固体超强酸SO42-/TiO2-Al2O3的制备及其催化合成冰片

采用溶胶-凝胶法和浸渍法制备了系列SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂,运用XRD、NH_3-TPD、FT-IR、PyFTIR、XPS、SEM等技术手段,研究了复合催化剂材料的结构与性质,初步探讨了固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的构效关系,得到适宜的催化剂制备条件为:n(TiO_2)/n(Al_2O_3)=1∶2、硫酸浸渍浓度1mol/L、催化剂焙烧温度500℃。考察了物料物质的量比、催化剂用量、反应时间等对催化合成冰片的影响。结果表明,在物料物质的量比为1∶0.4,催化剂用量为α-蒎烯质量的7%,采用程序升温方式(65℃-1h,75℃-4h,90℃-1h)加热的条件下,固体超强酸SO_4~(2-)/TiO_2-Al_2O_3催化剂的催化活性最高,α-蒎烯的转化率高达100%,龙脑的收率高达59.74%,SO_4~(2-)/TiO_2-Al_2O_3固体超强酸催化剂在重复使用6次的条件下,α-蒎烯的转化率均不变,龙脑的收率下降2.99%,催化剂的重复使用性良好。     

微波多元醇法制备单分散Ni1-xZnxFe2O4/MWCNTs与磁性能

以多壁碳纳米管(MWCNTs)为模板,三乙二醇(TREG)为溶剂,采用微波多元醇法制备MWC-NTs负载组成可控的Ni1-xZnxFe2O4(x=0.4、0.5、0.6)纳米复合材料Ni1-xZnxFe2O4/MWCNTs。其结构和形貌通过XRD、SEM、TEM和EDX进行表征,用VSM测试样品的磁性,并探讨了微波功率、微波时间对镍锌铁氧体负载的影响。结果表明立方系尖晶石结构的单分散Ni1-xZnxFe2O4磁性纳米粒子均匀负载在碳纳米管表面,平均粒径约为6nm;其磁性能与镍锌铁氧体的组成有关,随着Zn含量的增加,饱和磁化强度(Ms)先增大后减小,当x=0.5时Ms达到最大值。矫顽力(Hc)都比较小,在室温下表现为超顺磁性。     

Evaluation of CaO-SiO2-P2O5-Na2O-Fe2O3 bioglass-ceramics for hyperthermia application

Magnetic bioglass ceramics (MBC) are being considered for use as thermoseeds in hyperthermia treatment of cancer. While the bioactivity in MBCs is attributed to the formation of the bone minerals such as crystalline apatite, wollastonite, etc. in a physiological environment, the magnetic property arises from the magnetite [Fe3O4] present in these implant materials. A new set of bioglasses with compositions 41CaO x (52-x)SiO2 x 4P2O5 x xFe2O3 x 3Na2O (2 < or = x < or = 10 mol% Fe2O3) have been prepared by melt quenching method. The as-quenched glasses were then heat treated at 1050 degrees C for 3 h to obtain the glass-ceramics. The structure and microstructure of the samples were characterized using X-ray diffraction and microscopy techniques. X-ray diffraction data revealed the presence of magnetite in the heat treated samples with x > or = 2 mol% Fe2O3. Room temperature magnetic property of the heat treated samples was investigated using a Vibrating Sample Magnetometer. Field scans up to 20 kOe revealed that the glass ceramic samples had a high saturation magnetization and low coercivity. Room temperature hysteresis cycles were also recorded at 500 Oe to ascertain the magnetic properties at clinically amenable field strengths. The area under the magnetic hysteresis loop is a measure of the heat generated by the MBC. The coercivity of the samples is another important factor for hyperthermia applications. The area under the loop increases with an increase in Fe2O3 molar concentration and the. coercivity decreases with an increase in Fe2O3 molar concentration The evolution of magnetic properties in these MBCs as a function of Fe2O3 molar concentration is discussed and correlated with the amount of magnetite present in them.     

