Bi掺杂NaTaO3中Bi的化学价态对其光催化性能的影响

分别采用NaBiO3和Bi(NO3)3为Bi源制备了Bi掺杂NaTaO3光催化剂,研究了Bi离子的价态对NaTaO3光催化分解水制氢性能的影响.采用X射线衍射(XRD)、拉曼光谱、X射线光电子能谱(XPS)和紫外-可见吸收光谱研究了催化剂的晶体结构、Bi离子的化学状态和催化剂的光学吸收性能.以光催化分解水制氢反应研究了Bi离子掺杂NaTaO3的催化性能. XRD结果表明,对于两个不同Bi源掺杂的NaTaO3样品, Bi离子的掺杂没有改变催化剂的单斜相结构,但拉曼光谱证实Bi离子的掺杂致使Ta–O–Ta键角偏离了180o. XPS结果表明,以Bi(NO3)3为Bi源时, Bi离子以Bi3+掺杂于NaTaO3的A位;当以NaBiO3为原料时, Bi3+和Bi5+共掺杂于NaTaO3的A位.两种不同Bi源掺杂得到的样品在紫外-可见吸收光谱中给出了相似的光学吸收,但Bi3+的掺杂对NaTaO3光催化性能影响不大,而Bi3+和Bi5+共掺杂大大提高了NaTaO3的光解水制氢性能. Bi离子取代Na离子在A位的掺杂,在NaTaO3结构中引入了能够促进载流子分离的空位和缺陷;与此同时, Bi的掺杂导致Ta–O–Ta键角偏离180o而不利于载流子迁移.对于Bi3+掺杂的NaTaO3样品,这两种作用相互抵消,使得其催化性能与NaTaO3相比没有变化;而Bi3+和Bi5+的共掺杂和高价态Bi5+的掺杂引入了更多的空位和缺陷,提高了光生电子-空穴的分离效率,从而提高了光催化产氢性能.研究表明,光催化过程中载流子的迁移是影响催化性能的重要因素,而在ABO3钙钛矿结构的A位引入高价态离子是促进光生载流子分离的有效途径.     

InOOH hollow spheres synthesized by a simple hydrothermal reaction

Novel micrometer-sized indium oxyhydroxide (InOOH) hollow spheres were successfully synthesized via a citric acid (CA) assisted hydrothermal process. The morphology, crystal structure, and optical properties of the product were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and UV-vis diffuse reflectance spectroscopy (DRS). The optical band gap, E(g), was estimated to be 3.5 eV from the DRS spectrum, which is almost equal to that of indium oxide. Furthermore, on the basis of a series of SEM observations, phenomenological elucidation of a mechanism for the growth of the InOOH hollow spheres has been presented; key factors for the formation of the structures have been proposed.     

NaTaO3及NaTaO3∶Bi3+光催化剂的光致发光光谱研究

采用光致发光光谱技术对一系列不同条件下制备的NaTaO3及不同掺杂量的NaTaO3∶Bi3+进行了研究. 结果表明, NaTaO3的发光性质与其制备条件密切相关: 在钠离子不足的条件下合成的样品, 其发光带主要位于515和745 nm左右; 而在钠离子充足条件下合成的样品, 其发光带位于460 nm左右, 随着n(Na)/n(Ta)的降低, 发光带向长波长方向移动; 掺入Bi3+之后, 其发光峰由515 nm移至455 nm, 随着Bi3+掺入量的增加, 455 nm的发光带强度减弱. 515 nm的发光带与替位缺陷TaNa....相关; 745 nm的发光带与VNa`缺陷相关; 而460 nm的发光带与本征TaO6基团相关. 将Bi3+掺入到钽酸钠样品, TaNa....由BiNa..替代, 相应的发光带向高的n(Na)/n(Ta)方向移动, 从而呈现出本征TaO6基团的发光带.     

