Effect of capping and particle size on Raman laser-induced degradation of γ-Fe2O3 nanoparticles

Diol capped γ-Fe₂O₃ nanoparticles are prepared from ferric nitrate by refluxing in 1,4-butanediol (9.5 nm) and 1,5-pentanediol (15 nm) and uncapped particles are prepared by refluxing in 1,2-propanediol followed by sintering the alkoxide formed. X-ray diffraction (XRD) shows that all the samples have the spinel phase. Raman spectroscopy shows that the samples prepared in 1,4-butanediol and 1,5-pentanediol and 1,2-propanediol (sintered at 573 and 673 K) are γ-Fe₂O₃ and the 773 K-sintered sample is Fe₃O₄. Raman laser studies carried out at various laser powers show that all the samples undergo laser-induced degradation to α-Fe₂O₃ at higher laser power. The capped samples are however, found more stable to degradation than the uncapped samples. The stability of γ-Fe₂O₃ sample with large particle size (15.4 nm) is more than the sample with small particle size (10.2 nm). Fe₃O₄ having a particle size of 48 nm is however less stable than the smaller γ-Fe₂O₃ nanoparticles.     

Preparation of surface plasmon resonance biosensor based on magnetic core/shell Fe3O4/SiO2 and Fe3O4/Ag/SiO2 nanoparticles

In this paper, surface plasmon resonance biosensors based on magnetic core/shell Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were developed for immunoassay. With Fe(3)O(4) and Fe(3)O(4)/Ag nanoparticles being used as seeding materials, Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles were formed by hydrolysis of tetraethyl orthosilicate. The aldehyde group functionalized magnetic nanoparticles provide organic functionality for bioconjugation. The products were characterized by scanning electronic microscopy (SEM), transmission electronic microscopy (TEM), FTIR and UV-vis absorption spectrometry. The magnetic nanoparticles possess the unique superparamagnetism property, exceptional optical properties and good compatibilities, and could be used as immobilization matrix for goat anti-rabbit IgG. The magnetic nanoparticles can be easily immobilized on the surface of SPR biosensor chip by a magnetic pillar. The effects of Fe(3)O(4)/SiO(2) and Fe(3)O(4)/Ag/SiO(2) nanoparticles on the sensitivity of SPR biosensors were also investigated. As a result, the SPR biosensors based on Fe(3)O(4)/SiO(2) nanoparticles and Fe(3)O(4)/Ag/SiO(2) nanoparticles exhibit a response for rabbit IgG in the concentration range of 1.25-20.00 μg ml(-1) and 0.30-20.00 μg ml(-1), respectively.     

Characterization and application of Fe3O4/SiO2 nanocomposites

A sol-gel procedure was used to cover Fe₃O₄ nanoparticles with SiO₂ shell, forming a core/shell structure. The core/shell nanocomposites were synthesized by a two-step process. First, Fe₃O₄ nanoparticles were obtained through co-precipitation and dispersed in aqueous solution through electrostatic interactions in the presence of tetramethylammonium hydroxide (TMAOH). In the second step, Fe₃O₄ was capped with SiO₂ generated from the hydrolyzation of tetraethyl orthosilicate (TEOS). The structure and properties of the formed Fe₃O₄/SiO₂ nanocomposites were characterized and the results indicate that the Fe₃O₄/SiO₂ nanocomposites are superparamagnetic and are about 30 nm in size. Bioconjugation to IgG was also studied. Finally, the mechanism of depositing SiO₂ on magnetic nanoparticles was discussed.     

α-Fe2O3/SiO2纳米颗粒混合体系表面的酸碱性质及其对重金属离子的吸附行为

以Fe(NO₃)₃·9H₂O和正硅酸乙酯(TEOS)为原料, 通过溶胶-凝胶法和辅助模板法分别制备了纳米α-Fe₂O₃和SiO₂, 并对所合成样品进行了粉末X射线衍射(XRD)和BET表征. 使用自动电位滴定仪测定了α-Fe₂O₃/SiO₂纳米颗粒混合体系的表面酸碱性质. 研究了在不同pH下α-Fe₂O₃/SiO₂混合体系对Cu²⁺、Pb²⁺、Zn²⁺离子的吸附行为. 基于上述实验数据, 用WinSGW软件计算了α-Fe₂O₃/SiO₂混合体系表面酸碱配位常数, 并得出结论: α-Fe₂O₃/SiO₂混合体系表面反应为单一脱质子反应≡XOH ⇔ ≡XO^-+ H⁺(lg K = -8.19±0.15), 明显区别于同时具有加质子和脱质子反应的α-Fe₂O₃/SiO₂/γ-Al₂O₃, α-Fe₂O₃/γ-Al₂O₃和SiO₂/γ-Al₂O₃等纳米颗粒混合体系. 在此基础上拟合得到α-Fe₂O₃/SiO₂混合体系吸附重金属离子Cu²⁺、Pb²⁺、Zn²⁺的表面络合反应平衡常数分别为:
≡XOH + M²⁺ ⇔ ≡XOM⁺+ H⁺ [lg K = -3.1, -3.6, -3.8 (M = Cu, Pb, Zn)].
≡XOH＋M²⁺＋H₂O ⇔≡XOMOH＋2H⁺[lg K = -8.8, -8.0, -10.5 (M = Cu, Pb, Zn)]     

