铁掺杂TiO_2微米带的制备及其光催化性能

采用模板法与溶胶-凝胶法结合,以脱脂棉为模板制备了掺杂Fe3+的TiO2微米带光催化材料.并利用红外光谱(FTIR)、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)对掺杂不同比例Fe3+产物的表面形貌及晶型进行了表征.以甲基橙的脱色降解为模式反应,考察了样品的光催化性能.结果表明:以脱脂棉为模板在酸性条件下制备出了宽度5～8μm,厚度约100～500nm的TiO2带状体,此条件下生成的纳米TiO2晶体晶粒直径大小10～30nm,长度100～500nm,呈棒状.且得出当Fe3+掺杂量为0.04%时光催化效果最优,20min对甲基橙的催化效率为91%.     

海绵状纳米结构TiO2膜的制备及其光催化活性

采用电化学阳极氧化法在钛表面构筑了海绵状纳米结构TiO2膜. 应用扫描电子显微镜(SEM)和X射线衍射(XRD)对膜层的形貌和晶型进行了分析和表征, 考察了阳极氧化时间对膜层厚度的影响, 并通过海绵状纳米结构TiO2膜对甲基橙的光催化降解研究了膜层厚度与光催化活性的关系. 结果表明, 海绵状纳米结构TiO2膜对甲基橙具有光催化降解作用, 而且随着膜层厚度的增加, 光催化降解速率显著增大, 厚度为2.2 μm的海绵状纳米结构TiO2膜对甲基橙的光催化降解速率是厚度为480 nm的6.4倍.     

模板水热法纳米TiO2制备及光催化性能研究

以聚乙烯吡咯烷酮(PVP)为模板剂,钛酸四正丁酯(TBOT)为钛源,水热法制备纳米TiO2。采用XRD,SEM、TEM和UV-Vis DRS等测试手段对其形貌和结构进行表征。通过对甲基橙的光催化降解实验,探讨了焙烧温度、催化剂用量和溶液pH值对光催化性能的影响。结果表明,TiO2具有锐钛矿相,平均晶粒尺寸约为23.2 nm,TiO2颗粒呈片层状或由片层状堆积的疏松圆球形,经超声后即分散为八面体晶粒。550℃焙烧的样品,紫外光照3 h后,对甲基橙的降解率可达84.2%。相比普通水热法,采用模板剂法制得的TiO2吸收带发生红移,因而也具有较好的可见光催化活性。     

光催化活性二氧化钛溶胶的低温制备与表征

以钛酸丁酯为原料,在70 ℃制备了具有光催化活性的TiO2溶胶.用X射线衍射仪(XRD)和透射电子显微镜(TEM)表征了溶胶结构;用紫外-可见分光光度计研究了TiO2溶胶对甲基橙的吸附和光催化降解性能.XRD图谱表明TiO2溶胶粒子的一次粒径约4 nm,晶型主要为锐钛矿型,并含有少量结晶不完善的板钛矿型;TEM图像表明溶胶中TiO2粒子分散良好,二次粒径约10 nm.吸附实验表明TiO2溶胶使甲基橙溶液褪色约17%;光催化实验表明TiO2溶胶光催化性能优异,自然光催化降解甲基橙溶液(10 mg/L),16min后甲基橙浓度几乎降为0.     

Sn4+掺杂TiO2中空纤维材料的制备及光催化性能

以Ti(OCH2CH2CH2CH3)4为钛源,脱脂棉花纤维为模板,利用浸渍-热转化两步法制备了具有中空结构的Sn4+掺杂TiO2光催化纤维材料(Sn4+/TiO2),利用X-射线衍射(XRD)、扫描电子显微镜(SEM)和紫外-可见光谱(UV-vis)等技术对其晶体结构、形貌、尺寸、光吸收特性等进行了表征.以亚甲基蓝(MB)溶液的脱色降解为模型反应,考察了样品Sn4+/TiO,在太阳光下的光催化性能.结果表明:利用该法制得的Sn4+/TiO2材料具有中空纤维结构;煅烧温度影响材料Sn4+/TiO2的相结构、组成、尺寸、形貌以及催化性能;Sn4+的掺入能够显著改善TiO2在太阳光条件下的催化性能,600℃煅烧2h所得的Sn4+掺杂量x=0.29％的TiO2中空纤维材料具有最佳的光催化活性,太阳光下2h即可使MB溶液的脱色降解率达97.28％;重复使用5次仍可使MB溶液的脱色降解率保持在90％以上,且该催化剂材料易于离心分离去除.     

