三元异质结构Ag-Bi2MoO6/BiPO4光催化剂高效降解苯酚红

多组分复合体系有利于电荷的有效分离,减少电子空穴对的复合几率。通过低温液相法首次合成Ag-Bi₂MoO₆/BiPO₄三元异质结构光催化剂。利用XRD、SEM、EDX及XPS等技术对样品进行了表征。结果表明,Ag纳米粒子光照积累在Bi₂MoO₆/BiPO₄的表面,通过表面等离子共振增加对可见光的吸收,同时作为电子受体促进了光生电子的转移。Ag、BiPO₄和Bi₂MoO₆形成三元异质结构有效地抑制了光生电子空穴对的复合。Ag-Bi₂MoO₆/BiPO₄表现出优异的光催化性能,其光催化活性较BiPO₄、Bi₂MoO₆和Bi₂MoO₆/BiPO₄样品有较大提高。并且对Ag-Bi₂MoO₆/BiPO₄三元异质结构的光催化机制进行了讨论。光催化过程中反应活性物种捕获实验结果表明h⁺和O₂^·-是主要的活性基团.     

Bi2WO6光催化剂的γ射线辐射效应

本文首次研究了高能辐射(γ射线)对Bi₂WO₆纳米晶体结构和光催化性能的影响. 结果表明,尽管高能辐射不会改变Bi₂WO₆纳米晶体的形貌,但是Bi₂WO₆粉末的颜色在高吸收剂量辐照(507 kGy)后发生了明显的变化,并且辐照后Bi₂WO₆的XRD谱图也显示,随着吸收剂量的增加,(113)晶面对应的2θ从28.37°移到28.45°,说明晶格参数在γ射线辐照下还是发生了细微的变化. XPS表征结果证明,Bi₂WO₆晶体结构的变化源于高剂量辐射下氧空位缺陷的产生. Bi₂WO₆纳米晶体的禁带宽度(E_g)随吸收剂量的增加也出现减小的趋势. 用水溶液中亚甲基蓝的可见光照分解反应作为模型反应考察了辐照后的Bi₂WO₆纳米晶体的光催化活性,结果表明,辐照后的Bi₂WO₆纳米晶体的光催化活性随着吸收剂量的增加而逐渐升高. 将经过反应后的Bi₂WO₆纳米晶体再次回收,进行循环催化,发现这些辐照后的Bi₂WO₆纳米晶体在三次循环使用后光催化性能仍然能够保持,说明高能辐射产生的氧空位缺陷具有良好的稳定性.     

大规模合成具有氧空位的多孔Bi2O3用于有效降解亚甲基蓝

光催化降解有机污染物由于其具有低能耗和绿色环保的特点,已经成为研究的热点. 氧化铋纳米晶体的带隙在2.0∽2.8 eV之间,利用它催化可见光降解有机污染物具有较高的活性,从而引起了越来越多的关注. 尽管近年来已经开发了几种制备Bi₂O₃基半导体材料的方法,但是仍然难以用简单的方法大规模地制备高活性的Bi₂O₃催化剂. 因此,开发简单可行的大规模制备Bi₂O₃纳米晶体的方法对于工业废水处理的潜在应用具有重要意义. 本文通过蚀刻商用BiSn粉末,然后进行热处理,成功地大规模制备了多孔Bi₂O₃. 获得的多孔Bi₂O₃在亚甲基蓝(MB)的光催化降解中表现出优异的活性和稳定性. 对该机理的进一步研究表明,多孔Bi₂O₃合适的能带结构允许生成活性氧物种,例如O₂^-·和·OH,可有效降解MB.     

二维GaTe/Bi2Se3异质结：一类有潜力的Z型光解水催化剂

本文基于第一性原理方法,计算了二维GaTe/Bi₂Se₃异质结的电子结构、界面电荷转移、静电势分布、吸收光谱及光催化性质. 计算结果表明异质结是一个小能隙的准直接半导体,能有效捕获太阳光. 由于相对较强的界面內建极化电场和带边轻微弯曲,导致异质结中的光生电子和空穴分别有效分离在GaTe单层和Bi₂Se₃薄片上,可用于析氢和产氧. 这些理论计算结果意味着二维GaTe/Bi₂Se₃异质结是一类有潜力的Z型太阳能全解水催化剂.     

