GO/Fe3O4/有机胺复合材料的制备及对结晶紫染料的吸附性能

用改进的Hummers法制备了氧化石墨烯,用乙二胺、乙二胺与丁二胺/己二胺混溶来改性氧化石墨烯。用水热法制备了Fe3O4,并用物理混合法制备了GO/Fe3O4/有机胺的三元复合体系。用透射电镜、扫描电镜、红外光谱、热重分析、X射线衍射、VSM和XPS等对所制得的样品进行了结构表征和性能测试,研究了三元复合粒子对结晶紫染料的吸附性能及影响结晶紫染料吸附效果的因素。结果表明:所制备的Fe3O4的平均粒径约为200 nm,粒径分布均匀;复合物中GO为典型的片状结构,GO及有机胺的掺杂没有影响Fe3O4的尖晶石结构;复合物为超顺磁性,Ms为53.0 emu·g~(-1)。吸附结果表明:石墨烯/Fe3O4/有机胺的三元复合材料对结晶紫染料的最大吸附量随浓度增大而增大,而吸附结晶紫染料的移除率却随结晶紫染料浓度增大而减小,并趋向一定值;乙二胺和己二胺混溶比例为5∶1的GO/Fe3O4复合材料吸附性能最佳:结晶紫浓度为400 mg·L~(-1),最大吸附量为164.3 mg·L~(-1)。     

Fe3O4/PEI/GO复合材料的制备及其吸附效果研究

以氧化石墨烯(GO)和聚乙烯亚胺(PEI)为反应物,采用共混法制备PEI/GO,然后将Fe_3O_4纳米颗粒分散沉积到PEI/GO表面,得到了复合材料Fe_3O_4/PEI/GO。利用傅里叶红外光谱(FT-IR)、透射电子显微镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等方法对该材料进行表征,并研究了其对Cu~(2+)的吸附性能。结果表明,PEI与GO的羧基反应生成了酰胺键,Fe_3O_4成功沉积在GO表面,GO层状结构的规整性被破坏。Freundlich等温吸附模型和准二级动力学模型能更好地拟合Cu~(2+)在Fe_3O_4/PEI/GO表面的吸附过程,说明该吸附主要受化学作用控制,可能是Fe_3O_4/PEI/GO表面的胺基、羧基、羟基等活性基团与Cu~(2+)发生了离子交换或络合反应所致。     

中空分级结构Fe3O4@C/rGO复合材料的合成及其储锂性能

以氧化石墨烯(GO)为基底,Fe(NO_3)_3·9H_2O、异丙醇、甘油为原料,通过溶剂热法和后续热处理过程2步合成了Fe_3O_4@C/rGO复合材料,实现了碳包覆的Fe_3O_4纳米粒子自组装形成的分级结构空心球在氧化石墨烯片上的原位生长。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和恒流充放电等手段分析了材料的物理化学性能与储锂性能。结果表明,该复合材料在5.0 A·g~(-1)的电流密度下,仍有437.7 mAh·g~(-1)的可逆容量,在1.0 A·g~(-1)下循环200圈后还有587.3 mAh·g~(-1)的放电比容量。这主要归因于还原态氧化石墨烯(rGO)对碳包覆Fe_3O_4分级空心球整体结构稳定性和导电性的提高。     