多孔羰基铁/SiO2/聚吡咯核壳结构复合材料的制备及电磁特性

首先对羰基铁进行点腐蚀得到多孔羰基铁,然后采用St?ber法和原位聚合法将SiO_2和导电高分子聚吡咯包覆在多孔羰基铁表面,制备多孔羰基铁/SiO_2/聚吡咯电磁复合吸波材料。采用XRD、SEM、TEM、FT-IR对样品结构、微观形貌进行了表征,在网络分析仪中采用同轴法测试样品电磁参数,并根据传输线理论研究了2~18 GHz微波频段内吡咯含量及涂层厚度对样品吸波性能的影响。实验结果表明:制备的多孔羰基铁/SiO_2/聚吡咯复合电磁吸波材料具有核壳结构;随着吡咯加入量的增加,吸波材料吸收峰逐渐向低频方向移动;当涂层厚度为3.5 mm、吡咯加入量为6%(w/w)时,在9.44~17.56 GHz范围内反射率均低于-10 d B,频带宽度为8.12 GHz,损耗反射率达到-23 d B。良好的吸波性能归因于复合物有效的阻抗匹配特性及多重界面极化效应,多孔羰基铁/SiO_2/聚吡咯是一种轻质、宽频、强吸收的吸波材料。     

Eu3+掺杂SiO2-B2O3-NaF玻璃的制备及发光性质

The Eu-doped SiO₂-B₂O₃-NaF glass was prepared by sol-gel process, using tetraethoxy Silicane, boric acid and sodium fluoride as starting materials, 0.10 mol·L^-1 EuCl₃ solution as the dopant. The luminescent properties of Eu³⁺ doped SiO₂-B₂O₃-NaF phosphors were investigated. The phosphors showed prominent luminescence in pink, the strong emission of Eu³⁺ comes from electronic transition of ⁵D₀- ⁷F₁（591 nm）and ⁵D₀- ⁷F₂（615 nm）,which derived from two transition modes of magnetic-dipole and electric-dipole .The peak intensity of 591nm in SiO₂-B₂O₃-NaF matrix is much stronger than it in the other matrixes, it means that SiO₂-B₂O₃-NaF has sensitization on the transition of ⁵D₀- ⁷F₁ (Eu³⁺). If there are broad bonds in the range of 275～380 nm in the excitation spectrum of Eu³⁺ -doped SiO₂-B₂O₃-NaF glass, the emission peak intensity should be intensified. It is because the electron migration CT band of O^2--Eu³⁺. For all Eu³⁺ concentrations used, the investigation found that when the mass of fraction got to 29.19×10^-3, the luminescence intensity reached the summit. And there is a phenomenon of concentration quenching. Investigation with the same concentration of Eu³⁺ at different annealed temperature, we found that the sample annealed at 400 ℃, the luminescence intensity achieved its maximum value, and Eu³⁺ in this matrix had a phenomenon of temperature quenching. The structural characterization of these luminescent materials was carried by used XRD and TEM. The result showed that the phosphor was in amorphous phase.     

Synthesis and catalytic properties of porous α-Fe2O3/SiO2 catalyst

The synthesis of α-Fe₂O₃ supported on high specific surface area SiO₂ has been studied. The hydroxylation of phenol to hydroquinone/catechol mixture is described with the help of BET and XRD. The result indicates that the dispersity and specific surface area of support have an important influence on the catalytic activity.     

