Electrocatalytic Reduction of Oxygen at Multi‐Walled Carbon Nanotubes and Cobalt Porphyrin Modified Glassy Carbon Electrode

The multi‐walled carbon nanotubes (MWNTs) modified glassy carbon electrode exhibited electrocatalytic activity to the reduction of oxygen in 0.1 M HAc‐NaAc (pH 3.8) buffer solution. Further modification with cobalt porphyrin film on the MWNTs by adsorption, the resulted modified electrode showed more efficient catalytic activity to O₂ reduction. The reduction peak potential of O₂ is shifted much more positively to 0.12 V (vs. Ag/AgCl), and the peak current is increased greatly. Cyclic voltammetry (CV), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM), were used to characterize the material and the modified film on electrode surface. Electrochemical experiments gave the total number of electron transfer for oxygen reduction as about 3, which indicated a co‐exist process of 2 electrons and 4 electrons for reduction of oxygen at this modified electrode. Meanwhile, the catalytic activities of the multilayer film (MWNTs/CoTMPyP)_n prepared by layer‐by‐layer method were investigated, and the results showed that the peak current of O₂ reduction increased and the peak potential shifted to a positive direction with the increase of layer numbers.     

Enhanced Electrocatalysis for the Reduction of Hydrogen Peroxide at New Multiwall Carbon Nanotube Grafted Polydiphenylamine Modified Electrode

A new modified electrode having multiwall carbon nanotube (MWNT) grafted with polydiphenylamine (PDPA) as electrocatalytic layer is fabricated. FESEM image of the modified electrode shows a different morphology indicating the grafting of PDPA over MWNT. This morphology is in quite contrast from the conventional bilayer MWNT/conducting polymer modified electrode. The multiwall carbon nanotube grafted polydiphenylamine (MWNT‐g‐PDPA‐ME) shows excellent electrocatalytic activity towards the reduction of hydrogen peroxide. The combined presence of MWNT and PDPA as a single unit provides better sensitivity than the bilayer configuration (MWNT/PDPA‐ME). This modified electrode shows accelerated electron transfer at the interface with minimized surface fouling and surface renewability. The advantages of MWNT‐g‐PDPA‐ME over the bilayer electrode are demonstrated with chronoamperometric studies. The amperometric response to H₂O₂ obtained at ?300 mV (vs. SCE) is rapid and highly sensitive as evident from the higher (2.83×10^?3 cm³ mol^?1 s^?1) rate constant for the diffusion reduction process.     

Electrocatalytic Reduction of Dioxygen on the Surface of Glassy Carbon Electrodes Modified with Cobalt Porphyrin Complexes

The preparation and electrocatalytic behavior of glassy carbon electrodes modified with three different cobalt porphyrin complexes were investigated. The electrocatalytic ability of the modified electrodes for the reduction of dioxygen to hydrogen peroxide and water in air‐saturated aqueous solutions was examined by cyclic voltammetry and chronoamperometry techniques. The porphyrin‐adsorbed glassy carbon electrodes possess excellent electrocatalytic abilities for dioxygen reduction with overpotential about 0.5 V lower than that at a plain glassy carbon electrode. The experimental parameters were optimized and the mechanism of the catalytic process was discussed. The possible effects of the electron‐donating properties of groups in the meso‐position of the porphyrin ring were investigated.     

Pt/纳米碳管空气电极氧还原反应的电催化性能

以不同质量比的铂、纳米碳管、活性炭为催化层制备空气电极并测定其稳态极化曲线和交流阻抗.研究发现,纳米碳管经硝酸处理后其氧还原反应性能得到提高,特别是将表面氧化后再沉积Pt,对氧的电还原反应影响更显著.以质量比4∶1的活性炭/纳米碳管载Pt制备的空气电极,在过电位ηc为500～600mV下,氧还原电流可达600～700mA·cm-2.EIS测试表明,纳米碳管载Pt后的欧姆极化阻抗和电化学阻抗均非常小.     

