低量Yb3+掺杂的TiO2复合纳米粉体的制备及光催化活性

姜洪泉,王鹏,线恒泽. 低量Yb3+掺杂的TiO2复合纳米粉体的制备及光催化活性[J]. 化学学报, 2006, 64(2): 145-150.     

TiO2/Gd2O3纳米粉体的制备、表征及光催化活性

利用酸催化的溶胶-凝胶法制备了纯TiO₂和Gd³⁺(0.5wt%)掺杂的TiO₂纳米粉体，采用XRD、BET、XPS、紫外-可见漫反射谱(DRS)和表面光电压谱(SPS)等技术进行了表征；以亚甲基蓝(MB)的光催化降解为探针反应，评价了其光催化活性；探讨了Gd³⁺掺杂对TiO₂纳米粉体的光催化活性的影响机制。结果表明，TiO₂/Gd₂O₃纳米粒子对MB溶液的光催化活性提高到纯TiO₂的1.5倍。掺杂Gd³⁺可以强烈抑制TiO₂由锐钛矿相向金红石相的转变；阻碍TiO₂晶粒的生长；提高高温组织稳定性，改善粉体的表面织构特性；形成光生电子的浅势捕获陷阱，抑制e^-/h⁺复合，这些因素共同作用最终导致TiO₂/Gd₂O₃纳米粉体的光催化活性明显提高。XPS分析结果证实，掺杂Gd³⁺导致粉体的表面羟基含量降低。由于产生了量子尺寸效应，复合粉体的紫外吸收带边蓝移，光的吸收能力略有降低。     

Pr3+掺杂的TiO2纳米粉体的表面特性和光催化活性

利用酸催化的溶胶-凝胶法制备了纯的和不同Pr³⁺掺杂量的TiO₂纳米粉体.以亚甲基蓝(MB)溶液的光催化降解为探针反应,评价了它们的光催化活性.利用XRD和BET技术研究了Pr³⁺掺杂量和焙烧温度对TiO₂纳米粉体的相结构、晶粒尺寸和表面织构特性的影响,并用XPS和SPS技术研究了Pr³⁺掺杂的TiO₂纳米粉体的表面组成和表面光伏特性,探讨了Pr³⁺掺杂提高纳米TiO₂的光催化活性的机制.结果表明:适量Pr³⁺掺杂能显著提高纳米TiO₂的光催化活性.当Pr³⁺掺杂量为1.25%(以Pr³⁺/TiO₂质量比计),焙烧温度为600℃时,制得粉体的光催化活性最佳.Pr³⁺掺杂强烈地抑制TiO₂由锐钛矿相向金红石相的转变,减小晶粒尺寸,增大比表面积,增加表面羟基和吸附氧的含量,提高光生电子和空穴的分离效率,改善粉体表面的光吸收性能,上述因素均有利于光催化活性的提高.     

Photocatalytic degradation of methylene blue on Fe3+-doped TiO2 nanoparticles under visible light irradiation

Fe³⁺-doped TiO₂ composite nanoparticles with different doping amounts were successfully synthesized using sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultravioletvisible spectroscopy (UV-Vis) diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of Fe³⁺/TiO₂ nanoparticles under visible light irradiation. The influence of doping amount of Fe³⁺ (ω: 0.00%–3.00%) on photocatalytic activities of TiO₂ was investigated. Results show that the size of Fe³⁺/TiO₂ particles decreases with the increase of the amount of Fe³⁺ and their absorption spectra are broaden and absorption intensities are also increased. Doping Fe³⁺ can control the conversion of TiO₂ from anatase to rutile. The doping amount of Fe³⁺ remarkably affects the activity of the catalyst, and the optimum efficiency occurs at about the doping amount of 0.3%. The appropriate doping of Fe³⁺ can markedly increase the catalytic activity of TiO₂ under visible light irradiation. __________ Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(6): 55–56 [译自: 西北师范大学学报(自然科学版)]     

