酞菁钴/铁纳米填充母粒的制备及其稳定性

采用有机/无机原位复合技术,将酞菁钴（CoPc）的DMF溶液与Fe(CO)5混合、加热回流制备出稳定的、规则球形的、平均粒径为1.4μm的酞菁钴/铁纳米填充母粒。其内部为10～15nm的μ-Fe填充,外部为厚50～150nm的酞菁钴层包覆。纳米填充母粒的填实密度为3.664g/cm3,比饱和磁化强度为76.3Am2/kg,矫顽力为4.15kA/m。纳米填充母粒的热稳定性高于150℃,与甲基硅油组成的磁流变液有良好的抗沉降性。     

酞菁钴/纳米铁复合颗粒的结构与微波电磁特性

一些铁磁性金属及其合金超细粉末,具有比饱和磁化强度高、易于合成与粒径可控等优点,因此被广泛应用于磁流体、电磁流变液、微波吸收材料等领域,但由抗氧化性差、密度较大等主要缺点而使其应用受到限制,采用有机／无机复合技术可制备具有有机包覆层的有机／无机复合颗粒,不仅可以增强铁磁性颗粒的抗氧化性,减小了密度,而且可以提高与有机基体的亲和性,为该类材料向更高层次发展提供了可能。     

酞菁钴/SnO2纳米复合材料的原位合成及可见光光催化

酞菁钴/SnO2纳米复合材料的原位合成及可见光光催化;SnO2;酞菁钴;纳米复合材料;原位合成;光催化     

碳纳米纤维增强钴酞菁催化氧化染料的性能研究

将氨基钴酞菁（CoTAPc）以共价键的形式负载到碳纳米纤维（CNF）上制备碳纳米纤维负载钴酞菁催化剂（CoTAPc-CNF）,利用原子吸收光谱、紫外-可见光吸收光谱、衰减全反射-红外光谱等方法对CoTAPc-CNF进行表征.选用具有氧杂蒽结构的罗丹明6G（Rh6G）为主要研究对象,研究CoTAPc-CNF对Rh6G的催化氧化性能,考察了温度、pH、NaCl、异丙醇等对CoTAPc-CNF催化性能的影响.结果表明,CoTAPc-CNF在常温中性条件下能有效催化氧化Rh6G;随着温度和pH的增加,CoTAPc-CNF催化氧化Rh6G速率逐渐提高;NaCl和异丙醇的加入,没有抑制催化氧化反应的进行,相反大大提高了Rh6G的降解速率,这与一般羟基自由基占主导的高级氧化体系完全不同;进一步采用电子顺磁共振波谱法证实CoTAPc-CNF/H2O2体系确实为非羟基自由基催化机理.另外,研究发现CoTAPc-CNF还能有效催化氧化其他共轭结构的染料,如偶氮染料酸性橙7（AO7）、三芳甲烷染料碱性绿1（BG1）.因此,本文探索的CoTAPc-CNF/H2O2非羟基自由基催化反应体系在处理成分复杂的实际印染废水中具有较好的应用前景.     

新型钴酞菁接枝温敏聚合物的制备及性能

采用2,4,6-三氯-1,3,5-三嗪对四氨基钴酞菁进行改性,并以共价键接枝到聚N-异丙基丙烯酰胺上制得一种新型温敏性高分子催化剂——钴酞菁接枝温敏聚合物,并采用UV-Vis、TG等对其进行表征.对钴酞菁接枝温敏聚合物、温敏聚合物和小分子金属酞菁进行溶解性测试,结果表明与四氨基钴酞菁相比,所合成的钴酞菁接枝温敏聚合物能溶解于水和大多数有机溶剂,且该聚合物水溶液具有良好的温敏性,其最低临界溶解温度(LCST)为34.5℃.采用浊度法考察了不同比例的混合溶剂(乙醇/水、DMF/水)对LCST的影响,结果表明随着有机溶剂含量的增加,LCST先下降后升高,而当有机溶剂增加到一定程度时温敏性消失.本文还考察了钴酞菁接枝温敏聚合物对2-巯基乙醇的催化活性,结果表明随着温度升高,催化活性也不断提高,而当温度超过LCST时催化活性急剧下降,聚合物从溶液中析出.基于这些特性,该温敏聚合物负载酞菁作为一种新型的催化剂可实现均相催化、异相分离.     

