自掺杂TiO2纳米管：液相制备及光催化性能

采用水合肼（N₂H₄·H₂O）作为还原剂,在液相环境中制备了自掺杂TiO₂纳米管阵列（NTs）。利用FE-SEM、EDS、XPS、XRD、Raman、UV-Vis/NIR分光光度法以及半导体特性分析系统（Keithley 4200 SCS）分别对样品的形貌,晶体结构,光学特性以及电学性能进行了表征。结果表明：通过这种方法制备的自掺杂TiO₂NTs在带隙中引入了大量的氧空位,创造了氧空位能级,从而提高了样品的电导率,有效提高光生电子-空穴对的产生、分离和传输。此外,由于氧空位的作用,使得TiO₂NTs的带隙变窄,增强了可见光吸收能力,致使样品具有较高的光催化活性,并通过降解甲基橙溶液对样品的光催化活性进行评估。结果显示当光照150min后,自掺杂TiO₂NTs对甲基橙溶液的降解率达73%,并且这种催化剂便于回收和重复使用。     

Bi3.25Nd0.75Ti3O12纳米结构: 可控合成及其可见光催化活性

用水热法制备不同形貌的掺钕钛酸铋(Bi3.25Nd0.75Ti3O12,BNdT)纳米粉体.透射电子显微镜(TEM)结果表明,通过控制OH-浓度可以得到不同形貌的纳米粉体.基于不同条件下制备的样品微结构分析,提出了这些不同形貌的形成机制.紫外-可见漫反射光谱(UV-Vis DRS)表明BNdT样品的带隙能(Eg)约为1.984 eV.利用可见光照射下甲基橙降解实验评价了BNdT样品的光催化性能.结果表明,BNdT的光催化活性比商用TiO2催化剂P25和掺氮TiO2高得多.OH-浓度为10 mol·L-1时制备的BNdT纳米线光催化效率最高,经可见光照射360min,浓度为0.01 mmol·L-1甲基橙溶液的降解率可达到93.0%,且循环使用4次后,其光催化活性并没有明显降低,表明BNdT是一种稳定有效的可见光催化剂.     

层状、花形和棒状钛酸铋纳米结构的可控合成及光催化性能

通过可控水热法,制备出层状、花形和棒状钛酸铋(Bi4Ti3O12,BIT)纳米结构。通过X射线衍射(XRD)和场发射扫描电子显微镜(FESEM)观测其结构和形貌特征。XRD图显示,所制备的样品为层状钙钛矿结构。FESEM结果表明,通过控制水热过程的反应参数可以得到不同形貌的纳米粉体。紫外-可见漫反射光谱(UV-Vis DRS)表明BIT样品的带隙能约为2.63～2.95 eV。利用可见光(λ>420 nm)照射下的甲基橙降解实验评价了BIT样品的光催化性能。结果表明,BIT的光催化活性比掺氮TiO2(N-TiO2)高得多。所制备的层状BIT纳米结构光催化效率最高,经可见光照射360 min,甲基橙溶液的降解率可达95.0%。同时还研究了结构和形貌对不同条件下制备的BIT样品光催化活性的影响。     

掺镁钛酸钡纳米棒的水热合成和光催化性能

用水热法制备掺镁钛酸钡(Ba1-xMgxTiO3(x=0,0.10,0.20,0.30,0.40),BMT)纳米粉体。运用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、紫外可见漫反射光谱技术(DRS)等手段对样品进行了表征,并在可见光照射下于溶液中考察了其光催化降解甲基橙反应活性。结果表明,通过控制氢氧根浓度可以得到不同形貌的纳米粉体。基于不同条件下制备的样品的微结构分析,提出了这些不同形貌的形成机制。制备出的BMT材料的带隙能约为2.61 eV。光催化反应结果表明BMT的光催化活性比掺氮TiO2高得多。OH-浓度为8 mol·L-1时制备的BMT纳米棒光催化效率最高,经可见光照射360 min,浓度为0.01 mmol·L-1甲基橙溶液的降解率可达到93.0%,且循环使用4次后,其光催化活性并没有明显降低,表明BMT是一种稳定有效的可见光催化剂.     