Optical transitions of Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 glass

Optical absorption and emission properties of the Er3+/Yb3+ codoped TeO2-WO3-Bi2O3 (TWB) glass has been investigated. The transition probabilities, excited state lifetimes, and the branching ratios have been predicted for Er3+ based on the Judd-Ofelt theory. The broad 1.5 microm fluorescence was observed under 970 nm excitation, and its full width at half maximum (FWHM) is 77 nm. The emission cross-section is calculated using the McCumber theory, and the peak emission cross-section is 1.03 x 10(-21) cm2 at 1.531 microm. This value is much larger than those of the silicate and phosphate glasses. Efficient green and weak red upconversion luminescence from Er3+ centers in the glass sample was observed at room temperature, and the upconversion excitation processes have been analyzed.     

Intense blue up-conversion luminescence in Tm3+/Yb3+ codoped oxyfluoride glass-ceramics containing beta-PbF2 nanocrystals

Up-conversion luminescence properties of a Tm3+/Yb3+ codoped oxyfluoride glass-ceramics under 980 nm excitation are investigated. Intense blue emission centered at 476 nm, corresponding to 1G4-->3H6 transitions of Tm3+ was simultaneously observed in the transparent oxyfluoride glass ceramics at room temperature. The intensity of the blue up-conversion luminescence in a 1 mol% YbF3-containing glass-ceramic was found to be about 40 times stronger than that in the precursor oxyfluoride glass. The reason for the intense Tm3+ up-conversion luminescence in the oxyfluoride glass-ceramics is discussed. The dependence of up-conversion intensities on excitation power and possible up-conversion mechanism are also evaluated.     

Anti-Stokes Yb3+ emission--valuable structure information in spectra of rare earth compounds measured with FT-Raman spectrometers

Raman spectroscopy is a powerful and simple method which proved to be very useful in studies of solids. The most widely used Raman spectrometers are FT-Raman instruments with YAG:Nd(3+) laser as an excitation source. However, in the case of samples containing rare earth elements, the quality of FT-Raman spectra is often low due to strong fluorescence effects. We show that, in such cases, anti-Stokes part of the Raman spectra often contains strong, well resolved bands identified as multiphonon-assisted emission bands of Yb(3+) present as an impurity. We show on several examples that analysis of these bands may provide useful structure information, similar to that obtained by "Eu structure probe" method in optical spectroscopy. The Yb(3+) emission can be also measured using standard luminescence detection systems. However, the application of FT-Raman system allows one to obtain good quality spectra in a much cheaper, easier and faster way (in times as short as a few seconds). Moreover, high-sensitivity of FT-Raman spectrometers allows to detect even very small amounts of Yb(3+) impurity.     

Preparation and characterization of nylon 6/Cu2+-exchanged and Fe3+-exchanged montmorillonite nanocomposite

Nylon 6/Cu²⁺-exchanged and Fe³⁺-exchanged montmorillonite nanocomposites have been prepared by a melt intercalation technique directly from Cu²⁺-exchanged and Fe³⁺-exchanged montmorillonite. Hexadecyltrimethylammonium bromide was chosen as the clay/matrix reactive compatibilizer. The intercalation spacing and the degree of dispersion were determined by X-ray diffraction and transmission electron microscopy. Also the thermal character of the nanocomposites prepared was analyzed by thermogravimetric analysis.     

Upconversion Luminescence Properties of a LiNb0.3Ta0.7O3:Er3+,Yb3+ Ceramic

A co-doped LiNb_0.3Ta_0.7O₃:Er³⁺,Yb³⁺ ceramic was prepared by a high temperature solid state procedure. Under the excitation of 980 nm laser radiation, intense 660 nm red light and 550 nm green light emissions corresponding to the ⁴F_9/2→⁴I_15/2 and ²H_11/2/⁴S_3/2→⁴I_15/2 transitions of Er³⁺ were observed. The change of Yb³⁺ concentration has a more significant influence on luminous intensity than the Er³⁺ concentration. The emission of red and green lights is attributed to a two-photon process. The upconversion luminescence mechanisms were analyzed in detail.     

