Fe3O4/SiO2/Bi2WO6磁性复合光催化剂的制备及其光催化性能

钨酸铋(Bi₂WO₆),结构最简单的Aurivillius相化合物,是近期受到研究者关注的新型光催化材料。然而,光催化剂粉末在反应介质中难被回收,工业化应用成本较高。本文用三步方法合成了可回收的Fe₃O₄/SiO₂/Bi₂WO₆磁性复合光催化剂,通过溶剂热法合成具有磁性的Fe₃O₄,用溶胶凝胶法在Fe₃O₄表面覆盖SiO₂层,后将磁性颗粒与Bi₂WO₆纳米片相结合。光催化剂的形貌结构及性能通过XRD、SEM、PL、UV-vis进行表征测试。结果表明,直径约500 nm的Fe₃O₄微球附着在边长约500 nm的Bi₂WO₆纳米片的表面,SiO₂在两者之间起到了粘连作用。光催化剂Fe₃O₄/SiO₂/Bi₂WO₆对于罗丹明B的光降解活性较好,且有一定磁性,可以通过外加磁场将其从溶液中分离,有较大的应用潜力。     

WO3纳米片的制备、表征及气敏性能研究

论文采用水热法合成WO₃纳米片,利用扫描电镜(SEM)和X射线衍射(XRD)对WO₃纳米片的形貌特征和结构性能进行表征,并进一步系统地考察了利用WO₃纳米片制备的传感器的气敏性能。实验结果表明,合成的WO₃纳米片尺寸规则,边长在200-300 nm,厚度在50 nm左右,结晶性好。以WO₃纳米片为材料制备的气体传感器的最佳工作温度为300 _oC,在此工作温度下,WO₃纳米片传感器对乙醇表现出超快的响应(2-4秒)和恢复时间(4-16 S)。与其他还原性气体如甲醇,苯、二氯甲烷和正己烷对比检测发现,WO₃纳米片传感器对乙醇表现出高的灵敏度和选择性,表明WO₃纳米片在乙醇检测气体传感器方面具有极大的应用潜力。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

热电Bi2Te3/Bi2Se3纳米“弹簧”材料的电化学组装

为了探索制备具有高热电优值的一维纳米材料,采用脉冲电化学技术制备了一种热电Bi₂Te₃/Bi₂Se₃多层纳米线材料。对电沉积过程的监测结果表明,电沉积过程中体系电阻不断增大,随着电沉积的不断进行,体系电阻增大幅度越来越小。对电沉积产物进行退火处理,然后溶解掉模板,进行XRD测试,结果表明,所制备的产物是Bi₂Te₃/Bi₂Se₃,同时,有很多“卫星峰”出现在衍射图上,表明所制备的材料具有超晶格结构。运用FE-SEM、TEM对产物形貌进行分析,结果发现,所制备的材料是像“弹簧”一样形状的Bi₂Te₃/Bi₂Se₃多层纳米线。通过对脉冲时间的调节,可以实现对多层纳米线周期的调制。     

g-C3N4/MoS2纳米片异质复合物的球磨法制备及可见光催化性能研究

采用球磨法制备g-C₃N₄/MoS₂纳米片异质复合物,运用X-射线衍射仪、高分辨透射电镜、紫外可见漫反射光谱和荧光发射光谱对异质复合物的结构和形貌进行了表征。结果表明：MoS₂纳米片可进入g-C₃N₄的层间形成异质复合物。以罗丹明B为模拟污染物,在可见光照射下考察了复合物的光催化特性。结果显示,含有2%的MoS₂纳米片与g-C₃N₄形成的异质复合物在120min内对罗丹明B降解率为98%,其降解动力学常数是体相g-C₃N₄为的4.3倍。g-C₃N₄/MoS₂纳米片异质复合物具有十分优良的光催化特性。其催化活性的提高主要归因于光生电子和空穴的有效分离和传输,并根据光捕获实验提出复合物可能的光催化机理。     