棒状薄层色谱/氢火焰法分析磺化酞菁钴的组成

研究建立了一种采用棒状薄层色谱／氢火焰离子检测（TLC／FID）对磺化酞菁钴组成进行定性、定量分析的方法。用薄层色谱并结合质谱分析 表明工业磺化酞菁钴中含有一磺化酞菁钴的两种同分异构体,二磺化酞菁钴的5种同分异构体及三磺化酞菁钴;用棒状薄层色谱／氢离子火焰检测方法可以对磺化酞菁钴中各组分进行定量分析。该方法操作简便,测定时间短,灵敏度高,可用于磺化酞菁钴工业合成的产品质量控制。     

钴铁双金属氧化物多孔纳米棒的制备及其电解水析氧性能

通过简单的钴铁前躯体热分解法制备了系列一维Co_(1-x)Fe_xO_y(0≤x≤1)多孔纳米材料,并在1 mol·L~(-1) KOH溶液中研究了其电解水析氧催化性能。研究发现不同Fe掺杂量对材料的结构与电解水析氧催化性能有较大的影响,其中16%(n/n)Fe掺杂量的Co_(1-x)Fe_xO_y具有最优的析氧催化性能。在10 m A·cm~(-2)电流密度下其析氧过电位为345 mV,塔菲尔斜率为54 mV·dec~(-1),并表现出优异的析氧稳定性能。廉价、高效的Co_(1-x)Fe_xO_y多孔纳米棒材料有望成为优良的析氧催化剂用于电解水制氢。     

钴铁双金属氧化物多孔纳米棒的制备及其电解水析氧性能

通过简单的钴铁前躯体热分解法制备了系列一维Co_1-xFe_xO_y（0≤x≤1）多孔纳米材料,并在1 mol·L^-1 KOH溶液中研究了其电解水析氧催化性能。研究发现不同Fe掺杂量对材料的结构与电解水析氧催化性能有较大的影响,其中16%（n/n）Fe掺杂量的Co_1-xFe_xO_y具有最优的析氧催化性能。在10 mA·cm^-2电流密度下其析氧过电位为345 mV,塔菲尔斜率为54 mV·dec^-1,并表现出优异的析氧稳定性能。廉价、高效的Co_1-xFe_xO_y多孔纳米棒材料有望成为优良的析氧催化剂用于电解水制氢。     

AHOT/异辛烷反胶束体系制备铁酸钴纳米粒子

分别以阴离子表面活性剂二(2-乙基己基)丁二酸酯磺酸钠(AOT)和新型表面活性剂二(2-乙基己基)羟基丁二酸酯磺酸钠(AHOT)与异辛烷/水构建的反胶束体系为微反应器,合成了CoFe2O4纳米粒子;利用TGA,XRD,TEM等手段对产物进行了表征;讨论了两种表面活性剂构建的反胶束体系对产物合成过程及纳米粒子形貌和尺寸的影响.     

新型水溶性钴酞菁的制备及其催化氧化硫醇的性能

采用丁二酸酐、顺丁烯二酸酐对四氨基钴酞菁进行改性后制得两种新型水溶性钴酞菁衍生物, 测试了这两种改性钴酞菁对巯基乙醇的催化氧化性能, 并考察了溶液pH值、温度和时间对催化氧化活性的影响, 结果表明, 在pH＝11时, 两种改性钴酞菁对巯基乙醇的催化氧化性能最好;随着温度的升高, 催化氧化性能提高.     