氨基化修饰介孔Fe3O4@SiO2@mSiO2磁性核壳复合微球的可控制备及吸附性能

以水热法制备的高磁饱和强度Fe_3O_4纳米颗粒为核,正硅酸乙酯(TEOS)为前驱体,采用改进的St觟ber法,制备介孔SiO_2包覆Fe_3O_4磁性核壳复合微球。利用XRD、SEM、TEM、N2吸附-脱附、FTIR和VSM对制备样品的物相结构、形貌和磁性能进行了测试表征。研究结果表明,制备的复合材料呈球形,粒径分布均一,材料的比表面积和磁饱和强度分别为413 m2·g-1和68.93emu·g-1。研究了TEOS的添加量对复合微球形貌的影响,随着TEOS添加量的增加,SiO_2壳层增厚,复合粒子形貌均匀,饱和磁化强度有所下降,仍具有良好的超顺磁性。在此基础上,通过接枝法在复合微球的表面接枝-NH2,制备了一种新型磁性纳米吸附剂(Fe_3O_4@SiO_2@m SiO_2-NH2),进而研究了其对水中重金属离子Cr(Ⅵ)的吸附性能。通过动力学拟合,Fe_3O_4@SiO_2@m SiO_2-NH2对Cr(Ⅵ)的吸附过程是准二级动力学模型占主导地位,探究了该材料对Cr(Ⅵ)的吸附过程和吸附机理。结果表明,其吸附机理及吸附容量与Cr(Ⅵ)的离子形态及-NH2有关,并通过吸附剂与吸附质之间的电子共用或静电吸附实现。     

壳聚糖改性磁性碳基吸附剂的制备及其对水中Cr(Ⅲ)-EDTA的吸附机理

利用二茂铁制备磁性碳基材料(Fe_3O_4@C),通过壳聚糖(CS)功能化,制备CS改性Fe_3O_4@C复合吸附材料(Fe_3O_4@C-CS)。利用红外光谱(FTIR)、X射线衍射(XRD)、振动样品磁强计(VSM)、热重分析(TGA)和X射线光电子能谱(XPS)等对Fe_3O_4@C-CS表征分析,并通过改变浓度、温度、时间、pH和阳离子等条件系统研究对水中已配位的三价铬(Cr(Ⅲ)-EDTA)的吸附性能。结果表明Fe_3O_4@C已经成功被CS功能化,在pH=4.0、反应温度25℃、投加量0.4 g·L~(-1)时,吸附等温线符合Langmuir模型,理论最大吸附量为12.63 mg·g~(-1),吸附动力学符合拟二级动力学模型,吸附行为是自发进行的吸热过程。结合吸附实验结果和XPS表征分析,静电吸附和配位作用是Fe_3O_4@C-CS吸附剂去除水中Cr(Ⅲ)-EDTA的主要机制。4次吸附-脱附循环后,Fe_3O_4@C-CS对水中Cr(Ⅲ)-EDTA仍具有较高的吸附效率。     

Fe_3O_4/PAA/ATP纳米复合磁性微凝胶吸附剂对Pb(Ⅱ)吸附动力学和吸附热力学研究

用γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH-570)对纳米Fe_3O_4磁性粒子和凹凸棒黏土纳米棒晶进行表面改性,通过KH-570的桥接,在纳米Fe_3O_4磁性粒子和凹凸棒纳米棒晶的表面原位接枝聚合丙烯酸单体,制备Fe_3O_4/PAA/ATP纳米复合磁性微凝胶。将该复合微凝胶用作吸附剂,处理水体中的Pb(Ⅱ),研究其对Pb(Ⅱ)的吸附动力学和吸附热力学。     

新型磁性分子印迹聚合物快速萃取-高效液相色谱法测定牛血清白蛋白

以牛血清白蛋白(BSA)为模板分子,多巴胺为功能单体,磁性四氧化三铁-石墨烯-多壁碳纳米管(Fe_3O_4-G/MWNT)为载体,制备了一种新型磁性分子印迹聚合物材料(Fe_3O_4-G/MWNT@MIP),用于萃取牛血清白蛋白。用10 mmol·L~(-1)的磷酸盐缓冲溶液(pH 6.0,含1.0mmol·L~(-1) NaCl)将血清样品稀释10倍,加入20.0mg的Fe_3O_4-G/MWNT@MIP,振摇平衡20min,弃去液体,用5.0 mL的10 mmol·L~(-1) NaCl溶液(pH 6.0)洗涤固体,再用2.0 mL的0.5mmol·L~(-1) NaCl溶液(pH 5.0)解吸20min,将洗脱液移至超滤管中,以12 000转·min~(-1)离心20min后,取超滤液进行高效液相色谱分析。结果表明:Fe_3O_4-G/MWNT@MIP对BSA具有良好的选择性,最大吸附容量达56.79mg·g~(-1),重复使用20次后,最大吸附容量仅降低了7%。方法成功于应用于小牛血清中牛血清白蛋白的测定,加标回收率在90.0%～120%之间,测定值的相对标准偏差(n=7)小于3.0%。     