纳米碳管电极上氧的电催化还原

以聚四氟乙烯为粘结剂制成了多壁纳米碳管（MWNT）电极.采用恒电位阶跃法和循环伏安法研究了MWNT电极在碱性溶液中的电化学行为，并对碱性溶液中溶解氧在该电极上的电化学还原行为进行了研究.实验结果表明： MWNT电极具有比石墨电极更高的孔隙率和电化学表面积；MWNT电极上O2还原成的反应为准可逆过程；在5～50 mV•s－1的扫描速率范围内，阴极峰电流与扫描速度成线性关系，表明MWNT电极上O2还原成的反应受吸附控制；对碱性溶液中的氧还原反应， MWNT比石墨具有更高的催化活性.     

分子氧在金属配合物担载磷铝分子筛修饰玻碳电极上的电催化还原反应

采用循环伏安法研究了负载金属配合物MnSALEN(SALEN=N,N-双水杨醛缩乙二胺)的磷铝分子筛APO-5复合催化剂修饰玻碳电极在水溶液中对分子氧的还原反应的电催化行为.结果表明,氧气的还原峰电位随扫描速率的增大负移,Ep~lnv呈线性关系;其还原峰电流随扫描速率的增大而增强,ip~v1/2呈直线关系.这说明分子氧在修饰电极PS/MnSALEN/APO-5/GCE上的还原是扩散控制的.根据Ep~lnv和ip~v1/2的线性关系计算出中性电解质溶液中分子氧在此修饰电极上的还原反应的电子转移数n接近4.即氧气在此修饰电极上被还原为水.     

聚血红素修饰电极上氧还原的电催化研究

 采用循环伏安法和电位阶跃法,研究了水溶液中溶解氧在聚血红素修饰电极上还原反应的电催化作用．结果表明,还原峰电流随扫描速度的增大而增强,Ip～v1／2呈线性关系．根据电位阶跃实验的I～t曲线,计算出电极反应的电子转移数约为2,推断其催化机理属于ECE催化过程．     

碳纳米管负载纳米铂修饰电极及电催化氧化H2O2的研究

采用化学气相沉积法在碳纳米管(CNT)上负载Pt纳米颗粒,并制备了CNT-Pt修饰玻碳电极(CNT-Pt/GCE).研究了该修饰电极在磷酸缓冲液中对H2O2的电催化氧化作用以及实验条件的影响.计算了H2O2在CNT-Pt/GCE上的电极反应速率常数.结果表明,CNT-Pt/GCE对H2O2的电化学氧化具有良好的催化作用,电极反应速率常数比铂电极高约2.65倍.初步探讨了电催化氧化机理,为酶电化学传感器的研制提供了一条新的途径.     

Nicotinamide Adenine Dinucleotide Oxidation Studies at Multiwalled Carbon Nanotube/Polymer Composite Modified Glassy Carbon Electrodes

NADH oxidation has previously been investigated at carbon nanotube surfaces, although studies into the effect of the polymer binders are needed to fully understand whether the polymer binder affects the electrochemistry. This work details NADH oxidation at glassy carbon electrodes modified with composites containing multiwalled carbon nanotubes and selected polymer binders. NADH is shown to be oxidized at a lower potential than at glassy carbon electrodes and the oxidation potential is a function of the polymer binder. Hydrophobically modified Nafion, Nafion, linear poly(ethylenimine) (LPEI), octyl‐modified LPEI, and poly(vinylpyridine) binders were studied. Experiments showed the peak current and electrochemically assessible electrode area are dependent on the polymer binder. Overall, this paper shows that polymer binders affect NADH oxidation potential at carbon nanotube modified electrodes.     

氧在直接耐晒翠蓝GL修饰电极上的催化还原

有关过渡金属叶琳和酞蓄配合物对分子氧的电催化还原研究,近三十年来陆续不断地有大量的报导“－’‘．若这些配合物能取代或部分取代铂作为催化剂,将使燃料电池和空气电池的成本大为降低‘前人所使用的这类配合物大多为在实验室中合成的纯度高的试剂,有的价格也不低．而纺织工业中使用的酞育类染料其价格却低得多（后者价格仅为前者的几百分之一至千分之一）．如果其中某些酞育类染料也具有和上述试剂一样的催化活性,那么人们就有可能获得催化性能好而又便宜的催化剂,这是很有实用意义的．本文用循环伏安法研究了用水溶性染料直接耐晒…     