Electrodynamics of Noble Metal Nanoparticles and Nanoparticle Clusters

In this paper we examine the electrodynamics of silver nanoparticles and of clusters of nanoparticles, with an emphasis on extinction spectra and of electric fields near the particle surfaces that are important in determining surface-enhanced Raman (SER) intensities. The particles and clusters are chosen to be representative of what has been studied in recent work on colloids and with lithographically prepared particles. These include spheres, spheroids, truncated tetrahedrons, and clusters of two or three of these particles, with sizes that are too large to be described with simple electrostatic approximations but small compared to the wavelength of light. The electrodynamics calculations are mostly based on the discrete dipole approximation (DDA), which is a coupled-finite element approach which produces exact or nearly exact results for particles of arbitrary size and shape if fully converged. Mie theory results are used to study the validity of the DDA for spherical particles, and we also study the validity of the modified long wavelength approximation (MLWA), which is based on perturbative corrections to the electrostatic limit, and of the single dipole per particle approximation (SDA). The results show how the dipole plasmon resonance properties and the electric field contours around the particle vary with particle shape and size for isolated particles. For clusters of particles, we study the effect of interparticle spacing on plasmon resonance characteristics. We also show that the quadrupole resonance is much less sensitive to particle shape and interparticle interactions than the dipole plasmon resonance. These results provide benchmarks that will be used in future comparisons with experiment.     

Span/Tween混合表面活性剂微乳液制备纳米铁及脱硝研究

研究了以Span 80和Tween 60为混合表面活性剂的微乳液的形成。以电导率及目测法为表征手段,利用正交试验,分析了多因素对W/O型微乳液最大增容水量的影响,探明了该乳液形成的适宜条件。     

Extraction of Substance P by Functionalized Iron Oxide Nanoparticles for Matrix‐Assisted Laser Desorption/Ionization Mass Spectrometric Analysis

Functionalized iron oxide nanoparticles (IONPs) were used as concentrating probes to extract substance P (SP) from aqueous solution before matrix‐assisted laser desorption/ionization mass spectrometric (MALDI/MS) analysis. Adsorption of SP onto the nanoparticles was mainly due to electrostatic interaction. After simple washing, the SP‐adsorbed nanoparticles were directly analyzed by MALDI/MS. With this concentration strategy, the limit of detection (LOD) of SP in 500 μL buffer solution (pH 8) was 0.1 nM. In addition, the nanoparticles could isolate SP from a solution with high contents of salts and surfactants, thus alleviating suppression effect during MALDI/MS analysis. This new method was successfully applied to the determination of SP in rat spinal cord samples. The LOD and recovery of SP in a rat spinal cord sample were 3.1 nM and 85.7%, respectively.     

Electrochemical Detection of Positively Charged Carbon Nanoparticles Suspension in Flow

The electrochemical behaviour of suspended nanoparticles received some attention recently. Very few studies are performed in the flow system. Here, we have demonstrated that injection of positively charged (with ammonium functionalities) carbon nanoparticles suspension to flowing ascorbic acid solution significantly enhances its chronoamperometric response and can be used for these nanoparticles detection. This is because of electrocatalytic properties of these nanoparticles towards ascorbic acid electrooxidation. The magnitude of the signal depends on the type of flow system and is larger than in the case of suspension of negatively charged nanoparticles. It is also proportional to the concentration of nanoparticles. Their adsorption on the electrode surface plays the crucial role in the electrode process.     

Study of ITO Glass Electrode Modified with Iron Oxide Nanoparticles and Nafion for Glucose Biosensor Application

In this study, we report the fabrication of the indium tin oxide (ITO) glass electrode modified with iron oxide nanoparticles (IONPs) and nafion for glucose biosensor applications. The IONPs was synthesized using the precipitation method and functionalized with citric acid (CA) to provide hydrophilic surface and functional group for glucose oxidase (GOx) enzyme immobilization. The structural and morphological studies of CA-IONPs were characterized using X-ray diffractometer (XRD) and transmission electron microscope (TEM). The size of the IONPs measured from TEM image was ∼17 nm. The bioelectrode designated as Nafion/GOx/CA-IONPs/ITO was developed by drop casting of the CA-IONPs, GOx and nafion on the ITO glass. The Nafion/GOx/CA-IONPs/ITO bioelectrode showed good electrochemical performance for glucose detection. The functionalized CA-IONPs acted as the catalyst and help to improve the electron transfer rate between GOx and ITO electrode. In addition, thin nafion film was coated on the electrode to prevent interference and improve chemical stability. The Nafion/GOx/CA-IONPs/ITO bioelectrode showed high sensitivity of 70.1 μAmM^-1cm^-2 for the linear range of 1.0-8.0 mM glucose concentrations.     