Influences of Co doping on the structural,optical and magnetic properties of ZnO nanorods synthesized by hydrothermal route

Pure and Co-doped ZnO nanorods have been synthesized by a hydrothermal process. The structure, morphology and properties of as-prepared samples have been studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), photoluminescence (PL) spectrometer as well as by superconducting quantum interference device (SQUID). The structure and morphology analyses show that Co doping can slightly impede the ZnO crystallinity, influence the nanorods morphology, but cannot change the preferred growth orientation of ZnO nanorods. The amount of Co doping contents is about 3.0 at% in ZnO nanorods and dopant Co²⁺ ions substitute Zn²⁺ ions sites in ZnO nanocrystal without forming any secondary phase. The optical measurements show that the Co doping can effectively tune energy band structure and enrich surface states in both UV and VL regions, which lead to novel PL properties of ZnO nanorods. In addition, ferromagnetic ordering of the as-synthesized Zn_1?xCo_xO nanorod arrays has been observed at room temperature, which should be ascribed to sp–d and d–d carrier exchange interactions and presence of abundant defects and oxygen vacancies.     

Characterization of h-WO3 nanorods synthesized by hydrothermal process

Hexagonal tungsten oxide nanorods have been synthesized by hydrothermal strategy using Na₂WO₄·2H₂O as tungsten source, aniline and sulfate sodium as structure-directing templates. Techniques X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy have been used to characterize the structure, morphology and composition of the nanorods. The h-WO₃ nanorods are up to 5 μm in length, and 50–70 nm in diameter.     

化学反应过渡态的结构和动力学

化学反应过渡态决定了包括反应速率和微观反应动力学在内的化学反应的基本特性,而无论是从理论还是实验上研究和观测化学反应过渡态都是极具挑战性的课题.近年来,我国科学家们利用交叉分子束-里德堡氢原子飞行时间谱仪,结合高精度的量子动力学计算,对H＋H2和F＋H2这两个教科书式的典型反应体系进行了全量子态分辨的反应动力学研究,从中得出了关于这两个反应体系的过渡态的结构和动力学性质的结论性的研究成果.     

Effects of pH and temperature on photocatalytic activity of PbTiO3 synthesized by hydrothermal method

PbTiO₃ photocatalyst was synthesized successfully by facile hydrothermal method. The effects of the hydrothermal reaction temperatures and the pH values of the systems on the photocatalytic activities of PbTiO₃ were investigated in detail. The photocatalytic activities of samples were evaluated by the degradation of methyl orange (MO) aqueous solution under simulated solar irradiation. The as-obtained PbTiO₃ sample exhibits anisotropical growth along the (0 0 1) plane, and its photocatalytic activity is about 3 times higher than that of PbTiO₃ prepared by precipitation method. Moreover, the as-prepared PbTiO₃ has high stability during photocatalytic oxidation process, and does not cause secondary pollution.     

固相反应制备纳米CeO2粉体

氧化铈用途广泛,用量大。目前用氧化铈作为汽车尾气净化器助催化剂,细度和纯度直接影响的净化效率,因此需要加强高纯度纳米氧化铈的研究开发。     

Structural and optical properties of KTa0.77Nb0.23O3 nanoplates synthesized by hydrothermal method

Two-dimensional KTa(0.77)Nb(0.23)O(3) (KTN) nanoplates with edge sizes of about 100 nm and thickness of about 10 nm have been fabricated by hydrothermal method at 200 degrees C using Ta(2)O(5), Nb(2)O(5), and KOH served as the precursors. Detailed structural studies indicate that the synthesized products are made up of large quantity single crystalline nanoplates with quadrilateral shape, which have a cubic perovskite structure without any other impurity phase and (011) growth direction. The stacking faults may be the key in the formation and growth of the (011) plate. Room temperature photoluminescence spectra excited at different wavelengths exhibit a strong emission band centered at 470 nm (2.63 eV) as well as two weak emission peaking at 423 nm (3.06 eV) and 505 nm (2.46 eV), respectively. The electron-hole recombination of localized excitons should responsible for the light emissions at 423 and 470 nm. Room temperature Raman spectrum of KTN nanoplates reveal that the frequencies of vibration mode are lower slightly than that of KTN bulk materials, and the scattering profile is to be more diffused and enlarged, which may be induced by the crystal structure defects, such as stacking faults.     