微波原位制备作为锂离子电池电极材料的石墨烯/TiO2 纳米复合物

通过改造的家用微波炉,实现了原位高效制备石墨烯/TiO₂纳米复合物。结果表明：微波辅助法能够在商用锐钛矿型TiO₂纳米颗粒表面均匀制备石墨烯纳米片,通过SiO₂/Si的剧烈电晕放电,其制备时间仅需数分钟（最短3 min）。石墨烯纳米片的尺寸大约为50 nm且缺陷很少。TiO₂晶体结构仍为锐钛矿型,主要归功于极短的制备周期和较低的反应温度（600~700 ℃）。石墨烯具有优异的电导率,可以提升锂离子扩散速率、提高电子传输速率并降低接触电阻。在1 C（170 mA·g^-1）条件下石墨烯/TiO₂纳米复合物的电池放电比容量提高了2倍。与商业化锐钛矿型TiO₂纳米颗粒相比,在1 C到5 C的不同充放电倍率下,石墨烯/TiO₂纳米复合物的比容量差距显著扩大。     

WO3添加量对超粗硬质合金微观结构及性能影响*

本文以WC、WO₃、Co、C为原料,通过原位细晶溶解-析出长大法制备了超粗硬质合金,并分析了不同WO₃添加量对合金微观结构及性能影响规律。结果表明：初始粉末中加入的WO₃和C在烧结过程中将发生原位一步还原碳化反应转化为高活性的细WC,促进溶解-析出长大现象,使超粗硬质合金WC平均晶粒度随着WO₃含量增加而增大。同时,WO₃添加能够减少粗WC晶粒微观缺陷和曲边的阶梯状表面,平直化晶粒边界,使其形貌趋于形成完整的三角棱柱体,其(0 0 0 1)晶面占比高,能够有效提高合金硬度,阻碍裂纹扩展,增加钴相韧性断裂比例。当WO₃添加量为4.20wt.%时,制备的超粗硬质合金具有最大的硬度(1085kgf/mm₂⁾和抗弯强度(2692MPa)。     

钨酸铯粉体的水热合成与表征研究

本文采用水热法制备钨酸铯(Cs_xWO₃)粉体,研究了反应物铯钨摩尔比、柠檬酸用量对钨酸铯粉体晶相、微观形貌及粒径的影响,分别采用X射线衍射仪(XRD)、广角静态动态同步激光散射仪(DLS)、扫描电镜(SEM)对制备的钨酸铯粉体进行表征。结果表明在200℃水热反应三天,适量增加反应物铯钨摩尔比和柠檬酸用量,可制得结晶性较好、粒径较小且分散较好的钨酸铯(Cs_xWO₃)粉体。     

309不锈钢表面CeO2 改性铝化物涂层的循环氧化行为

以NH₄Cl为活化剂,采用包埋法在309不锈钢上制备了纳米CeO₂改性铝化物涂层。采用X射线衍射分析仪、扫描电子显微镜和能谱仪对涂层以及循环氧化50次后的表面和横截面进行了分析。微观结构研究表明,改性涂层中包含Fe₄Al₁₃相,由于基底金属的向外扩散,改性涂层捕获了少量的CeO₂纳米颗粒。与不添加CeO₂纳米颗粒的普通铝化物涂层相比,在900 ℃的大气环境下,分散CeO₂改性铝化物涂层表现出更好的防氧化剥落性能;在50次循环氧化后,CeO₂改性铝化物涂层上仍然可以发现一些Fe₂Al₅相,并存在向外扩散的Al层、中间的FeAl层和外部的Fe₂Al₅+FeAl混合层,这表明CeO₂纳米颗粒可以延缓铝化物涂层的降解。     

