Ti与Ag离子顺次注入SiO2合成TiO2纳米结构及其光催化活性

通过Ti离子单注入或与Ag离子顺次注入、结合后续的N₂气氛下热退火处理,在SiO₂基体的浅表面层合成TiO₂纳米结构,详细研究了该纳米结构的形貌、结构、光学特性及其光催化性能。结果表明：Ti离子单注入或与Ag离子顺次注入并经热处理后均能在SiO₂中产生TiO₂纳米颗粒,700℃退火后形成的纳米颗粒主要为锐钛矿相,继续升高退火温度,TiO₂纳米颗粒逐渐转变为金红石相。Ag的附加注入不仅能促进TiO₂纳米颗粒的生长,而且可以降低其形成的温度及光学带隙。此外,光催化实验结果还显示,Ag的附加注入能够提高所合成的TiO₂纳米颗粒光催化活性。结合光致发光和X射线光电子能谱测试结果分析并给出了附加Ag离子注入导致所合成的TiO₂ 纳米结构光催化活性提升的可能机理。     

耐久型β-FeOOH纳米棒/聚酯织物复合材料制备及其高效双功能水净化研究

中国近30年的快速发展对环境造成了严重破坏,尤其是对水资源的破坏,严重威胁着生态平衡及人类健康。工业含油/可溶性高毒废水是水净化过程中亟需解决的问题,然而,制备能够同时实现油水分离和降解有机物污染物的材料仍然是一个严峻的挑战。本研究制备了耐久型β-FeOOH纳米棒/聚酯织物复合材料,用于解决上述问题。实现在对油/水混合物进行分离的同时,将水中可溶性有机物原位降解的双重净化效果。实验结果表明,油/水分离效率及对水中高毒、可溶性有机物的去除率分别达到99%及90%以上;材料经过多轮循环降解实验和加速洗涤试验后,油/水分离效率和有害有机物的去除率仍保持基本不变。     

SiO2纳米干凝胶对锆的动态吸附

研究了模拟高放废液中的锆在成型后的SiO2纳米干凝胶上的动态吸附行为。结果表明低流速、温度低、酸度高、SiO2干凝胶的颗粒小时,交换柱穿透得较慢;反之,穿透较快。SiO2纳米干凝胶对Zr的吸附选择性高,模拟高放废液中的Fe和Mo略有吸附,其它元素不被吸附。     

压水堆燃料棒UO2燃料芯块与锆合金包壳化学相互作用层研究

反应堆运行期间,锆合金包壳与燃料接触后不断氧化,与燃料结合形成牢固的化学相互作用层,影响燃料间隙热导、包壳力学性能和燃料包壳机械相互作用。本文以压水堆核电站燃耗45 GWd·t U-1完整燃料棒为研究对象,利用金相显微镜(Metallographic Microscope)、扫描电子显微镜及能谱分析(Scanning Electron Microscopy-Energy Dispersive Spectroscopy,SEM-EDS)和热室内拉曼光谱(Raman Spectroscopy)方法对其化学相互作用层形貌及结构进行分析,国内首次获得堆内辐照后包壳和芯块化学相互作用层相关分析数据。结果表明：运行至45 GWd·t U-1燃耗后,燃料芯块与包壳间隙形成14～19μm的化学相互作用层,不同位置机械接触的时间顺序差异,导致作用层的不连续形成与长大。SEM-EDS结果表明,相互作用层呈“蠕虫”状形貌,且由U、Zr、O三元素构成形成混合相(U,Zr)O_x化合物,并且发现化学相互作用层由化学黏附和机械作用共同作用的结果。拉曼光谱显示,化学相互作用层主要由四方相氧化锆(...     

UiO-66-(COOH)2的合成及其对锂同位素吸附分离性能研究

为研究金属有机骨架材料对⁷Li的吸附分离性能,本研以水作为溶剂,四氯化锆和均苯四甲酸为起始原料,采用水热法合成金属有机骨架材料UiO-66-(COOH)₂,对合成材料的形貌、孔径、热稳定性等进行表征与分析;通过静态吸附实验探讨吸附时间、反应温度、溶液浓度对UiO-66-(COOH)₂锂离子吸附性能及同位素分离因子的影响;并对Li⁺浓度、⁶Li/⁷Li同位素丰度进行测定。结果表明,UiO-66-(COOH)₂可实现对锂的吸附以及⁷Li的分离,且在293 K Li₂CO₃溶液中,每0.05 g UiO-66-(COOH)₂对10 mL 0.05 mol/L Li₂CO₃进行4 h的静态吸附,最大吸附量Q为9.53 mg/g,分离因子S（⁷Li/⁶Li）为1.019 54。研究结果为⁷Li的分离提供了新途径。     

Tuning Effect of N2 on Atmospheric-Pressure Cold Plasma CVD of TiO2 Photocatalytic Films