水热法制备的LuFeO3晶粒的超声催化活性

超声波在水中传播时会产生大量空化气泡,空化气泡经历成核、生长和瞬间崩塌等过程,并在崩塌瞬间产生局部高温和高压,过程中会发出瞬间闪光,即声致发光.局部高温高压及声致发光可将半导体价带上的电子激发至导带,形成电子/空穴对,电子和空穴迁移至半导体颗粒表面,参与一系列氧化还原反应致使有机污染物发生分解.由于超声波在各种液体中都具有很强的穿透能力,因此与半导体光催化技术相比,半导体超声催化技术在降解高浓度和不透明染料废水时具有明显优势. LuFeO3是稀土正铁氧体中的一员,具有独特磁结构、巨介电常数及多铁性,近年来引起了人们极大的研究兴趣.同时, LuFeO3也是一种窄带隙半导体材料,使其可以作为一种潜在的超声催化剂,但相关报道很少.半导体材料的晶粒尺寸及形貌对其超声催化活性的影响非常大,因此制备出不同晶粒尺寸及形貌的LuFeO3颗粒并研究其超声催化性能具有重要意义.目前LuFeO3的主要制备方法为传统的固相反应法,该法需要反复研磨和高温煅烧使原料彻底反应,而且制备出的颗粒尺寸较大,相互粘连严重,形貌难以控制.在众多纳米材料制备方法中,水热法在调控晶粒尺寸及形貌上具有巨大优势.本课题组曾采用水热法成功制备了单相的LuFeO3颗粒,通过改变NaOH浓度,可以对产物的晶粒尺寸及形貌进行调控.基于此,本文以酸性橙(AO7)、罗丹明B (RhB)、甲基橙(MO)和亚甲基蓝(MB)为目标降解物,考察了水热法所制备的LuFeO3颗粒在超声辐照下的超声催化性能,并系统研究了晶粒尺寸及形貌、无机离子和乙醇对LuFeO3颗粒超声催化活性的影响及LuFeO3颗粒重复利用性能.以对苯二甲酸(TPA)为分子荧光探针,采用光致发光(PL)技术检测在超声辐照下LuFeO3反应液中产生羟基自由基(?OH)的情况,探讨了LuFeO3颗粒的超声催化机理.超声催化反应结果表明,采用水热法制备的LuFeO3颗粒在超声辐照下表现出良好的超声催化活性.在NaOH浓度为0.625 mol/L时制备的LuFeO3颗粒尺寸最小,表现出最好的超声催化活性;经过30 min超声催化反应后,AO7,RhB,MO和MB的超声降解率分别为89%,82%,73%和67%.加入Cl?, NO3?, SO42?, PO43?和HCO3?对LuFeO3颗粒的超声催化活性有抑制作用.向反应液中加入2%(v/v)乙醇后, LuFeO3颗粒在超声辐照下对AO7几乎没有降解,表明?OH在超声催化中起重要作用.重复回收实验结果表明, AO7的降解率随着循环次数增加有所下降,这可能是由于催化剂回收时的损失所致.尽管如此,催化剂仍能保持较高的催化活性,经4次循环后,反应30min时AO7的降解率为65%.PL结果表明, LuFeO3颗粒在超声催化反应中产生了大量的?OH,添加乙醇可以消耗?OH并抑制染料的超声催化降解.由此可见,?OH是超声催化降解RhB的主要活性物种.我们对LuFeO3导带和价带的电位进行了估算,从热力学角度对LuFeO3颗粒超声催化降解染料的机理做出了初步解释.     

