Fe3O4纳米微球的溶剂热法合成及其对二甲酚橙的催化降解研究

以FeCl₃·6H₂O为单一铁源、1, 2-丙二醇为还原剂和溶剂、尿素为均相沉淀剂、顺丁烯二酸为添加剂, 通过简单一步溶剂热法于160℃制备出了形貌均一、单分散性好、尺寸约为200 nm的Fe₃O₄纳米微球。所制备的Fe₃O₄纳米微球不仅具有很高的磁化强度, 而且在利用过氧化氢氧化降解二甲酚橙(XO)的过程中显示出很好的催化活性。紫外可见分光光度法考察表明, 不加入Fe₃O₄催化剂时, 1 h内双氧水对二甲酚橙的脱色率仅为6.2%, 而加入Fe₃O₄纳米微球后, 双氧水对二甲酚橙的脱色率在1 h内即可达到100%, 循环使用10次后, Fe₃O₄纳米微球仍保持高的催化活性和结构稳定性。     

磁性Fe3O4/石墨烯Photo-Fenton催化剂的制备及其催化活性

采用共沉淀法制备磁性Fe3O4/GE(石墨烯)催化剂,实现Fe3O4纳米颗粒生长和氧化石墨烯还原同步进行,采用FTIR、XRD、TEM及低温氮吸附-脱附等对Fe3O4/GE纳米催化剂的物相、颗粒粒径及比表面积进行了表征。在H2O2存在条件下,以亚甲基蓝为目标降解物,考察了在模拟太阳光下Fe3O4/GE的催化活性,当氧化石墨烯与Fe3O4的质量比为1∶10时,经过2 h催化反应,在pH=6条件下,对亚甲基蓝的降解率达到98.7%,经过10次循环使用后对染料溶液的降解率仍保持在95.7%以上,明显优于纯的Fe3O4。     

磁性可见光催化剂BiVO4/Fe3O4的制备及催化活性

采用超声法将磁基体Fe3O4和BiVO4复合,制备了易于固液分离的磁性可见光催化剂BiVO4/Fe3O4。采用X射线衍射(XRD)、傅立叶转换红外光谱(FTIR)、紫外-可见漫反射光谱(DRS)、透射电子显微镜(TEM)和磁学性质测量系统(MPMS)对产物进行了表征,并以亚甲基蓝为目标降解物,考察了BiVO4/Fe3O4的可见光催化活性。当BiVO4与Fe3O4质量比为5:1时,BiVO4/Fe3O4的催化活性最高,反应经过5 h,对亚甲基蓝的降解率达到92.0%,而单独使用BiVO4为催化剂,降解率仅为72.5%。这表明Fe3O4不仅起到磁基体的作用,还起到助催化剂的作用。BiVO4/Fe3O4在外加磁场的作用下很容易被分离,撤消外加磁场后,通过搅拌又可重新分散。BiVO4/Fe3O4 3次回收后的降解率仍高于80%。     

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。     

柠檬酸根辅助多元醇法制备直径和磁性可控的Fe_3O_4亚微球

以柠檬酸三钠作辅助剂,用多元醇溶剂热还原法制备了纳米晶粒和微球直径可控的、单分散的超顺磁Fe3O4亚微球.发现与铁原子有强亲和力的柠檬酸根能有效吸附在还原产生的初始Fe3O4纳米粒子表面,阻碍其晶粒生长和影响其静电排斥力的大小,从而能在较大范围内调控最终产物Fe3O4亚微球的直径和饱和磁化强度.改变柠檬酸根或铁盐浓度不但可以调控初始Fe3O4纳米粒子的粒径,而且可以在220-550nm范围内调控单分散Fe3O4亚微球的直径,从而得到粒径均一的超顺磁Fe3O4亚微球.     

