纳米二氧化钛负载棉织物的制备及性能

以棉织物为基体,通过紫外辐照和超声法将不同表面性质的TiO_2纳米粒子负载到棉织物上,制备自清洁材料.利用扫描电子显微镜、能谱分析、接触角、紫外-可见光谱及降解甲基橙溶液等手段分别对样品表面的结构形貌、元素分布、光催化活性、紫外屏蔽性能和耐久性等进行分析.结果表明,棉织物经紫外辐照后,TiO_2纳米粒子与其结合更牢固,耐久性更佳;TiO_2负载后的棉织物表现出超疏水性能及优异的光催化活性和紫外屏蔽性能;与未改性的TiO_2纳米粒子相比,由聚乙烯醇(PVA)改性的TiO_2纳米粒子制备的自清洁棉织物的可见光光催化活性更高,其可见光的光催化效率是前者的3.9倍.PVA改性的纳米TiO_2对290~400 nm范围内的紫外光有较好的吸收作用,其紫外屏蔽效果更佳.     

Direct electrodeposition of gold nanoparticles onto indium/tin oxide film coated glass and its application for electrochemical biosensor

A novel electrochemical deposition method for growth of gold nanoparticles (GNPs) on indium tin oxide (ITO) thin film coated glass was investigated. The resulting electrode surface was characterized by SEM, UV–Vis spectroscopy and electrochemical methods. The GNPs directly attached on the electrode surface with a quasi-spherical shape and their sizes of diameters were in the range of 20–35 nm with a quite symmetric distribution. With increasing electrodeposition cycles of cyclic voltammetry, the density of GNPs on ITO electrode surface was increased. The potential utility of the GNPs modified ITO electrode was investigated. Superoxide dismutase (SOD) was successfully immobilized on GNPs modified ITO electrode and the direct electron transfer between enzyme and electrode surface realized. The enzyme electrode exhibited a rapid and high response to superoxide anion.     

Preparation,Characterization and Electrocatalytic Studies on Copper Complex Dye Film Modified Electrodes

Copper complex dye (C.I. Direct Blue 200) film modified electrodes have been prepared by multiple scan cyclic voltammetry. The effect of solution pH and nature of electrode material on film formation was investigated. The optimum pH for copper complex film formation on glassy carbon was found to be 1.5. The mechanism of film formation on ITO seems to be similar to that on GC surface but completely different mechanism followed with gold electrode. Cyclic voltammetric features of our modified electrodes are in consistent with a surface‐confined redox process. The voltammetric response of modified electrode was found to be depending on pH of the contacting solution. UV‐visible spectra show that the nature of copper complex dye is identical in both solution phase and after forming film on electrode. The electrocatalytic behavior of copper complex dye film modified electrode towards oxidation of dopamine, ascorbic acid and reduction of SO₅^2? was investigated. The oxidation of dopamine and ascorbic acid occurred at less positive potential on film electrode compared to bare glassy carbon electrode. Feasibility of utilizing our modified electrode in analytical estimation of dopamine, ascorbic acid was also demonstrated.     

基于纳米二氧化锆与铂微粒复合修饰玻碳电极的甲醛传感器研究

采用循环伏安法在玻碳电极表面依次电沉积纳米二氧化锆和铂微粒,制备了一种检测甲醛的新型电化学传感器。用电镜扫描对该修饰电极表面进行了表征,循环伏安法和线性扫描伏安法研究了甲醛在该修饰电极上的电催化氧化作用,优化了实验参数。结果表明,该修饰电极对甲醛有很好的电催化氧化作用,在0.1 mol/L H2SO4溶液中,甲醛的氧化峰电流与其浓度在1.0×10-6~5.0×10-3mol/L范围内呈良好线性关系,回归方程为Ip(μA)=79.95+2.005×105c(mol/L),相关系数r=0.999 3,检出限为5.0×10-7mol/L。     

Size-dependent ultrafast electronic energy relaxation and enhanced fluorescence of copper nanoparticles

