Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₂Ti₂O₇/TiO₂/Bi₄Ti₃O₁₂复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明：TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂     

Bi2Ti2O7/TiO2/Bi4Ti3O12多异质结的构筑及其增强的可见光催化性能

以静电纺丝技术制备的TiO₂纳米纤维为基质,硝酸铋为铋源,KOH为矿化剂,成功制备了多异质结Bi₄Ti₃O₁₂/TiO₂/Bi₂Ti₂O₇复合纳米纤维光催化剂。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外可见漫反射光谱(UV-Vis DRS)等一系列表征,对其物相组成、微观形貌和光学性质等进行分析。结果表明： TiO₂纳米纤维的介入,将Ⅰ型异质结Bi₂Ti₂O₇/Bi₄Ti₃O₁₂分离为2个Ⅱ型异质结Bi₂Ti₂O₇/TiO₂和Bi₄Ti₃O₁₂/TiO₂。Bi₂Ti₂O₇、Bi₄Ti₃O₁₂和TiO₂三者的协同作用,有效提高了可见光吸收能力,改变了光生载流子的传输路径,降低了光生电子与空穴的复合几率,从而获得高效的光催化降解CH₃CHO性能。可见光照8 h,Bi₄Ti₃O₁₂/TiO₂/Bi₂Ti₂O₇复合纳米纤维对CH₃CHO的降解率达到87.1%。     

Phase formation, crystal chemistry, and properties in the system Bi2O3-Fe2O3-Nb2O5

Subsolidus phase relations have been determined for the Bi₂O₃-Fe₂O₃-Nb₂O₅ system in air (900-1075 °C). Three new ternary phases were observed—Bi₃Fe_0.5Nb_1.5O₉ with an Aurivillius-type structure, and two phases with approximate stoichiometries Bi₁₇Fe₂Nb₃₁O₁₀₆ and Bi₁₇Fe₃Nb₃₀O₁₀₅ that appear to be structurally related to Bi₈Nb₁₈O₅₇. The fourth ternary phase found in this system is pyrochlore (A₂B₂O₆O′), which forms an extensive solid solution region at Bi-deficient stoichiometries (relative to Bi₂FeNbO₇) suggesting that ≈4-15% of the A-sites are occupied by Fe³⁺. X-ray powder diffraction data confirmed that all Bi-Fe-Nb-O pyrochlores form with positional displacements, as found for analogous pyrochlores with Zn, Mn, or Co instead of Fe. A structural refinement of the pyrochlore 0.4400:0.2700:0.2900 Bi₂O₃:Fe₂O₃:Nb₂O₅ using neutron powder diffraction data is reported with the A cations displaced (0.43 Å) to 96g sites and O′ displaced (0.29 Å) to 32e sites (Bi_1.721Fe_0.190(Fe_0.866Nb_1.134)O₇, Fd3¯m (#227), ). This displacive model is somewhat different from that reported for Bi_1.5Zn_0.92Nb_1.5O_6.92, which exhibits twice the concentration of small B-type cations on the A-sites as the Fe system. Bi-Fe-Nb-O pyrochlores exhibited overall paramagnetic behavior with large negative Curie-Weiss temperature intercepts, slight superparamagnetic effects, and depressed observed moments compared to high-spin, spin-only values. The single-phase pyrochlore with composition Bi_1.657Fe_1.092Nb_1.150O₇ exhibited low-temperature dielectric relaxation similar to that observed for Bi_1.5Zn_0.92Nb_1.5O_6.92; at 1 MHz and 200 K the relative permittivity was 125, and above 350 K conductive effects were observed.     

Raman scattering investigations on lanthanum-doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

The ferroelectric ceramics of Bi₄Ti₃O₁₂, SrBi₄Ti₄O₁₅, and lanthanum-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ were synthesized, and their Raman spectra were investigated. La-doping resulted in the enlargement of remnant polarization of Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The structure of the Bi₂O₂ layers and TiO₆ octahedra of the intergrowth was found to be different from those of Bi₄Ti₃O₁₂ and SrBi₄Ti₄O₁₅. La³⁺ ions exhibit pronounced selectivity for the occupation of A site as La content is lower than 0.50, and tend to be incorporated into Bi₂O₂ layers when the La content is higher than 0.50. Lanthanum substitution brings about the structural phase transition in Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The variation of ferroelectric property may be attributed to combined contribution from the decreasing of the oxygen vacancies, the relaxation of the lattice distortion, the destroying of the insulation and the space charge compensation effects of the Bi₂O₂ slabs.     

