A comparative XPS and UPS study of VOx layers on mineral TiO2(001)‐anatase supports

Four vanadium oxide layers on mineral TiO₂(001)‐anatase supports with different thickness (3–33 Å) were prepared with reactive d.c. magnetron sputtering and were extensively studied with photoelectron spectroscopy. Al Kα radiation and 150 eV synchrotron radiation were used as excitation sources. The evolution of the 2p, 3s and 3p core level line shapes of V and Ti as a function of the vanadium oxide thickness was studied, as well as the O1s and O2s core lines and the valence band. All the V2p spectra of the deposited vanadium oxide layers consist of at least 60% V⁵⁺, the rest being V⁴⁺. The V3p region is complicated by multiplet splitting, which prevents the determination of the vanadium oxidation state. The V3p multiplet splitting is different for the two excitation energies. No reduction of the titania support surface due to the vanadium oxide deposition was observed. Copyright © 2006 John Wiley & Sons, Ltd.     

Sr1-xLaxTiO3的高温高压合成及XPS研究

 利用高温高压方法合成了有稀土元素La掺杂的钙钛矿氧化物Sr_1-xLa_xTiO₃。XRD测试表明，在x≤0.5时，样品基本为单相，呈立方相；晶胞体积随x的增加而增加，在x=0.4时开始减小。XPS测量发现，样品中存在Ti离子的变价。讨论了Ti离子价态的变化对晶格参数的影响。     

CuO—ZnO／Al2O3—TiO2催化剂中TiO2的结构和电子效应

采用XPS,XRD,TPR,TPD和指标反应等方法研究了TiO_2在负载型CuO-ZnO/Al_2O_3-TiO_2催化剂中所起的作用.发现TiO_2起双重作用,即结构效应和电子效应,TiO_2的结构效应主要表现为它改善了CuO在载体上的分布.TiO_2的电子效应表现为它对Cu~0具有吸电子的作用,从而削弱了Cu和S之间的吸附力,使S容易脱除.另外,部分还原形成的Ti~(3+)具有促进CuS中的Cu~(2+)还原为Cu~0的能力,TiO_2的上述效应的综合结果使催化剂的抗硫中毒性能大大增强.     

TiO2一维纳米材料及其纳米结构的合成

本文对合成TiO₂一维纳米材料及其有序纳米阵列的阳极氧化法、模板法以及水热法进行了全面而系统的评述，着重介绍了它们的最新研究进展。阳极氧化法能制备牢固负载于基体上的TiO₂纳米管阵列，这有助于构筑TiO₂纳米结构及其在纳米器件上的应用；与多种制备技术如溶胶－凝胶工艺、电化学沉积以及原子层沉积等相结合，模板法可以合成出多种形貌的TiO₂纳米材料如纳米管、纳米线和纳米棒，并可以通过改变所用模板的微观尺寸来调控TiO₂一维纳米材料及其有序阵列的微结构参数；水热合成法可以制备出直径小且比表面积大的TiO2纳米管粉末。但从目前看来，该法还不能制备出牢固负载于基体上的有序纳米阵列。文章最后指出了TiO₂一维纳米材料及其有序纳米阵列合成中存在的问题及今后发展方向。     

高介电常数TiO2纳米晶的表面态研究

将钛酸四丁酯和硬脂酸在熔融状态下混合均匀后置于冷水浴中,使其凝固成凝胶,通过控制烧结过程中氧气的含量,成功地制备出粒度均匀、介电性能好的纳米晶TiO2.通过采用X射线光电子能谱和表面光电压谱对纳米晶TiO2表面状态的分析发现,材料表面存在大量的氧空位缺陷,暴露在粒子表面上的主要是一些金属Ti4+.纳米材料的这种表面状态对其极化性质具有重要的影响,使其在接近静态条件下的低频介电常数远大于常规材料的介电常数.     

The effect of lanthanide on the degradation of RB in nanocrystalline Ln/TiO2 aqueous solution

A series of Nd³⁺, Pr³⁺, Er³⁺, and Dy³⁺ (0.25–5 at.%) homogeneously doped nanocrystalline titanium dioxides (Ln/TiO₂) were prepared by an easy sol–gel technique, and the roles of lanthanide doping on the photocatalytic activity in the degradation of rhodamine B (RB) in aqueous solution were studied. Both the concentration of the lanthanide dopant and calcination temperature showed significant effect to the photodegradation of RB. The photocatalytic activity of pure titania was drastically decreased when calcination temperature was at 700 °C, while the high photocatalytic activity was still maintained for lanthanide-doped samples. HPLC-MS method was used to study the degradation process, and it is demonstrated that the degradation of RB catalyzed by Ln/TiO₂ was principally go through with a stepwise de-ethylation photochemical process.     

不同晶型和粒径的二氧化钛微粉对金属离子的吸附行为

考察了在流动注射的微柱分离富集体系中不同晶型和粒径的TiO2微粉对Cu2 , Cr3 , Mn2 , Ni2 , La3 , Eu3 , Ga3 , Mo(Ⅵ)和W(Ⅵ) 等金属离子的吸附pH条件及动态吸附容量, 并进行了比较; 初步探讨了TiO2微粉的吸附机制. 结果表明, 当TiO2的粒径大小相近时, 晶型对吸附容量的影响不可忽略; 当晶型相同时, 粒径的大小则起着重要的作用.     

