单分散双相可溶四氧化三铁纳米微粒的多醇法制备及磁性

以具有生物相容性的三嵌段共聚物聚氧乙烯-聚氧丙烯-聚氧乙烯为表面活性剂,利用多醇合成法制备了Fe3O4纳米微粒;采用X射线粉末衍射仪、傅立叶变换红外光谱仪及透射电子显微镜分析了Fe3O4纳米微粒的晶体结构、化学结构及显微结构,采用振动样品磁强计测定了其磁性能.结果表明,所制得的Fe3O4磁性纳米微粒结晶度高,在室温下显示近似超顺磁性.采用Langevin方程对Fe3O4纳米微粒的磁滞回线进行拟合,结果显示其为磁性单畴.此外,Fe3O4磁性纳米微粒在无机和有机溶剂中均具有很好的分散性,显示出广阔的应用前景.     

Fe_3O_4/SiO_2/PMMA磁性纳米粒子的制备及其磁性能

通过沉淀氧化法制得Fe3O4磁性粒子(1);通过Stber法用Si O2对Fe3O4进行表面改性制得Fe3O4/Si O2磁性纳米粒子(2);通过原子转移自由基聚合法将聚甲基丙烯酸甲酯(PMMA)接枝到2上,制得Fe3O4/Si O2/PMMA磁性高分子纳米粒子(3),其结构和磁性能经IR,扫描电镜(SEM),透射电镜(TEM),磁性分析(VSM)和热重分析(TGA)表征。结果表明,3的粒径小且磁性强,平均粒径约为220 nm,饱和磁化强度为44.3 emu·g-1,室温下具有超顺磁性。     

叶酸对磁性Fe_3O_4纳米粒子的表面修饰

以FeCl3·6H2O作为单一铁源,1,6-己二胺作为胺化试剂,利用无模板的溶剂热方法制备了胺基功能化的磁性Fe3O4纳米粒子,并利用其键合叶酸分子,制备出表面修饰了叶酸的磁性Fe3O4复合纳米粒子。利用傅里叶变换红外光谱仪、X-射线衍射仪、透射电镜、差热-热重分析仪和振动样品磁强计对所得纳米粒子的形貌、粒径、化学组成和磁性能进行了表征。结果表明,叶酸分子通过化学键牢固键合在磁性纳米Fe3O4粒子表面,叶酸修饰的复合纳米粒子仍然具有良好的磁性能。     

磁性Fe3O4纳米晶的电化学制备及在线混凝过程研究

以铁片和碳纤维为电极,采用电化学法实现了磁性Fe3O4纳米晶混凝剂的快速制备、在线混凝和磁性过滤的预处理过程.采用X射线衍射仪(XRD)和扫描电子显微镜(SEM)等对磁性Fe3O4纳米晶进行了表征.结果表明,所制备的磁性Fe3O4纳米晶具有均匀的晶体尺寸,粒子尺寸分布在30~100 nm之间.利用Fe3O4纳米晶对高浊度高岭土悬浊液进行了混凝研究,并在外加磁场的作用下实现了絮凝体和水体的快速分离.结果证实电化学法磁混凝技术能够快速高效去除污水浊度,省去了机械过滤过程.理论研究结果表明,磁性Fe3O4纳米晶去除浊度的过程是电荷中和与沉淀卷扫共同作用的结果,而电荷中和过程发生是由于电化学制备Fe3O4纳米晶时表面电荷种类的均一性.     

超顺磁性高分子微球的制备与表征

用化学共沉淀方法制备了Fe3O4纳米微粒,并用油酸(十八烯酸)和十二烷基苯磺酸钠为双层表面活性剂进行表面修饰,制备了稳定的水分散性纳米Fe3O4可聚合磁流体.在Fe3O4磁流体存在下,将苯乙烯与甲基丙烯酸通过乳液聚合方法制备了磁性高分子微球.透射电镜研究表明,Fe3O4微粒的平均粒径在10nm左右,乳液聚合形成的磁性高分子微球的粒径平均约为130nm;用超导量子干涉仪对微粒及高分子微球进行了磁性表征,结果表明,合成的Fe3O4纳米微粒以及磁性高分子微球均具有超顺磁性.同时,还用红外光谱及X射线衍射表征了磁性高分子微球的化学成分和晶体结构.用热失重方法测得磁性高分子微球中磁性物质的含量为23.6%.     