锰/磷、钛/磷二元团簇的激光溅射产生与光解

利用激光溅射法直接产生了锰/磷、钛/磷二元团簇正、负离子MxPy±(M=Mn、Ti),并用串级飞行时间质谱仪研究了团簇离子的组成与激光光解规律.实验表明钛与磷间成簇的能力强于锰与磷间成簇的能力,且MPy+(M=Ti、Mn)团簇离子系列表现出峰强度随所含磷原子数目的奇偶性变化,这可能与P4结构的特殊稳定性有关.激光光解实验表明,失去中性P2、P4的通道为主要光解通道.随着团簇离子的生长,锰/磷团簇正离子逐渐由富磷簇向富金属簇过渡,钛/磷则趋向于形成钛原子数目与磷原子数目接近相等的团簇正离子,而二者与磷形成的团簇负离子MxPy-(M=Mn、Ti)逐渐趋向于x≈y,随样品中磷含量增加,锰/磷易形成富磷簇,钛/磷的组成趋向不改变.     

Synthesis,Characterization, and X‐ray Crystal Structure of Macrocyclic Nickel/Iron/Sulfur Cluster Complexes

A series of macrocyclic Ni/Fe/S cluster complexes were synthesized and structurally characterized. The macrocyclic type of (diphosphine)Ni‐bridged double butterfly Fe/S complexes [μ‐SCH₂CH₂OCH₂CH₂S‐μ][(μ‐S=CS)Fe₂(CO)₆]₂‐[Ni(diphosphine)] ( 1 – 3 ; diphosphine = dppe, dppv, dppb) were prepared by treatment of the dianion [{μ‐SCH₂CH₂OCH₂CH₂S‐μ}{(μ‐CO)Fe₂(CO)₆}₂]^2–, generated in situ from Fe₃(CO)₁₂, Et₃N, and HSCH₂CH₂OCH₂CH₂SH with excess CS₂ followed by treatment of the resulting dianion [{μ‐SCH₂CH₂OCH₂CH₂S‐μ}{(μ‐SC=S)Fe₂(CO)₆}₂]^2– with (diphosphine)NiCl₂. The three complexes 1 – 3 were characterized by elemental analysis and IR, ¹H NMR, and ³¹P NMR spectroscopy. In addition, the molecular structures of 2 and 3 were established by X‐ray crystallography.     

Photochemical Synthesis,Spectral-Optical and Electrophysical Properties of Composite Nanoparticles of ZnO/Ag

The photochemical synthesis of nanoparticles of ZnO/Ag in isopropanol solutions has been carried out. Their optical properties have been studied and the parameters of the plasma resonance of the nanoparticles of silver in the ZnO/Ag composites have been calculated. It has been established that the hypsochromic shift of the plasma band of silver observed on irradiation of the nanocomposite is a result of accumulation of excess electrons on the ZnO/Ag particles which leads to equalization of the potentials of the conductions zones of the semiconductor and the metallic components of the nanocomposite.     

Preparation of Highly Dispersed Supported Metal Catalysts via Solvated Metal Atom Impregnation ( V) --The Effects of Hydroxyl Group on the Surface Concentrations of SiO2 on the Properties of Supported Fe Clusters

Two kinds of small iron clusters supported on SiO2-200 (dehydroxylated at 200℃ and SiO2-600 (de-hydroxylated at 600℃) were prepared by Solvated Metal Atom Impregnation (SMAI) techniques. The iron atom precursor complex, bis (toluene) iron(0) formed in the metal atom reactor, was impregnated into SiO2 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by THM, Mosbauer and chemisorption measurements, and the resules show that higher concentration of surface hydroxyl groups of SiO2-200 favours the formation of more positively charged support iron cluster Fen/SiO2-200 and the lower concentration of surface hydroxyl groups of SiO2-600 favours the formation of basically neutral supported iron cluster Fe2/SiO2-600. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the precursor complex,bis(toluene) fron(0), to d