To deposit TiO2 films through plasma CVD, the partial pressure ratio of O2 to TiCl4 should be greater than the stoichiometric ratio (pO2 /pTiCl4>1). However, this may lead to the formation of powder instead of film on the substrate when using volume dielectric barrier discharge (volume-DBD) at atmospheric pressure. In this study, by adding N2 into the working gas Ar, TiO2 photocatalytic films were successfully fabricated in the presence of excess O2 (pO2 /pTiCl4=2.6) by using a wire-to-plate atmospheric-pressure volume-DBD. The tuning effect of N2 on the deposition of TiO2 film was studied in detail. The results showed that by increasing the N2 content, the deposition rate and particle size of the TiO2 film were reduced, and its photocatalytic activity was enhanced. The tuning mechanism of N2 is further discussed.     

D-D中子辐照单晶TiO2的损伤特性

利用兰州大学强流中子发生器出射的单能D-D中子对单晶TiO2(金红石相)进行辐照,分别测量了样品的正电子寿命谱及XRD谱。中子辐照会在样品内部产生大量的空位缺陷,由于晶格中Ti原子的位移阈能约为O原子的2倍,因此中子辐照在样品内部产生的空位缺陷以氧空位(VO)为主。结果表明,单晶内部捕获正电子的陷阱Ti空位(VTi)在中子辐照后电子密度增大,可能与Ti空位周围O空位的引入有关,O空位的出现减弱了Ti空位处的库仑排斥作用,使空位体积减少。后续测试的XRD也得到相同的结果,样品由于中子辐照而在c轴方向的晶面间距发生变化,并导致单晶TiO2的结晶度变差。     

TiO2/SFP铀吸附材料的制备及其吸附性能

本工作旨在合成一种高吸附性能、高选择性的吸附材料,实现重金属离子的去除和海水中铀资源的提取。将天然葵花粉(SFP)通过溶胶凝胶法与TiO₂颗粒进行复合,得到TiO₂/SFP复合材料。将合成材料进行扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、能谱分析(EDS)、X射线光电子能谱(XPS)等表征和吸附测试;在pH值为6.0时,材料最大吸附容量可达到215.7 mg/g。复合材料对于溶液中铀的吸附符合准二级动力学模型,是一个吸热、可自发的过程,其吸附等温线符合Langmuir模型,在模拟海水中材料对铀的去除率超过90%。     

Room temperature ferromagnetism of Co doped TiO2 using ion implantation and defect engineering

Ferromagnetic (FM) semiconductors obtained by doping ferromagnetic elements into a nonmagnetic semiconductor matrix are essential for the second generation of spintronics devices. In this study, we investigate Co doping behavior and subsequent magnetic properties in Co implanted and thermally annealed TiO₂. In TiO₂ single crystals, a decrease in the oxygen partial pressure during thermal annealing is found to enhance the Co substitutional fraction by increasing the concentration of oxygen vacancies. Magnetic properties determined from superconducting quantum interference device magnetometer (SQUID) measurements show that TiO₂ crystals with a large fraction of substitutional Co are ferromagnetic at room temperature. In addition to single crystals, the feasibility of Co doping via ion implantation is studied in sol–gel synthesized TiO₂ thin films. Results from grazing incidence X-ray diffraction (GIXRD) show that the implantation can produce Co doped TiO₂ thin films and that the Co incorporation into Ti lattice site accompanies the transition from rutile to anatase phase. These results show that ion beam synthesis is a useful tool for producing ferromagnetic TiO₂ with a high Curie temperature (T_C).     

Structural changes in anatase TiO2 thin films irradiated with high-energy heavy ions

In order to investigate possible structural changes due to high-density electronic excitation, anatase TiO₂ thin film specimens were irradiated with 230 MeV ¹³⁶Xe¹⁵⁺ ions and 200 MeV ¹⁹⁷Au¹³⁺ ions. X-ray diffraction (XRD) patterns were measured before and after irradiation. The intensity of the XRD peak assigned to the (0 0 4) planes of anatase TiO₂ decreases in an exponential manner as a function of ion-fluence. This result can be explained by the formation of the cylindrical damaged regions (i.e. ion tracks) with diameters of 9.6 and 16.3 nm for 230 MeV Xe and for 200 MeV Au ion irradiations, respectively. The difference in the track diameter between Xe ion irradiation and Au ion irradiation can be attributed to the difference in the electronic stopping power (and to the ion-velocity effect, if any). For 200 MeV Au ion irradiation, splitting of the (0 0 4) peak is observed. The original (0 0 4) TiO₂ peak remains in the same position, but the new peak shifts to higher angles as fluence increases.     

