拓扑结构不同金属有机聚合物的电化学聚合行为和光谱电化学性质北大核心CSCD

金属有机聚合物的拓扑结构是影响其光电性质的重要原因之一。通过吡啶配体不同位点引入的电化学活性基团乙烯基或乙炔基,在电极表面电化学聚合制备了拓扑结构不同的钌金属有机聚合物薄膜,并利用循环伏安、紫外-可见吸收光谱、红外反射光谱、扫描电子显微镜等手段对其电化学特性、光电性质、表面形貌等性质进行了表征。结果表明,电活性配合物反应活性位点的空间位阻效应影响了电化学聚合的效率,其不同拓扑结构的聚合产物具有明显的光谱电化学性质差异。     

电聚合苯胺过程的在线紫外-可见光谱

用在线紫外-可见光谱电化学的方法对0.5mol/L硫酸水溶液中苯胺在ITO导电玻璃电极上的电化学聚的过程进行了研究.结果表明在循环伏安条件下苯胺发生了电聚合,聚合速率与苯胺浓度成正关系;而且在线紫外-可见电化学光谱表明,在0.01mol/L苯胺溶液的电聚合过程的诱导期较长.恒电位条件下的在线紫外-可见电化学光谱显示苯胺浓度为0.05mol/L,电位为0.8V时,在ITO电极上苯胺低聚合物中间体可能产生于聚苯胺形成之前;而0.01mol/L苯胺在0.8V电位下不发生聚合,但在线紫外-可见光谱又显示此时在电极上可能存在小的苯胺低聚物的中间体;在线紫外-可见光谱表明这种中间体是可能产生并存在电极表面上的.     

Electropolymerization of Methylene Blue on Carbon Ionic Liquid Electrode and Its Electrocatalysis to 3,4‐Dihydroxybenzoic Acid

In this paper an ionic liquid modified carbon paste electrode (CILE) was prepared and methylene blue (MB) was electropolymerized on the CILE by using the cyclic voltammetric technique in the potential range from −1.0 V to 0.8 V (vs. SCE). A stable polymer film was obtained and exhibited a pair of redox peaks. The morphology and characteristics of poly(methylene blue) (PMB) film was studied by the techniques such as scanning electron microscopy and electrochemical impedance spectroscopy. This PMB modified CILE (PMB/CILE) showed excellent electrocatalytic response to 3,4‐dihydroxybenzoic acid with the increase of the electrochemical responses. The oxidation peak current had a linear relationship with 3,4‐dihydroxybenzoic acid concentration in the range of 5.0 × 10⁻⁴ ∼ 3.0 × 10⁻² mol L⁻¹ and the detection limit was 1.72 × 10⁻⁴ Mol L⁻¹ (3 σ).     

2,2‐Bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane Modified Glassy Carbon Electrodes as Selective and Sensitive Voltammetric Sensors. Selective Detection of Dopamine and Uric Acid

2,2‐bis(3‐Amino‐4‐hydroxyphenyl)hexafluoropropane (BAHHFP) was electro‐polymerized oxidatively on glassy carbon by cyclic voltammetry. The activity of the modified electrode towards ascorbic acid (AA), uric acid (UA) and dopamine (DA) was characterized with cyclic voltammetry and differential puls voltammetry (DPV). The findings showed that the electrode modification drastically suppresses the response of AA and shifts it towards more negative potentials. Simultaneously an enhancement of reaction reversibility is seen for DA and UA. Unusual, selective preconcentration features are observed for DA when the polymer‐modified electrode is polarized at negative potential. In a ternary mixture containing the three analytes studied, three baseline resolved peaks are observed in DPV mode. At physiological pH 7.4, after 5 min preconcentration at ?300 mV, peaks positions were ?0.073, 0.131 and 0.280 V (vs. Ag/AgCl) for AA, DA and UA, respectively. Relative selectivities DA/AA and UA/AA were over 4000 : 1 and 700 : 1, respectively. DA response was linear in the range 0.05–3 μM with sensitivity of 138 μA μM^?1 cm^?2 and detection limit (3σ) of 5 nM. Sensitive quantification of UA was possible in acidic solution (pH 1.8). Under such conditions a very sharp peak appeared at 630 mV (DPV). The response was linear in the range 0.5–100 μM with sensitivity of 4.67 μA μM^?1 cm^?2 and detection limit (3σ) of 0.1 μM. Practical utility was illustrated by selective determination of UA in human urine.     

Electrochemical and Raman spectroscopic study of polyaniline; influence of the potential on the degradation of polyaniline

The polymerization of aniline has been studied employing in-situ electrochemical and Raman spectroscopical techniques. Aniline was polymerized by cyclic voltammetry on a Pt surface in sulfuric acid solutions of aniline. The Raman bands were assigned for degradation products of the overoxidized form of polyaniline. A discussion of the degradation mechanism is given. Received: 12 November 1997 / Accepted: 20 January 1998     

A novel electrosynthesized polymer applied to molecular imprinting technology

Poly(2-macaptobenzimidazole) (PMBI) films are prepared at the gold electrode surface by electropolymerization using imprinting technology and the target analyte cholesterol is used as the template. A cholesterol-selective sensor based on PMBI film was employed in conjunction with differential pulse voltammetry (DPV) and ferricyanide as mediator. Concentration of cholesterol up to 100 μM could be detected with a linear determination range up to 20 μM and a detection limit of 0.7 μM. The molecular imprinting approach offers a relatively nice selectivity for the sensor toward cholesterol with respect to common coexisting substances. The method is simple and the stability of the electrode prepared is satisfactory. The results of this research show the feasibility of using molecular imprinting methodology for preparing sensing devices for analytes that are electrochemically inactive.     