掺铋BaF2晶体的制备及其近红外发光研究

通过温度梯度法制备了Bi₂O₃:BaF₂以及BiF₃:BaF₂晶体.在Bi₂O₃:BaF₂晶体中观察到了发光峰位于961 nm,半高宽202 nm的超宽带红外发光.在BiF₃:BaF₂晶体中检测到Bi²⁺和Bi³⁺可见区的发光,但是没有观察到红外发光.通过γ射线辐照实现了BiF₃:BaF₂晶体的近红外发光, 发光峰位于1135 nm,半高宽192 nm.讨论了Bi₂O₃和BiF₃掺杂BaF₂晶体的红外发光的机理.     

复合层状Bi7Ti4NbO21铁电陶瓷的结构与介电和压电性能研究

制备了Bi₇Ti₄NbO_{21，Bi4Ti3O12及Nb掺杂Bi4Ti3O12(Nb-Bi4Ti3O12)层状结构铁电陶瓷材料.结合Nb-Bi 4Ti3O12的介电温谱和 退极化实验结果，研究了Bi7Ti4NbO21的晶体结构 对其介电、压电性能的影响 .高分辨透射电镜结果表明，在Bi7Ti4NbO21中， 沿着c轴方向，(Bi2Ti3O10)^2-和(BiTiNbO7)^2-两个类钙钛矿层分别 与(Bi2O2)²⁺层叠加堆积而成.这种晶体结构决定了Bi7Ti4NbO21的 介电温谱在668℃和845℃出现介 电双峰.结合极化样品的退化实验分析，说明材料在这两个温度附近发生了铁电—铁电相变 、铁电—顺电相变，分别是(Bi2Ti3O10)^{2-< /sup>和(BiTiNbO7)2-层状 结构发生微观结构相变的结果.在退极化过程中，由于受热时钙钛矿层内空位引起的缺陷偶 极子的定向排列受到破坏，引起材料部分退极化，表现为300℃热处理后Bi7Ti 4NbO 21的压电活性降低了10%，显示了室温下材料的压电性能来源于自发极化的固有电 偶极子和缺陷偶极子的共同贡献.}}     

pH值对水热法制备的Bi4Ti3O12晶体光催化活性的影响

采用无助剂、非模板的水热法可控制备Bi₄Ti₃O₁₂ (BIT)晶体．通过调节反应物的pH值可以选择性地获得BIT纳米球、纳米带和纳米片．通过对不同pH值制备的样品的结构分析研究了这些不同形貌的形成机制．pH值为1制备的BIT样品在可见光下光催化活性最高．基于不同pH值制备的BIT样品的形状、尺寸和局部结构振动分析了光催化活性不同的原因．     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

网状钼酸铋的可见光催化活性

采用无助剂、无模板的水热法成功合成网状Bi₂MoO₆. pH值对这一形貌的形成起重要作用. 所制备的网状Bi₂MoO₆样品表现出优异的可见光催化活性,其光催化活性比固相法合成的块状Bi₂MoO₆样品高得多.     

掺Bi的GeO2-Al2O3-Na2O玻璃的热学和光学性质

 用高温熔融法制备了96GeO-(3-χ)Al₂O₃-χNa₂O-1NaBiO₃ （将χ分别为0，0.5，1.5的玻璃命名为A1，A2，A3）和 96GeO-(3.5-ψ)Al₂O₃-ψχNa₂O-0.5Bi₂O₃（将ψ分别为0，0.5，2的玻璃命名为B1，B2，B3）玻璃。观察到样品在1 220 nm处（800 nm 激光二极管激发）的超宽带发光特性（半高宽约250 nm）。结果表明，以NaBiO₃形式引入Bi⁵⁺到玻璃原料中比以Bi₂O₃形式引入Bi³⁺到原料中得到的玻璃在1 220 nm处的发光强度大4.6倍，且荧光寿命和荧光半高宽也分别从280 μs和195 nm增加到了434 μs和275 nm。从A3，A2和A1的吸收边带的红移可初步推断出A3，A2及A1玻璃中Bi5+的含量逐步增加。总结吸收光谱与发射光谱的变化规律，认为Bi离子近红外高发射强度和宽荧光半高宽是由Bi⁵⁺的发光引起的。在两组玻璃中，热稳定性以及荧光发射截面积与荧光寿命的乘积值和荧光发射截面积与荧光半高宽的乘积值随着Na₂O含量的增加而增加。     

