均匀Fe_3O_4胶体粒子形成过程的Mssbauer研究

应用经过改进的实验方法制得均匀球状Fe_3O_4胶体粒子,通过对多种Fe_3O_4粒子的Mossbauer测量并结合化学分析,我们发现,在制备过程中,反应浓度、加液次序以及陈化时间的不同,对所生成的Fe_3O_4晶体的基本骨架与结构影响极小,而随着陈化时间的不断增加,Fe_3O_4粒子的组成将逐渐接近化学计量.以这些实验结果及文献报道为基础,本文讨论了均匀Fe_3O_4胶体粒子的形成机理.     

均匀Fe_3O_4胶体粒子形成机理 Ⅱ.低温Mssbauer谱研究

在液氮温度下,测定了均匀Fe_3O_4胶体粒子制备过程中陈化时间为1小时内的不同时间所得样品的Μssbauer谱,结果表明,γ-FeOOH为Fe_3O_4均匀胶粒形成过程的中间产物,并提出均匀Fe_3O_4胶粒的形成机理为:     

均匀球形α-Fe_2O_3胶体粒子的形成机理

在有关均匀胶体粒子的研究中,人们大多关注的是均匀胶体粒子的制备方法和实验条件的控制,其中包括溶液的组成,陈化温度和时间以及起决定作用的特殊阴离子.然而涉及其形成机理的分析很少,因为均匀胶体粒子的形成是个微观过程:成核、成长、相转变和微粒子的聚集等过程瞬息完成,难于捕捉到各个过程发生的具体时机.Sugimoto和Matijevic将含一定比例的FeSO_4,KOH和KNO_3溶液经85℃陈化制备均匀球状Fe_3O_4的实验中发现,陈化液中最初生成的Fe(OH)_2在硝酸根离子作用下经相转化生成Fe_3O_4微粒子,     

EDTA对均匀胶体粒子形成的影响

特殊阴离子是决定金属盐升温水解制备均匀胶体粒子形态的重要因素之一. EDTA的存在强烈影响三价铁盐水解产物-均匀α-Fe_2O_3和β-FeOOH胶体粒子的形态. 其影响机理是EDTA在成长中的微粒子上络合吸附和溶液中的EDTA与Fe~(3+)离子间络合反应的复合结果. 前者趋于形成较大的聚合粒子; 后者趋于形成较小粒子. 进而, 凡是能够改变EDTA络合吸附状态和吸附量的. 存在于陈化液中的一切其它阴离子均会改变EDTA的作用程度.     

Fe_3O_4/g-C_3N_4复合催化剂增强芬顿/光-芬顿和类过氧化酶反应的活性及稳定性(英文)

