Preparation and photoluminescence properties of Y2SiO5:Eu3+ nanocrystals

The sol-emulsion-gel method is used for the preparation of about 5-7 nm size Eu2O3 doped and coated Y2SiO5 nanoparticles at 1300 degrees C. Here, we report the role of surface coating, dopant concentration and temperature of heating on the modification of crystal structure and the photoluminescence properties of Y2SiO5:Eu3+ nanocrystals. It is found that photoluminescence properties are sensitive to the crystal structure which is again controlled by surface coating, concentration and heating temperature. The decay times are 0.76, 1.14, 1.23 and 1.40 ms for 0.25, 0.5, 1.0 and 2.5 mol% Eu2O3 doped Y2SiO5 nanocrystals prepared at 1100 degrees C (X1-Y2SiO5). However, in X2-Y2SiO5 crystal phase (at 1300 degrees C) the average decay times are 1.05, 1.35, 1.55 and 1.60 ms for 0.25, 0.5, 1.0 and 2.5 mol% Eu2O3 doped Y2SiO5 nanocrystals, indicating the photoluminescence properties depend on both the crystal structure and the concentration of ions. The emission intensity of the peak at 612 nm (5D0-->7F2) of the Eu3+-ions is found to be sensitive to the doping and surface coating of Y2SiO5 nanocrystals. The decay times are 1.55 and 1.70 ms for 1300 degrees C heated 1.0 mol% Eu2O3 doped and coated Y2SiO5 nanocrystals, respectively. Our analysis suggests that the site symmetry of ions plays a most important role in the modification of radiative relaxation mechanisms and as a result on the overall photoluminescence properties.     

Role of dopant concentration and surface coating on photophysical properties of CdS: Eu3+ nanocrystals

Here, we report the role of dopant concentration and surface coating of CdS: Eu3+ nanocrystals on the modification of crystal structure and their photoluminescence properties by steady-state and time resolved fluorescence studies. It is found that photoluminescence properties are sensitive to the crystal structure which is controlled by surface coating and dopant concentration. The emission intensity of the peak at 614 nm (5D0 --> 7F2) of the Eu3+-ions is found to be sensitive to the doping and surface coating of CdS nanocrystals. It is found that the average decay times tau are 248, 353 and 499 micros for 0.25, 0.5 and 1.0 mol% Eu ions doped into CdS nanocrystals, respectively. From the decay time measurements, it is evident that the energy transfer occurs from CdS nanoparticles to Eu3+ ions and the calculated energy transfer efficiency from CdS nanoparticles to Eu3+ ions is 9.2 and 35% for Eu3+ ions coated and doped CdS nanoparticles, respectively. Our analysis suggests that site symmetry of ions plays a very important role in the modifications of radiative and nonradiative relaxation mechanisms.     

Role of surface coating in ZrO2/Eu3+ nanocrystals

The sol-emulsion-gel method is used for the preparation of Eu3+ ion-doped and coated ZrO2 nanocrystals. Here, we report the role of surface coating, dopant concentration, and temperature of heating in the modification of their crystal structure and photoluminescence properties. It is found that the volume fraction of the tetragonal phase increases from 28.08 to 91.56% because of surface coating. This is a significant modification of the crystal phase in ZrO2 nanocrystals due to surface coating by Eu2O3. It is found that the photoluminescence properties are sensitive to the crystal structure, which is again controlled by surface coating, concentration, and heating temperature. It is found that the decay time (tau) of Eu-doped ZrO2 nanocrystals increases with increasing the concentration of dopant and with increasing the temperature of heating because of changes in their crystal phase. The emission intensity of the peak at 611-617 nm (5D0 --> 7F2) of the Eu3+ ion-activated ZrO2 nanocrystals (doped and coated) is also found to be sensitive to the nanoenvironment. The average decay times are 770 and 488 mus for 1100 degrees C-heated 1.0 mol % Eu2O3-doped and coated ZrO2 nanocrystals, respectively. Our analysis suggests that the site symmetry of the ions plays the most important role in the modifications of the radiative and nonradiative relaxation mechanisms as a result of the overall photoluminescence properties.     