过冷液态Zr48Cu36Ag8Al8块体非晶合金的相分离及组织演变

本文通过x射线衍射(XRD)、差示扫描量热法(DSC)和透射电子显微镜(TEM)研究了退火温度对Zr₄₈Cu₃₆Ag₈Al₈金属玻璃微观结构演化的影响。结果表明,快速凝固获得的样品为典型的非晶态结构。当样品在703K保温20分钟时,均一的非晶基体相分离成两种非晶合金,即,发生相分离。由于相分离结构与非晶基体在等温退火过程是竞争的关系,这个结构很容易向晶化态进行转变,形成AlZr₂ AlAg₃相。Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构在过冷液相区等温退火过程中经历了的局部结构转变,相分离以及纳米晶转变,这个过程意味着Zr₄₈Cu₃₆Ag₈Al₈金属玻璃的微观结构对退火温度十分敏感。此外,相分离的形成可以加速纳米晶的形成。     

Subsolidus phase relations in the ZnO-WO3-Bi2O3 system

The subsolidus phase relations of the ternary system ZnO-WO₃-Bi₂O₃ were investigated by means of X-ray diffraction (XRD). Six binary compounds and seven 3-phase regions were determined, and no ternary compounds were found in this ternary system. The phase diagram of pseudobinary system ZnO-Bi₂WO₆ was also constructed through XRD and differential thermal analysis (DTA) methods, which forms eutectic system with eutectic temperature about 945 °C, the corresponding eutectic component is 35 mol% ZnO and 65 mol% Bi₂WO₆.     

Bismuth tungstate nano/microstructures: Controllable morphologies, growth mechanism and photocatalytic properties

A facile hydrothermal process was utilized to synthesize bismuth tungstate (Bi₂WO₆) hierarchical nano/microstructures, by which various morphologies could be achieved, including caddice clew-like, nest-like, flower-like and plate-like nanostructures. From the scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, the morphologies and phases of the as-synthesized Bi₂WO₆ exhibited a strong dependence on the pH value of the precursor solutions. Moreover, the formation mechanisms of the controllable assembly of these Bi₂WO₆ nano/microstructures under different pH values were investigated. The photocatalytic performances of Bi₂WO₆ with different morphologies were also discussed, and the nest-like Bi₂WO₆ displayed the best photocatalytic activity due to the effective visible absorption and the large surface areas.     

空心结构ZnSn(OH)6立方体制备及其可见光催化性能研究

以乙酸锌、锡酸钠、氟化铵为原料,利用NH₄F刻蚀,采用水热法制备了尺寸250 nm的空心结构ZnSn(OH)₆立方体,通过X射线衍射(XRD)、红外光谱(FTIR)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)、荧光光谱(PL)等来表征ZnSn(OH)₆的晶体结构、形貌和光学性能,研究水热时间对ZnSn(OH)₆形貌的影响,通过降解亚甲基蓝(MB)来探索不同形貌的ZnSn(OH)₆的光催化性能。结果表明,水热2 h制备的ZnSn(OH)₆具有完整的空心结构,且对亚甲基蓝(MB)在可见光下降解效率最优,在降解过程中·O^2-起主要作用,其稳定性良好。说明空心ZnSn(OH)₆立方体光催化材料是一种具有广阔应用前景的可见光催化降解材料。     

Effect of bismuth tungstate with different hierarchical architectures on photocatalytic degradation of norfloxacin under visible light

The photocatalytic degradation of norfloxacin by bismuth tungstate (Bi₂WO₆) with different hierarchical architectures was investigated under visible light irradiation. Bi₂WO₆ was prepared by hydrothermal method with the reaction solution pH ranging from 4 to11. The relatively ultrathin Bi₂WO₆ nanoflakes prepared at pH 4 showed excellent adsorption and photodegradation efficiency towards norfloxacin. The characterization results showed that Bi₂WO₆ prepared at pH 4 had a larger specific area and faster photo-generated carrier separation rate. The decay rate reached the maximum in weak alkaline reaction solution, which could be attributed to the presence of moderate OH^? anions. The present study demonstrated that the smaller size of Bi₂WO₆ could be an efficient photocatalyst on the degradation of norfloxacin in the aquatic environment.     