P(St-co-MMA)微球表面包覆磁性氧化石墨烯的制备与表征

以单分散的苯乙烯-甲基丙烯酸甲酯共聚物(P(St-co-MMA))微球为载体,FeSO_4·7H_2O和FeCl_3·6H_2O为铁源,NaOH为沉淀剂,在氧化石墨烯(GO)存在下,利用反相共沉淀法通过原位复合技术在P(St-co-MMA)微球表面包覆磁性氧化石墨烯(P(St-co-MMA)/Fe_3O_4/GO)。通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)、振动样品磁强计(VSM)和氮吸附-脱附等温线对P(St-co-MMA)/Fe_3O_4/GO样品的结构和性能进行表征分析。研究结果表明:纳米级的磁性氧化石墨烯成功地负载在了微米级的共聚物P(St-co-MMA)表面,所制备的P(St-co-MMA)/Fe_3O_4/GO微纳米复合物平均孔径为14.55nm,孔体积为0.204 2cm~3/g,比表面积为56.14m~2/g。该复合物具有超顺磁性和良好的磁响应性,能够满足磁分离的要求。     

一锅共缩聚法制备氨基改性Fe3O4@SiO2及其Cr(Ⅵ)吸附性能增强

采用一锅共缩聚法制备了不同N原子个数的硅烷偶联剂改性并且SiO_2包覆的球形磁性Fe_3O_4@SiO_2-x N(x=1,2,3)复合吸附剂,其中1N、2N、3N分别代表γ-氨丙基三甲氧基硅烷、γ-氨乙基氨丙基三甲氧基硅烷、二乙烯三胺基丙基三甲氧基硅烷。采用XRD、SEM、N2吸附-脱附、元素分析、FT-IR和ζ电位等手段对典型样品的物理化学性质进行了对比表征。结果表明,改性后的复合材料均具有良好的球形形貌和较高的等电点,其含N量呈现出Fe_3O_4@SiO_2-1NFe_3O_4@SiO_2-2NFe_3O_4@SiO_2-3N的趋势。对Cr(Ⅵ)的静态吸附实验表明,其最大吸附量随着N含量的增加而降低,即Fe_3O_4@SiO_2-1N(79.74 mg·g~(-1))Fe_3O_4@SiO_2-2N(63.05 mg·g~(-1))Fe_3O_4@SiO_2-3N(55.37 mg·g~(-1)),并对其呈现这种趋势的机理进行了分析。对模拟废水的吸附实验表明,样品Fe_3O_4@SiO_2-1N可以同时吸附废水中的多种重金属离子,并且可以在30 s内实现磁性分离。     

部分还原氧化石墨烯-Fe_3O_4对水中Mn(Ⅱ)的快速去除

采用改进的Hummers法制备了氧化石墨烯(GO),继而用一步共沉淀法制备了部分还原氧化石墨烯-四氧化三铁复合物(PRGO-Fe_3O_4).采用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、X射线能量色散光谱(EDX)、高分辨透射电子显微镜(HRTEM)、选区电子衍射(SAED)及傅里叶变换红外光谱(FTIR)等技术对其进行了分析表征;考察了p H值、接触时间、吸附材料用量、共存物质、GO的还原、循环使用次数等因素对Mn(Ⅱ)吸附行为的影响.结果表明,PRGO-Fe_3O_4中Fe_3O_4颗粒分布均匀,大小为15~20 nm,剩磁和矫顽力均很小.因Fe_3O_4颗粒的锚定作用,石墨烯片层很薄,使PRGO-Fe_3O_4对Mn(Ⅱ)表现出高效的吸附性能和良好的循环使用性能:当p H=7、PRGO-Fe_3O_4用量为500 mg/g时,对201.3211 mg/L的Mn(Ⅱ)溶液仅3 min即达吸附平衡,吸附率和吸附量分别为99.35%和404.49 mg/g,磁分离仅需10 s,经5次循环吸附后,容量保持率为首次的78%.机理与热力学研究结果表明,吸附为吸热、自发的单层化学吸附.     