Preparation and characterization of nitrogen-doped TiO2 photocatalyst in different acid environments

Nitrogen-doped TiO₂ powders were successfully prepared by a wet method, i.e., a micro-emulsion-hydrothermal method, in different acid environments. Several characterization techniques, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV-visible diffuse reflectance spectra, were combined to determine the crystal phase, concentration and chemical states of the nitrogen doped in TiO₂. The high photocatalytic activity of the nitrogen-doped TiO₂ was evaluated through the decomposition of rhodanmine B under visible light irradiation. It was suggested that the doped nitrogen formed oxynitride (NO) and produced impurity states at higher above the valence band of TiO₂. Therefore, the nitrogen doping could enhance the response of photocatalyst to the visible light and improve the photocatalytic activity because of the narrowing of band gap of TiO₂.     

Ho3+/Yb3+共掺ZnO-Al2O3-GeO2-SiO2玻璃陶瓷的制备和上转换发光性质

综合ZnO-Al₂O₃-SiO₂系和锗酸盐玻璃陶瓷的优点,采用熔融-晶化法首次制备了Ho³⁺/Yb³⁺共掺以ZnAl₂O₄为主晶相的ZnO-Al₂O₃-GeO₂-SiO₂系玻璃陶瓷。因[GeO₄]四面体和[SiO₄]四面体都是玻璃网络形成体,讨论了GeO₂取代SiO₂对玻璃陶瓷样品硬度及发光性能的影响,最终确定GeO₂的取代量为10.55%（w/w）时,玻璃陶瓷综合性能最佳。在980 nm泵浦光的激发下,发现强的绿色（546 nm）和弱的红色（650 nm）上转换发光,并研究了不同Ho³⁺/Yb³⁺掺杂比对样品上转换发光的影响,最终结果表明当Ho³⁺/Yb³⁺掺杂比为1：11（n/n）时样品荧光强度最强,在绿色上转换发光材料方面具有潜在的应用。     

Er~(3+)-Yb~(3+)双掺Li_2O-ZnO-SiO_2系透明玻璃陶瓷的制备及表征

采用熔融-晶化技术合成了Er3+-Yb3+掺杂的Li2O-ZnO-SiO2系(LZS)透明玻璃陶瓷。利用DTA,XRD,SEM,UV-Vis-NIR等对样品进行了表征,并分析了影响玻璃陶瓷析晶的因素。结果表明,LZS系玻璃具有良好的结晶性能,其最佳热处理温度为700℃,最佳热处理时间为50min,其主晶相为石英和Li8Zn10Si7O28。该玻璃陶瓷在可见光区的透过率可达85%。经SEM分析,粒子直径为30~40nm。荧光光谱显示,玻璃陶瓷的发射光谱较之基质玻璃有了极大的提高,而且在1530nm附近获得一较强发射峰。     

Er3+-Yb3+掺杂SiO2-SrO-NaF玻璃陶瓷的制备及表征

采用熔融晶化法制备了主晶相为SrF₂的Er³⁺-Yb³⁺共掺透明氟氧化物玻璃陶瓷,利用DSC、XRD、SEM、UV-Vis-NIR和荧光光谱对样品的结构、形貌、发光性能进行了测试与表征。研究表明：该体系玻璃最佳热处理温度为620℃,最佳热处理时间为2 h,并讨论了Yb³⁺不同掺杂浓度对Er³⁺-Yb³⁺共掺玻璃陶瓷样品上转换发光性能的影响,确定Er³⁺-Yb³⁺最佳掺杂浓度比为1：7,同时观察到了明亮的绿光（522,540 nm）和较弱的红光（656 nm）,对Er³⁺和Yb³⁺之间的能量传递过程进行了讨论。     