Controlled synthesis of TiO2 mesoporous microspheres via chemical vapor deposition

Anatase titanium dioxide (TiO₂) mesoporous microspheres with core-shell and hollow structure were successfully prepared on a large scale by a one-step template-free chemical vapor deposition method. The effects of various reaction conditions on the morphology, composition and structure of the products were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) technique and photoluminescence (PL) method. The results indicate that the product near the source was composed of core-shell structure TiO₂ microspheres with diameters from 3 to 5 μm. With increasing the distance between the source materials and the substrate, the hollow TiO₂ spheres with 1-2 μm dominant the products. A localized Ostwald ripening can be use to explain the formation of core-shell and hollow structures, and the size of the initial TiO₂ solid nanoparticles plays an important role in determining the evacuation manner of the solid in the ripening-induced hollowing process. The surface area of TiO₂ hollow microspheres determined by the adsorption isotherms was measured to be 74.67 m²/g. X-ray photoelectron spectroscopy (XPS) analysis revealed that the O-H peaks of hollow structures have a chemical shift compared with the core-shell structures. The optical property of the products was also discussed.     

Effect of Bi2O3 on structure and wetting studies of Bi2O3-ZnO-B2O3 glasses

Glasses with different Bi₂O₃ contents (37-42 mol%) have been prepared by conventional melt quench technique. The IR and Raman studies indicate that these glasses are made up of [BiO₆], [BiO₃], [BO₃] and [BO₄] basic structural units. The vibrations of [BiO₃] and [BO₃] become stronger as the content of Bi₂O₃ increases, which makes glass structure loosened. Viscosity of the glasses was measured by using a Rheotronic III paralleled plate rheometry, which shows that the viscosity of glass samples decreased when the content of Bi₂O₃ increased at the same temperature (400-460 °C). The temperature range which suits for glasses sealing was calculated by using the approximation of Arrhenian behaviour. The wetting performance of Bi₂O₃-ZnO-B₂O₃ glasses was described by using high-temperature microscope, which also proves that the structure of investigated Bi₂O₃-ZnO-B₂O₃ glasses become loosened due to the increasing of the content of Bi₂O₃.     

Synthesis of WO3 nanoparticles for photocatalytic O2 evolution by thermal decomposition of ammonium tungstate loading on g-C3N4

Tungsten trioxide (WO₃) nanoparticles have been successfully synthesized by thermal decomposition of ammonium tungstate loading on g-C₃N₄. The as prepared nanoparticles were characterized by XRD, UV-vis, photoluminescence spectra (PL) and TEM. The XRD results indicate that the g-C₃N₄ decomposed completely with WO₃ remaining at calcination temperature higher than 550 °C. The WO₃ prepared at temperature below 750 °C exhibits orthorhombic phase, and monoclinic phase at temperature higher than 850 °C. The UV-vis absorption onset wavelength of the obtained samples is approximately 470 nm, and the absorption intensity increases with calcination temperature, and reaches a maximum at 750 °C. The as prepared WO₃ powders, loaded with 0.5 wt% Pt as cocatalyst, were used as photocatalysts for O₂ evolution from an aqueous KIO₃ solution. The WO₃ nanoparticles prepared from ammonium tungstate loading on g-C₃N₄ showed photocatalytic activity in O₂ evolution up to 77 times higher than that of WO₃ samples prepared from ammonium tungstate without loading on g-C₃N₄.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

Luminescence of complex ion WO12 in Dy doped nanocrystal Gd6WO12 phosphor

Nanocrystal Gd₆WO₁₂ phosphor doped with Dy³⁺ was prepared by a co-precipitation method. X-ray diffraction (XRD), scanning electron microscopy (SEM) and selected area electron diffraction (SAED) were used to characterize the structure and morphology of the resultant phosphor. It was found that the phosphor exists in tetragonal phase and the phosphor particles show sphere-like shape with an average size of 31 nm. In aid of excitation and emission spectra, the energy levels of the complex ion WO₁₂¹⁸⁻ were confirmed, and that the possible luminescent mechanisms for various wavelengths excitation were analyzed. The cross relaxation and energy transfer between complex ion and Dy³⁺ were discussed. The dependence of luminescent intensity and color coordinates on the excitation wavelength was also investigated.