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.     

Phase relations in the K2W2O7-K2WO4-KPO3-Bi2O3 system and structure of K6.5Bi2.5W4P6O34

The phase relations in the cross-section of the K₂W₂O₇-K₂WO₄-KPO₃ containing 15 mol% Bi₂O₃ were undertaken using flux method. Crystallization fields of K_6.5Bi_2.5W₄P₆O₃₄, K₂Bi(PO₄)(WO₄), Bi₂WO₆, KBi(WO₄)₂ and their cocrystallization areas were identified. Novel phase K_6.5Bi_2.5W₄P₆O₃₄ was characterized by single-crystal X-ray diffraction: sp. gr. P−1, a=9.4170(5), b=9.7166(4), c=17.6050(7) Å, α=90.052(5)°, β=103.880(5)° and γ=90.125(5)°. It has a layered structure, which contains {K₇Bi₅W₈P₁₂O₆₈}_∞ layers stacked parallel to ab plane and sheets composed by potassium atoms separating these layers. Sandwich-like {K₇Bi₅W₈P₁₂O₆₈}_∞ layers are assembled from [W₂P₂O₁₃]_∞ and [BiPO₄]_∞ building units, and are penetrated by tunnels with K/Bi atoms inside. FTIR-spectra of K₂Bi(PO₄)(WO₄) and K_6.5Bi_2.5W₄P₆O₃₄ were discussed on the basis of factor group theory.     

Li2SO4-Na2SO4-H2O和Li2SO4- K2SO4-H2O溶液的体积性质

本文用高精度数字式振荡管密度计测定了288K至318K温度范围内Li₂SO₄ + Na₂SO₄ + H₂O和 Li₂SO₄ + K₂SO₄ + H₂O三元体系的密度。混合溶液的离子强度范围从0.1到4.5 mol.kg_–1,混合溶液中Na₂SO₄和K₂SO₄的离子强度分数为0.2,0.4,0.6和0.8。用密度实验值拟合得到了不同温度下Pitzer离子相互作用模型混合参数θ_V和 ψ_V,模型的计算值与实验值的偏差在±0.002 g.cm_–3以内。用Pitzer模型计算了不同离子强度下三元体系的混合体积。     

Extension of the La7Mo7O30 structural type with La7Nb3W4O30 and La7Ta3W4O30 compounds

Two compounds of formula La₇A₃W₄O₃₀ (with A=Nb and Ta) were prepared by solid-state reaction at 1450 and 1490 °C. They crystallize in the rhombohedric space group R-3 (No. 148), with the hexagonal parameters: , and , . The structure of the materials was analyzed from X-ray, neutron and electronic diffraction. These oxides are isostructural of the reduced molybdenum compound La₇Mo₇O₃₀, which are formed of perovskite rod along [111]. An order between (Nb, Ta) and W is observed.     

KCl-KBO2-K2CO3, K2MoO4-KBO2-K2CO3, and K2WO4-KBO2-K2CO3 ternary systems

phase diagrams of KCl-KBO₂-K₂CO₃, K₂MoO₄-KBO₂-K₂CO₃, and K₂WO₄-KBO₂-K₂CO₃ ternary systems were studied by a calculation-experimental method and differential thermal analysis (DTA). The coordinates of ternary eutectics were determined to be E ₁: 622°C, 8.5 mol % KBO₂, 56.5 mol % KCl, and 35 mol % K₂CO₃; E ₂: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂MoO₄; E ₃: 710°C, 23 mol % KBO₂, 43 mol % K₂CO₃, and 34 mol % K₂WO₄. The specific heats of melting of the eutectics were determined.     