The energy relaxation of the electrons in the conduction band of 12 and 30 nm diameter copper nanoparticles in colloidal solution was investigated using femtosecond time-resolved transient spectroscopy. Experimental results show that the hot electron energy relaxation is faster in 12 nm copper nanoparticles (0.37 ps) than that in 30 nm copper nanoparticles (0.51 ps), which is explained by the size-dependent electron-surface phonon coupling. Additional mechanisms involving trapping or energy transfer processes to the denser surface states (imperfection) in the smaller nanoparticles are needed to explain the relaxation rate in the 12 nm nanoparticles. The observed fluorescence quantum yield from these nanoparticles is found to be enhanced by roughly 5 orders of magnitude for the 30 nm nanoparticles and 4 orders of magnitude for the 12 nm nanoparticles (relative to bulk copper metal). The increase in the fluorescence quantum yield is attributed to the electromagnetic enhancement of the radiative recombination of the electrons in the s-p conduction band below the Fermi level with the holes in the d bands due to the strong surface plasmon oscillation in these nanoparticles.     

表面修饰Ag_2S纳米微粒的合成及摩擦学行为研究

在水醇混合介质中,采用同阳离子共沉淀法合成了有机化合物表面修饰的Ａｇ２Ｓ纳米微粒,在高速钢基底上制备成膜,研究了它的摩擦学特性。结果表明：修饰后的Ａｇ２Ｓ纳米微粒粒径小,性能稳定,在有机介质中分散成透明溶液。ＡｇＤＤＰ膜和Ａｇ２Ｓ ＤＤＰ膜均可显著降低钢基底的摩擦系数。研究证实表面修饰Ａｇ２Ｓ纳米微粒的摩擦作用机制是在较低负荷下表面修饰层起主要作用,在较高负荷下Ａｇ２Ｓ纳米核起主要的承载和减摩抗磨作用。     

Aggregation of photolytic gold nanoparticles at the surface of chitosan films

Formation and aggregation of photolytic gold nanoparticles at the surface of chitosan (CTO) films have been investigated. When thin films of chloroauric acid salt of CTO were irradiated with UV light in wet air at room temperature for 10 min, gold nanoparticles of approximately 10 nm size are formed at the film surface. Detailed X-ray photoelectron spectroscopy (XPS) study and field emission type scanning electron microscopy (FE-SEM) observation have been carried out to characterize gold nanoparticles at the film surface. The shift of Au(4f) peak to the higher energy side and broadening of full width at half-maximum in the XPS spectrum are the direct evidence of the existence of gold atoms and small clusters in the early stage of photolysis. According to FE-SEM observation, growth in the particle diameter and aggregation of nanoparticles were observed after prolonged irradiation, and, finally, the film surface was densely covered with gold particles of 20-100-nm size. Gold atoms and clusters could move in the film and precipitate to the irradiated surface. Chemical composition analysis further suggests that gold particles at the surface are covered with an ultrathin CTO layer, which is partly oxidized by oxygen and chlorinated by chlorine during photochemical reactions.     

Assembly process of CuHCF/MPA multilayers on gold nanoparticles modified electrode and characterization by electrochemical SPR

Gold nanoparticles were deposited onto 2-mercaptoethylamine (MEA)-assembled planar gold thin film to construct gold nanoparticles modified electrode by virtue of a solution-based self-assembly strategy. Subsequently, 3-mercaptopropionic acid (MPA)-bridged copper hexacyanoferrate (CuHCF) multilayers were constructed on the as-prepared gold nanoparticles modified electrode. The resulted multilayer nanostructures were investigated by electrochemical surface plasmon resonance (EC-SPR) and atomic force microscopy (AFM) with primary emphasis upon the effect of the gold nanoparticles on the MPA/CuHCF multilayers growth and their surface morphology. Compared with the multilayer system on a planar gold electrode, the different electrochemical and optical properties might result from higher curvature effect and extraordinary surface-to-volume ratio characteristic of gold nanoparticles and the nanoparticle-selective growth of CuHCF. A dendrimer-like assembly process was proposed to explain the experiment results. This new motif of multilayer on the gold nanoparticles modified electrode was different from that of on a planar gold electrode, indicating a potential application of EC-SPR technique in the study of nanocomposite materials.     