Chemical twinning of the pyrochlore structure in the system Bi2O3-Fe2O3-Nb2O5

New ternary bismuth iron niobates having structures based on chemical twinning of pyrochlore are described. Bi_5.67Nb₁₀FeO₃₅ has hexagonal symmetry, P6₃/mmc, , , Z=2 and Bi_9.3Nb_16.9Fe_1.1O_57.8 has rhombohedral symmetry, R-3m, , , Z=3. The structures of both phases were determined and refined to R₁=0.04 using single-crystal X-ray data. They can be described as being derived from the pyrochlore structure by chemical twinning on (111)_py oxygen planes. The chemical twin operation produces pairs of corner-connected hexagonal tungsten bronze (HTB) layers as in the HTB structure, so the structures may alternatively be described as pyrochlore:HTB unit-cell intergrowth structures. In the hexagonal phase the pyrochlore blocks have a width of 12 Å, whereas the rhombohedral phase has pyrochlore blocks of two widths, 6 and 12 Å, alternating with HTB blocks. It is proposed that the previously reported binary 4Bi₂O₃:9Nb₂O₅ phase has a related structure containing pyrochlore blocks all of width 6 Å. A feature of the structures is partial occupancy (∼65%) of the Bi sites and displacement of the Bi atoms from the ideal pyrochlore A sites towards the surrounding oxygen atoms, as observed in Bi-containing pyrochlores.     

球形Bi4Ti3O12制备及其可见光催化性能

采用水热法合成球形钛酸铋复合氧化物光催化剂,利用SEM、XRD和UV-Vis DRS等表征手段对复合氧化物的晶体结构、微观形貌和光学性能进行了分析,结果表明,制备的钛酸铋复合氧化物为10 nm的球形颗粒,具有良好的晶型结构,禁带宽度为2.7 nm,有较好的可见光吸收能力。以亚甲基蓝、甲基橙及酸性品红为目标污染物,研究了复合氧化物在可见光下的光催化降解有机污染物的性能,并对光催化降解机理进行了探讨。结果表明,在可见光照射下,该复合氧化物对酸性品红降解效果明显优于亚甲基蓝和甲基橙,光照150 min下,降解率可达91%。     

球形Bi_4Ti_3O_(12)制备及其可见光催化性能

采用水热法合成球形钛酸铋复合氧化物光催化剂,利用SEM、XRD和UV-Vis DRS等表征手段对复合氧化物的晶体结构、微观形貌和光学性能进行了分析,结果表明,制备的钛酸铋复合氧化物为10 nm的球形颗粒,具有良好的晶型结构,禁带宽度为2.7 nm,有较好的可见光吸收能力。以亚甲基蓝、甲基橙及酸性品红为目标污染物,研究了复合氧化物在可见光下的光催化降解有机污染物的性能,并对光催化降解机理进行了探讨。结果表明,在可见光照射下,该复合氧化物对酸性品红降解效果明显优于亚甲基蓝和甲基橙,光照150 min下,降解率可达91%。     

Defect and dopant properties of the Aurivillius phase Bi4Ti3O12

Computer modelling techniques have been used to investigate the defect and oxygen transport properties of the Aurivillius phase Bi₄Ti₃O₁₂. A range of cation dopant substitutions has been considered including the incorporation of trivalent ions (M³⁺=Al, Ga and In). The substitution of In³⁺ onto the Bi site in the [Bi₂O₂] layer is predicted to be the most favourable. The calculations suggest that lanthanide (Ln³⁺) doping at the dilute limit preferentially occurs in the [Bi₂O₂] layer, with probable distribution over both the [Bi₂O₂] and the perovskite A-site at higher dopant levels. It is predicted that the reduction process involving Ti³⁺ and oxygen vacancy formation is energetically favourable. The energetics of oxide vacancy migration between various oxygen sites in the structure have been investigated.     

Phase relations in the system Bi2O3CdO

Phase relations in the system Bi₂O₃CdO were studied in the composition range from 90-30 mole% Bi₂O₃. A new phase, Bi₂O₃ · CdO, was found to exist up to 925 K. At this temperature it decomposes to form CdO and the 5Bi₂O₃ · 3CdO phase. The 5Bi₂O₃ · 3CdO phase is stable between 925 and 963 K and melts incongruently. Below 925 K it decomposes to Bi₂O₃ · CdO and 6Bi₂O₃ · CdO. The phase 5Bi₂O₃ · 3CdO has cubic symmetry. The Sillenite-type bcc phase 6Bi₂O₃ · CdO forms above 897 K from oxide mixtures in the solid state or from fused oxide mixtures, but the compound could never be prepared as a single phase.     

不同形貌Bi4Ti3O12粒子的可控合成及光催化性能

研究了用一步水热法制备的不同形貌的钛酸铋(Bi₄Ti₃O₁₂, BIT)粒子的光学和可见光催化性能, 并对其晶体结构和微观结构用X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等手段进行了表征. XRD结果表明, 所制备的BIT 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粒子. 紫外-可见漫反射光谱(UV-Vis DRS)表明BIT 样品的带隙能约为2.88-2.93 eV. 利用可见光(λ>420 nm)照射下的甲基橙(MO)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. 研究了形貌对BIT 光催化性能的影响. 所制备的BIT纳米带光催化效率最高, 经可见光照射360 min, 甲基橙溶液的降解率可达到95.0%.     