石墨相的氮化碳(g-C_3N_4)已被广泛用于光催化、水分解、光子检测器、电池、以及光电阴极.与其他光催化材料相比,g-C_3N_4具有价格低廉,易制备,无毒无污染等优点.此外,C_3N_4具有适宜的带隙(2.7 eV),能有效地吸收可见光.有关C_3N_4的光催化研究很多,但是其降解效率受限于电子空穴对的快速复合.因此,为了提高C_3N_4光催化反应效率,需要对其进行改性.磁铁矿(Fe_3O_4)广泛用于光催化和芬顿/光-芬顿反应.Fe_3O_4晶体具有反式尖晶石结构,其中Fe~(2+)和Fe~(3+)同时存在.研究表明,磁铁矿在酸性条件下催化效果显著,然而,它的比表面积小,随着反应时间的推移,铁离子会溶出,不利于有机物降解反应.因此,近来许多研究着重于磁铁矿复合物的制备,以提高磁铁矿的稳定性及催化性能.本文通过惰性氛围高温焙烧三聚氰胺制备了g-C_3N_4,再通过氯化铁和乙酸钠在乙醇中于180°C溶剂热反应,制备Fe_3O_4纳米粒子,最后通过静电自组装过程制备出Fe_3O_4/g-C_3N_4纳米复合材料.利用X射线衍射(XRD),扫描电子显微镜(SEM)及X射线光电子光谱(XPS)等手段验证其组成和结构.XRD结果表明,Fe_3O_4/g-C_3N_4复合材料中可以清晰看到Fe_3O_4和g-C_3N_4的衍射峰,说明这两种材料的晶相得以保持.SEM和TEM结果表明,Fe_3O_4纳米颗粒很好地附着在g-C_3N_4薄片上.XPS结果表明,氮化碳中存在典型的三种N峰;此外还存在铁的两种价态.光-芬顿活性测试中,相同条件下,Fe_3O_4/g-C_3N_4在60 min内将罗丹明B(RhB)几乎降解完全,而单组份的Fe_3O_4或g-C_3N_4对RhB的降解小于50%.可见,复合后的Fe_3O_4/g-C_3N_4光催化性能得到很大提升.单g-C_3N_4本身由于快速的电子空穴复合以及对双氧水的弱亲和力,因而对Rh B降解效果差.单独的Fe_3O_4由于在中性或者碱性条件下反而会抑制光催化芬顿活性.对于制备的Fe_3O_4/g-C_3N_4复合材料,具有以下优点:(1)电子在Fe~(3+)和g-C_3N_4的LUMO轨道上的转移降低了电子-空穴对的复合;(2)Fe_3O_4均匀分布在g-C_3N_4上,对于H_2O_2的吸附提供了有利的高比表面积;(3)Fe_3O_4和g-C_3N_4之间的界面相互作用使得Fe_3O_4的稳定性提高.通过降解RhB的动力学研究,得到反应速率为0.02 min~(–1),属准一级反应.分析检测结果表明,光-芬顿反应后,RhB分子被彻底矿化降解,没有中间产物生成,最终降解为CO_2和水.同时,通过对辣根过氧化物酶(HRP)模拟催化进行测试,以3,3',5,5'-四甲基联苯胺盐酸盐(TMB)作为基质,同时添加双氧水和Fe_3O_4/g-C_3N_4,在pH值为4.5条件下,TMB可以被有效氧化.实验表明,Fe_3O_4/g-C_3N_4添加量为25 mg/ml时,对TMB氧化性能最佳.复合催化剂还用于多巴胺的催化氧化反应.结果表明,多巴胺的氧化反应速率常数为1.21 min~(–1),属一级动力学反应.总之,复合材料提高了Rh B的光催化降解活性和稳定性;对TMB和HRP亲和性好,表现出高的类过氧化酶反应活性;有效的多巴胺氧化反应表明其有望用于生物基氧化反应中.实验结果表明,本文发展的Fe_3O_4/g-C_3N_4复合材料为其他类型复合材料的制备与应用提供了新的思路.     

均匀铁氧化物（含水）胶体粒子的制备

均匀胶体具有广阔的应用前景,开展这种胶体的研究具有重要的理论和实际意义。铁氧化物(含水)均匀胶体粒子首先在Matijevi’c的实验室制得。不久前,我们在无防尘设备的一般实验室条件下成功地制得了二种直径为0.090μm的球状α-Fe_2O_3胶体粒子,并开展了均匀胶体的性质研究。为了进一步开展均匀胶体特性及其表面性质的研究,就要制取不同大小和不同形状的胶体粒子,并掌握其制备规律。本文旨在探讨制备铁氧化物胶体粒子对反应液铁离子的浓度、盐酸量以及陈化时间等因素对粒子物相、形状等的影响。     

ATP适体接枝Fe_3O_4纳米粒子的制备及化学发光酶检测应用

制备了油酸修饰的Fe_3O_4纳米粒子,利用盐酸多巴胺对其表面进行氨基化改性,制得水分散性良好的Fe_3O_4纳米粒子,用X射线衍射、透射电镜、傅里叶变换红外光谱仪、振动样品磁强计和紫外-可见吸收光谱进行表征。随后,将氨基修饰的三磷酸腺苷(ATP)适体接枝到Fe_3O_4纳米粒子上,结合荧光素酶化学发光法进行ATP的定量检测,并应用于市售酸奶中乳酸菌ATP含量的检测,其灵敏度高、重现性好。各项实验结果表明所制备的Fe_3O_4纳米粒子是一种分散性好、易分离的载体,其粒径均一、稳定、磁性强、与适体结合性能好,拓展了Fe_3O_4纳米粒子在分析检测领域的应用。     

影响Fe3O4超微粒子性能因素的研究

超微Fe_3O_4粒子正在广泛地应用到磁流体和催化等领域。化学共沉淀法制备Fe_3O_4是将碱液滴入一定温度的Fe~(2+)、Fe~(3+)混合液中。反应式为Fe~(2+)+2Fe~(3+)+8OH~-=Fe_3O_4+4H_2O。本文研究了Fe_3O_4超微粒子的磁性、粒度与工艺条件的关系。 1 实验 配制一定浓度的FeCl_2和FeCl_3溶液,按一定比例混合并置于三颈瓶中恒温。搅拌后,缓     