Cu2ZnSnS4(CZTS)纳米微球的制备及表征

为研究PVP含量对CZTS颗粒形貌以及分散性的影响,本文采用溶剂热法,以CuCl2·2H2O、Zn(Ac)2·2H2O、SnCl4·5H2O作金属源,硫脲作硫源,乙二醇为溶剂,在体系中加入不同含量的PVP,成功制备了CZTS微球。通过XRD、Raman、SEM、TEM、UVVis等方法检测分析CZTS纳米微球的物相、结构、形貌以及光学性能。结果表明:所得CZTS纳米颗粒具有锌黄锡矿结构;当体系中PVP含量为0.2 g时,颗粒分散性较好,制备的颗粒形貌为表面嵌有纳米薄片的微球,纳米片较在体系中加入0.1 g PVP更致密;光学带隙约为1.47 eV,与太阳能电池所需的最佳带隙接近。最后,对表面嵌有纳米薄片的CZTS微球可能的形成机理进行了推测。     

Mn0.6 Zn0.4 Fe2 O4 磁性亚微球的可控合成及磁性能

采用溶剂热法制备了单分散Mn0.6Zn0.4Fe2O4磁性亚微米球, 研究了反应工艺参数对磁性亚微米球结构形貌、 直径和静磁性能的影响规律. 研究发现, 随着反应时间的延长, 体系中的金属离子首先水解沉淀, 形成羟基氧化铁及Mn, Zn氢氧化物, 然后脱水转化为Mn0.6Zn0.4Fe2O4球形纳米粒子, 这些纳米粒子发生团聚, 形成结构疏松、 大小不均匀的亚微米粒子, 最后通过Ostwald熟化过程, 形成致密的单分散亚微米球. 降低反应溶液的pH值、 增加乙二醇或聚乙二醇的用量, 均会使亚微球的直径增大, 并可在150~500 nm范围内调控微球的粒径; 但组成磁性亚微球的纳米粒子的粒径逐渐减小, 产物的饱和磁化强度增大, 矫顽力和剩磁减小.     

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%.     

控制自由基聚合制备Fe_3O_4/SiO_2/P(AA-MMA-St)磁性复合微球

用原硅酸乙酯对Fe3O4纳米粒子进行表面改性得到Fe3O4/SiO2磁流体.在Fe3O4/SiO2磁流体存在下,以1,1-二苯基乙烯(DPE)为自由基聚合控制剂,利用乳液聚合法制备了Fe3O4/SiO2/P(AA-MMA-St)核-壳磁性复合微球.用红外光谱(FTIR)、振动样品磁强计(VSM)、透射电镜(TEM)、X光电子能谱(XPS)、热重分析(TGA)、示差扫描量热仪(DSC)对所制备的磁流体、磁性高分子复合微球的结构、形态、性能进行了表征.研究发现,原硅酸乙酯水解后能在Fe3O4表面形成硅膜保护层从而避免Fe3O4的酸蚀,使Fe3O4/SiO2/P(AA-MMA-St)复合微球的比饱和磁化强度比同样条件下制备的Fe3O4/P(AA-MMA-St)微球提高了28%;DPE能有效控制自由基在Fe3O4/SiO2磁流体表面均匀地引发单体聚合,得到平均粒径为422 nm,无机粒子含量为40%,比饱和磁化强度为34.850 emu/g,表面羧基含量为0.176 mmol/g的磁性复合微球.     

荧光磁性双功能Fe_3O_4/Alendronate@CdSe/CdS纳米复合物的制备与表征

采用化学共沉淀法制备了磁性Fe3O4纳米颗粒,并用四甲基氢氧化铵(TMAOH)、阿伦磷酸钠、丙烯酸丁酯和无水乙二胺对Fe3O4纳米颗粒表面进行修饰,制备出3代表面胺基化的Fe3O4树状分子.采用油相合成的方法制备CdSe/CdS量子点,再用巯基乙酸进行修饰,使其具有良好的水溶性和较好的稳定性.将制备的Fe3O4树状分子与修饰后的量子点进行连接,制备出双功能树状Fe3O4/Alendronate@CdSe/CdS微球.通过这种方法得到的材料的荧光性能明显增强,但材料的荧光性能并不随代数成线性变化的.     

Sol-gel synthesis of K3InF6 and structural characterization of K2InC10O10H6F9, K3InC12O14H4F18 and K3InC12O12F18