纳米γ-Fe2O3粉体的合成与磁性增强研究

采用微乳法合成出氧化铁的前驱体——纳米β-FeOOH, 分别以β-FeOOH与添加剂壬基酚聚氧乙烯醚(NP-4)以物质量的比(n)为4, 5, 100添加NP-4, 混合煅烧. 采用拉曼光谱分析了样品中炭含量及分布, 并且用透射电镜观测产物的形貌和粒径, 采用磁强计观测产物磁性的变化. 结果得出, 对n＝5或破乳所得凝胶煅烧, 所得样品皆为分散均匀的四方形颗粒状, 且为磁性明显增强的纳米氧化铁γ-Fe₂O₃. 还分别讨论了样品中炭含量以及颗粒形状对比饱和磁化强度σ_s、矫顽力、矩形比的影响.     

MgFe2O4-Fe2O3纳米粉体的软化学合成及电磁学特性

Nano-MgFe₂O₄-Fe₂O₃ magnetic powders were synthesized by citrate gel under microwave irradiation. The structure，particle size distribution，electromagnetic characteristics of nano-MgFe₂O₄-Fe₂O₃ were characterized by using TG-DTA, X-ray, electronic microscope, nano-size measurement and electromagnetism measurement apparatus。The results show that the product is a mixture of MgFe₂O₄ and Fe₂O₃ with average size of 44 nm, tanδ for the product is 0.265 and 0.610 at frequency of 1.0 GHz and 1.8 GHz respectively.     

Synthesis of Fe3O4\SiO2\Ag nanoparticles and its application in surface-enhanced Raman scattering

To obtain a recyclable surface-enhanced Raman scattering (SERS) material, we developed a composite of Fe₃O₄\SiO₂\Ag with core\shell\particles structure. The designed particles were synthesized via an ultrasonic route. The Raman scattering signal of Fe₃O₄ could be shielded by increasing the thickness of the SiO₂ layer to 60 nm. Dye rhodamine B (RB) was chosen as probe molecule to test the SERS effect of the synthesized Fe₃O₄\SiO₂\Ag particles. On the synthesized Fe₃O₄\SiO₂\Ag particles, the characteristic Raman bands of RB could be observed when the RB solution was diluted to 5 ppm (1×10⁻⁵ M). Furthermore, the synthesized particles could keep their efficiency till four cycles.     

Synthesis and characterization of Fe2O3/SiO2 nanocomposites

Fe₂O₃/SiO₂ nanocomposites based on fumed silica A-300 (S_BET = 337 m²/g) with iron oxide deposits at different content were synthesized using Fe(III) acetylacetonate (Fe(acac)₃) dissolved in isopropyl alcohol or carbon tetrachloride for impregnation of the nanosilica powder at different amounts of Fe(acac)₃ then oxidized in air at 400–900 °C. Samples with Fe(acac)₃ adsorbed onto nanosilica and samples with Fe₂O₃/SiO₂ including 6–17 wt% of Fe₂O₃ were investigated using XRD, XPS, TG/DTA, TPD MS, FTIR, AFM, nitrogen adsorption, Mössbauer spectroscopy, and quantum chemistry methods. The structural characteristics and phase composition of Fe₂O₃ deposits depend on reaction conditions, solvent type, content of grafted iron oxide, and post-reaction treatments. The iron oxide deposits on A-300 (impregnated by the Fe(acac)₃ solution in isopropanol) treated at 500–600 °C include several phases characterized by different nanoparticle size distributions; however, in the case of impregnation of A-300 by the Fe(acac)₃ solution in carbon tetrachloride only α-Fe₂O₃ phase is formed in addition to amorphous Fe₂O₃. The Fe₂O₃/SiO₂ materials remain loose (similar to the A-300 matrix) at the bulk density of 0.12–0.15 g/cm³ and S_BET = 265–310 m²/g.     

Phase formation, crystal chemistry, and properties in the system Bi2O3-Fe2O3-Nb2O5