溴化银/二氧化钛复合材料的可见光催化性能

将硝酸银的乙醇溶液与溶胶凝胶TiO2混合得到前驱体,随后经共沉淀-煅烧制备得到AgBr/TiO2复合材料;采用扫描电镜、X射线衍射仪、X射线光电子能谱仪分析了复合材料的形貌、晶体结构、Ag元素的价态,采用紫外-可见漫反射光谱仪测定了其光吸收性能;进而以甲基橙(MO)的可见光降解为探针反应测定了AgBr/TiO2复合材料的可见光催化性能.结果表明,当前驱体在不同温度下煅烧后,无定形TiO2颗粒逐渐增大,并逐渐转变为锐钛矿结构;担载的AgBr可明显拓展TiO2的可见光吸收范围;Ag物种主要以Ag+形式存在.当煅烧温度为300℃时,复合材料的光催化活性最高,MO的降解率在60min内达到90%以上;随着煅烧温度的增加,催化活性逐渐降低.     

纳米复合材料Ag/TiO_2-ZrO_2的制备及其微波增强光催化降解甲基橙

采用EO20PO70EO20(P123)作模板剂,通过溶胶-凝胶-程序升温溶剂热一步法,并经萃取处理制备了具有光催化活性的纳米复合材料Ag/TiO2-ZrO2.用X射线衍射(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、N2吸附-脱附测定和扫描电子显微镜配合X射线能量色谱仪(SEM-EDS)等测试手段对其组成、结构及形貌等进行了表征.结果表明,复合材料Ag/TiO2-ZrO2中Ag以单质形式存在,材料具有双孔结构,颗粒分布较均匀,结构也较规整,平均孔径约为3.6和9.0nm.通过微波增强光催化降解染料甲基橙的实验,对复合材料Ag/TiO2-ZrO2的光催化活性进行了探究.实验结果表明,微波辅助光催化效果优于紫外辐射,并且萃取后的合成产物Ag/TiO2-ZrO2在90min内对甲基橙的降解率可达81.5%,其活性高于市售P25以及TiO2-ZrO2.     

糖葫芦状二氧化钛纳米线阵列的制备及其光催化性能

 采用溶胶-电泳技术,在多孔阳极氧化铝(PAA)模板的有序孔洞中制备了高度取向的糖葫芦状TiO2纳米线阵列光催化剂,通过扫描电镜(SEM)和X射线衍射对样品进行了表征. 结果表明, TiO2纳米线为锐钛矿晶型,纳米线直径与PAA模板的孔径一致,且分布均匀. 纳米线取向性极好,每根纳米线都具有周期性凹凸,形似糖葫芦,因此命名为糖葫芦状TiO2纳米线阵列. 以甲基橙的降解反应评价了光催化剂的活性,与相同条件下制备的TiO2/玻璃膜相比, TiO2纳米线阵列在光照1 h时对甲基橙的降解率达到93.6%, 比前者提高了40.2%, 具有很好的光催化活性.     

活性炭负载纳米TiO2光催化降解性能研究

本文研究活性炭负载纳米TiO2的光催化降解性能和影响甲基橙废水处理的主要因素。结果表明:用溶胶-凝胶法制备的TiO2-活性炭催化剂具有比表面积大、分散性高、光催化降解性能好、可重复利用等优点;采用30W高硼紫外光灯,TiO2-活性炭光催化降解浓度为1500mg/L甲基橙废水的最优工艺条件是:催化剂活化温度为700℃、用量为1.0g/L、废水起始pH值为1、反应温度为45℃、光照时间为50m in。在此条件下,甲基橙和CODC r的去除率分别达99.8%和99.7%。     

树叶为模板网状TiO2的制备及其光催化性能

采用模板法与溶胶-凝胶法相结合的方法, 以羽状网脉的洋槐树叶为模板制备出网状的二氧化钛光催化材料. 利用红外光谱仪(FT-IR)、扫描电子显微镜(SEM)、能量色散型X射线光谱仪(EDX)、X射线衍射仪(XRD)对样品的表面形貌、成分和晶型进行表征, 以甲基橙的脱色降解为模式反应, 考察了宏观形貌对TiO₂光催化性能的影响. 结果表明: 以树叶为模板制得的TiO₂, 呈网状结构, 网孔直径约为5～10 μm, 且有少量直径约为2～3 μm规则球形和直径约5 μm管状的TiO₂; 当pH＝3时, 网状TiO₂在3 h内对甲基橙的降解率分别比粉末TiO₂高37.2%, 比商品粉末TiO₂高44.6%, 且重复使用4次后, 降解率仍能保持在90%以上, 明显优于粉末TiO₂, 同时为制备其它形貌的TiO₂提供一种新思路.     

Li_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3,Na_(1.3)Ti_(1.7)Al_(0.3)(PO_4)_3的离子交换研究

研究了在不同温度下的NaNO3和AgNO3水溶液中Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3离子交换行为.实验表明Li1.3Ti1.7Al0.3(PO4)3和Na1.3Ti1.7Al0.3(PO4)3均显示出了高选择性与Na+和Ag+进行离子交换的特征,且对Ag+的选择性高于Na+.升高温度可显著提高Ag/Li和Ag/Na的交换反应速度.     