PEI改性磁性壳聚糖微球的制备及其对布洛芬的吸附性能

采用共沉淀法制备磁性Fe_3O_4纳米粒子,然后在乳化体系中,以戊二醛为交联剂,通过席夫碱反应制备了改性磁性壳聚糖微球(Fe_3O_4@CS)以及聚乙烯亚胺(PEI)改性磁性壳聚糖微球(Fe_3O_4@CS/PEI)。采用红外光谱、X射线粉末衍射、磁滞回线测定、扫描电子显微镜和动态光散射对微球的结构、粒径以及磁性进行了表征,通过紫外-可见分光光度计研究了微球对布洛芬的吸附能力和重复利用率。结果表明,在微球制备过程中发生的席夫碱反应不会对纳米Fe_3O_4的晶型产生影响。微球均呈现出规整的球形,分布较窄,且具有一定的磁响应性,对布洛芬的吸附模型符合Langmuir吸附等温模型和二级动力学模型。随着PEI用量的增加,微球对布洛芬的吸附能力增强,经Langmuir吸附方程拟合的最大吸附量为138.63 mg/g。同时,微球具有良好的重复使用效率,重复5次后仍能达到初始吸附量的90%以上。     

均匀Fe3O4胶体粒子形成过程的Mossbauer研究

应用经过改进的实验方法制得均匀球状Fe3O4胶体粒子, 通过对多种Fe3O4粒子的Mossbauer测量并结合发析, 我们发现, 在制备过程中, 反应浓度、加液次序以及陈化时间的不同对所生成的Fe3O4晶体的基本骨架与结构影响极小, 而随着陈化时间的不断增加, Fe3O4粒子的组成将逐渐接近化学计量, 以这些实验结果及文献报道为基础, 本文讨论了均匀Fe3O4胶体粒子的形成机理。     

Unraveling the origin of band shapes in infrared spectra of N2O-12CO2 and 12CO2-13CO2 ice particles

Band structures in the region of strong infrared absorption bands for different N2O-12CO2 and 12CO2-13CO2 composite particles are investigated by combining quantum mechanical exciton calculations with systematic experimental investigations. The ice particles are generated by collisional cooling and characterized with rapid-scan infrared spectroscopy. The size of the particles lies between approximately 10 and 100 nm. The calculated spectra show excellent agreement with the experimental data. This work leads to a detailed understanding on a molecular level of shape effects in pure and statistically mixed particles as well as of the characteristic features observed for core-shell particles.     

Autostratification in drying colloidal dispersions: effect of particle interactions

When particles differing in size or charge are mixed and cast, vertical segregation is an inevitable phenomenon in the produced films. Apart from the Peclet number, which is the ratio of evaporation to diffusion rates, particle interactions play a crucial role in determining the distribution of particles in the dried films. Trueman et al. (1) developed a model for vertical segregation of particles during drying. Their numerical solution assumed that the chemical potentials were determined entirely by entropy. We report the effect of particle interactions in various systems: (i) charged particles with different Peclet numbers and (ii) charged particles with the same Peclet numbers. An experimental study has also been carried out for particles with Peclet numbers straddling unity; the experimental results conform with the behavior predicted theoretically.     

Effect of particle shape on crossflow filtration flux

In an effort to further increase the understanding of crossflow filtration, experiments were performed on the influence of particle shape on permeation flux. Five particles of similar density and size distribution but of different shapes were used to test the influence of particle shape, while varying experimental parameters such as crossflow velocity, filtration pressure, solids concentration, membrane morphology and pore size. Particle shape was found to influence the equilibrium flux by the structure of the cake layer formed. Irregularly shaped particles such as branched carbon particles provided higher fluxes due to the high voidage cakes. More regularly shaped particles such as glass spheres resulted in lower fluxes. Platelet aluminium particles had relatively high filtration rates due to the gaps between the plates. The effects of the other experimental parameters typically showed results consistent with previous publications. Using the measured cake mass, a theoretical model based on D'Arcy and Kozeny gave reliable filtration flux compared to the experimental results.     

Influence of surface properties of particles on their adhesion and removal

The effect of surface properties of particles on their adhesion and removal was investigated using an immersed system consisting of nylon particles and a quartz plate. The nylon particles were dyed with a reactive dye in order to change their properties and were used for the adhesion and removal experiments in comparison with undyed particles. The electrokinetic potentials of the particles were measured by micro-electrophoresis and the Hamaker constants were independently evaluated using experimental values of dispersive component of surface free energy determined by the Wilhelmy technique. The experimental results were used for the discussion of particle adhesion and removal on the basis of the heterocoagulation theory. The differences in adhesion and removal efficiencies between dyed and undyed particles were explained in terms of the electrostatic and dispersive van der Waals interaction by considering the differences in thier properties, the electrokinetic potential and the Hamaker constant, due to dyeing.     