Control of the morphology and particle size of boehmite nanoparticles synthesized under hydrothermal conditions

The spontaneous nucleation under hydrothermal conditions often leads to aggregation of crystallizing particles, which is an undesired phenomenon when the goal is the preparation of nanocrystals with narrow particle size distribution. The present paper reports on the synthesis of boehmite nanocrystals under hydrothermal conditions. An aqueous aluminum chloride salt solution was first prepared, and the pH was increased to 11 using a 5 M sodium hydroxide solution. The hydrothermal treatment was performed at 160 degrees C for different periods of time. The system yielded relatively small (15-40 nm) boehmite crystallites aggregated into larger (160 nm) particles. To avoid the aggregation, a biocompatible polymer, sodium polyacrylate (NaPa) 2100, was employed as a size-/morphology-controlling agent. Thus, stable colloidal suspensions of rounded boehmite nanoparticles having a size between 15 and 40 nm were obtained at 160 degrees C for 24 h. Further, the effect of synthesis time on the morphological features of boehmite synthesized in such a NaPa-containing system was investigated. The increase of the synthesis time from 24 to 168 h resulted in the formation of very long boehmite fibers (1000-2000 nm) with an average diameter of about 10 nm. The boehmite samples were characterized by XRD, DLS, TEM, IR, N2 adsorption, and zeta potential measurements. The colloidal stability of the obtained suspension was also studied.     

Soluble conductive polypyrrole synthesized by in situ doping with β-naphthalene sulphonic acid

Soluble polypyrrole (PPy) with high conductivity (27 S/cm) has been prepared by chemical polymerization of pyrrol monomer in the presence of β-naphthalene sulphonic acid (NSA) as a dopant. The solubility of the resulting conducting polymer of PPy-NSA in m-cresol increases with increasing the concentration of NSA in the polymerization media, and the highest solubility of PPy-NSA in m-cresol is about 1.2 g/100 mL. The room-temperature conductivity of PPy-NSA significantly increases with the concentration of NSA when the concentration of NSA is less than 0.1 mol/L, while it slightly decreases with increasing the concentration of NSA after the concentration of NSA is higher than 0.1 mol/L. UV-VIS spectra and ESR measurements demonstrate that both polaron and bipolaron are present as a charge carrier. The resulting PPy-NSA exhibits unusual fibrillar morphology with a diameter of about 0.5 μm, which is quite different from the granular morphology of PPy doped with dodecyl benzene sulfonic acid (DBSA) and HCl. Moreover, the polymerization conditions greatly influence the morphology of the obtained PPy-NSA. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 3689–3695, 1997     

Nanostructured Bi2Te3 synthesized by low temperature aqueous chemical route

Chemical and physical reactions during the low temperature aqueous chemical synthesis of nanostructured Bi₂Te₃ powders were investigated in-situ by pH measurement, color observation of the solution and X-ray diffraction analysis of the powders. It was found that Bi₂Te₃ could be synthesized only in a strong alkaline solution. Bi₂Te₃ nanocapsules were synthesized by the aqueous chemical route at 65 °C with the addition of disodium ethylenediaminetetraacetate salt. High-resolution transmission electron microscopy observation indicates that the nanocapsules are hollow-structured with a wall thickness of about 6 nm. __________ Translated from CHIMICA SINICA, 2005, 63(16)(in Chinese)     

Promoted NH3-SCR activity and hydrothermal stability of Cu-SSZ-50 catalyst synthesized by one-pot method

Nitrogen oxide(NO_x) is one of the most critical contaminants in the air, and the control of NO_x emission from diesel vehicles is very important. Cu-based small-pore zeolites have already been applied for NO_x abatement on diesel vehicles. Among the small-pore zeolites, Cu-SSZ-50 catalysts with good NH₃-SCR catalytic activity were believed to have potential for application. In this study, a one-pot synthesis method for Cu-SSZ-50 catalysts was developed f...     

Selective synthesis of vitamin K3 over mesoporous NbSBA-15 catalysts synthesized by an efficient hydrothermal method

Well hexagonally ordered NbSBA-15 catalysts synthesized by an efficient hydrothermal method were used, for the first time, for the selective synthesis of vitamin K(3) by liquid-phase oxidation of 2-methyl-1-naphthol (2MN1-OH) under various reaction conditions. The recyclable NbSBA-15 catalysts were also reused to find their catalytic activities. To investigate the leaching of non-framework niobium species on the surface of silica networks, the results of original and recyclable NbSBA-15 catalysts were correlated and compared. To find an optimum condition for the selective synthesis of vitamin K(3), the washed NbSBA-15(2.2pH) was extensively used in this reaction with various reaction parameters such as temperature, time and ratios of reactant (2M1N-OH to H(2)O(2)), and the obtained results were also demonstrated. Additionally, the liquid-phase oxidation of 2M1N-OH was carried out with different solvents to find the best solvent with a good catalytic activity. Based on the all catalytic studies, the vitamin K(3) selectivity (97.3%) is higher in NbSBA-15(2.2pH) than that of other NbSBA-15 catalysts, and the NbSBA-15(2.2pH) is found to be a highly active and eco-friendly heterogeneous catalyst for the selective synthesis of vitamin K(3).     