Crystal growth, structure determination, and optical properties of new potassium-rare-earth silicates K3RESi2O7 (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu)

Single crystals of K₃RESi₂O₇ (RE=Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) were grown from a potassium fluoride flux. Two different structure types were found for this series. Silicates containing the larger rare earths, RE=Gd, Tb, Dy, Ho, Er, Tm, Yb crystallize in a structure K₃RESi₂O₇ that contains the rare-earth cation in both a slightly distorted octahedral and an ideal trigonal prismatic coordination environment, while in K₃LuSi₂O₇, containing the smallest of the rare earths, lutetium is found solely in an octahedral coordination environment. The structure of K₃LuSi₂O₇ crystallizes in space group P6₃/mmc with a=5.71160(10) Å and c=13.8883(6) Å. The structures containing the remaining rare earths crystallize in the space group P6₃/mcm with the lattice parameters of a=9.9359(2) Å, c=14.4295(4) Å, (K₃GdSi₂O₇); a=9.88730(10) Å, c=14.3856(3) Å, (K₃TbSi₂O₇); a=9.8673(2) Å, c=14.3572(4) Å, (K₃DySi₂O₇); a=9.8408(3) Å, c=14.3206(6) Å, (K₃HoSi₂O₇); a=9.82120(10) Å, c=14.2986(2) Å, (K₃ErSi₂O₇); a=9.80200(10) Å, c=14.2863(4) Å, (K₃TmSi₂O₇); a=9.78190(10) Å, c=14.2401(3) Å, (K₃YbSi₂O₇). The optical properties of the silicates were investigated and K₃TbSi₂O₇ was found to fluoresce in the visible.     

Near infrared study of aqueous rare-earth ethylsulfates

The near infrared spectra of aqueous solutions of the ethylsulfates of La, Nd, Gd, Tb, Er, Yb, Lu, Y, and Na have been determined from about 0.2 mol-dm^–3 to nearly saturation. The extinction coefficients of water have been calculated taking into account the absorption of ethylslfate anions determined in separate experiments. Their values appeared to be nearly the same as that of pure water. The relative contents of free OH groups in 0.5 and 0.7M solutions have been estimated from the absorbances at 1160 nm. They were lower in solutions of the heavy rare-earth ethylsulfates (Tb, Er, Yb, Lu) than in equimolar solutions of the lighter ones (La, Nd), confirming our previous view that secondary hydration of the heavy trivalent rare-earth cations is distinctly stronger than that of the lighter ones. A comparison of the spectra of these aqueous ethylsulfates with those of perchlorates shows that the structure-breaking ability of the C₂H₅SO ₄ ^– ion is much smaller than that of perchlorate anion.     

The crystal chemistry of Bi6TP2O15+x, T=Fe, Ni, Zn: Isomorphism and polymorphism, structural relationship to Bi6TiP2O16

The crystal structures of compounds with nominal compositions Bi₆FeP₂O_15+x (I), Bi₆NiP₂O_15+x (II) and Bi₆ZnP₂O_15+x (III) were determined from single-crystal X-ray diffraction data. They are monoclinic, space group I2, Z=2. The lattice parameters for (I) are a=11.2644(7), b=5.4380(3), c=11.1440(5) Å, β=96.154(4)°; for (II) a=11.259(7), b=5.461(4), c=11.109(7) Å, β=96.65(1)°; for (III) a=19.7271(5), b=5.4376(2), c=16.9730(6) Å, β=131.932(1)°. Least squares refinements on F² converged for (I) to R1=0.0554, wR₂=0.1408; for (II) R₁=0.0647, wR₂=0.1697; for (III) R₁=0.0385, wR₂=0.1023. The crystals are complexly twinned by 2-fold rotation about , by inversion and by mirror reflection. The structures consist of edge-sharing articulations of OBi₄ tetrahedra forming layers in the a-c plane that then continue by edge-sharing parallel to the b-axis. The three-dimensional networks are bridged by Fe and Ni octahedra in (I) and (II) and by Zn trigonal bipyramids in (III) as well as by oxygen atoms of the PO₄ moieties. Bi also randomly occupies the octahedral sites. Oxygen vacancies exist in the structures of the three compounds due to required charge balances and they occur in the octahedral coordination polyhedron of the transition metal. In compound (III), no positional disorder in atomic sites is present. The Bi-O coordination polyhedra are trigonal prisms with one, two or three faces capped. Magnetic susceptibility data for compound (I) were obtained between 4.2 and 350 K. Between 4.2 and 250 K it is paramagnetic, μ_eff=6.1 μ_B; a magnetic transition occurs above 250 K.     