Physical insights into the photoactivated Ullmann coupling process producing highly conjugated oligothiophene films on a copper substrate

This paper describes the details of surface reactions producing >100-nm-thick conjugated polymer films. When 2,5-diiodothiophene films deposited on copper are irradiated with UV at room temperature in Ar environments, oligothiophene films are synthesized. The average conjugation length of the produced film varies from approximately 7 to 3-4 as the film thickness increases from approximately 100 to approximately 500 nm. The X-ray photoelectron spectroscopy analysis of the produced films reveals evidence for the formation of organo-copper intermediate species at the copper-monomer film interface and their diffusion from the copper surface into the monomer film during the photochemical process. A one-dimensional diffusion-reaction model is presented to explain the formation, diffusion, and reaction of organo-copper intermediates in the multilayer film during the photochemical reaction. The model simulation results qualitatively explain the decrease of the Ullmann coupling contribution in the photochemical reaction with the film thickness.     

Cu/dioxidine hybrid nanocomposites: cryochemical synthesis and antibacterial activity

Hybrid nanocomposites consisting of an antibacterial drug, dioxidine, and copper nanoparticles are obtained by cryochemical synthesis. It is shown by UV spectroscopy, X-ray diffraction, PAM, and low temperature argon adsorption that the obtained hybrid systems represent dioxidine particles with a size of 100 to 400 nm, including copper particles with the size of 50 to 150 nm. The resulting composites possessed higher antibacterial activity against E. coli 52 than the initial dioxidine and copper nanoparticles.     

Preparation of conductive,flexible and transparent films by in situ deposition of polypyrrole nanoparticles on polyethylene terephthalate

In this study polypyrrole (PPy) nanoparticles were deposited as a thin film on the modified surface of polyethyleneterephthalate (PET) by in situ chemical polymerization in the presence of sodium dodecylsulfate (SDS), sodium dodecylbenzenesulfonate (DBSNa) and mixture of them as the surfactant. The surface of PET was modified by KOH before deposition and was investigated for conductivity and adhesion of PPy nanoparticles to PET. Resulting conductive flexible films were characterized by UV–Vis spectroscopy, fieldemission scanning electron microscopy, contact angle measurements and four-point-probe technique for conductivity. Direct morphological observation (FESEM) and electrical measurements indicated that the morphology, conductivity and the nature of deposited PPy films depend on surfactant, surface modification of PET and monomer concentration. In optimized process condition, uniform conductive films of PPy were obtained with good adhesion to PET.     

Self‐Assembly and Surface Photovoltage Response of ZnS Nanoparticulate Films Sensitized by Tetrasulfonated Copper Phthalocyanine

Composite films of ZnS nanoparticle‐polyelectrolyte were fabricated by the layer‐by‐layer self‐assembly technique. The optical properties and structure of the films were characterized by UV‐vis absorption spectra and AFM. The films sensitized by tetrasulfonated copper phthalocyanine (CuTsPc) show wide photovoltaic response range. The surface photovoltages corresponding to the ZnS nanoparticle interband transition and CuTsPc Q band transition in the sensitized film are approximately three to four times stronger than those in the ZnS nanoparticle‐polyelectrolyte film and CuTsPc film, respectively, which is attributed to the electron transition from the excited state of CuTsPc to the conduction band of ZnS nanoparticles.     