Electrochemical behavior of polyaniline synthesized by chemical oxidation

The slow voltammetry was taken on the paste electrode consisting of polyaniline powder and Teflon binder which was applied to pyrographite disc electrode. The potential cycle range was +0.6V→ ? 0.2V→+0.8V→+0.6V vs. SCE. It was found that the voltammetry curves are similar for both polyanilines obtained chemically and electrochemically. The difference of the voltammetry curves in various acids might be attributed to some exchange of doping anions in polyaniline. The first redox couple peaks shifted to positive potential direction with increase of pH and it might be associated with the proton addition-elimination reaction. It was shown that polyaniline prepared from very dilute or concentrated acid solution was electrochemically inactive.     

A separation mechanism of photogenerated charges and magnetic properties for BiFeO3 microspheres synthesized by a facile hydrothermal method

BiFeO(3) (BFO) microspheres were synthesized by a facile hydrothermal method. The optical absorption spectrum indicates that on site Fe(3+) crystal-field transitions and the charge transfer excitations can be observed. Magnetic measurements show a spin-glass behavior and room temperature weak ferromagnetism. The surface photovoltage spectroscopy of the BFO shows two response peaks centered at about 370 and 400 nm, respectively. Under an ambient atmosphere, the maximum surface photovoltage of the BFO reaches 180 μV with the bias (+2 V) and is three times larger than that with zero bias. It is found that the surface photovoltage response intensity increases with an increase in applied bias, regardless of positive or negative bias. It is suggested that the surface photovoltaic properties are related to both the depolarization field owing to ferroelectric polarization and the build-in electric field due to the Schottky barrier. The micro-process and the physical mechanism of the separation of photogenerated charges for BFO are fully explained.     

Studies on the magnetism of cobalt ferrite nanocrystals synthesized by hydrothermal method

Fe-Co/CoFe₂O₄ nanocomposite and CoFe₂O₄ nanopowders were prepared by the hydrothermal method. The structure of magnetic powders were characterized by X-ray diffraction diffractometer (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), thermal gravity analysis (TGA) and differential thermal analysis (DTA) analysis, X-ray photoelectron spectrometry (XPS), and Fourier transform infrared spectra (FTIR) techniques, while magnetic properties were determined by using a vibrating sample magnetometer (VSM) at room temperature. The effects of hydrothermal reaction conditions on magnetic properties were also discussed in details. The values of saturation magnetization (M_s) and coercive fore (H_c) for Fe-Co/CoFe₂O₄ nanocomposite are 113 emu/g and 1.4 kOe, respectively. Furthermore, CoFe₂O₄ ferrite with a single-domain critical size of 70 nm was fabricated by controlling the hydrothermal reaction conditions carefully, which presents high coercive force (ca. 4.6 kOe) and high squareness ratio (ca. 0.65). One interesting thing is M_s value of CoFe₂O₄ ferrite with a diameter of 40 nm is 86 emu/g which is comparable to that of the bulk counterpart.     

Shape control of nickel selenides synthesized by a simple hydrothermal reduction process

Nickel selenide (NiSe) nanoparticles were prepared from the reaction of a SeCl₄ aqueous solution with a NiCl₂·6H₂O aqueous solution in the presence of polyvinyl alcohol (PVA) as a capping agent and hydrazine hydrate (N₂H₄·H₂O) as a reductant through a hydrothermal method. The size, morphology, chemical composition and purity of these nanoparticles depend on the capping agent, reductant, reaction temperature and time.