A novel method for the preparation of Bi4Ti3O12 nanoparticles in w/o microemulsion

Nanometer-sized Bi₄Ti₃O₁₂ particles have been prepared by chemical reaction of bismuth nitrate pentahydrate, titanium sulfate and ammonia solution in a reverse microemulsion system consisting of water, OP (P-octyl polyethylene glycol phenylether, non-ionic surfactant), n-butanol (co-surfactant), and cyclohexane (oil). Precursor hydroxides precipitated in the droplets of water-in-oil (w/o) microemulsion were calcined at 800 °C for 4 h to form Bi₄Ti₃O₁₂ nanoparticles. The samples were investigated with X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared spectrophotometer (FT-IR) and ultraviolet visible spectrophotometer (UV–vis). It was found that the as-prepared Bi₄Ti₃O₁₂ nanoparticles had small particle sizes (35 nm), high crystallinity, narrow size distributions and strong light absorption properties not only in the ultraviolet light but also in the visible light region.     

Structural Behavior of the Four-Layer Aurivillius-Phase Ferroelectrics SrBi4Ti4O15 and Bi5Ti3FeO15

Rietveld refinement of powder neutron diffraction data has been used to study the crystal structures of the four-layer Aurivillius-phase ferroelectrics Bi₅Ti₃FeO₁₅ (at 25°C) and SrBi₄Ti₄O₁₅ (at a series of temperatures up to 800°C). At 25°C both materials adopt the polar orthorhombic space group A2₁am, in common with two-layer analogues such as SrBi₂Ta₂O₉. At temperatures well above the ferroelectric Curie temperature (i.e., at temperatures of 650°C and above, with T_c∼550°C) SrBi₄Ti₄O₁₅ transforms to the centrosymmetric tetragonal space group I4/mmm. However, there is good evidence from the raw diffraction data of a very subtle intermediate paraelectric orthorhombic phase, of Amam symmetry, in the region 550>650°C. The distortion in the ferroelectric phase can be traced to displacements of the cations in the A site of the perovskite block, with cooperative tilting of the BO₆ octahedra. The nature of the octahedral tilt system, cation disorder at the perovskite A and B sites, and the phase transition sequence in SrBi₄Ti₄O₁₅, which parallels that found in SrBi₂Ta₂O₉, are discussed.     

Bi3.25La0.75Ti3O12纳米线的可见光催化性能

研究了用一步水热法制备的掺镧钛酸铋(Bi_3.25La_0.75Ti₃O₁₂, BLT)纳米线的光学和可见光催化性能, 并对其晶体结构和微观结构用X射线衍射(XRD)、透射电子显微镜(TEM)和高分辨透射电子显微镜(HRTEM)等手段进行了表征. 结果表明, 制备的纳米线为纯相的Bi_3.25La_0.75Ti₃O₁₂, 平均直径约为25 nm. 室温光致发光谱(PL)显示BLT纳米线在433和565 nm附近有较强的发射峰, 分别对应激子发射和表面缺陷发光. 紫外-可见漫反射光谱(UV-Vis DRS)表明BLT样品的带隙能约为2.07 eV. 利用可见光(λ>420 nm)照射下的甲基橙降解实验评价了BLT样品的光催化性能. 结果表明, BLT的光催化活性比商用TiO₂催化剂P25、掺氮TiO₂和纯相钛酸铋(Bi₄Ti₃O₁₂, BIT)高得多. BLT光催化剂具有更高催化活性的原因是La³⁺离子掺杂拓展了BIT对可见光的吸收范围, 同时抑制了BIT的光生电子-空穴的复合.     

Soft chemistry synthesis of the perovskite CaCu3Ti4O12

The perovskite CaCu₃Ti₄O₁₂ (CCT) has been obtained after calcination of oxalate precursors at 900–1000 °C in air. Those precursors are prepared using a soft chemistry method, the coprecipitation. The oxalate powders consist of disk-like particles of 2–3 μm diameter and 300–400 nm thickness. By varying the ratio of the initial amounts of metal chlorides, additional phases (CaTiO₃, TiO₂ and CuO) could be obtained besides CCT. The corresponding multiphased ceramics present improved dielectric properties.     

MgFe2O4-Fe2O3纳米粉体的软化学合成及电磁学特性

Nano-MgFe₂O₄-Fe₂O₃ magnetic powders were synthesized by citrate gel under microwave irradiation. The structure，particle size distribution，electromagnetic characteristics of nano-MgFe₂O₄-Fe₂O₃ were characterized by using TG-DTA, X-ray, electronic microscope, nano-size measurement and electromagnetism measurement apparatus。The results show that the product is a mixture of MgFe₂O₄ and Fe₂O₃ with average size of 44 nm, tanδ for the product is 0.265 and 0.610 at frequency of 1.0 GHz and 1.8 GHz respectively.     