Microwave absorption enhancement of multifunctional composite microspheres with spinel Fe3 O4 Cores and Anatase TiO2 shells

Multifunctional composite microspheres with spinel Fe(3)O(4) cores and anatase TiO(2) shells (Fe(3)O(4)@TiO(2)) are synthesized by combining a solvothermal reaction and calcination process. The size, morphology, microstructure, phase purity, and magnetic properties are characterized by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, selected-area electron diffraction, electron energy loss spectroscopy, powder X-ray diffraction, and superconducting quantum interference device magnetometry. The results show that the as-synthesized microspheres have a unique morphology, uniform size, good crystallinity, favorable superparamagnetism, and high magnetization. By varying the experimental conditions such as Fe(3)O(4) size and concentration, microspheres with different core sizes and shell thickneses can be readily synthesized. Furthermore, the microwave absorption properties of these microspheres are investigated in terms of complex permittivity and permeability. By integration of the chemical composition and unique structure, the Fe(3)O(4)@TiO(2) microspheres possess lower reflection loss and a wider absorption frequency range than pure Fe(3)O(4). Moreover, the electromagnetic data demonstrate that Fe(3)O(4@TiO(2) microspheres with thicker TiO(2) shells exhibit significantly enhanced microwave absorption properties compared to those with thinner TiO(2) shells, which may result from effective complementarities between dielectric loss and magnetic loss. All the results indicate that these Fe(3)O(4)@TiO(2) microspheres may be attractive candidate materials for microwave absorption applications.     

EPR and Magnetic Susceptibility Investigations of Fe Containing TeO2-B2O3-SrF2 Glasses

1. IntroductionTellurite-borate vitreous systems[1] and binajry tellurite oxide systems containing transition metal ions[2]were investigated in detail due to their interestingproperties having a number of applications in microelectronics. They are optical glajsses with high refraction index (n>2) and a good iR transmission,being suitable as laser and opto-acoustical materials. Tellurite systems containing FeZO3 were studied to reveal their electrical properties as well asthe structural onesl…     

Microwave remediation of soil contaminated with hexachlorobenzene

This study describes the remediation of hexachlorobenzene (HCB) contaminated soils by microwave (MW) radiation in a sealed vial. When powdered MnO2 was used as MW absorber, a complete removal of HCB was obtained with 10 min MW by the addition of H2SO4 (50%). But no significant decomposition was observed by the addition of NaOH (10 mol/L) or H2O in the same conditions. In contrast, when powdered Fe was used instead of MnO2, the difference of HCB removals between H2SO4 and NaOH were not obvious. It is noteworthy that more than 95% removal was achieved in any case when the sole aqueous solution of H2SO4, NaOH, H2O or Na2SO4 was added without MnO2 or Fe. As a result, it is possible that water itself contained in the damp soil may act as MW absorber and remediate the contaminated soil without addition of any other MW absorbers. Gas chromatograph/mass spectrum (GC/MS) analysis detected no intermediates in all the processes. The decomposition mechanism of HCB by MW radiation was suggested as the binding of HCB and soil. Whatever fragments formed from HCB by heat were tightly bound to the soil, making it impossible to extract them out. In the end, treatment of practical HCB contaminated soil by MW reduced HCB from 55.8 mg/kg to 0.91 mg/kg.     

Fe3O4/Ni复合纳米颗粒的制备及其微波吸收特性

采用电爆炸技术,合成了粒径约为70nm 的Ni纳米颗粒,以3-巯基丙基三甲氧基硅烷偶联剂(MPTS)对Ni颗粒进行表面改性,利用共沉淀法对改性Ni颗粒进行包覆得到核-壳结构的复合纳米颗粒。将获得的复合纳米颗粒作为微波吸收剂, 并以不同比例分散到热固性酚醛树脂中,涂刷在200mm×200mm的金属板上,用RAM反射率远场RCS测量法研究了微波吸收特性。研究表明,核-壳结构Fe₃O₄/Ni复合颗粒作为微波吸收剂,在相同质量比条件下,其微波吸收性能明显优于纯Ni纳米颗粒或Fe₃O₄纳米颗粒的情况,并且在Fe₃O₄/Ni核-壳结构复合纳米颗粒中随着镍含量的提高,微波吸收增强,而随着Fe₃O₄含量的增加,微波吸收频段向高频段移动。     

微波辐射乳液聚合制备聚氰基丙烯酸正丁酯磁性微球

通过化学共沉淀法制备Fe3O4纳米粒子,再用油酸钠和十二烷基磺酸钠(SDS)对Fe3O4进行改性,制得稳定的水基磁流体。在自制的磁流体存在下,以氰基丙烯酸正丁酯(BCA)为单体,用微波辐射乳液聚合的方法制备了Fe3O4/聚氰基丙烯酸正丁酯磁性微球。并用X射线衍射仪(XRD),透射电子显微镜(TEM),傅立叶红外光谱仪(FT-IR),振动样品磁强计(VSM)对制备的磁性高分子微球的结构形貌和磁性能进行表征测试。结果表明,在适当的pH值条件下,得到了粒径为150 nm~200 nm,饱和磁化强度为20.23 emμ/g,粒径均一的聚氰基丙烯酸正丁酯磁性微球。     