Influence of particle coating on dynamic mechanical behaviors of magnetorheological elastomers

In this paper, core-shell structured poly methyl methacrylate (PMMA) coated carbonyl iron (CI) particles were prepared to study the influence of particle coating on the dynamic properties of magnetorheological elastomers (MREs). The CI-PMMA composite particles were encapsulated via an emulsion polymerization method. Two MRE samples were prepared with CI-PMMA composite particles and CI particles, respectively. Their microstructure was observed by using a scanning electron microscope (SEM). Dynamic properties of these two samples under various strain and magnetic fields were measured with a dynamic mechanical analyzer (DMA). The experimental results indicate that the MRE sample with CI-PMMA composite particles has larger storage modulus, smaller loss factor and smaller Payne effect than that of the sample with only CI particles. The analysis indicates that the use of CI-PMMA particles would increase the bond strength between particles and matrix. These experimental results were also verified by the SEM images.     

Experimental investigation of electrostatic particle-particle interactions in optoelectronic tweezers

This paper reports experimental and theoretical investigation of electrostatic attraction and repulsion of microparticles in an optoelectronic tweezers (OET). When we manipulate dielectric particles suspended in a fluid using OET, the electrostatic interactions of the polarized particles occur, limiting the effective manipulation of microparticles using a light-induced dielectrophoresis. In this study, we first demonstrate the electrostatic particle-particle interactions in the OET device using a liquid crystal display. At the same time, the experimental investigation of the dipole interactions between two spherical particles has been performed using the OET device. On the basis of the point-dipole model, simulation studies on the dipole forces acting on the particles and their trajectories by the forces are also performed. The experimental results show good agreement with the previously reported numerical studies as well as the results of our simulation studies.     

Interference of surface plasmon resonances causes enhanced depolarized light scattering from metal nanoparticles

We show that the strongly depolarized light scattering from noble metal particles is a result of interference of two surface plasmon resonances on the same particle. The maximum depolarization occurs between two resonances. Under favorable conditions the anisotropy of the scattering light can be much lower than what is possible for dielectric particles. This explanation is discussed in relation to earlier published experimental measurements. Comparison of experimental results with theoretical calculations provides information on the shape distribution of metallic particles in the suspension.     

Surface charge density and electrokinetic potential of highly charged minerals: experiments and Monte Carlo simulations on calcium silicate hydrate

In this paper, we are concerned with the charging and electrokinetic behavior of colloidal particles exhibiting a high surface charge in the alkaline pH range. For such particles, a theoretical approach has been developed in the framework of the primitive model. The charging and electrokinetic behavior of the particles are determined by the use of a Monte Carlo simulation in a grand canonical ensemble and compared with those obtained through the mean field theory. One of the most common colloidal particles has been chosen to test our theoretical approach. That is calcium silicate hydrate (C-S-H) which is the main component of hydrated cement and is known for being responsible for cement cohesion partly due to its unusually high surface charge density. Various experimental techniques have been used to determine its surface charge and electrokinetic potential. The experimental and simulated results are in excellent agreement over a wide range of electrostatic coupling, from a weakly charged surface in contact with a reservoir containing monovalent ions to a highly charged one in contact with a reservoir with divalent ions. The electrophoretic measurements show a charge reversal of the C-S-H particles at high pH and/or high calcium concentration in excellent agreement with simulation predictions. Finally, both simulation and experimental results clearly demonstrate that the mean field theory fails not only quantitatively but also qualitatively to describe a C-S-H dispersion under realistic conditions.     

Stability in Colloidal Mixtures Containing Particles with a Large Disparity in Size

An experimental approach, based on turbidity measurements, is proposed for studies of the stability in colloidal mixtures containing particles with large disparity in size. The main advantage of this approach is that it permits investigations even under conditions of comparable particle number concentrations of the two colloidal populations. Binary mixtures containing a poly(vinyl acetate) (PVAc) latex and a Ludox AS-40 silica sol were investigated. The silica particles were much smaller than the latex ones. The experimental stability factors were compared with the theoretical values computed on the basis of the Kihira-Ryde-Matijevic model (J. Chem. Soc., Faraday Trans. 88(16), 2379 (1992)) for interaction between spherical particles with unevenly distributed surface charges. All the experimental results support the idea that, even when both sols are negatively charged, the small silica particles are adsorbed onto the latex surface. Under these conditions, the heteroaggregates, which are composed of PVAc cores surrounded with silica particles, can be modeled as PVAc particles having "modified" surface characteristics (i.e., average Stern potential and varying extents of the surface charge segregation). Copyright 2001 Academic Press.