻ and oxalate that are usually serious interfering species for most of cyanide selective electrodes, did not have any interfering effect for this proposed electrode.     

Organically nanoporous silica gel based on carbon paste electrode for potentiometric detection of trace Cr(III)

A new ion-selective electrode (ISE) for the detection of trace chromium(III) was designed by using 2-acetylpyridine and nanoporous silica gel (APNSG)-functionalized carbon paste electrode (CPE). The presence of APNSG acted as not only a paste binder, but also a reactive material. With 7.5 wt% APNSG proportions, the developed electrode exhibited wide dynamic range of 1.0 × 10⁻⁸ to 1.0 × 10⁻³ M toward Cr(III) with a detection limit of 8.0 × 10⁻⁹ M and a Nernstian slope of 19.8 ± 0.2 mV decade⁻¹. The as-prepared electrode displayed rapid response (∼55 s), long-time stability, and high sensitivity. Moreover, the potentiometric responses could be carried out with wide pH range of 1.5-5.0. In addition, the content of Cr(III) in food samples, e.g. coffee and tea leaves, has been assayed by the developed electrode, atomic absorption spectrophotometer (AAS) and atomic emission spectrometer (ICP-AES), respectively, and consistent results were obtained. Importantly, the response mechanism of the proposed electrode was investigated by using AC impedance and UV-vis spectroscopy.     

Caffeic acid modified glassy carbon electrode for electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH)

A new modified electrode was prepared by electrodeposition of caffeic acid (CFA) at the surface of an activated glassy carbon electrode. Cyclic voltammetry was used to investigate the redox properties of this electrode at various solution pH values and at various scan rates. The pH dependence of the electrode response was found to be 58.5 mV/pH, which is very close to the expected Nernstian value. The electrode was also employed to study electrocatalytic oxidation of reduced nicotinamide adenine dinucleotide (NADH), using cyclic voltammetry, chronoamperometry and rotating disk voltammetry as diagnostic techniques. It was found that the modified electrode exhibits potent and persistent electrocatalytic properties toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 450 mV compared to the process at an unmodified electrode. The electrocatalytic current increases linearly with NADH concentration in the range tested from 0.05 to 1.0 mM. The apparent charge transfer rate constant and transfer coefficient for electron transfer between the electrode surface and immobilized CFA were calculated as 11.2 s⁻¹ and 0.43, respectively. The heterogeneous rate constant for oxidation of NADH at the CFA-modified electrode surface was also determined and found to be about 3 × 10³ M⁻¹ s⁻¹. Finally, the diffusion coefficient of NADH was calculated as 3.24 × 10⁻⁶ cm² s⁻¹ for the experimental conditions, using chronoamperometric results. Received: 6 January 1999 / Accepted: 11 May 1999     

Water hyacinth modified carbon paste electrode for simultaneous electrochemical stripping analysis of Cd (II) and Pb (II)

In this study, we demonstrated a highly sensitive electrochemical sensor for the simultaneous detection of Pb (II) and Cd (II) in aqueous solution using carbon paste electrode modified with Eichhornia crassipes powder by square wave anodic stripping voltammetry. The effect of modifier composition, pH, preconcentration time, reduction potential and time, and type of supporting electrolyte on the determination of metal ions were investigated. Pre-concentration on the modified surface was performed at open circuit. The modified electrode exhibited well-defined and separate stripping peaks for Pb (II) and Cd (II). Under optimum experimental conditions, a linear range for both metal ions was from 10 to 5000 μg L^?1 with the detection limits of 4.9 μg L^?1, 2.1 μg L^?1 for Cd(II) and Pb (II), respectively. The modified electrode was found to be sensitive and selective when applied to determine trace amounts of Cd (II) and Pb (II) in natural water samples.     

Simultaneous voltammetric measurement of ascorbic acid and dopamine on poly(caffeic acid)-modified glassy carbon electrode

A poly(caffeic acid) thin film was deposited on the surface of a glassy carbon electrode by potentiostatic technique in an aqueous solution containing caffeic acid. The poly(caffeic acid)-modified electrode was used for the determination of ascorbic acid (AA), dopamine (DA), and their mixture by cyclic voltammetry. This modified electrode exhibited a potent and persistent electron-mediating behavior followed by well-separated oxidation peaks toward AA and DA at a scan rate of 10 mV s⁻¹ with a potential difference of 135 mV, which was large enough to determine AA and DA individually and simultaneously. The catalytic peak current obtained was linearly dependent on the AA and DA concentrations in the range of 2.0 × 10⁻⁵−1.2 × 10⁻³ and 1.0 × 10⁻⁶−4.0 × 10⁻⁵ mol L⁻¹ in 0.15 mol L⁻¹ phosphate buffer (pH 6.64). The detection limits for AA and DA were 9.0 × 10⁻⁶ and 4.0 × 10⁻⁷ mol L⁻¹, respectively. The modified electrode shows good sensitivity, selectivity, and stability and has been applied to the determination of DA and AA in real samples with satisfactory results.     

Preparation of iron molybdate catalysts for methanol to formaldehyde oxidation based on ammonium molybdoferrate(II) precursor

It was demonstrated that iron molybdate catalysts for methanol oxidation can be prepared using Fe(II) as a precursor instead of Fe(III). This would allow for reduction of acidity of preparation solutions as well as elimination of Fe(III) oxide impurities which are detrimental for the process selectivity. The system containing Fe(II) and Mo(VI) species in aqueous solution was investigated using UV–Vis spectroscopy. It was demonstrated that three types of chemical reactions occur in the Fe(II)–Mo(VI) system: (i) formation of complexes between Fe(II) and molybdate(VI) ions, (ii) inner sphere oxidation of coordinated Fe(II) by Mo(VI) and (iii) decomposition of the Fe–Mo complexes to form scarcely soluble Fe(III) molybdate, Mo(VI) hydrous trioxide and molybdenum blue. Solid molybdoferrate(II) prepared by interaction of Fe(II) and Mo(VI) in solution was characterized by EDXA, TGA, DTA and XRD and a scheme of its thermal evolution proposed. The iron molybdate catalyst prepared from Fe(II) precursor was tested in methanol-to-formaldehyde oxidation in a continuous flow fixed-bed reactor to show similar activity and selectivity to the conventional catalyst prepared with the use of Fe(III).     

A novel chemically modified carbon paste electrode based on a new mercury(II) complex for selective potentiometric determination of bromide ion

A new modified carbon paste electrode based on a recently synthesized mercury (II) complex of a pyridine containing proton transfer compound as a suitable carrier for Br⁻ ion is described. The electrode has a linear dynamic range between 3.00×10⁻² and 1.0×10⁻⁵ M with a near-Nernastian slope of 61.0±0.9 mV per decade and a detection limit of 4.0×10⁻⁶ M (0.32 ppm). The potentiometric response is independent of the pH of the solution in the pH range 4.0–8.3. The electrode possesses the advantages of low resistance, fast response and good over a variety of other anions. It was applied as an indicator electrode in potentiometric titration of bromide ions and for the recovery of Br⁻ from tap water.