Study of the liquidus in the system Bi2O3TiO2

The liquidus in the system Bi₂O₃TiO₂ has been determined in the range 2 to 22 mole % TiO₂ by a thermobalance technique and by DTA. It has been confirmed that Bi₁₂TiO₂₀ melts incongruently at 875°C and that the eutectic composition between Bi₁₂TiO₂₀ and Bi₂O₃ melts at 795°C.     

Synthesis and crystal chemistry of BaNd2Ti3O10, BaNd2Ti5O14, and Nd4Ti9O24

Two new ternary compounds BaNd₂Ti₃O₁₀ (1:1:3) and BaNd₂Ti₅O₁₄ (1:1:5) have been identified in the BaONd₂O₃TiO₂ system. Single crystals of the compounds were grown and unit cell dimensions and space group symmetry were determined. BaNd₂Ti₃O₁₀ is orthorhombic with a = 3.8655 ± 0.0003, b = 28.156 ± 0.003 and c = 7.6221 ± 0.0007 Å and possible space groups are Cmcm or Cmc2. The compound melts congruently at 1640 ± 20°C. BaNd₂Ti₅O₁₄ is also orthorhombic with a = 22.346 ± 0.002, b = 12.201 ± 0.001 and c = 3.8404 ± 0.0003 Å and possible space groups are Pbam and Pba2. This compound melts congruently at 1540 ± 20°C. Single crystals of the binary compound Nd₄Ti₉O₂₄ were also grown and found to be orthorhombic with a = 35.289 ± 0.003, b = 13.991 ± 0.001, c = 14.479 ± 0.001 Å, space group Fddd.     

Effect of carbon nanotubes addition on electrochemical performance and thermal stability of Li4Ti5O12 anode in commercial LiMn2O4/Li4Ti5O12 full-cell

Li₄Ti₅O₁₂ (LTO)/carbon nanotubes (CNTs) composite material is synthesized based on a solid-state method by sand-milling, spray-drying and calcining at 850 ℃ under N₂ flow. The LTO/CNTs samples with 1 wt% and 3 wt% weight ratio of CNTs addition and the pristine LTO sample are prepared. The rate performance and the thermal stability of these samples are investigated based on LiMn₂O₄ (LMO)/LTO full-cell. The results show that theweight ratio of CNTs addition has distinct effect on LTO performances. The composite materials of LTO composited CNTs have better performance at high-rate due to the intercalation enhancement by conductive network of CNTs. At second, the overcharging temperature response of the cell's surface with 1 wt% CNTs addition is the lowest. The particle size distribution is measured and the most uniform particles are obtained with 1 wt% CNTs addition. This trend could explain that the mediumquantity of CNTs is optimal to improve the heat and mass transfer and prevent the problems of crystallite growing interference and aggregation during the calcination process.     

Synthesis and structural study of stoichiometric Bi2Ti2O7 pyrochlore

Bi₂Ti₂O₇ has been synthesized using a co-precipitation route from H₂O₂/NH_3(aq) solutions of titanium with aqueous bismuth nitrate. The stoichiometric material crystallizes into a pale yellow cubic pyrochlore phase. A powder X-ray diffraction study showed this crystallization to be very temperature sensitive, the pure phase can only be obtained within a few degrees of 470°C. Time-of-flight powder neutron diffraction studies of Bi₂Ti₂O₇ (Space group , a=10.37949(4) Å at ambient temperature, Z=8, R_p=3.95%, R_wp=4.75%) revealed positional disorder in the bismuth site and in the O′ oxide site both at ambient temperature and at 2 K.     

On the mechanism of propene oxidation on Bi3Mo2FeO12 and Bi2Mo2Fe2O12 catalysts

Oxidation of propene on Bi₃Mo₂FeO₁₂ and Bi₂Mo₂Fe₂O₁₂ and Bi₂(MoO₄)₃ has been compared with the interaction of allyl iodide and diallyl oxalate with these compounds. Bi₂Mo₂Fe₂O₁₂ was found to be the most active and the least selective in propene oxidation. The three compounds show at the same time the same activity in acrolein formation from allyl iodide and oxalate. The results are interpreted in terms of the two-center mechanism of propene oxidation [9, 10]. The role of iron in elementary steps of propene oxidation on Bi–Mo–Fe–O catalysts is also discussed.

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Bi₃Mo₂FeO₁₂, Bi₂Mo₂Fe₂O₁₂ Bi₂(MoO₄)₃ . Bi₂Mo₂Fe₂O₁₂ . . , . Bi–Mo–Fe–O.