Fe3O4表面原位引发可控/“活性”聚合制备磁性聚苯乙烯纳米粒子

采用化学共沉淀方法合成了Fe3O4纳米粒子, 用3-甲基丙烯酰氧基丙基三甲氧基硅烷(3-MPS)对其进行表面接枝修饰, 然后以苯乙烯(St)为单体, 过氧化苯甲酰(BPO)为引发剂, 4-羟基-2,2,6,6-四甲基哌啶-1-氧化物自由基(HTEMPO·)为稳定自由基介质, 采用可控/“活性”自由基聚合技术在修饰后的Fe3O4纳米粒子表面原位引发聚合, 制备了粒径小、分布窄、磁含量高的磁性聚苯乙烯（PS）纳米粒子. X射线衍射(XRD)研究表明, 所合成的Fe3O4粒子为尖晶石结构. 凝胶渗透色谱(GPC)分析表明, 聚苯乙烯的分子量与反应时间呈较好的线性关系. 透射电镜(TEM)观察表明, 所制备的磁性聚苯乙烯纳米粒子的粒径在20-30 nm之间. 热重(TG)分析得到磁性聚苯乙烯纳米粒子的磁含量为62.6%. 振动样品磁强计(VSM)测试结果表明, 磁性聚苯乙烯纳米粒子的比饱和磁化强度为31.7 emu·g-1, 呈现单磁畴结构.     

聚丙烯酰胺修饰Fe_3O_4磁性纳米粒子的制备与表征

首先通过化学处理在Fe3O4磁性纳米粒子表面引入Si—H键,然后通过选择性的硅氢加成反应制备了一个端基带溴的磁性引发剂,并利用原子转移自由基聚合(ATRP)技术,在该磁性引发剂表面接枝了聚丙烯酰胺高分子,该聚丙烯酰胺高分子展现出分子量高度可控性和窄的分子量分布.经聚丙烯酰胺修饰后Fe3O4磁性纳米粒子的比饱和磁化强度为58.5 emu.g-1,与未修饰纳米Fe3O4相比下降约20%.     

原子转移自由基聚合法制备表面聚合物接枝四氧化三铁纳米粒子

为制备表面具有柔性高分子链的磁性微球,采用化学共沉淀法制备了具有超顺磁性的Fe3O4纳米微球,用KH550对Fe3O4纳米微球进行化学改性得到表面氨基化的Fe3O4纳米微球,与2-溴代异丁酰溴反应后制得含有引发官能团的Fe3O4纳米微球,随后将含溴的Fe3O4纳米微球与小分子单体与之通过原子转移自由基聚合(ATRP)法共聚。测试结果表明聚合物链成功地接枝到了Fe3O4纳米微球表面。     

链霉亲和素-异硫氰酸荧光素偶联核壳型Fe_3O_4/Au纳米晶的合成及性质

采用改进的Polyol合成法,以PEO-PPO-PEO为表面活性剂制备了链霉亲和素-异硫氰酸荧光素偶联的Fe3O4/Au纳米粒子;利用透射电镜和X射线衍射仪分析证实了Fe3O4/Au的核壳型纳米结构,确定了其粒径和分布;采用紫外-可见吸收光谱仪和荧光光谱仪测定了所制备的纳米粒子的光学活性和荧光特性,并采用振动样品磁强计(VSM)测量了其磁化率.结果表明,所制备的Fe3O4/Au纳米粒子具有光学活性和荧光特性,以及优异的磁性.     