Fabrication and efficient visible light-induced photocatalytic activity of Bi2MoO6/BiPO4 composite

Novel Bi₂MoO₆/BiPO₄ composites with heterojunction structure were fabricated by a one-step hydrothermal method. The photocatalytic properties of Bi₂MoO₆/BiPO₄ composites were evaluated by photocatalytic degradation of rhodamine B (Rh B) under visible light irradiation (λ>420 nm). The results showed that Bi₂MoO₆/BiPO₄ photocatalysts showed much higher photocatalytic activity for the Rh B degradation than the pure BiPO₄ and Bi₂MoO₆ under visible light. The best photocatalytic performance of Bi₂MoO₆/BiPO₄ with about 98.0% Rh B degradation located at molar ratio of 2:1 under visible light illumination for 30 min. The enhanced photocatalytic activity could be mainly ascribed to the formation of heterojunction interface in Bi₂MoO₆/BiPO₄ composites, which is beneficial to the transfer and separation of photogenerated electron–hole pairs, as well as the strong visible light absorption resulting from the sensitization role of Bi₂MoO₆ to BiPO₄. It was also observed that the photodegradation of Rh B is chiefly attributed to the oxidation action of the generated O₂⁻ radicals and the action of h_vb⁺ through direct hole oxidation process.     

Flowerlike PtCl4/Bi2WO6 composite photocatalyst with enhanced visible-light-induced photocatalytic activity

Flowerlike PtCl₄/Bi₂WO₆ composite photocatalyst was successfully synthesized through a simple two-step method involving a template-free hydrothermal process and the following impregnation treatment. The samples were fully characterized by the study of X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis absorption spectra. The results indicated that the doping of Pt species did not affect the crystal structure and the morphology of Bi₂WO₆ photocatalyst, but it had great influences on the photocatalytic activity of Bi₂WO₆ towards rhodamine-B (RhB) degradation. Besides, the Pt species was found to be present as PtCl₄ in the composite samples, and also an optimal Pt species content on the surface of Bi₂WO₆ photocatalyst was discovered with the highest photocatalytic ability. The improved photocatalytic performance could be ascribed to the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Meanwhile, a possible mechanism for RhB photocatalytic degradation over PtCl₄/Bi₂WO₆ catalyst was also proposed.     

A facile preparation strategy for hollow-structured Bi2O3/Bi2WO6 heterojunction with high visible light photocatalytic activity

A hollow-structured heterojunction consisting of Bi₂WO₆ nanoplatelets and Bi₂O₃ nanoparticles was successfully prepared by a facile solvothermal process. Bi₂O₃/Bi₂WO₆ heterojunction is the aggregate of some hollow spheres with diameter ranging from several hundred nanometers to 1.5 μm and is connected to each other by tube-like cavums. On the basis of scanning and transmission electron microscopy observation and X-ray diffraction analysis of the samples synthesized at different reaction stages, a possible growth mechanism was proposed for the growth of hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction. Its photocatalytic activity was evaluated by degradation of rhodamine B under visible-light irradiation (λ>400 nm). The results indicate that the hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction exhibits much higher photocatalytic activity than both pure Bi₂WO₆ and pure Bi₂O₃. The improved photocatalytic performance can be ascribed to the heterojunction of Bi₂O₃ and Bi₂WO₆ in the framework in which the hierarchical hollow structure possesses good permeability and large surface area. More importantly, the hollow-structured Bi₂O₃/Bi₂WO₆ heterojunction is not only highly stable but also easy to be separated by simple sedimentation for recycle.     