K₃InF₆ is synthesized by a sol-gel route starting from indium and potassium acetates dissolved in isopropanol in the stoichiometry 1:3, with trifluoroacetic acid as fluorinating agent. The crystal structures of the organic precursors were solved by X-ray diffraction methods on single crystals. Three organic compounds were isolated and identified: K₂InC₁₀O₁₀H₆F₉, K₃InC₁₂O₁₄H₄F₁₈ and K₃InC₁₂O₁₂F₁₈. The first one, deficient in potassium in comparison with the initial stoichiometry, is unstable. In its crystal structure, acetate as well as trifluoroacetate anions are coordinated to the indium atom. The two other precursors are obtained, respectively, by quick and slow evaporation of the solution. They correspond to the final organic compounds, which give K₃InF₆ by decomposition at high temperature. The crystal structure of K₃InC₁₂O₁₄H₄F₁₈ is characterized by complex anions [In(CF₃COO)₄(OH_x)₂]^(5−2x)− and isolated [CF₃COOH_2−x]^(x−1)− molecules with x=2 or 1, surrounded by K⁺ cations. The crystal structure of K₃InC₁₂O₁₂F₁₈ is only constituted by complex anions [In(CF₃COO)₆]³⁻ and K⁺ cations. For all these compounds, potassium cations ensure only the electroneutrality of the structure. IR spectra of K₂InC₁₀O₁₀H₆F₉ and K₃InC₁₂O₁₂F₁₈ were also performed at room temperature on pulverized crystals.     

Li2O-TiO2-SiO2-P2O5和Li2O-TiO2-Al2O3-P2O5体系锂离子固体电解质的制备及性能研究

一些具有NASICON型网格结构的固体电解质具有高的电导率和好的稳定性,NASICON的意思是Na Super Ionic Conductor[1]。当NaZr2(PO4)3中P5 被Si4 部分取代时便可以得到具有NASICON结构的Na1 xZr2SixP3-xO12体系,其具有高的钠离子电导率。然而有相同结构的Li1 xZr2SixP3-xO12体系的离子电导率却很低,这是因为Li 半径太小,而NASICON三维网格结构的离子通道太大,两者不匹配而使电导率下降[2]。但当LiZr2(PO4)3中Zr4 被离子半径小些的Ti4 取代,所得LiTi2(PO4)3的通道就与Li 半径相匹配,适合于锂离子的迁移,从而使其电导率…     

Non-centrosymmetric Ba3Ti3O6(BO3)2

The compound previously reported as Ba₂Ti₂B₂O₉ has been reformulated as Ba₃Ti₃B₂O₁₂, or Ba₃Ti₃O₆(BO₃)₂, a new barium titanium oxoborate. Small single crystals have been recovered from a melt with a composition of BaTiO₃:BaTiB₂O₆ (molar ratio) cooled between 1100°C and 850°C. The crystal structure has been determined by X-ray diffraction: hexagonal system, non-centrosymmetric space group, a=8.7377(11) Å, c=3.9147(8) Å, Z=1, wR(F²)=0.039 for 504 unique reflections. Ba₃Ti₃O₆(BO₃)₂ is isostructural with K₃Ta₃O₆(BO₃)₂. Preliminary measurements of nonlinear optical properties on microcrystalline samples show that the second harmonic generation efficiency of Ba₃Ti₃O₆(BO₃)₂ is equal to 95% of that of LiNbO₃.     

Ion-beam irradiation of lanthanum compounds in the systems La2O3-Al2O3 and La2O3-TiO2

Thin crystals of La₂O₃, LaAlO₃, La_2/3TiO₃, La₂TiO₅, and La₂Ti₂O₇ have been irradiated in situ using 1 MeV Kr²⁺ ions at the Intermediate Voltage Electron Microscope-Tandem User Facility (IVEM-Tandem), Argonne National Laboratory (ANL). We observed that La₂O₃ remained crystalline to a fluence greater than 3.1×10¹⁶ ions cm⁻² at a temperature of 50 K. The four binary oxide compounds in the two systems were observed through the crystalline-amorphous transition as a function of ion fluence and temperature. Results from the ion irradiations give critical temperatures for amorphisation (T_c) of 647 K for LaAlO₃, 840 K for La₂Ti₂O₇, 865 K for La_2/3TiO₃, and 1027 K for La₂TiO₅. The T_c values observed in this study, together with previous data for Al₂O₃ and TiO₂, are discussed with reference to the melting points for the La₂O₃-Al₂O₃ and La₂O₃-TiO₂ systems and the different local environments within the four crystal structures. Results suggest that there is an observable inverse correlation between T_c and melting temperature (T_m) in the two systems. More complex relationships exist between T_c and crystal structure, with the stoichiometric perovskite LaAlO₃ being the most resistant to amorphisation.     

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.     