Competitive Contribution of Catalyst and Adsorption Roles of TiO2 on the Degradation of AO7 Dye During Plasma Treatment

In order to investigate the role of TiO2 during plasma treatment,the degradation of the dye AO7 has been studied by gliding arc discharge in the presence of a TiO2 catalyst(CGAD).The results revealed that the adsorption of the dye on TiO2 is a physical adsorption in accordance with Langmuir isotherm,with a constant of adsorption KL=0.52 mg/L and a maximum adsorption capacity b=18.1 mg/g.The temperature variation of the reaction medium made it possible to consider thermodynamic parameters.Indeed,the adsorption is exothermic(enthalpy:△H 0),and spontaneous(free enthalpy:△G 0).The negative entropy(△S0) confirms the afnity of the dye molecules for TiO2.20 min of CGAD treatment in the presence of an optimal quantity of TiO2(2 g/L enabled us to bleach the solution of AO7(100 μM) completely.The discoloration rate with and without the addition of TiO2 was 100% and 28%,respectively.40 additional minutes of treatment allowed a total abatement of the chemical oxygen demand.The elimination of AO7 molecules during the plasma-catalytic treatment follows Langmuir-Hinshelwood(L-H) model kinetics.According to this model,the speed constant is kr=14.97 mg · L 1· min 1and the adsorption coefcient is KL-H = 0.010 L/mg.The latter being negligible compared to kr,adsorption is therefore weakly performed during the plasma treatment.     

High resolution TEM of high burnup UO2 fuel

High-resolution TEM (HRTEM) observations and nano-area EDX analyses were carried out on small intragranular bubbles in the outer region of high burnup UO₂ pellets. Sample was prepered from the outer region of UO₂ pellet, which had been irradiated to the pellet average burnups of 49 GWd/t in a BWR. HRTEM observations and element analyses were made with a 200 KV cold-type field emission TEM (Hitachi FE-2000) having an ultra-thin window EDX (Noran Voyager). Lattice image and nano-area EDX results indicate the presence of 4-8 nm size Xe-Kr bubbles along with fission products of five metal particles, Mo-Tc-Ru-Rh-Pd. Nano-diffraction patterns from bubbles show two different new patterns besides matrix UO₂. From the Xe/U proportion obtained by nano-area EDX peak and nano-diffraction patterns from bubbles, it was concluded that Xe in the small bubbles was present in a solid or near solid state at very high pressure. Furthermore, from the results of high resolution images and diffractions obtained from recrystallized grains in rim structure region, neighboring recrystallized grains were clarified to be present with high angle grain boundaries.     

Blue luminescence from poly(methyl methacrylate) modified ZnO and anatase TiO2 nanocrystals prepared using γ radiation

The surface of ZnO and anatase TiO₂ nanocrystals was modified by PMMA through γ radiation. The modified nanocrystals were investigated with photoluminescence (PL) and Fourier transform infrared (FTIR) spectra. A stable blue luminescence peak (420 nm) can be observed for the modified ZnO and anatase TiO₂ nanocrystals. The intensities of luminescence of the modified ZnO and anatase TiO₂ in aqueous solution are very stable, even unchanged after storage time of one month.     

Exothermic hydrogen production system in supercritical water from biomass and usual domestic wastes with an exploitation of RuO2 catalyst

This paper deals with a method of producing hydrogen from biomass and sewage disposals in supercritical water by use of ruthenium dioxides as a catalyst. Experiments were carried out under argon atmosphere with a batch reactor made of INCONEL625. Reaction temperatures and pressures were changed in the ranges of 400–500 °C and 30–50 MPa, respectively. The gas produced was quantitatively analyzed by on-line gas chromatography. In conclusion, considerably high ratios of hydrogen up to 38.5% were produced from the sewage disposals. This value was even higher than the hydrogen production ratios from other biomass: 15.0% from cellulose, 14.1% from pulp, 16.0% from waste paper, and 27.0% from paper sludge. The heat balance was calculated in the present reaction system using ruthenium oxide as the catalyst in supercritical water for the reaction of naphthalene and cellulose. The result showed that the total reaction was exothermic. This is rather surprising, because most of the hydrogen forming reactions are endothermic. The present result should be due to the excess heat derived by the partial formation of carbon dioxide.     

Depth profiling of Al2O3 + TiO2 nanolaminates by means of a time-of-flight energy spectrometer

Atomic layer deposition (ALD) is currently a widespread method to grow conformal thin films with a sub-nm thickness control. By using ALD for nanolaminate oxides, it is possible to fine tune the electrical, optical and mechanical properties of thin films. In this study the elemental depth profiles and surface roughnesses were determined for Al₂O₃ + TiO₂ nanolaminates with nominal single-layer thicknesses of 1, 2, 5, 10 and 20 nm and total thickness between 40 nm and 60 nm. The depth profiles were measured by means of a time-of-flight elastic recoil detection analysis (ToF-ERDA) spectrometer recently installed at the University of Jyväskylä. In TOF-E measurements ⁶³Cu, ³⁵Cl, ¹²C and ⁴He ions with energies ranging from 0.5 to 10 MeV, were used and depth profiles of the whole nanolaminate film could be analyzed down to 5 nm individual layer thickness.