可见光响应Gd-N-TiO2纳米光催化剂的溶胶-水热制备及表征

利用溶胶-水热法制备了未掺杂、N掺杂、Gd掺杂和Gd-N共掺杂TiO2纳米光催化剂,以甲基橙(MO)溶液在紫外光和可见光照射下的光催化脱色评价其光活性;采用XRD、XPS、BET、UV-Vis和PL分析技术表征样品的物理化学性能,探讨Gd-N共掺杂对TiO2光活性的影响机制。结果表明,Gd掺杂能有效抑制光生e-/h+的复合,提高光量子效率;抑制TiO2晶粒生长,改善样品表面织构特性,明显提高紫外光活性。N掺杂窄化TiO2带隙,拓宽光吸收范围至可见光区,从而提高了可见光活性。Gd-N共掺杂进一步窄化带隙增加可见光吸收,减小晶粒尺寸,改善样品的表面织构特性,增强织构的热稳定性。与单掺杂样品相比,Gd-N-TiO2在可见光照射下对MO的光催化脱色活性进一步提高,这归因于Gd-N共掺杂的协同效应。     

碳修饰二氧化钛纳米管的制备及其光催化性能研究

本文以钛酸丁酯为前躯体,蔗糖为碳源,采用溶胶-凝胶法和水热法相结合的方法制备了不同含量碳修饰的TiO2纳米管光催化剂(C/TiO2NTs)。通过元素分析(EA)、X射线衍射(XRD)、透射电镜(TEM)、N2吸附-脱附和紫外-可见漫反射吸收光谱(UV-vis-DRS)等手段对所制备的催化剂进行了表征分析。研究了C/TiO2NTs在紫外光及模拟日光条件下光催化降解甲基橙溶液的活性,并讨论了焙烧温度和碳含量对催化性能的影响。结果表明:碳修饰催化剂中的TiO2为锐钛矿型,碳修饰后使TiO2光催化剂的禁带宽度变窄,在可见光区吸收增强,可有效提高TiO2在紫外和可见光下的光催化活性,而且当焙烧温度为400℃,碳含量为0.90wt.%时,其光催化活性最好。     

Au掺杂方式对锐钛矿TiO2光催化性能的影响

结合超临界乙醇干燥技术, 采用沉积-沉淀(DP)和共沉淀(CP)法分别制备了具有单一锐钛矿晶相的Au/TiO2和Au(0.2%, 原子分数)-TiO2光催化剂, 通过XRD、BET、TEM、XPS和Raman手段表征样品中Au的掺杂形态, 以光催化降解甲基橙为模型反应考察了样品的光催化活性. 结果表明, DP法制备的Au/TiO2在110 ℃干燥处理后, 表面存在的Au3+能有效地促进锐钛矿TiO2光催化性能, 其一级反应速率常数比纯锐钛矿TiO2提高了3.2倍, 比商用光催化剂Degussa-P25提高了4.1倍, 而当Au3+被还原为Au0后光催化活性下降. 用CP法制备的Au-TiO2并没有较大地提高锐钛矿TiO2光催化性能, 在焙烧温度达到800 ℃时, Au向表面迁移聚集, 造成锐钛矿TiO2晶格氧空位和缺陷位增加, 使光催化活性下降.     

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.     

层状纳米光催化复合材料H0.8Fe0.8Ti1.2O4/TiO2的合成及性质

用固相合成法制备出K0.8Fe0.8Ti1.2O4,并用离子交换反应制备出H0.8Fe0.8Ti1.2O4;通过C3H7NH2层间膨胀,TiO2粒子的插入和紫外光分解等反应,合成出一种新的层状光催化纳米复合材料-H0.8Fe0.8Ti1.2O4/TiO2.X射线衍射和漫反射等表征结果表明 该样品的层间高度为0.47nm,禁带能隙为2.18和2.88eV.用(>400 nm的光照射30 min,0.4 g样品可使甲基橙溶液(20 mg/L)的降解率达到22.1%.而同样条件下标准TiO2(P-25)仅为6.2%,表明所研制的层状纳米复合材料具有较高的光催化活性.     

