多层膜组装及其电催化研究

本论文主要是利用在化学修饰电极基础上建立起来的有序分子自组装膜技术，来制备能高效催化氧还原的有机一无机复合膜以及贵金属纳米粒子膜，以达到对氧的四电子还原。具体工作为：1．金属叶琳如钻叶琳单独修饰在电极表面通常只能通过两电子还原氧生成过氧化氢。而杂多酸是一种很好的电子媒介体，对很多小分子比如过氧化氢等都有很好的催化作用。我们用杂多阴离子作为对离子制备了含金属叶琳的复合膜，由于这两种物质的协同催化作用，所制备有机一无机复合膜表现了很高的催化活性，几乎达到了氧的四电子还原。2．很早人们就发现杂多酸电聚合在电极表面在酸性介质中可以催化析氢。我们通过层层组装的方法在功能化玻碳电极表面制备SiW_(12)／CoTMPyP多层复合膜，该复合膜可以高效催化析氢，同时该多层膜又能两电子催化氧还原。3．通过在一定电位下直接还原在CoTMPyP夹层间的氯铂酸根离子，在电极表面合成了三维铂纳米粒子膜。该纳米粒子膜对氧有很高的催化作用，旋转圆盘电极实验和旋转环盘电极实验证明该铂纳米粒子膜在0.5 MH_2SO_4溶液中可以实现对氧的四电子还原。4．在裸的金电极表面成功地欠电位沉积了把纳米粒子单层膜，该纳米粒子单层膜对氧还原有很好的催化作用。在这一工作基础上，研制了DO在线监侧仪。5．通过层层组装的方法，金溶胶纳米粒子与CoTMPyP的复合膜成功地组装在各种基底上。被聚丙烯酸稳定的金纳米粒子很容易吸附在CoTMPyP上，形成非常紧密分布的纳米粒子膜。6．在多壁碳纳米管表面吸附MP-11，实现了MP-11的直接电化学，同时研究了其对氧和过氧化氢的催化作用。

Highly ordered mesoporous carbons as electrode material for the construction of electrochemical dehydrogenase- and oxidase-based biosensors

In this work, the excel lent catalytic activity of highly ordered mesoporous carbons (OMCs) to the electrooxidation of nicotinamide adenine dinucleotide (NADH) and hydrogen peroxide (H2O2) was described for the construction of electrochemical alcohol dehydrogenase (ADH) and glucose oxidase (GOD)-based biosensors.

Metal nanomaterials and carbon nanotubes - synthesis, functionalization and potential applications towards electrochemistry

This review focuses on the synthesis, assembly, surface functionalization, as well as application of inorganic nanostructures. Electrochemical and wet- chemical methods are demonstrated to be effective approaches to make metal nanostructures under control without addition of a reducing agent or protecting agent. Owing to the unique physical and chemical properties of the nano-sized materials, novel applications are introduced using inorganic nanomaterials, such as electrocatalysis, photoelectricity, spectrochemistry, and analytical chemistry.

The characteristics of highly ordered mesoporous carbons as electrode material for electrochemical sensing as compared with carbon nanotubes

In this paper, the unique properties of highly ordered mesoporous carbons modified glassy carbon electrode (OMCs/GE) are illustrated from comparison with carbon nanotubes modified glassy carbon electrode (CNTs/GE) for the electrochemical sensing applications.

Sensing H2O2 with layer-by-layer assembled Fe3O4-PDDA nanocomposite film

It was found that Fe3O4 nanoparticles (Fe3O4 NPs) possess intrinsic enzyme mimetic activity similar to that found in natural peroxidase. Here, we applied Fe3O4 NPs to the construction of efficient electrochemical sensor to detect the concentration of hydrogen peroxide. The sensor was fabricated with layer-by-layer assembly of Fe3O4 NPs and poly(diallyldimethylammonium chloride) (PDDA) through the electrostatic interaction, and the multilayer film was characterized with UV-vis absorption spectra, atomic force microscopy, and cyclic voltammetry.

Properties of poly(sodium 4-styrenesulfonate)-ionic liquid composite film and its application in the determination of trace metals combined with bismuth film electrode

A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) can be effectively improved at the PSS-BMIMPF6 modified GC.

Monodisperse raspberry-like gold submicrometer spheres: Large-scale synthesis and interface assembling for colloid sphere array

We first suggested a one-pot method to synthesize monodisperse raspberry-like submicrometer gold spheres (MRSGS) with high yield. The resulting gold spheres were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersed X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical technology. It was found that the rough structure provided by raspberry-like gold spheres led to a tremendous electrochemical active area, which was very important because these novel hierarchical gold spheres will probably find important applications in biosensors, electrocatalysis, and others.

Direct electrochemistry of horseradish peroxidase immobilized in calcium carbonate microsphere doped with phospholipids

Protein electrochemistry affords a direct method to study the biological electron transfer processes. However, supplying a biocompatible environment to maintain the native state of protein is all-important and challengeable. Here, we chose vaterite, one of the crystalline polymorphs of calcium carbonate, with highly porous nature and large specific surface area, which was doped with phospholipids, as the matrix to immobilize horseradish peroxidase (HRP). The integrity of HRP was kept during the simple immobilization procedure. By virtue of this organic/inorganic complex matrix, the direct electrochemistry of HRP was realized, and the activity of HRP for catalyzing reduction of O-2 and H2O2 was preserved.