表面含羧基的交联磁性高分子复合微球的合成

首先用化学共沉淀法制备了Fe3O4纳米微粒,并对其表面进行改性。然后在分散介质水中,以二乙烯基苯(DVB)为交联剂,采用改进的乳液聚合法,制备了磁性Fe3O4为核、苯乙烯和丙烯酸的共聚物为壳的交联复合微球,并利用FT-IR、TEM、XRD和XPS等对其进行表征。结果表明:该复合微球的粒度分布均匀、表面含有一定羧基,为单分散性、表面功能化的交联磁性高分子纳米复合微球。     

Correlation between spin-orbital coupling and the superparamagnetic properties in magnetite and cobalt ferrite spinel nanocrystals

The superparamagnetic properties of CoFe2O4 and Fe3O4 nanocrystals have been systematically investigated. The observed blocking temperature of CoFe2O4 nanocrystals is at least 100 deg higher than that of the same sized Fe3O4 nanocrystals. The coercivity of CoFe2O4 nanocrystals at 5 K is over 50 times higher than the same sized Fe3O4 nanocrystals. The drastic difference in superparamagnetic properties between the similar sized spherical CoFe2O4 and Fe3O4 (or FeFe2O4) spinel ferrite nanocrystals was correlated to the coupling strength between electron spin and orbital angular momentum (L-S) in magnetic cations. Compared to the Fe2+ ion, the effect of much stronger spin-orbital coupling at Co2+ lattice sites leads to a higher magnetic anisotropy and results in the dramatic discrepancy of superparamagnetic properties between CoFe2O4 and Fe3O4 nanocrystals. These results provide some insight to the fundamental understanding of the quantum origin of superparamagnetic properties. Furthermore, they suggest that it is possible to control the superparamagnetic properties through magnetic coupling at the atomic level in spinel ferrite nanocrystals for various applications.     

Fe3O4 nanocrystals with novel fractal

Fe3O4 novel fractal nanocrystals have been synthesized by a surfactant-assisted solvothermal process for the first time. X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), M?ssbauer spectroscopy (MS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) have been used to investigate the novel fractal nanocrystals. The lengths of the fractals are about 2-3 microm, and the trunks and branches of Fe3O4 fractals have almost the same diameters of ca. 30-50 nm. The roles of surfactant PEG-20000 and N2H4 have been discussed in detail. One key fact has been found that the ferrocene concentration has a vital effect on the morphologies of the products. The side-branching process and the oscillation of the concentration have been proposed to illustrate the formation mechanisms of the fractal nanocrystals. In addition, magnetic properties of Fe3O4 fractal nanocrystals have also been detected by a vibrating sample magnetometer, showing relatively high saturation magnetization (Ms) of ca. 78.75 emu/g.     

Gelification: an effective measure for achieving differently sized biocompatible Fe3O4 nanocrystals through a single preparation recipe

Biocompatible Fe(3)O(4) nanocrystals were synthesized through the pyrolysis of ferric acetylacetonate (Fe(acac)(3)) in diphenyl oxide, in the presence of α,ω-dicarboxyl-terminated polyethylene glycol (HOOC-PEG-COOH) and oleylamine. Unusual gelification phenomena were observed from the aliquots extracted at different reaction stages after they were cooled to room temperature. By reaction time, the average size of the Fe(3)O(4) nanocrystals was tuned from 5.8 to 11.7 nm with an equilibrium size around 11.3 nm. By increasing the gelification degree of the stock solution, the equilibrium size of the Fe(3)O(4) nanocrystals was further increased from 11.3 to 18.9 nm. The underlying gel formation mechanism was investigated by using ultraviolet-visible absorption spectroscopy and Fourier transform infrared spectroscopy. The results suggest that the complexation between HOOC-PEG-COOH and Fe(acac)(3), with the help of oleylamine, results in large molecular networks, which are responsible for the gelification of the stock solution, while the interaction between the fragment of the molecular network and Fe(3)O(4) nanocrystal is responsible for the second gelification process observed during the early stage of reflux. To further investigate the particle growth behavior, small molecules released during the preparation were collected and analyzed by using photoelectron spectroscopy/photoionization mass spectroscopy (PES/PIMS). It was demonstrated that the pyrolysis of the Fe precursor is strongly correlated with the particle growth process. Further numerical simulations reveal that the first gelification process induced by the complexation between HOOC-PEG-COOH and Fe(acac)(3) largely alters the pyrolysis behavior of the Fe precursor; consequently, the equilibrium size of the resultant Fe(3)O(4) nanocrystals can effectively be tuned by the gelification degree of the stock solution.     