Effect of Laser Pulse Energy on the Characteristics of Cu Nanoparticles Produced by Laser Ablation Method in Acetone

The effect of laser fluence on the characteristics of Cu nanoparticles, prepared by laser ablation method, is investigated experimentally. 1–6 nm Cu nanoparticles were synthesized by the pulsed laser ablation of a high purity copper bulk in acetone. Effect of laser fluence on the size, morphology and structure of produced nanoparticles has been studied. Pulses of a Q-switched Nd:YAG laser of 1,064 nm wavelengths at 7 ns pulse width at different fluences was employed to irradiate the Cu target in acetone. The UV–Vis–NIR absorption spectra of nanoparticles exhibit surface plasmon resonance absorption peak in the visible region. TEM and SEM micrographs indicate that with increasing the laser fluence the average size of spherical Cu nanoparticles is decreased and only the sample which is produced with the highest fluence shows exceptional behavior. It is found that Cu nanoparticles exhibit photoluminescence emission with single peak due to its interband transition.     

Photo and Chemical Reduction of Copper onto Anatase‐Type TiO2 Nanoparticles with Enhanced Surface Hydroxyl Groups as Efficient Visible Light Photocatalysts

In this study, the photocatalytic efficiency of anatase‐type TiO₂ nanoparticles synthesized using the sol–gel low‐temperature method, were enhanced by a combined process of copper reduction and surface hydroxyl groups enhancement. UV–light‐assisted photo and NaBH₄‐assisted chemical reduction methods were used for deposition of copper onto TiO₂. The surface hydroxyl groups of TiO₂ were enhanced with the assistance of NaOH modification. The prepared catalysts were immobilized on glass plates and used as the fixed‐bed systems for the removal of phenazopyridine as a model drug contaminant under visible light irradiation. NaOH‐modified Cu/TiO₂ nanoparticles demonstrated higher photocatalytic efficiency than that of pure TiO₂ due to the extending of the charge carriers lifetime and enhancement of the adsorption capacity of TiO₂ toward phenazopyridine. The relationship of structure and performance of prepared nanoparticles has been established by using various techniques, such as XRD, XPS, TEM, EDX, XRF, TGA, DRS and PL. The effects of preparation variables, including copper content, reducing agents rate (NaBH₄ concentration and UV light intensity) and NaOH concentration were investigated on the photocatalytic efficiency of NaOH‐modified Cu/TiO₂ nanoparticles.     

A Novel Electrochemical Method for the Analysis of Hydrogen Peroxide with the Use of a Glassy Carbon Electrode Modified by a Prussian Blue/Copper‐Gold Bimetallic Nanoparticles Hybrid Film

A novel Prussian blue/copper‐gold bimetallic nanoparticles hybrid film modified electrode was prepared by electrochemical deposition on a glassy carbon electrode (PB/Cu‐AuNPs/GCE). Morphology and electrochemistry of this electrode were studied by UV‐vis spectroscopy, scanning electron microscopy, X‐ray diffraction, cyclic voltammetry and electrochemical impedance spectroscopy. The sensor showed significantly better electrocatalytic activity for the reduction of hydrogen peroxide in comparison with the single PB/GCE and PB/AuNPs/GCE. This was attributed to the synergistic effect of PB and Cu‐Au bimetallic nanoparticles. Also, the sensor demonstrated an overall high level of performance for the analysis of H₂O₂ in the concentration range from 0.002 to 0.84 mM.     

有序介孔硅片粒子表面的修饰及其表征

采用溶胶-凝胶的方法制备了粒径在50~300nm,具有正六边形的介孔二氧化硅片,用1,6-己二异氰酸酯(hexamethylene diisocyanate,HDI)对有序介孔硅片粒子表面进行有机化修饰,使其表面接枝能够参与反应的N=C=O活性基团。用FTIR、热重分析、TEM等分析方法对修饰后的有序介孔硅片粒子进行了表征,以确定HDI接在了有序介孔硅片粒子的表面。     

Biosynthesis,characterization, biological and photo catalytic investigations of Elsholtzia blanda and chitosan mediated copper oxide nanoparticles