SO_4~(2-)/ZrO_2型固体超强酸改性及其催化氧化脱除噻吩类硫化物

通过掺杂不同金属元素对SO_4~(2-)/ZrO_2型固体超强酸进行改性,应用共沉淀法制备了一系列固体酸催化剂SO_4~(2-)/ZrO_2、SO_4~(2-)/ZrO_2-ZnO、SO_4~(2-)/ZrO_2-Fe_2O_3、SO_4~(2-)/ZrO_2-CuO、SO_4~(2-)/ZrO_2-Al_2O_3,利用氧气作氧化剂进行催化氧化脱除噻吩硫化物动力学实验.研究结果表明,掺杂了Zn、Fe和Cu的SO_4~(2-)/ZrO_22型催化剂催化氧化效果较SO_4~(2-)/ZrO_2都有明显提高,其中添加了金属Zn的SO_4~(2-)/ZrO_2-ZnO催化氧化效果最好,在反应温度为50℃,能达到100%的脱硫率.对合成的系列固体酸进行了X射线衍射(XRD)、氨程序升温脱附(NH3-TPD)的表征,结果表明,催化剂样品中四方相ZrO_2的含量越高,表面酸含量越大,其催化氧化噻吩硫化物的活性越高.     

EPR and Magnetic Susceptibility Investigation of Fe Ions in B2O3—SrF2 Glass Matrix

The structural and magnetic properties of an oxide-fluoride mixed vitreous matrix 2B2O3-SrF2, were explored by using Fe impurities as probes.Information about the structural units involving iron ions,their valence state,the strengths and type of interactions involving them was obtained using EPR spectroscopy and magnetic susceptibility measurements.     

The enhanced microwave absorption property of CoFe(2)O(4) nanoparticles coated with a Co(3)Fe(7)-Co nanoshell by thermal reduction

CoFe(2)O(4) nanoparticles were fabricated by a sol-gel method and then were coated with Co(3)Fe(7)-Co by means of a simple reduction process at different temperatures under 2% H(2) with the protection of argon to generate the dielectric-core/metallic-shell structure. The optimum reflection loss (RL) calculated from permittivity and permeability of the 80 wt% CoFe(2)O(4)/Co(3)Fe(7)-Co and 20 wt% epoxy resin composites reached - 34.4 dB, which was much lower than that of unreduced CoFe(2)O(4) and epoxy resin composites, at 2.4 GHz with a matching thickness of 4.0 mm. Moreover the RL exceeding - 10 dB in the maximum frequency range of 2.2-16 GHz was achieved for a thickness of composites of 1.0-4.5 mm with 600?°C thermal reduction process. The improved microwave absorption properties are a consequence of a proper electromagnetic match and the enhanced magnetic loss besides its dielectric loss due to the existence of the core/shell structure in CoFe(2)O(4) composites. Thus, the reductive CoFe(2)O(4) nanoparticles have great potential for being a highly efficient microwave absorber.     

Microwave properties of polymer composites containing combinations of micro- and nano-sized magnetic fillers

We investigated the microwave absorbing properties of composite bulk samples with nanostructured and micron-sized fillers. As magnetic fillers we used magnetite powder (Fe3O4 with low magnetocrystalline anisotropy) and strontium hexaferrite (SrFe12O9 with high magnetocrystalline anisotropy). The dielectric matrix consisted of silicone rubber. The average particle size was 30 nm for the magnetite powder and 6 micro/m for the strontium hexaferrite powder. The micron-sized SrFe12O19 powder was prepared using a solid-state reaction. We investigated the influence of the filler concentration and the filler ratio (Fe3O4/SrFe12O19) in the polymer matrix on the microwave absorption in a large frequency range (1 / 18 GHz). The results obtained showed that the highly anisotropic particles become centers of clusterification and the small magnetite particles form magnetic balls with different diameter depending on the concentration. The effect of adding micron-sized SrFe12O19 to the nanosized Fe3O4 filler in composites absorbing structures has to do with the ferromagnetic resonance (FMR) shifting to the higher frequencies due to the changes in the ferrite filler's properties induced by the presence of a magnetic material with high magnetocrystalline anisotropy. The two-component filler possesses new values of the saturation magnetization and of the anisotropy constant, differing from those of both SrFe12O1919 and Fe3O4, which leads to a rise in the effective anisotropy field. The results demonstrate the possibility to vary the composite's absorption characteristics in a controlled manner by way of introducing a second magnetic material.     