A new 2212-type stair like structure: Bi14Sr21Fe12O61, m=5 member of the generic [Bi2Sr3Fe2O9]m[Bi4Sr6Fe2O16] family

A new oxide, Bi₁₄Sr₂₁Fe₁₂O_61, with a layered structure derived from the 2212 modulated type structure Bi₂Sr₃Fe₂O₉, was isolated. It crystallizes in the I2 space group, with the following parameters: a=16.58(3) Å, b=5.496(1) Å, c=35.27(2) Å and β=90.62°. The single crystal X-ray structure determination, coupled with electron microscopy, shows that this ferrite is the m=5 member of the [Bi₂Sr₃Fe₂O₉]_m[Bi₄Sr₆Fe₂O₁₆] collapsed family. This new collapsed structure can be described as slices of 2212 structure of five bismuth polyhedra thick along , shifted with respect to each other and interconnected by means of [Bi₄Sr₆Fe₂O₁₆] slices. The latter are the place of numerous defects like iron or strontium for bismuth substitution; they can be correlated to intergrowth defects with other members of the family.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃‐Bi₂O₃‐ZnO‐Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1364,介电损耗低至1.2%。     

Synthesis, crystal structure, infrared and Raman spectra of Sr4Cu3(AsO4)2(AsO3OH)4·3H2O and Ba2Cu4(AsO4)2(AsO3OH)3

The two new compounds, Sr₄Cu₃(AsO₄)₂(AsO₃OH)₄·3H₂O (1) and Ba₂Cu₄(AsO₄)₂(AsO₃OH)₃(2), were synthesized under hydrothermal conditions. They represent previously unknown structure types and are the first compounds synthesized in the systems SrO/BaO-CuO-As₂O₅-H₂O. Their crystal structures were determined by single-crystal X-ray diffraction [space group C2/c, a=18.536(4) Å, b=5.179(1) Å, c=24.898(5) Å, β=93.67(3)°, V=2344.0(8) Å³, Z=4 for 1; space group P4₂/n, a=7.775(1) Å, c=13.698(3) Å, V=828.1(2) Å³, Z=2 for 2]. The crystal structure of 1 is related to a group of compounds formed by Cu²⁺-(XO₄)³⁻ layers (X=P⁵⁺, As⁵⁺) linked by M cations (M=alkali, alkaline earth, Pb²⁺, or Ag⁺) and partly by hydrogen bonds. In 1, worth mentioning is the very short hydrogen bond length, D···A=2.477(3) Å. It is one of the examples of extremely short hydrogen bonds, where the donor and acceptor are crystallographically different. Compound 2 represents a layered structure consisting of Cu₂O₈ centrosymmetric dimers crosslinked by As1φ₄ tetrahedra, where φ is O or OH, which are interconnected by Ba, As2 and hydrogen bonds to form a three-dimensional network. The layers are formed by Cu₂O₈ centrosymmetric dimers of CuO₅ edge-sharing polyhedra, crosslinked by As1O₄ tetrahedra. Vibrational spectra (FTIR and Raman) of both compounds are described. The spectroscopic manifestation of the very short hydrogen bond in 1, and ABC-like spectra in 2 were discussed.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃-Bi₂O₃-ZnO-Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1 364,介电损耗低至1.2%。     

Crystal growth, structural characterization and magnetic properties of Ca3CuRhO6, Ca3Co1.34Rh0.66O6 and Ca3FeRhO6

Single crystals of Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆ and Ca₃FeRhO₆ were synthesized by high temperature flux growth in molten K₂CO₃ and structurally characterized by single crystal X-ray diffraction. While Ca₃Co_1.34Rh_0.66O₆ and Ca₃FeRhO₆ crystallize with trigonal (rhombohedral) symmetry in the space group , Z=6: Ca₃Co_1.34Rh_0.66O₆a=9.161(1) Å, c=10.601(2) Å; Ca₃FeRhO₆a=9.1884(3) Å, c=10.7750(4) Å; Ca₃CuRhO₆ adopts a monoclinic distortion of the K₄CdCl₆ structure in the space group C2/c, Z=4: a=9.004(2) Å, b=9.218(2) Å, c=6.453(1) Å, β=91.672(5). All crystals of Ca₃CuRhO₆ examined were twinned by pseudo-merohedry. Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆, and Ca₃FeRhO₆ are structurally related and contain infinite one-dimensional chains of alternating face-sharing RhO₆ octahedra and MO₆ trigonal prisms. In the monoclinic modification, the copper atoms are displaced from the center of the trigonal prism toward one of the rectangular faces adopting a pseudo-square planar configuration. The magnetic properties of Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆, and Ca₃FeRhO₆ are discussed.