Subsolidus phase relations have been determined for the Bi₂O₃-Fe₂O₃-Nb₂O₅ system in air (900-1075 °C). Three new ternary phases were observed—Bi₃Fe_0.5Nb_1.5O₉ with an Aurivillius-type structure, and two phases with approximate stoichiometries Bi₁₇Fe₂Nb₃₁O₁₀₆ and Bi₁₇Fe₃Nb₃₀O₁₀₅ that appear to be structurally related to Bi₈Nb₁₈O₅₇. The fourth ternary phase found in this system is pyrochlore (A₂B₂O₆O′), which forms an extensive solid solution region at Bi-deficient stoichiometries (relative to Bi₂FeNbO₇) suggesting that ≈4-15% of the A-sites are occupied by Fe³⁺. X-ray powder diffraction data confirmed that all Bi-Fe-Nb-O pyrochlores form with positional displacements, as found for analogous pyrochlores with Zn, Mn, or Co instead of Fe. A structural refinement of the pyrochlore 0.4400:0.2700:0.2900 Bi₂O₃:Fe₂O₃:Nb₂O₅ using neutron powder diffraction data is reported with the A cations displaced (0.43 Å) to 96g sites and O′ displaced (0.29 Å) to 32e sites (Bi_1.721Fe_0.190(Fe_0.866Nb_1.134)O₇, Fd3¯m (#227), ). This displacive model is somewhat different from that reported for Bi_1.5Zn_0.92Nb_1.5O_6.92, which exhibits twice the concentration of small B-type cations on the A-sites as the Fe system. Bi-Fe-Nb-O pyrochlores exhibited overall paramagnetic behavior with large negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. The single-phase pyrochlore with composition Bi_1.657Fe_1.092Nb_1.150O₇ exhibited low-temperature dielectric relaxation similar to that observed for Bi_1.5Zn_0.92Nb_1.5O_6.92; at 1 MHz and 200 K the relative permittivity was 125, and above 350 K conductive effects were observed.     

The Al2O3-Fe2O3 Mixed Oxidic System, I. Preparation and Characterization

A series of Al₂O₃-Fe₂O₃ mixed oxidic solids with composition ranging from 0 to 100% of Fe₂O₃ were prepared and examined for structural characteristics. XRD diagrams showed the presence of α-Al₂O₃ and hematite phases. The analysis of M?ssbauer spectra revealed the existence of two iron containing phases. The specific surface area of the mixture decreases by the addition of iron and depends on the crystal phases of the mixture. This revised version was published online in June 2006 with corrections to the Cover Date.     

Magnetic diphase nanostructure of ZnFe2O4/γ-Fe2O3

Magnetic diphase nanostructures of ZnFe₂O₄/γ-Fe₂O₃ were synthesized by a solvothermal method. The formation reactions were optimized by tuning the initial molar ratios of Fe/Zn. All samples were characterized by X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, and Raman spectra. It is found that when the initial molar ratio of Fe/Zn is larger than 2, a diphase magnetic nanostructure of ZnFe₂O₄/γ-Fe₂O₃ was formed, in which the presence of ZnFe₂O₄ enhanced the thermal stability of γ-Fe₂O₃. Further increasing the initial molar ratio of Fe/Zn larger than 6 destabilized the diphase nanostructure and yielded traces of secondary phase α-Fe₂O₃. The grain surfaces of diphase nanostructure exhibited a spin-glass-like structure. At room temperature, all diphase nanostructures are superparamagnetic with saturation magnetization being increased with γ-Fe₂O₃ content.     

电位对α-Fe2O3和掺钛α-Fe2O3光氧化水电荷转移速率常数的影响

外加一定的阳极电位可提高未掺杂的α-Fe₂O₃和Ti掺杂的α-Fe₂O₃(Ti-Fe₂O₃)电极的光电流或光电化学氧化水的速率, 但文献中通常假定电位全部降落在半导体固体一侧(带边钉扎), 其对界面电荷转移速率常数的影响鲜见报道. 本文应用电化学阻抗谱研究了外加电位对这两种电极光电化学氧化水时界面电荷转移速率常数的影响.结果表明: 随着外加阳极电位增大,两种电极的界面电荷转移速率常数均增大,但速率常数增幅比理论预期的要小, 表明电位并不是全部降落在电极的亥姆霍兹层, 而是同时降落在空间电荷层和亥姆霍兹层(费米能级钉扎). 表面态电容测量结果表明光生电荷可在表面态中积累, 导致了电位在电极界面重新分布并提高了界面电荷转移速率常数.相同电位下, 光强越强, 光生空穴在表面态积累越多, 降落在亥姆霍兹层中的电位增加,电荷转移速率常数也更大. 与α-Fe₂O₃相比,外加阳极电位对Ti-Fe₂O₃的界面转移速率常数提高更为明显.     