ZnO和TiO2纳米粒子的光致发光性能及其与光催化活性的关系

采用沉淀法和溶胶-凝胶法制备了ZnO和TiO2及掺Zn2+的TiO2纳米粒子,用XRD和荧光光谱(FS)等手段对样品进行了表征,重点探讨了样品光致发光机制及与光催化活性的关系.结果表明,ZnO和TiO2样品在大于带隙能的光激发下均表现出明显的FS信号,热处理温度升高,FS信号强度下降,并且二者的FS信号类似,这可能与二者具有类似的电子能带结构有关,同时也说明FS信号主要源于表面氧空位以及吸附氧物种等引起的激子或表面态能级.掺杂Zn2+使TiO2纳米粒子FS信号增强,这主要与表面氧空位和缺陷等量增加有关;此外,在光催化氧化苯酚实验中,样品光催化活性与其FS信号强度顺序一致,即FS信号越强,活性越高.这是由于在光致发光过程中,FS信号主要源于表面氧空位,而在光催化反应中,表面氧空位有利于氧化反应进行.     

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.     

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.     

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。     

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%。     

Preparation of ZrO2-TiO2-CeO2 and Its Application in the Selective Catalytic Reduction of NO with NH3

TiO₂,ZrO₂-TiO₂,andZrO₂-TiO₂-CeO₂ were prepared by co-precipitation method and characterized by X-ray diffraction (XRD), specific surface area measurements (BET), temperature programmed desorption (NH₃-TPD), oxygen storage capacity (OSC), and temperature programmed reduction (H₂-TPR). The results showed that ZrO₂-TiO₂-CeO₂ exhibited large number of surface strong acid, possessed some oxygen storage capacity, and strong redox property. The three materials were used as supports and the monolith catalysts were prepared with 1% (w) V₂O₅ and 9% (w)WO₃ for selective catalytic reduction (SCR) of NO with ammonia in the presence of excessive O₂, and the results of catalytic activity showed that the catalyst used ZrO₂-TiO₂-CeO₂ as support yielded nearly 100% NO conversion at 275 °C at a gas hourly space velocity (GHSV) of 10000 h⁻¹, and it had the best catalytic activity and showed great potential for practical application.     

The Phase Relations in the System In2O3–TiO2–MgO at 1100 and 1350°C

The phase relations in the system In₂O₃–TiO₂–MgO at 1100 and 1350°C are determined by a classical quenching method. In this system, there are four pseudobinary compounds, In₂TiO₅, MgTi₂O₅ (pseudobrookite type), MgTiO₃ (ilmenite type), and Mg₂TiO₄ (spinel type) at 1100°C. At 1350°C, in addition to these compounds there exist a spinel-type solid solution Mg_2−xIn_2xTi_1−xO₄ (0≤x≤1) and a compound In₆Ti₆MgO₂₂ with lattice constants a=5.9236(7) Å, b=3.3862(4) Å, c=6.3609(7) Å, β=108.15(1)°, and q=0.369, which is isostructural with the monoclinic In₃Ti₂FeO₁₀ in the system In₂O₃–TiO₂–MgO. The relation between the lattice constants of the spinel phase and the composition nearly satisfies Vegard's law. In₆Ti₆MgO₂₂ extends a solid solution range to In₂₀Ti₁₇Mg₃O₆₇ with lattice constants of a=5.9230(5) Å, b=3.3823(3) Å, c=6.3698(6) Å, β=108.10(5)°, and q=0.360. The distributions of constituent cations in the solid solutions are discussed in terms of their ionic radius and site preference effect.     

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.