Thermal stability and spectroscopic properties of Er3+-doped antimony-borosilicate glasses

This paper reports on the optical spectroscopic properties and thermal stability of Er(3+)-doped antimony-borosilicate glasses for developing 1.5mum optical amplifiers. Upon excitation at 980nm laser diode, an intense 1.5mum infrared fluorescence has been observed with the maximum full width at half maximum (FWHM) of 90nm for Er(3+)-doped antimony-borosilicate glasses. The emission cross-section and the lifetime of the (4)I(13/2) level of Er(3+) ions are 6.3x10(-21)cm(2) and 0.30ms, respectively. It is noted that the product of the emission cross-section and FWHM of the glass studied is as great as 567x10(-21)cm(2)nm, which is comparable or higher than that of bismuthate and tellurite glasses.     

复合光催化剂CeO2/TiO2的制备及性能研究

采用溶胶-凝胶-浸渍法制备了CeO2／TiO2二元复合纳米光催化剂,用XRD、FTIR等对其进行了表征。以紫外灯为光源,直接耐晒兰(DFB)的脱色为模型反应,研究了CeO2／TiO2的光催化活性。结果表明：掺杂摩尔百分比x(CeO2)=1．44％、600℃煅烧2h时,该催化剂的催化活性最高,比纯TiO2高近1倍。DFB脱色的最佳条件为：pH9．0～10．0,投加量200mg／50mL,空气流量200mL／min。     

Modulating the Inclusive and Coordinating Ability of Thiacalix[4]arene and Its Antenna Effect on Yb3+-Luminescence via Upper-Rim Substitution

The present work introduces the series of thiacalix[4]arenes (H₄L) bearing different upper-rim substituents (R = H, Br, NO₂) for rational design of ligands providing an antenna-effect on the NIR Yb³⁺-centered luminescence of their Yb³⁺ complexes. The unusual inclusive self-assembly of H₃L⁻ (Br) through Br…π interactions is revealed through single-crystal XRD analysis. Thermodynamically favorable formation of dimeric complexes [2Yb³⁺:2HL³⁻] leads to efficient sensitizing of the Yb³⁺ luminescence for H₄L (Br, NO₂), while poor sensitizing is observed for ligand H₄L (H). X-ray analysis of the single crystal separated from the basified DMF solutions of YbCl₃ and H₄L(NO₂) has revealed the transformation of the dimeric complexes into [4Yb³⁺:2L⁴⁻] ones with a cubane-like cluster structure. The luminescence characteristics of the complexes in the solutions reveal the peculiar antenna effect of H₄L(R = NO₂), where the triplet level at 567 nm (17,637 cm⁻¹) arisen from ILCT provides efficient sensitizing of the Yb³⁺ luminescence.     

Enhanced ultraviolet up-conversion emissions of Tm/Yb codoped YF3 nanocrystals

Tm³⁺/Yb³⁺ codoped rod-like YF₃ nanocrystals were synthesized through a facile hydrothermal method. After annealing in an argon atmosphere, the nanocrystals emitted bright blue and intense ultraviolet (UV) light under a 980-nm continuous wave diode laser excitation. Up-conversion emissions centered at ∼291 nm (¹I₆ → ³H₆), ∼347 nm (¹I₆ → ³F₄), ∼362 nm (¹D₂ → ³H₆), ∼452 nm (¹D₂ → ³F₄), ∼476 nm (¹G₄ → ³H₆), ∼642 nm (¹G₄ → ³F₄), and ∼805 nm (³H₄ → ³H₆) were recorded using a fluorescence spectrophotometer. Especially, enhanced UV emissions were studied by changing Yb³⁺/Tm³⁺ doping concentrations, the annealing temperatures, and the excitation power densities. A possible mechanism, energy transfer-cross relaxation-energy transfer (ET-CR-ET), was proposed based on a simple rate-equation model to elucidate the process of the enhanced UV emissions.     