金纳米粒子/碳纳米管复合修饰玻碳电极对对苯二酚氧化还原反应的电催化性能

以对苯二酚为目标化合物比较研究了金纳米粒子、碳纳米管、金纳米粒子/碳纳米管3种纳米粒子修饰电极的电催化性能,结果发现:3种纳米粒子修饰电极均对对苯二酚的电化学信号具有增强作用。电化学阻抗谱和修饰层数试验表明:金纳米粒子的增强效果来自于金纳米粒子的电催化作用,碳纳米管的增强作用来自于电催化作用与大的电极表面积,金纳米粒子/碳纳米管复合修饰电极综合利用了两种纳米粒子的特性,表现出了更为优良的电催化行为。对苯二酚在修饰电极上的电化学过程均为扩散控制过程。     

Glassy Carbon Electrodes Modified with Multiwall Carbon Nanotubes Dispersed in Polylysine

We report the analytical performance of glassy carbon electrodes (GCE) modified with a dispersion of multiwall carbon nanotubes (MWCNT) in polylysine (Plys) (GCE/MWCNT‐Plys). The resulting electrodes show an excellent electrocatalytic activity towards different bioanalytes like ascorbic acid, uric acid and hydrogen peroxide, with important decrease in their oxidation overvoltages. The dispersion of 1.0 mg/mL MWCNT in 1.0 mg/mL polylysine is highly stable, since after 2 weeks the sensitivity for hydrogen peroxide at GCE modified with this dispersion remained in a 90% of the original value. The MWCNT‐Plys layer immobilized on glassy carbon electrodes has been also used as a platform to build supramolecular architectures by self‐assembling of polyelectrolytes based on the polycationic nature of the polylysine used to disperse the nanotubes. The self‐assembling of glucose oxidase has allowed us to obtain a supramolecular multistructure for glucose biosensing. The influence of glucose oxidase concentration and adsorption time as well as the effect of using polylysine or MWCNT‐Plys as polycationic layers for further adsorption of GOx is also evaluated.     

Amperometric Detection of Morphine at Preheated Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A highly sensitive and fast responding sensor for the determination of morphine is described. The multiwall carbon nanotubes immobilize on preheated glassy carbon electrode (5 min at 50 °C) by gently rubbing of electrode surface on a filter paper supporting the carbon nanotubes.The results indicated that carbon nanotubes(CNTs) modified glassy carbon electrode exhibited efficiently electrocatalytic oxidation for morphine with relatively high sensitivity, stability and long life. Under conditions of cyclic voltammetry, the potential for oxidation of morphine is lowered by approximately 100 mV and the current is enhanced significantly (10 times) in comparison to the bare glassy carbon electrode at wide pH range (2–9). The electrocatalytic behavior is further exploited as a sensitive detection scheme for morphine determination by hydrodynamic amperometry. Under the optimized conditions the calibration plots are linear in the concentration range 0.5–150 μM with the calculated detection limit (S/N=3) of 0.2 μM and sensitivity of 10 nA/μM and a relative standard deviation (RSD) of 2.5% (n=10). The amperometric response is extremely stable, with no loss in sensitivity over a continual 30 min operation. Such attractive ability of multiwall carbon nanotubes (MWCNTs) modified GC electrode, suggests great promise for a morphine amperometric sensor. Finally the ability of the modified electrode was evaluated for simultaneous determination of morphine and codeine.     

蒿甲醚在单壁碳纳米管修饰电极上的电催化还原

研制了单壁碳纳米管(SWCNTs)修饰玻碳电极。用交流阻抗谱法(EIS)和扫描电镜(SEM)研究了电极膜性能,应用循环伏安法(CV)、计时库仑法(CC)、计时电流法(CA)研究了蒿甲醚在修饰电极上的电化学行为。结果表明,SWCNTs修饰电极对蒿甲醚的还原有良好的电催化活性,其还原反应为双电子过程,电极反应的扩散系数及速率常数分别为6·67×10-4cm2·s-1及8·54×10-2mol·L-1·s-1。在优化实验条件下,还原峰的峰电位位于-0·85V,其峰电流与蒿甲醚浓度在6·71×10-7~2·45×10-4mol·L-1范围内呈良好线性,检出限达4·02×10-7mol·L-1,相对标准偏差(n=10)为4·2%,可用于蒿甲醚样品的含量测定。     