Electrochemistry of Microperoxidase-11 (MP-11) on Glassy Carbon Electrode Modified with Chitosan

In this paper, microperoxidase-11 (MP-11) was immobilized on glassy carbon electrode surface modified with chitosan by physical adsorption. The direct electrochemistry and the electrocatalytic behaviours to O-2 and the H2O2 of MP-11 on glassy carbon electrode modified with chitosan were characterized by cyclic voltammetry. The results indicate that MP-11 on modified electrode displays a quasi-reversible electrochemical process coupled with proton transfer in the phosphate buffer solutions(pH = 7.12). Direct electrochemical reaction of MP-11 on modified electrode has been realized. MP-11 on modified electrode can catalyze reduction for O-2 and H2O2. Both of the catalytic reductions are surface-controlled electrochemical process.

Preparation of gold nanoparticles/functionalized multiwalled carbon nanotube nanocomposites and its glucose biosensing application

Gold nanoparticles stabilized by amino-terminated ionic liquid (Au-IL) have been in situ noncovalently deposited on poly(sodium 4-styrene-sulfonate) (PSS)-functionalized multiwalled carbon nanotubes (MWCNTs) to form a MWCNTs/PSS/Au-IL nanocomposite. PSS can interact with MWCNTs through hydrophobic interaction. Amino-terminated ionic liquid was applied to reduce aqueous HAuCl4, and the resulting gold nanoparticles were attached to the PSS-functionalized MWCNTs simultaneously. Most gold nanoparticles dispersed well on the functionalized MWCNTs. Transmission electron microscopy, Raman and X-ray photoelectron spectroscopy were used to confirm the composition and structure of the nanocomposites. The resulting MWCNTs/PSS/Au-IL composite exhibits good electrocatalysis toward oxygen and hydrogen peroxide reduction.

Biosynthesis of gold nanoparticles assisted by Escherichia coli DH5 alpha and its application on direct electrochemistry of hemoglobin

In this communication, biosynthesis of gold nanoparticles assisted by Escherichia coli DH5 alpha and its application on direct electrochemistry of hemoglobin are reported. The gold nanoparticles formed on the bacteria surface are mostly spherical. The direct electrochemistry of hemoglobin can be achieved by incorporated into the bio-nanocomposite films on a glassy carbon electrode.

Synthesis and electrochemical applications of gold nanoparticles

This review covers recent advances in synthesis and electrochemical applications of gold nanoparticles (AuNPs). Described approaches include the synthesis of AuNPs via designing and choosing new protecting ligands; and applications in electrochemistry of AuNPs including AuNPs-based bioelectrochemical sensors, such as direct electrochemistry of redox-proteins, genosensors and immunosensors, and AuNPs as enhancing platform for electrocatalysis and electrochemical sensors.

An effective hydrothermal route for the synthesis of multiple PDDA-protected noble-metal nanostructures

In this Article, we demonstrate an effective hydrothermal route for the synthesis of multiple PDDA-protected (PDDA = poly(diallyl dimethylammonium) chloride) noble-metal (including silver, platinum, palladium, and gold) nanostructures in the absence of any seeds and surfactants, in which PDDA, an ordinary and water-soluble polyelectrolyte, acts as both a reducing and a stabilizing agent. Under optimal experimental conditions, Ag nanocubes, Pt and Pd nanopolyhedrons, and Au nanoplates can be obtained, which were characterized by transmission electron microscopy, scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction. More importantly, the nanostrucfures synthesized show potential applications in surface-enhanced Raman scattering and electrocatalysis, in which Ag nanocubes and Pt nanopolyhedrons were chosen as the examples, respectively.

Assembly of polyoxometalates on carbon nanotubes paste electrode and its catalytic behaviors

Carbon nanotubes paste (CNTP) electrode was prepared with multi-walled carbon nanotubes and methyl silicone oil. Polyoxometalates (POMs) were assembled on the electrode surface with different methods, and investigated by cyclic voltammetry and Raman spectroscopy. Experiments showed that POMs/CNTP electrode prepared by direct method had better performance. K6P2Mo18O62 center dot 14H(2)O (P2Mo18) assembled CNTP electrode (P2Mo18/CNTP) electrode possessed good reversibility and could catalyze the reduction of bromate and iodate in 0.1 M H2SO4 Solution. Further, the multilayer films of P2Mo18 assembled CNTP electrodes were fabricated by layer-by-layer technique, which showed higher electrocatalytic activities. All these POMs assembled CNTP electrodes prepared exhibited good stability.

Rotating minidisk-disk electrodes

Rotating minidisk-disk electrode (RMDDE) was developed by replacing ring electrode of rotating ring-disk electrode (RRDE) with a minidisk electrode. Its applications were demonstrated by studying electrochemical reactions of ferricyanide and divalent copper. The replacement of ring electrode by minidisk electrode results in following advantages. First, the fabrication of RMDDE is easier than that of RRDE with the same electrode material. Second, there is more freedom in choosing electrode materials and sizes, since it is difficult to make thin ring electrodes of RRDE with fragile materials. Third, the replacement of ring electrode by minidisk electrode saves electrode materials, especially rare materials. Finally, the substitution of minidisk electrode for ring electrode allows using multiple minidisks for simultaneous monitoring of multiple components. Therefore, RMDDE is a promising generator-collector system, especially when special generator-collector systems are not commercially available, such as corrosion study and electrocatalysis study of new electrode materials.