Yb3+/Tm3+共掺杂的钨酸镉纳米晶发光性能的研究

本文采用水热法制备了稀土离子Yb3+/Tm3+共掺杂的钨酸镉纳米晶。运用X-射线粉末衍射、场发射环境扫描电子显微镜和光谱分析对制备的样品的结构和发光性能进行了表征。根据XRD图谱可知,钨酸镉为单斜晶系,晶粒平均尺寸在28 nm左右。从ESEM图片可明显看出,钨酸镉呈纳米棒结构,直径在30 nm左右,长径比在5~8之间。利用980 nm半导体激光器激发钨酸镉纳米晶得到样品的发射光谱,存在一个较强的蓝光发射,发光峰位于481 nm,对应于Tm3+的1G4→3H6能级的跃迁,分析了Tm3+/Yb3+离子共掺体系的发光机制。讨论了发光强度随稀土离子浓度的变化,当Tm3+离子的掺杂浓度在2mol%,Yb3+/Tm3+物质的量浓度比cTm3+/cYb3+=10时钨酸镉纳米晶的发光强度最强。根据泵浦功率与发光强度之间的关系,可知处于481 nm的蓝光发射属于三光子过程,由发光强度与掺杂浓度之间的双对数衰减曲线可知,引起蓝光发射源于Tm3+的电偶极跃迁。     

Yb3+/Tm3+共掺杂的钨酸镉纳米晶发光性能的研究

本文采用水热法制备了稀土离子Yb³⁺/Tm³⁺共掺杂的钨酸镉纳米晶。运用X-射线粉末衍射、场发射环境扫描电子显微镜和光谱分析对制备的样品的结构和发光性能进行了表征。根据XRD图谱可知, 钨酸镉为单斜晶系, 晶粒平均尺寸在28 nm左右。从ESEM图片可明显看出, 钨酸镉呈纳米棒结构, 直径在30 nm左右, 长径比在5~8之间。利用980 nm半导体激光器激发钨酸镉纳米晶得到样品的发射光谱, 存在一个较强的蓝光发射, 发光峰位于481 nm,对应于Tm³⁺的¹G₄→³H₆能级的跃迁, 分析了Tm³⁺/Yb³⁺离子共掺体系的发光机制。讨论了发光强度随稀土离子浓度的变化, 当Tm³⁺离子的掺杂浓度在2%, Yb³⁺/Tm³⁺物质的量浓度比为10:1时钨酸镉纳米晶的发光强度最强。根据泵浦功率与发光强度之间的关系, 可知处于481 nm的蓝光发射属于三光子过程, 由发光强度与掺杂浓度之间的双对数衰减曲线可知, 引起蓝光发射源于Tm³⁺的电偶极跃迁。     

Y2O3:Eu3+纳米线阵列的制备与表征

Y2O3:Eu3+红色荧光粉由于色纯度高、化学性质稳定和量子效率接近100%而广泛用于荧光灯和投影电视等方面.近年来,Y2O3:Eu3+的大量研究工作主要集中于纳米粉末的制备方法及其与体相材料不同的发光特性[1～3].最近,有关Y2O3:Eu3+及其稀土化合物的纳米管、纳米线和纳米带一维材料的制备成为研究热点.Wu Changfeng等[4,5]利用表面活性剂合成了Y2O3 : Eu3+纳米管.激光格位选择激发测试结果表明,Eu3+在纳米管中占据3个不同的格位,其611 nm处的红色发光峰出现了宽化.He Yu等[6]采用水热法及退火处理制备出了Y2O3:Eu3+纳米带,发现Eu3+的发射峰不仅宽化,而且出现了625 nm的新峰.Li Yadong等[7～9]采用水热法制备了稀土氧化物、硫氧化物和氢氧化物等的纳米线和纳米管,并探索了其形成机理,同时发现Y2O3S : yb3+,Er3+具有上转换的性质.