B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究Ⅱ.焙烧温度的影响

采用XRD、FT-IR和NH3-TPD等方法，研究了载体预焙烧温度和催化剂活化焙烧温度对B2O3/TIO2-ZRO2催化剂的结构、酸性和催化环己酮肟气相Beckmann重排反应性能的影响。结果表明，在383-773K范围内，载体预烧温度对催化剂性能的影响不大，但经973K高温预焙烧后，由于生成了ZrTiO4晶相，使其与H3BO3的相互作用减弱，从而导致催化剂的酸性和反应性能降低，提高催化剂活化焙烧温度，有利于B2O3与TiO2-ZrO2的相互作用，生成更多的Beckmann重排反应所需的中等强度酸中心，使催化剂的活性和选择性提高；但活化焙烧温度过高，会使催化剂中大量的B2O3晶粒析出，引起酸中心数量和催化活性的明显下降。     

PREPARATION OF POLYSULFONAMIDE/TiO2 NANOCOMPOSITES BY SOL-GEL

Polysulfonamide (PSA) was synthesized at room temperature, the polymerization based on terephthaloyl chloride and 3,3 '-diaminodiphenylsulfone in the common solvent N,N -Dimethyl-acetamide (DMAc). Polysulfonamide/titanium oxide nanocomposites were prepared by sol-gel method. Tetrabutyl titanate(TBT) was added into the polysulfonamide solution, at the same time ,some water was mixed to make the TBT hydrolyze. In the process, hydrochloric acid was used to catalyze the reaction. The polysulfonamide chemistry structure was characterized by FT-IR spectrum. Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA.The results show that we have succeeded to synthesize the polysulfonamide, TiO2particles were well distributed in the composite film and average size was about 20 nm on average, the heat-resistance of nanocomposite was batter than the pure polysulfonamide.     

微波辅助快速制备2D/1D ZnIn2S4/TiO2 S型异质结及其光催化制氢性能

The threat and global concern of energy crises have significantly increased over the last two decades. Because solar light and water are abundant on earth, photocatalytic hydrogen evolution through water splitting has been considered as a promising route to produce green energy. Therefore, semiconductor photocatalysts play a key role in transforming sunlight and water to hydrogen energy. To date, various photocatalysts have been studied. Among them, TiO₂ has been extensively investigated because of its non-toxicity, high chemical stability, controllable morphology, and high photocatalytic activity. In particular, 1D TiO₂ nanofibers (NFs) have attracted increasing attention as effective photocatalysts because of their unique 1D electron transfer pathway, high adsorption capacity, and high photoinduced electron–hole pair transfer capability. However, TiO₂ NFs are considered as an inefficient photocatalyst for the hydrogen evolution reaction (HER) because of their disadvantages such as a large band gap (~3.2 eV) and fast recombination of photoinduced electron–hole pairs. Therefore, the development of a high-performance TiO₂ NF photocatalyst is required for efficient solar light conversion. In recent years, several strategies have been explored to improve the photocatalytic activity of TiO₂ NFs, including coupling with narrow-bandgap semiconductors (such as ZnIn₂S₄). Recently, microwave (MW)-assisted synthesis has been considered as an important strategy for the preparation of photocatalyst semiconductors because of its low cost, environment-friendliness, simplicity, and high reaction rate. Herein, to overcome the above-mentioned limiting properties of TiO₂ NFs, we report a 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction synthesized through a microwave (MW)-assisted process. Herein, the 2D/1D ZnIn₂S₄/TiO₂ S-scheme heterojunction was constructed rapidly by using in situ 2D ZnIn₂S₄nanosheets decorated on 1D TiO₂ NFs. The loading of ZnIn₂S₄ nanoplates on the TiO₂ NFs could be easily controlled by adjusting the molar ratios of ZnIn₂S₄ precursors to TiO₂ NFs. The photocatalytic activity of the as-prepared samples for water splitting under simulated solar light irradiation was assessed. The experimental results showed that the photocatalytic performance of the ZnIn₂S₄/TiO₂ composites was significantly improved, and the obtained ZnIn₂S₄/TiO₂ composites showed increased optical absorption. Under optimal conditions, the highest HER rate of the ZT-0.5 (molar ratio of ZnIn₂S₄/TiO₂= 0.5) sample was 8774 μmol·g^-1·h^-1, which is considerably higher than those of pure TiO₂ NFs (3312 μmol·g^-1·h^-1) and ZnIn₂S₄nanoplates (3114 μmol·g^-1·h^-1) by factors of 2.7 and 2.8, respectively. Based on the experimental data and Mott-Schottky analysis, a possible mechanism for the formation of the S-scheme heterojunction between ZnIn₂S₄ and TiO₂ was proposed to interpret the enhanced HER activity of the ZnIn₂S₄/TiO₂heterojunctionphotocatalysts.