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%。     

电感耦合等离子体光谱法(ICP-AES)测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量

针对银精矿样品复杂,难消解的特点,研究了不同酸溶法和碱熔法对样品的消解情况,建立了硝酸,盐酸,氢氟酸,高氯酸消解银精矿的方法。根据元素灵敏度和抗干扰性,选定各元素的测定波长。通过酸溶样和碱熔样测定结果比对,验证了方法准确性。建立了四酸消解-电感耦合等离子体光谱法测定银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的方法,元素的线性相关系数均在0.9999以上。通过共存元素干扰实验,确定了银精矿中高含量元素(铜、铅、锌、铁、锑、铋等)对测定元素结果没有影响。方法检出限：Cu 0.0063 mg/L, Pb 0.0159 mg/L ,Zn 0.0090 mg/L,As 0.0192 mg/L, Cd 0.0093 mg/L ,Ca 0.0084 mg/L, Mg 0.0075 mg/L, Mn 0.0081 mg/L。测定下限：Cu 0.0105mg/L,Pb 0.0265 mg/L, Zn 0.0150 mg/L, As 0.0320 mg/L, Cd 0.0155 mg/L, Ca 0.0140 mg/L, Mg 0.0125 mg/L,Mn 0.0135 mg/L。3个样品的相对标准偏差在0.87%~3.56%之间,加标回收率在95.00%~103.56%之间。方法流程短,操作简单,快速,灵敏度和再现性高,结果准确可靠,可以满足银精矿中铜、铅、锌、砷、镉、钙、镁、锰含量的测定。     

Structural studies of five layer Aurivillius oxides: A2Bi4Ti5O18 (A=Ca, Sr, Ba and Pb)

The room temperature structures of the five layer Aurivillius phases A₂Bi₄Ti₅O₁₈ (A=Ca, Sr, Ba and Pb) have been refined from powder neutron diffraction data using the Rietveld method. The structures consist of [Bi₂O₂]²⁺ layers interleaved with perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks. The structures were refined in the orthorhombic space group B2eb (SG. No. 41), Z=4, and the unit cell parameters of the oxides are a=5.4251(2), b=5.4034(1), c=48.486(1); a=5.4650(2), b=5.4625(3), c=48.852(1); a=5.4988(3), b=5.4980(4), c=50.352(1); a=5.4701(2), b=5.4577(2), c=49.643(1) for A=Ca, Sr, Ba and Pb, respectively. The structural features of the compounds were found similar to n=2-4 layers bismuth oxides. The strain caused by mismatch of cell parameter requirements for the [Bi₂O₂]²⁺ layers and perovskite-like [A₂Bi₂Ti₅O₁₆]²⁻ blocks were relieved by tilting of the TiO₆ octahedra. Variable temperature synchrotron X-ray studies for Ca and Pb compounds showed that the orthorhombic structure persisted up to 675 and 475 K, respectively. Raman spectra of the compounds are also presented.     

Structure Study of Bi2.5Na0.5Ta2O9 and Bi2.5Nam−1.5NbmO3m+3 (m=2-4) by Neutron Powder Diffraction and Electron Microscopy

The crystal structures of Bi_2.5Na_0.5Ta₂O₉ and Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=3,4) have been investigated by the Rietveld analysis of their neutron powder diffraction patterns (λ=1.470 Å). These compounds belong to the Aurivillius phase family and are built up by (Bi₂O₂)²⁺ fluorite layers and (A_m-1B_mO_3m+1)^2- (m=2-4) pseudo-perovskite slabs. Bi_2.5Na_0.5Ta₂O₉ (m=2) and Bi_2.5Na_2.5Nb₄O₁₅ (m=4) crystallize in the orthorhombic space group A2₁am, Z=4, with lattice constants of a=5.4763(4), b=5.4478(4), c=24.9710 (15) and a=5.5095(5), b=5.4783(5), c=40.553(3) Å, respectively. Bi_2.5Na_1.5Nb₃O₁₂ (m=3) has been refined in the orthorhombic space group B2cb, Z=4, with the unit-cell parameters a=5.5024(7), b=5.4622(7), and c=32.735(4) Å. In comparison with its isostructural Nb analogue, the structure of Bi_2.5Na_0.5Ta₂O₉ is less distorted and bond valence sum calculations indicate that the Ta-O bonds are somewhat stronger than the Nb-O bonds. The cell parameters a and b increase with increasing m for the compounds Bi_2.5Na_m-1.5Nb_mO_3m+3 (m=2-4), causing a greater strain in the structure. Electron microscopy studies verify that the intergrowth of mixed perovskite layers, caused by stacking faults, also increases with increasing m.     

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.     

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%。