Controlled synthesis of magnetic Pd/Fe3O4 spheres via an ethylenediamine-assisted route

A simple route based on time-dependent growth was employed to synthesize solid and hollow spheres of Pd/Fe(3)O(4) nanocomposite. Transmission electron microscopic (TEM) imaging shows that the spheres are composed of nanocrystals with the solid spheres having a diameter of 533 nm whereas the hollow ones having a diameter of 520 nm and a shell thickness of 100 nm. An assembly-then-growth mechanism for the formation of the magnetic Pd/Fe(3)O(4) nanocomposite has also been elucidated on the basis of the experimental observations. It is demonstrated that the Pd/Fe(3)O(4) nanocomposite functions as a heterogeneous catalyst for the hydrogenation reaction of p-nitrophenol at room temperature under atmospheric pressure. Both the solid and hollow spheres possess unique magnetic properties so that they may be conveniently separated and recovered by a magnet after the catalytic reaction.     

Understanding of the finite size effects on lattice vibrations and electronic transitions of nano alpha-Fe2O3

Alpha-Fe(2)O(3) nanocrystals with controlled diameters ranging from 10 to 63 nm were successfully prepared. The finite size effects in alpha-Fe(2)O(3) nanocrystals were probed by X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, UV-visible spectrum, and magnetization measurements. With a size reduction, alpha-Fe(2)O(3) nanocrystals showed a lattice expansion and an enlarged axial ratio of c/a that is in apparent contradiction to the previous conjecture of high lattice symmetry for alpha-Fe(2)O(3) nanocrystals at small sizes. The surface terminations of alpha-Fe(2)O(3) nanocrystals were found to be highly hydrated with a size dependence that surprisingly follows the surface hydration chemistry of anatase TiO2 nanocrystals reported recently by us. The lattice vibrations, electronic transitions, and magnetic properties of alpha-Fe(2)O(3) nanocrystals were significantly modified by surface hydration and lattice expansion. The finite size effects that occurred in alpha-Fe(2)O(3) nanocrystals at small sizes were first found to give a red shift in frequencies of perpendicular mode at 540 cm(-1), a blue shift in the electronic transition of double exciton process in visible region, and a significant decrease in the coercive force.     

Controlled synthesis and magnetic properties of bimagnetic spinel ferrite CoFe2O4 and MnFe2O4 nanocrystals with core-shell architecture

A combination of hard phase CoFe(2)O(4) and soft phase MnFe(2)O(4) as the bimagnetic nanocrystals in a core-shell architecture has been synthesized, and their magnetic properties have been systematically studied. Both HRTEM and EDS results confirmed the formation of bimagnetic core-shell structured nanocrystals. On the basis of the systematic and comparative studies of the magnetic properties of a mechanical mixture of pure CoFe(2)O(4) and MnFe(2)O(4) nanocrystals, chemically mixed Co(1-x)Mn(x)Fe(2)O(4) nanocrystals, and bimagnetic core-shell CoFe(2)O(4)@MnFe(2)O(4) and MnFe(2)O(4)@CoFe(2)O(4) nanocrystals, the bimagnetic core-shell nanocrystals show very unique magnetic properties, such as the blocking temperature and coercivity. Our results show that the coercivity correlates with the volume fraction of the soft phase as the theoretical hard-soft phase model has suggested. Furthermore, switching the hard phase CoFe(2)O(4) from the core to the shell shows great changes in the coercivity of the nanocrystals. The bimagnetic core-shell nanocrystals evidently demonstrate the rational design capability to separately control the blocking temperature and the coercivity in magnetic nanocrystals by varying the materials, their combination, and the volume ratio between the core and the shell and by switching hard or soft phase materials between the core and shell. Such controls via a bimagnetic core-shell architecture are highly desirable for magnetic nanocrystals in various applications.     