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…     

Preparation and structure of NaSr0.5Al2B2O7 and NaCa0.5Al2B2O7

Two compounds NaSr_0.5Al₂B₂O₇ and NaCa_0.5Al₂B₂O₇, have been found to crystallize into a new structure type by Rietveld refinement from X-ray powder diffraction data. Their structure belongs to hexagonal space group P6₃/m, with lattice parameters of , for NaSr_0.5Al₂B₂O₇ and , for NaCa_0.5Al₂B₂O₇, respectively. The structure is built up by [Al₂B₂O₇]²⁻ double layer and Na⁺/Ca²⁺ or Na⁺/Sr²⁺ ions alternatively stacking along the c-axis. The sites in the inter-double layer are fully occupied jointly by Na and Ca or Sr, but the intra-double layer sites are only half occupied solely by Na. A mechanism of the transition of the structure from CaAl₂B₂O₇ to present structure type by replacing only 1% Ca by Na (2%) as observed by Chang and Keszler (Mater. Res. Bull. 33 (1998) 299) is also proposed.     

SnSbBiS4-SnS and SnSbBiS4-Sn2Sb6S11 sections of the SnS-Sb2S3-Bi2S3 ternary system

SnSbBiS₄-SnS and SnSbBiS₄-Sn₂Sb₆S₁₁ sections were studied by physicochemical methods (DTA, X-ray powder diffraction, microstructure observation, and microhardness measurements). These sections were found to be eutectic quasi-binary sections of the SnS-Sb₂S₃-Bi₂S₃ ternary system. Solid solution regions based on the initial components were found on either side of the sections. Alloys in the solid solution region are p-type semiconductors.     

Synthesis and characterization of quaternary selenides Sn2Pb5Bi4Se13 and Sn8.65Pb0.35Bi4Se15

Quaternary selenides Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅ were synthesized from the elements in sealed silica tubes; their crystal structures were determined by single-crystal and powder X-ray diffraction. Both compounds crystallize in monoclinic space group C2/m (No.12), with lattice parameters of Sn₂Pb₅Bi₄Se₁₃: a = 14.001(6) Å, b = 4.234(2) Å, c = 23.471(8) Å, V = 1376.2(1) Å³, R₁/wR₂ = 0.0584/0.1477, and GOF = 1.023; Sn_8.65Pb_0.35Bi₄Se₁₅: a = 13.872(3) Å, b = 4.2021(8) (4) Å, c = 26.855(5) Å, V = 1557.1(5) Å³, R₁/wR₂ = 0.0506/0.1227, and GOF = 1.425. These compounds exhibit tropochemical cell-twinning of NaCl-type structures with lillianite homologous series L(4, 5) and L(4, 7) for Sn₂Pb₅Bi₄Se₁₃ and Sn_8.65Pb_0.35Bi₄Se₁₅, respectively. Measurements of electrical conductivity indicate that these materials are semiconductors with narrow band gaps; Sn₂Pb₅Bi₄Se₁₃ is n-type, whereas Sn_8.65Pb_0.35Bi₄Se₁₅ is a p-type semiconductor with Seebeck coefficients −80(5) and 178(7) μV/K at 300 K, respectively.     

Structural chemistry of Sr3Cr2WO9, Ca3Cr2WO9, and Ba3Cr2WO9

We have studied the preparation and crystallographic structure of three perovskite-type compounds: Sr₃Cr₂WO₉, cubic, the lattice parameter of which is a = 7.812Å; Ca₃Cr₂WO₉, tetragonal, the lattice parameters of which are a = 5.408 Å and c = 7.635Å; and Ba₃Cr₂WO₉, hexagonal, the lattice parameters of which are a = 5.691 Å and c = 13.957Å. We have compared these three structures and shown the relationship between the dimensions of the alkaline-earth metal and the existence of the different structures.