Bio synthesis of nanoparticles using plant parts has gained considerable attention, given the fact that the method is green, environment friendly, cheaper, simple and involves no hazardous substances. The present study involves the green synthesis of copper oxide nanoparticles (CuO NPs) using chitosan and the aqueous leaf extract of Elsholtzia blanda, an aromatic medicinal herb. The synthesized E.blanda-chitosan mediated copper oxide nanoparticles (CPCE) and E. blanda mediated copper oxide nanoparticles (PCE) were subjected to different characterization techniques, Ultraviolet–visible (UV–Vis), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Energy Dispersive X-ray Analysis (EDAX), High Resolution Transmission Electron Microscopy (HRTEM) and Selected Area Electron Diffraction (SAED). The absorbance peaks in UV–Vis spectroscopy at 286 nm and 278 nm for CPCE and PCE respectively indicated the formation of nanoparticles. TEM and SEM employed for studying the surface morphology showed rod-like and spherical morphology bearing average size of 47.71 nm for CPCE and 36.07 nm for PCE. The antibacterial activities of the prepared nanoparticles were tested against Enterococcus faecalis, Staphylococcus aureus, Escherichia coli and Salmonella typhi by agar well diffusion method. The results indicate that CuO NPs possess effective antibacterial potential against all tested bacteria with a maximum zone of inhibition of 18 mm for Enterococcus faecalis. Antioxidant studies revealed the highest DPPH scavenging activity of 89% at 25 μg/mL concentration of the nanoparticles. The percentage of the photo catalytic degradation of Congo red was found to be 95% after 10 h.     

铜纳米粒子改性酚醛树脂的合成及其性能

利用甲醛与硫酸铜还原反应,通过添加铜晶核,控制反应液的pH和温度等条件,在酚醛树脂合成体系内原位生成了球形、粒度分布30~50 nm的铜纳米粒子,制得铜纳米粒子改性酚醛树脂,其结构和性能经红外光谱、X-射线衍射、透射电镜、热重分析和冲击试验表征。结果表明：与纯酚醛树脂相比,铜纳米粒子对酚醛树脂的耐热性和韧性有显著影响,初始分解温度提高51 ℃,冲击强度可提高约52%。     

Au nanoparticle-enhanced surface plasmon resonance sensing of biocatalytic transformations

N-(3-Aminopropyl)-N'-methyl-4,4'-bipyridinium is coupled to tiopronin-capped Au nanoparticles (diameter ca. 2 nm) to yield methyl(aminopropyl)viologen-functionalized Au nanoparticles (MPAV(2+)-Au nanoparticles). In situ electrochemical surface plasmon resonance (SPR) measurements are used to follow the electrochemical deposition of the bipyridinium radical cation modified Au nanoparticles on an Au-coated glass surface and the reoxidation and dissolution of the bipyridinium radical cation film. The MPAV(2+)-functionalized Au nanoparticles are also employed for the amplified SPR detection of NAD(+) and NADH cofactors. By SPR monitoring the partial biocatalyzed dissolution of the bipyridinium radical cation film in the presence of diaphorase (DP) NAD(+) is detected in the concentration range of 1x10(-4) M to 2x10(-3) M. Similarly, the diaphorase-mediated formation of the bipyridinium radical cation film on the Au-coated glass surface by the reduction of the MPAV(2+)-functionalized Au nanoparticles by NADH is used for the amplified SPR detection of NADH in the concentration range of 1x10(-4) M to 1x10(-3) M.     

ZnSe;Cu纳米晶/聚电解质多层膜制备和结构研究

采用分子沉积方法制备了ZnSe;Cu纳米晶/聚电解质多层膜,通过X射线光电子能谱(XPS)和透射电镜(TEM)等方法对薄膜的组成及结构进行了表征.XPS结果证实了回流处理对ZnSe;Cu微粒的表面结构以及铜离子价态的影响,从而很好地解释了经表面修饰后,微粒荧光增强的现象.TEM结果确定ZnSe;Cu的平均尺寸为3nm.X射线粉末衍射结果进一步确认ZnSe;Cu具有纤锌矿晶体结构.