铁酸钴纳米晶的低温合成、谱学表征及磁性

以十六烷基三甲基溴化铵（CTAB）为模板,Fe(NO3)3·9H2O和Co(NO3)2·6H2O为前躯体,NaOH为沉淀剂,低温回流合成了磁性铁酸钴纳米晶。利用X射线衍射、透射电子显微镜、红外光谱、拉曼光谱等测试技术对产品的结构进行了表征,借助振动样品磁强计测定了样品的室温磁性能。结果表明,铁酸钴纳米晶为单相立方尖晶石结构,纳米晶的平均粒径为15-20 nm。铁酸钴纳米晶在室温外加磁场下表现出明显的磁滞现象,饱和比磁化强度MS=36.5 A.m2/kg,矫顽力HC=5.89×104 A/m。     

Fe3O4超顺磁纳米晶的超声共沉淀法制备及表征

利用超声强化的共沉淀法结合阴离子表面活性剂十二烷基硫酸钠(SDS)修饰技术, 制备出Fe3O4超顺磁纳米晶, 采用X射线粉末衍射仪(XRD)、傅立叶转换红外线光谱仪(FT-IR)、高分辨透射电子显微镜(HRTEM)、N2吸附-脱附及热重-差示扫描同步热分析仪(TG-DSC)等方法对样品进行表征, 系统研究了样品的表面电性及磁学性质, 并探索了超顺磁纳米晶的生长机理. 结果表明: 所制备的Fe3O4超顺磁纳米晶结晶完整, 分散性良好, 平均粒径在10 nm左右; 其比表面积高达91.6 m2•g－1, 具有优异的热稳定性, 蒸馏水中等电点pHpzc＝5.7; 其饱和磁强度(Ms)可达65.0 emu•g－1, 属超顺磁性纳米材料; 超声强化及SDS表面修饰, 对Fe3O4超顺磁纳米晶的生长起着非常重要的作用. 这种Fe3O4超顺磁纳米材料可望被较好地应用于细胞或酶的固定化等生物和医药领域.     

Superdispersible PVP-coated Fe3O4 nanocrystals prepared by a "one-pot" reaction

Poly( N-vinyl-2-pyrrolidone) (PVP)-coated Fe3O4 nanocrystals were prepared by a "one-pot" synthesis through the pyrolysis of ferric triacetylacetonate (Fe(acac)3) in N-vinyl-2-pyrrolidone (NVP). The polymerization of NVP was followed by measuring the shear viscosity of the reaction mixture. The PVP molecules formed in the reaction mixture was investigated by gel permeation chromatography. As the resultant Fe3O4 nanocrystals presented superdispersibility in 10 different types of organic solvents and aqueous solutions with different pH, including 0.01 M phosphate-buffered saline buffer, their hydrodynamic properties in both organic and aqueous systems were investigated by dynamic light-scattering. The results indicated that the PVP-coated Fe3O4 nanocrystals can completely be dispersed forming stable colloidal solutions in both organic solvents and water. Fourier transform infrared spectroscopy results suggested that PVP interacted with Fe3O4 via its carbonyl groups. Further surface analysis by X-ray photoelectron spectroscopy revealed that there were both coordinating and noncoordinating segments of PVP on the particle surface; the molar ratio between them was of 1:2.6.     

Synthesis of ferrite nanocrystals stabilized by ionic-liquid molecules through a thermal decomposition route

A series of M(x) Fe(3-x) O(4) (M=Fe, Co, Ni, Zn; 0≤x≤1) ferrite nanocrystals stabilized by ionic-liquid molecules have been successfully synthesized through a thermal decomposition route. Instead of the widely used long-chain lipid surfactants and high-boiling solvents, the ionic-liquid molecules not only played the role of surfactants, but also served as reaction and dispersion media simultaneously in the preparation of ferrite nanocrystals. Due to their good fluidity under magnetic fields and high ionic conductivity, the ionic-liquid molecules and M(x) Fe(3-x) O(4) ferrite nanocrystal-based conducting ferrofluids were successfully used as electrolytes in an AC circuit. The open or closed state of the circuit was directly controlled by moving a permanent magnet so as to tune the position of the ferrofluids, and consequently, resulted in the "off" or "on" state of the four indicative yellow-light-emitting diodes. These results demonstrate that the conducting ferrofluids successfully play the role of "magnetic switch".