Adsorption CO2 on the perfect and oxygen vacancy defect surfaces of anatase TiO2 and its photocatalytic mechanism of conversion to CO

The adsorption energies for physisorption and the most stable chemisorption of CO₂ on the neutral charge of perfect anatase [TiO₂] (0 0 1) are −9.03 and −24.66 kcal/mol on the spin-unpolarized and −12.98 and −26.19 kcal/mol on the spin-polarized surface. The small activation barriers of 1.67 kcal/mol on the spin-unpolarized surface and of 6.66 kcal/mol on the spin-unpolarized surface were obtained. The adsorption mechanism of CO₂ on the oxygen vacancy defect [TiO₂ + V_O] surface of anatase TiO₂ using density functional theory calculations was investigated. The energetically preferred conversion of CO₂ to CO was found either on the spin-unpolarized or spin-polarized surfaces of oxygen vacancy defect surface [TiO₂ + V_O] as photocatalyst.     

利用透射电镜衬度像变化判定位错环类型及注氢纯铁中形成的位错环分析

本文分两部分,第一部分研究了利用透射电镜衬度像变化判定材料中位错环类型的方法,即采用所谓inside-outside方法来判断位错环为空位型位错环或间隙型位错环. 第二部分讨论了加速器注氢纯铁在673—773 K时效后形成的位错环的类型. 关键词： 透射电镜 空位型位错环 间隙型位错环 氢     

Oxygen deficiency effect on resistive switching characteristics of copper oxide thin films

In this Letter, bilayered Cu₂O/CuO thin films were grown on Nb doped SrTiO₃ (Nb:STO) substrates by plasma assisted molecular beam epitaxy. The current-voltage characteristics of Pt/Cu₂O/CuO/Nb:STO devices show reproducible and pronounced current-voltage hysteresis which was induced by the CuO/Nb:STO junctions. By comparing the current-voltage curves of the bilayered and single-layered CuO thin films, we attribute the prominent switching behavior to the oxygen-vacancies-mediated-carriers-trapped-detrapped process with the aid of the applied forward (reversed) bias voltage.     

Study of CO adsorption on perfect and defective pyrite(100)surfaces by density functional theory

First-principles calculations based on density functional theory (DFT) and the generalized gradient approximation (GGA) have been used to study the adsorption of CO molecule on the perfect and defective FeS 2 (100) surfaces. The defective Fe 2 S(100) surfaces are caused by sulfur deficiencies. Slab geometry and periodic boundary conditions are employed with partial relaxations of atom positions in calculations. Two molecular orientations, Cand O-down, at various distinct sites have been considered. Total energy calculations indicated that no matter on perfect or deficient surfaces, the Fe position is relatively more favored than the S site with the predicted binding energies of 120.8 kJ/mol and 140.8 kJ/mol, respectively. Moreover, CO was found to be bound to Fe atom in vertical configuration. The analysis of density of states and vibrational frequencies before and after adsorption showed clear changes of the C–O bond.     

Electrode metal penetration of amorphous indium gallium zinc oxide semiconductor thin film transistors

Penetration effects of various electrode materials, namely Al, Au, and Cu, on the physical and electrical characteristics of amorphous oxide semiconductor thin film transistors (TFTs) were investigated. Amorphous indium gallium zinc oxide (a-IGZO) TFTs were fabricated with conventional staggered bottom gate structures on a p-type Si substrate. X-ray photoemission spectroscopy (XPS) analysis under the electrode deposition area revealed variations in the oxygen bonding states and material compositions of the a-IGZO layer. Field-emission scanning electron microscopy (FE-SEM) with the line scan of energy dispersive spectroscopy (EDS) showed lateral penetration by the electrode metal. To compare the electrical characteristics of the tested TFTs, the initial current–voltage (I–V) transfer characteristics were examined. In addition, the tested TFTs fabricated using various electrode materials were tested under bias stress to verify the correlations between variations in TFT characteristics and both the metal work function and penetration-induced oxygen vacancies in the channel around the contact area.     