TiO2 and SnO2 magnetic nanocomposites: influence of semiconductors and synthetic methods on photoactivity

A number of reports have been published on use of TiO2 in thin films, magnetic nanocomposites, or heterostructures such as TiO2/Ag and TiO2/SnO2, as catalysts for water decontamination. Hence, semiconductor materials such as SnO2, associated with TiO2 in such nanocomposites, should be assessed in depth for such applications, especially those involving complex structures, such as magnetic photocatalytic nanocomposites. The present study describes the synthesis, characterization and testing of the photocatalytic potential of TiO2 or SnO2 magnetic nanocomposites obtained by the polymeric precursor and the hydrolytic sol-gel methods. The nanocomposites TiO2/CoFe2O4 and SnO2/CoFe2O4 were synthesized from polymeric precursors while TiO2/Fe3O4 and SnO2/Fe3O4 were synthesized by the hydrolytic sol-gel method. The materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (FEG/SEM) and transmission electron microscopy (TEM). The photocatalytic potentials were evaluated by rhodamine B dye photodegradation under UV-C radiation. Compared to SnO2, the nanocomposites with a coating of TiO2 were found to show better photocatalytic activity, but the SnO2 magnetic nanocomposites showed some photocatalytic activity, even though SnO2 is reported to be inactive for these purposes. As for the synthesis method, the nanocomposites obtained from polymeric precursors had smaller surface areas, but higher photocatalytic activity, than those obtained by the hydrolytic sol-gel method. This observation was attributed to the higher crystallinity and a more active surface resulting from calcination of the polymeric precursor material.     

纳米Co_(1-x)Zn_xFe_2O_4/SiO_2复合材料的结构和磁性

为了研究Zn2+含量对CoZn铁氧体结构和磁性的影响,以正硅酸乙酯和硝酸盐为原料,用溶胶-凝胶法制备了纳米Co1-xZnxFe2O4/Si O2(0≤x≤1)复合材料。利用XRD、TEM、VSM和M ssbauer效应分析了样品的结构、形貌和磁性。结果表明,经900℃热处理后,Co1-xZnxFe2O4/Si O2复合材料中Co1-xZnxFe2O4为晶粒分布均匀的尖晶石铁氧体结构。Zn2+替代Co2+后引起Co1-xZnxFe2O4晶格膨胀。随Zn2+含量的增加,样品的矫顽力减小,而比饱和磁化强度先增大后减小,样品从磁有序状态转变为顺磁状态。Zn2+的掺杂对Fe3+核处的s电子密度有较大的影响,对尖晶石结构对称性影响较小。     

Fe3O4/CdTe磁性荧光纳米复合物的逐步杂凝聚法合成及其表征

采用逐步杂凝聚法合成了Fe3O4/CdTe磁性荧光纳米复合物.以化学共沉淀法制备Fe3O4纳米颗粒,经油酸修饰后分散在表面活性剂中形成磁流体.CdTe量子点以巯基乙酸为稳定剂制得.最后以聚乙烯亚胺(PEI)为联接剂,成功制备了Fe3 O4 /CdTe磁性荧光双功能纳米复合物颗粒.该复合物颗粒平均尺寸为(30±5)nm,荧光产率为0.186,饱和磁化强度为15.745emu/g,该纳米粒子既具有优异的荧光特性,也具有较强的超顺磁性.     

Microwave absorption behavior of ZnO whisker modified by nanosized Fe3O4 particles

Tetra-needle-like ZnO whisker was magnetic modified through in situ synthesis of nanosized Fe3O4 particles on the surface of the whisker, and the microwave absorption behavior of the as-prepared product was investigated in detail. The result of the comparative microwave absorbing experiment showed that the magnetic modified ZnO whisker appeared more superior property of microwave absorption than that of the original ZnO whisker in 2-18 GHz. Further investigation indicated that the microwave absorption behavior of the product was influenced by ferrite content and Fe3O4 particles' distribution in the product. When the ferrite content of the product changed from 2 wt% to 9 wt%, the microwave absorbing ability of the product was increased; then, the microwave absorbing ability of the product decreased with the further increasing of ferrite content from 9 wt% to 16 wt%. The product with uniform distribution of Fe3O4 particles showed better microwave absorption property than that with irregular distribution of Fe3O4 particles, and this result inferred that the biphase interface between ZnO and Fe3O4 contributed to microwave absorption through interface polarization.     