Co或Ni促进的Cu/SiO2-Al2O3催化剂上丙三醇和苯胺气相合成3-甲基吲哚

对丙三醇和苯胺在Co或Ni促进的Cu/SiO2-Al2O3催化剂上气相合成3-甲基吲哚进行了研究.采用N2吸附、氢气程序升温还原(H2-TPR)、电感耦合等离子体(ICP)发射光谱、X射线衍射(XRD)、透射电子显微镜(TEM)、氨程序升温脱附(NH3-TPD)及热重(TG)分析等技术对催化剂进行了表征.结果表明,向Cu/SiO2-Al2O3催化剂加入钴或镍助剂改善了催化剂的催化性能,钴比镍更加有效.在催化剂Cu-Co/SiO2-Al2O3和Cu-Ni/SiO2-Al2O3上,反应第3 h,3-甲基吲哚收率分别达到47%和45%,而且催化剂经过6次再生收率仍能达到44%和42%.各种表征表明,向Cu/SiO2-Al2O3催化剂加入钴或镍助剂能增强铜和载体之间的相互作用,其结果不仅促进了铜粒子在载体表面的分散度,而且有效减少了反应过程中铜组分的流失.另外,加入钴或镍助剂还能减少催化剂的中强酸中心数,从而提高3-甲基吲哚的选择性,并且抑制积炭的形成.此外,钴助剂还能增加催化剂的弱酸中心数,促进3-甲基吲哚的生成.提出了金属铜与弱酸中心共同促进3-甲基吲哚合成的催化反应机理.     

SiO_2/Co_3O_4核壳催化剂对AP热分解的催化性能研究

采用改良的St觟ber法制备粒径约为200 nm的单分散球形SiO2颗粒,以此为内核,分别通过液相沉淀法和尿素均匀沉淀法制备包覆形式不同的新型SiO2/Co3O4核壳式纳米催化剂。采用X-射线衍射分析(XRD)、透射电子显微镜(TEM)、红外光谱分析(IR)、拉曼光谱分析(Raman)、BET比表面积测试等手段对产物进行表征,利用差式扫描量热仪(DSC)考察SiO2/Co3O4复合物对高氯酸铵(AP)热分解反应的催化作用,探讨不同包覆形式对其催化活性的影响。结果表明,两种方法制备得到的SiO2/Co3O4复合物分别为层包覆和粒子包覆,比表面积大,具有明显的核壳结构,且粒子包覆形式的SiO2/Co3O4对AP热分解反应的催化效果最好,使AP的高温分解温度降低了110℃,放热量增加了662 J·g-1。     

Synthesis of Silica@α-Fe2O3 nanospheres by surface-initiated ATRP

We reported a new method to prepare Silica@α-Fe₂O₃ nanospheres by surface-initiated atom transfer radical polymerization (ATRP). Firstly, polymerizable surfactants-modified α-Fe₂O₃ nanoparticles were prepared in water-toluene microemulsion. Then, as-synthesized α-Fe₂O₃ nanoparticles acted as the macro-monomer of surface-initiated ATRP on silica nanospheres to make target product. Morphological characterization of the product was performed using transmission electron microscopy (TEM). Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS) and diffuse reflectance UV-vis spectroscopy were used to verify the incorporation of α-Fe₂O₃ nanoparticles on silica nanosphere.     

SiO2/Co3O4核壳催化剂对AP热分解的催化性能研究

采用改良的Stöber法制备粒径约为200 nm的单分散球形SiO₂颗粒,以此为内核,分别通过液相沉淀法和尿素均匀沉淀法制备包覆形式不同的新型SiO₂/Co₃O₄核壳式纳米催化剂。采用X-射线衍射分析(XRD)、透射电子显微镜(TEM)、红外光谱分析(IR)、拉曼光谱分析(Raman)、BET比表面积测试等手段对产物进行表征,利用差式扫描量热仪(DSC)考察SiO₂/Co₃O₄复合物对高氯酸铵(AP)热分解反应的催化作用,探讨不同包覆形式对其催化活性的影响。结果表明,两种方法制备得到的SiO₂/Co₃O₄复合物分别为层包覆和粒子包覆,比表面积大,具有明显的核壳结构,且粒子包覆形式的SiO₂/Co₃O₄对AP热分解反应的催化效果最好,使AP的高温分解温度降低了110 ℃,放热量增加了662 J·g^-1。     

SiO2 /Au核壳结构纳米粒子的制备及表征

通过以金纳米粒子为表面晶种和壳生长的方法制备了金纳米壳包覆二氧化硅的复合纳米粒子。采用TEM 和UV-Vis对复合粒子进行了表征和研究，结果表明所得到的复合粒子粒径均匀、金纳米壳光滑完整，且壳厚度可通过反应物的用量来控制。当核半径与壳厚度之比在4到13之间变化时,复合粒子的光学共振峰在可见光区到近红外光区范围内可发生大于500 nm波长的移动。