Bi2MoO6纳米片/TiO2纳米棒阵列复合材料的制备及其可见光响应光电催化性能研究

Novel Bi₂MoO₆/TiO₂ heterojunction was fabricated by growing Bi₂MoO₆ nanosheets arrays on the vertically aligned TiO₂ nanorods arrays via a two-step solvothermal method. The obtained Bi₂MoO₆/TiO₂ hierarchical heterojunction showed excellent visible light photoelectrochemical performance. Compared with the pure TiO₂ and Bi₂MoO₆, the photocurrent density of the heterojunction was increased 57 and 29 times, respectively. Furthermore, the hydrogen generation rate of the Bi₂MoO₆/TiO₂ for photoelectrocatalytic water-splitting was about 6 times higher than that of the pure Bi₂MoO₆. The improved performance can be attributed to the synergistic effects of enhanced absorption of visible light, increase of migration rate and separation efficiency of photo-induced carriers.     

Structural, photochemical and photocatalytic properties of zirconium oxide doped TiO2 nanocrystallites

Composite photocatalysts composed of TiO₂ and ZrO₂ have been prepared via the sol-gel method. The as-prepared nanocomposites are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-vis spectrometry and fluorescence emission spectra. The results shows that TiO₂/ZrO₂ nanocomposites are composed of mainly anatase titania and tetragonal ZrO₂. Incorporating TiO₂ particles with ZrO₂ plays an important role in promoting the formation of nanoparticles with an anatase structure and leads to decreased fluorescence emission intensity. Most of the TiO₂/ZrO₂ nanocomposites exhibited comparable photocatalytic activity compared with commercial TiO₂ for the degradation aqueous methyl orange (MO) under ultraviolet irradiation, while the composite with Zr/Ti mass ratio of 15.2% shows the highest photocatalytic performances. Furthermore, the as-prepared nanocomposites can be reused with little photocatalytic activity loss. Without any further treatment besides rinsing, the photocatalytic activity of TiO₂/ZrO₂ (15.2%) composites is still higher than after five-cycle utilization.     

Luminescence properties of Y2WO6:Eu incorporated with Mo or Bi ions as red phosphors for light-emitting diode applications

In this study, the red phosphors, Y₂W_1−xMo_xO₆:Eu³⁺ and Y₂WO₆:Eu³⁺,Bi³⁺, have been investigated for light-emitting diode (LED) applications. In Y₂WO₆:Eu³⁺, the excitation band edge shifts to longer wavelength with the incorporation of Mo⁶⁺ or Bi³⁺ ions. The emission spectra exhibit ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transition of Eu³⁺ ion at 588, 593, and 610 nm, respectively. Moreover, the bluish-green luminescence of the WO₆⁶⁻ at about 460 nm is observed to decrease with the incorporation of Mo⁶⁺, which results in pure red color. Thus, this study shows that the red phosphor, Y₂WO₆:Eu³⁺, incorporated with Mo⁶⁺ or Bi³⁺ ions is advantageous for LEDs applications.     

Hydrothermal synthesis of graphitic carbon nitride–BiVO4 composites with enhanced visible light photocatalytic activities and the mechanism study

Novel graphitic carbon nitride (C₃N₄) and bismuth vanadate (BiVO₄) composite photocatalysts were successfully synthesized by a facile hydrothermal method. The scanning electron microscopy (SEM) revealed that an intimate interface between C₃N₄ and BiVO₄ formed in the composites. Compared with the pure C₃N₄ and BiVO₄, the C₃N₄–BiVO₄ photocatalysts showed remarkably the higher photocatalytic activities in degrading rhodamine B (Rh B). The best active heterojunction proportion was 0.5C₃N₄–0.5BiVO₄. Over this catalyst, the 100% degradation of Rh B (0.002 mmol L⁻¹) was obtained under visible light irradiation (λ>420 nm) for 40 min. The active species in Rh B degradation were examined by adding a series of scavengers. The study on photocatalytic mechanism revealed that the electrons injected directly from the conduction band of C₃N₄ to that of BiVO₄, resulting in the production of superoxide radical (O₂^•−) and hydroxyl radical (OH^•) in the conduction band of BiVO₄. Simultaneously, the rich holes in the valence band of g-C₃N₄ oxidized Rh B directly to promote the photocatalytic degradation reaction.