盐酸伪麻黄碱在多壁碳纳米管修饰玻碳电极上的电催化氧化及其电化学动力学性质

盐酸伪麻黄碱;碳纳米管修饰电极;电催化氧化;电化学动力学     

Electrocatalytic Reduction of Dioxygen at Carbon Paste Electrode Modified with a Novel Cobalt(III) Schiff's Base Complex

A carbon paste modified electrode with a new cobalt(III) Schiff's base complex (CPME) and its application to electrocatalytic activity for dioxygen reduction is developed. The electrochemical behavior and stability of the CPME as well as the two‐electron reduction of O₂ at the electrode were investigated using cyclic voltammetry, chronoamperometry and rotating disk electrode methods. At the CPME, the reduction of dioxygen to hydrogen peroxide occurs at potentials where it is not observed at a bare carbon paste electrode. The CPME exhibited potent and persistent electrocatalysis for O₂ reduction in acetate buffer solutions of pH 4.0 with an overpotential of about 800 mV lower than unmodified CPE and drastic increase in the peak current. The heterogeneous rate constant for the reduction of O₂ at the surface of CPME was determined by hydrodynamic voltammetry using the Koutecky–Levich plot. A possible catalytic mechanism is proposed and discussed.     

Electrocatalytic Oxidation of Sulfite on a Cobalt Pentacyanonitrosylferrate Film Modified Glassy Carbon Electrode

The electrocatalytic oxidation of sulfite has been studied on the cobalt pentacyanonitrosylferrate modified glassy carbon electrode (CoPCNF). The CoPCNF films on the glassy carbon electrodes show an excellent electrocatalytic activity toward the oxidation of sulfite in 0.5 M KNO₃. The kinetics of the catalytic reaction was investigated by using cyclic voltammetry, rotating disk electrode (RDE) voltammetry and chronoamperometry. The average value of the rate constant, K, for the catalytic reaction and the diffusion coefficient, D, were evaluated by different approaches for sulfite and found to be 2.9×10² M^?1s^?1 and 4.6×10^?6 cm²s^?1, respectively. At a fixed potential under hydrodynamic conditions (stirred solutions), the oxidation current is proportional to the sulfite concentration and the calibration plot was linear over the concentration range 5×10^?6–1×10^?4 M. The detection limit of the method is 3×10^?6 M., low enough for the trace sulfite determination.     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

Electrochemical Determination of Tannins Using Multiwall Carbon Nanotubes Modified Glassy Carbon Electrode

A novel chemically modified electrode is prepared on the basis of the attachment of multiwall carbon nanotubes (MWNTs) to the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant. The electrochemical behavior of tannins at the MWNTs-modified GCE is investigated. Tannins yield a well-defined oxidation at about 0.30 V (SCE) at the MWNTs-modified GCE. MWNT-film shows remarkable enhancement effect on the oxidation peak current of tannins. The experimental parameters are optimized, and a direct electrochemical method to detect tannins is proposed. The oxidation peak current is proportional to the concentration of tannins over the range from 4 × 10^–7 to 2 × 10^–4 M, and the detection limit is 1 × 10^–7 mol/l after 5 min of accumulation. The relative standard deviation of 6% for determination of 2 × 10^–6 mol/l tannins indicates excellent reproducibility. The analysis method is demonstrated by using tea and Chinese gall samples.     

Electrochemical Sensing of Uric Acid Using Glassy Carbon Modified with Multiwall Carbon Nanotubes Dispersed in Polyethylenimine

This work reports the advantages of using glassy carbon electrodes modified with multiwall carbon nanotubes (MWCNT) dispersed in polyethylenimine (PEI). The presence of MWCNTs wrapped by PEI largely facilitated the strong adsorption of uric acid (UA) and allowed its highly sensitive and selective quantification even in the presence of high excess of ascorbic acid. The selected conditions for the electrochemical sensing were 5 s accumulation at ?0.300 V under stirring and quantification in a 0.050 M phosphate buffer solution pH 7.40 by differential pulse voltammetry adsorptive‐stripping after medium exchange. The platform allowed the successful application in the quantification of UA in urine.