S空位调节扶手型二硫化钼纳米带的电子性质

二硫化钼纳米带按边界结构特征可分为锯齿型和扶手型,在制备过程中,不可避免地会存在一定的缺陷,其中硫空位(VS)最为常见,它将改变纳米结构,进而影响其电子性质。本文采用密度泛函理论来研究S空位对扶手型二硫化钼纳米带性质的影响。计算结果表明：纯扶手型二硫化钼纳米带（AMoS2NRs）为非磁性半导体,但其物性受S空位的位置及浓度所调制。当S空位出现在纳米带内部时,其性质不变。但当S空位在纳米带边缘时,AMoS2NRs被调节成半金属;并随着S空位的浓度的增加,其物性从半金属转变为稀磁半导体。这一有趣的发现将使得低维MoS2纳米材料在自旋电子学上有更宽广的应用。     

钯氮共掺杂TiO2的制备与表征及其可见光催化活性

在空气气氛和N₂中热处理表面均匀分散有尿素和氯化钯的纳米管钛酸,制备了两个系列Pd/N共掺杂的TiO₂光催化剂,并对所得样品进行了X射线衍射、透射电镜、X射线光电子能谱、紫外-可见漫反射光谱、荧光光谱和电子自旋共振等表征.结果表明,焙烧气氛对样品的形貌、晶体结构、光谱吸收、生成的氧空位浓度和可见光光催化性能的影响很大,其中在空气气氛中制备的样品光催化性能优于在N₂中制备的样品.在可见光(λ≥420nm)照射下,以丙烯为模型污染物考察了样品的光催化活性,发现在空气中400℃下焙烧的样品具有最佳的可见光催化活性.另外,讨论了Pd/N共掺杂TiO₂光催化剂具有可见光响应的机理,认为掺杂的Pd/N元素和制备过程中生成的氧空位是影响可见光催化性能的重要因素.     

Suppression of Photoinduced BBO Defects Generation on TIO2（110） by Water

We have investigated creation of variable concentrations of defects on TIO2（110）-（1×1） surface by 266 nm laser using temperature programmed desorption technique. Oxygen-vacancy defects can be easily induced by ultraviolet light, the defects concentration has a linear dependence on power density higher than 50 mW/cm2 for 90 s irradiation. No observation of O2 molecule and Ti atom desorption suggests that UV induced defects creation on TiO2（110）-（1×1） is an effective and gentle method. With pre-dosage of thin films of water, the rate of defects creation on TiO2（110）-（1×1） is slower at least by two orders of magnitude than bare TiO2（110）-（1×1） surface. Further investigations show that water can be more easily desorbed by UV light, and thus desorption of bridging oxygen is depressed.     

K促进的纳米片状水滑石衍生CoAlO金属氧化物催化碳烟燃烧

采用水热法合成了负载K的纳米片状水滑石衍生CoAlO金属氧化物,其表现出优异的催化碳烟燃烧活性.氢气-程序升温还原（H₂-TPR）实验结果表明,K与Co之间的相互作用提高了催化剂的氧化还原性能.X射线光电子能谱（XPS）分析结果表明,K的负载增大了表面Co²⁺/Co³⁺的比例,促进了氧空位的产生,提高了催化剂对气相氧的吸附能力.碳烟-程序升温还原（Soot-TPR）实验结果表明,K的负载增加了表面吸附氧数量.动力学实验结果表明,K的负载增加了单位质量催化剂上的活性氧数量、反应速率和转化频率（TOF）,从而提高了催化剂的本征活性.另外,碳烟颗粒可以分散在纳米片的层间,与活性位点的接触效率得到提高,也有利于提高催化碳烟燃烧活性.     

一锅法合成Ce_xZr_(1-x)O_2固溶体催化剂用于热化学循环分解CO_2制CO

采用一锅蒸发诱导自组装法(EISA)制备了一系列不同铈锆物质的量比的铈锆固溶体催化剂,用TGA研究了其热化学循环分解CO_2制CO的催化性能,并采用XRD、Raman光谱、H2-TPR、XPS、SEM和N_2吸附-脱附等手段对催化剂的物相结构、还原性能和表面化学性质进行了表征分析,用热重分析(TGA)研究了铈锆固溶体对热化学循环分解CO_2制CO的催化性能。结果表明,随着Ce/Zr物质的量比增加,铈锆固溶体催化剂的CO_2高温分解活性先增大后减小。Ce/Zr物质的量比为1的Ce_(0.5)Zr_(0.5)O_2催化剂由于具有较多的晶格缺陷和氧空穴,氧迁移能力强,催化活性高,而Ce/Zr物质的量比为3的Ce_(0.75)Zr_(0.25)O_2催化剂具有相对稳定的氧空穴数,循环稳定性好。循环反应后,所有的催化剂均出现了一定程度的烧结,且富锆固溶体发生了相分离,这可能会影响催化剂的性能。