Electrochemically aided solid phase microextraction: conducting polymer film material applicable for cationic analytes

The cation uptake and release properties of a poly(pyrrole-sulfated β-cyclodextrin) (PPy-SβCD) film electrode have been investigated under both open circuit and controlled potential conditions for prospective applications in electrochemically aided solid-phase microextraction (EA SPME). The EDAX and ion chromatography results show that the K⁺ and Na⁺ cation uptake is enhanced if a small negative potential is applied to the electrode in the range where PPy is in its neutral form. These cations are released rapidly from the film if the applied potential is switched to the value at which PPy is converted to its positively charged form, i.e., oxidized state. The cation ingress and egress mechanism is affected both by the cation exchange at the negative sulfate moiety on the cyclodextrin sites and electrostatic interactions generated by the applied potential. The electrochemical "switching" capability increases the speed of the cation uptake and release, presumably due to electro migration, as compared to the open circuit ion exchange which is controlled solely by diffusion. Our preliminary fundamental results show that the PPy-SβCD film is suitable for the future design of EA SPME devices. Electronic Publication     

Functionalized Multiwalled Carbon Nanotubes Through In Situ Electropolymerization of Brilliant Cresyl Blue for Determination of Epinephrine

In this work, a polymeric brilliant cresyl blue (BCB) and dihexadecyl phosphate (DHP) dispersed Multi‐walled carbon nanotubes (MWNTs) composite film modified glass carbon electrode (PBCB‐MWNTs‐DHP/GCE) denoted as epinephrine (EP) sensor was prepared by an in‐situ electropolymerization method. The electrochemical response of EP at the sensor is much better. Voltammetric investigations indicated that the improved response of EP at the sensor mainly arose from the enhanced adsorption of EP at PBCB‐MWNTs‐DHP film, perhaps through the hydrogen bonding and π–π interactions between EP and PBCB. The sensor was applied to the determination of EP in injection by a standard addition method and the results were satisfied.     

Electrocatalytic Oxidation of Some Carbohydrates by Nickel/Poly(o‐Aminophenol) Modified Carbon Paste Electrode

This study investigates the electrocatalytic oxidation of glucose and some other carbohydrates on nickel/poly(o‐aminophenol) modified carbon paste electrode as an enzyme free electrode in alkaline solution. Poly(o‐aminophenol) was prepared by electropolymerization using a carbon paste electrode bulk modified with o‐aminophenol and continuous cyclic voltammetry in HClO₄ solution. Then Ni(II) ions were incorporated to electrode by immersion of the polymeric modified electrode having amine group in 1 M Ni(II) ion solution. Cyclic voltammetric and chronoamperometric experiments were used for the electrochemical study of this modified electrode; a good redox behavior of Ni(OH)₂/NiOOH couple at the surface of electrode can be observed, the capability of this modified electrode for catalytic oxidation of glucose and other carbohydrates was demonstrated. The amount of α and surface coverage (Γ*) of the redox species and catalytic chemical reaction rate constant (k) for each carbohydrate were calculated. Also, the electrocatalytic oxidation peak currents of all tested carbohydrates exhibit a good linear dependence on concentration and their quantification can be done easily.     

Electrodeposition of polyaniline, poly(2-iodoaniline), and poly(aniline-co-2-iodoaniline) on steel surfaces and corrosion protection of steel

Polyaniline (PANi), poly(2-iodoaniline) (PIANi), and poly(aniline-co-2-iodoaniline) (co-PIANi) were synthesized using cyclic voltammetry in acetonitrile solution containing tetrabuthylammonium perchlorate (TBAP) and perchloric acid (HClO₄) on 304-stainless steel electrodes. Adherent and black polymer films were obtained on the electrodes. The structure and properties of these polymer films were characterized by FTIR and UV-vis spectroscopy and electrochemical method. The corrosion performance of PANi, PIANi, and co-PIANi coated electrodes were investigated in 0.5 M hydrochloric acid (HCl) solutions by potentiodynamic polarization technique, open circuit potential-time curves and electrochemical impedance spectroscopy, EIS. It was found that the PANi film could provide much better protection than PIANi, and co-PIANi and PANi films have barrier property as well as acting as passivator. On the other hand PIANi and co-PIANi films are acting as barrier coatings which were related with the prevention of cathodic reaction taking place at metal\electrolyte interface. EIS measurement shows that every coating gives protection efficiency of greater than 75% after 48 h of immersion time in corrosive test solution.