(La2/3Ca1/3)(Mn(3-x)/3)Fex/3)O3体系磁电阻行为的研究

通过系统地测量（La2/3Ca1/3）（Mn（3-x）／3Fex／3）O3（x＝0、0.1、0．2、0．3的体系样品的电阻率-温度关系以及一定温度下磁电阻率与磁场的关系,发现随x的变化其磁电阻率峰和电阻率峰均发生位移,磁电阻率峰值增大,并伴生磁电阻率峰展宽效应．作者认为由于Fe的替代,引起体系中Mn3 ／Mn4 比率及磁矩的变化,加之外场对磁有序结构的调制作用,从而影响了Mn3 －O－Mn4 的双交换作用,最终导致磁电阻行为发生变化．     

Synthesis and characterization of SiO2/(PMMA/Fe3O4) magnetic nanocomposites

Magnetic silica nanocomposites (magnetic nanoparticles core coated by silica shell) have the wide promising applications in the biomedical field and usually been prepared based on the famous St?ber process. However, the flocculation of Fe3O4 nanoparticles easily occurs during the silica coating, which limits the amount of magnetic silica particles produced in the St?ber process. In this paper, PMMA/Fe3O4 nanoparticles were used in the St?ber process instead of the "nude" Fe3O4 nanoparticles. And coating Fe3O4 with PMMA polymer beforehand can prevent magnetic nanoparticles from the aggregation that usually comes from the increasing of ionic strength during the hydrolyzation of tetraethoxysilane (TEOS) by the steric hindrance. The results show that the critical concentration of magnetic nanoparticles can increase from 12 mg/L for "nude" Fe3O4 nanoparticles to 3 g/L for PMMA/Fe3O4 nanoparticles during the St?ber process. And before the deposition of silica shell, the surface of PMMA/FeO4 nanoparticles had to be further modified by hydrolyzing them in CH3OH/NH3 x H2O mixture solution, which provides the carboxyl groups on their surface to react further with the silanol groups of silicic acid.     

核壳结构SrFe12O19NiFe2O4复合纳米粉体的吸波性能

以Fe(NO₃)₃、 Ni(NO₃)₂和Sr(NO₃)₂为主要原料, 通过两步柠檬酸盐溶胶-凝胶法, 制备出核-壳结构SrFe₁₂O₁₉-NiFe₂O₄磁性纳米复合粉体。采用XRD、 TEM、 VSM及矢量网络分析仪对合成的粉体的结构、 形貌及吸波性能进行了分析研究。结果表明, 复合粉体的相结构与NiFe₂O₄含量有关, 当SrFe₁₂O₁₉与NiFe₂O₄的质量比为1∶2、 烧结温度为1050℃时, 复合纳米粉体的相与NiFe₂O₄接近, 核-壳结构SrFe₁₂O₁₉-NiFe₂O₄纳米复合粉体的饱和磁化强度(M_s)(51.4 emu/g)比单体SrFe₁₂O₁₉纳米粉体 (42.6 emu/g)的大; 但矫顽力(H_c) (336 Oe)比单体SrFe₁₂O₁₉纳米粉体的小, 在SrFe₁₂O₁₉ 与NiFe₂O₄的矫顽力5395～160 Oe之间。在频率为8～18 GHz范围内, 微波吸收逐渐增强, 当频率为12 GHz时, SrFe₁₂O₁₉-NiFe₂O₄纳米复合粉体的微波吸收达到最大值-9.7 dB, 是一种性能优良的吸波材料。      

Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles

The Fe(3)O(4)-Ca(3)(PO(4))(2) core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe(3)O(4) and the bioactive functions of Ca(3)(PO(4))(2) into single entities. The Fe(3)O(4) nanoparticles were pre-formed first by thermal reduction of Fe(acac)(3) and then the Ca(3)(PO(4))(2) layer was coated by simultaneous deposition of Ca(2+) and PO(4)(3-). The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca(3)(PO(4))(2) shell forms an hcp phase (a = 7.490 ?, c = 9.534 ?) on the Fe(3)O(4) surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca(3)(PO(4))(2) and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe(3)O(4) and Ca(3)(PO(4))(2) in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.