Effects of Y (Ⅲ) Ions on the Fluorescence Properties of Ce(Ⅲ) Ion and the Organic Ligands in the Complex

The enhancement effects of Y ( Ⅲ) ions on the fluorescence of Ce ( Ⅲ) in Ce ( Ⅲ)-Y ( Ⅲ)-PMMA (polymethylmethacrylate ) or Ce ( Ⅲ)-Y ( Ⅲ)-PVC (polyvinyl chloride ) complex systems were observed. The influence of Y ( Ⅲ) ions on the emission spectra of PMMA ligands in PMMA-Y ( Ⅲ) and the fluorescent enhance- ment of Y( Ⅲ) on Ce( Ⅲ) emission in PMMA-Ce-Y by Y( Ⅲ) ion were studied. It was also of interest to note that when Y ( Ⅲ) ions were added into PMMA and into bpy(bipyridine ), respectively, the emission spectrum of PMMA ligands was split into fine structure bands by Y ( Ⅲ), and the fluorescence intensities of bpy ligands in bpy-Y ( Ⅲ) complexes were considerably increased.     

Surface versus volume effects in luminescent ceria nanocrystals synthesized by an oil-in-water microemulsion method

Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.     

Microwave-assisted synthesis of hydrophilic BaYF5:Tb/Ce,Tb green fluorescent colloid nanocrystals

Hydrophilic Ce, Tb doped BaYF(5) nanocrystals with uniform size were synthesized by a microwave-assisted route. The synthesized nanocrystals can be well dispersed in hydrophilic solutions (DMSO, DMF, EG, H(2)O). This synthesis procedure represents a less time consuming method, with high product yield and without using any assistant or/and template reagents, which may be expected to be a general method for rapid synthesis of other hydrophilic RE doped fluoride fluorescent nanocrystals. The Ce(3+), Tb(3+) codoped BaYF(5) nanocrystals show bright green fluorescence emission. The Ce(3+) acts as an effective energy transfer medium and the emission at the high (5)D(3) energy level of Tb is enhanced in this host material.     

CuInS2/CdS基掺杂纳米晶的晶体结构、光谱性质及性能调控研究

多功能纳米晶的制备、性能及其应用是材料、化学、能源、生物医学等领域十分关注的课题之一。基于掺杂调控纳米晶生长和性能的思想,发展了纳米晶修饰和复合的概念和技术,使用绿色安全的化学溶液法结合外延生长技术合成了巯基丙酸(MPA)包覆的掺杂CuInS₂/CdS基纳米晶材料。通过适当调整掺杂异价离子的种类,实现了对CuInS₂/CdS基纳米晶显微结构和性能的调控,获得了具有特定相结构、组分、尺度和光学性能(吸收性质、光学带隙、发光强度)的纳米晶。存在于基质晶体中不同金属掺杂离子,会造成半导体的禁带中间产生掺杂能级,导致二次跃迁,进而产物体现出不同的禁带宽度。掺杂Co ²⁺、Fe ²⁺、Er ³⁺离子的CuInS₂/CdS纳米晶光致发光(PL)峰强度降低明显,这是由于Co ²⁺、Fe ²⁺、Er ³⁺离子掺杂有效地抑制了空穴-电子对的复合,降低了纳米晶的光生电子-空穴复合几率,使得其光催化活性得到增强。这些半导体纳米材料在光催化、能量转换与储存方面具有良好的应用潜力。     

铕、铈、钇离子对TiO2催化剂的改性作用

用浸渍法在微米级TiO2中添加Eu,Y,Ce离子，研究了其对微米级TiO2的改性作用。并以DBS的光降解反应为实验模型，比较催化剂的催化活性。与未加修饰的微米级TiO相比，自制的Y／TiO2,Ce/TiO2催化剂对DBS的光催化活性均有很大的提高。     

Influence of Nd:Zn codoping in near-stoichiometric lithium niobate

Near-stoichiometric lithium niobate (SLN) crystals doped with up to 1.6 mol % Zn and codoped with various Nd concentrations in the melt (0.2, 0.5, 0.9, and 1.5 mol %) (Nd:Zn:SLN) are grown from 58.6 mol % Li(2)O using conventional Czochralski technique. Crystals are pulled at the rate of 0.35 mmh with seed rotation at 9 rpm. Concentrations of Zn and Nd in the crystal are varied by adding appropriate amounts of ZnO and Nd(2)O(3) to the starting composition. Unit cell parameters of the grown crystals are calculated by Rietveld refinement method using FULLPROFF software. Domain structure studies are carried out by chemical etching followed by microscopic examination. Dielectric studies reveal the existence of piezoelectric resonance at high frequencies. Enhancement in dielectric constant and tan delta in Nd doped samples has been attributed to the space charge polarization. Nd doped samples exhibit reduction in the relative permittivity after oxygen annealing. Transmission spectra of Nd:Zn:SLN crystals in the UV region exhibit blueshift in the cutoff wavelength. In Mid Infrared (MIR) region crystals doped with 1.6 mol % Zn have shift in the OH absorption peak from 2873 to 2833 nm. Judd-Ofelt analysis carried out on the absorption spectra of codoped crystal yields the lifetime of 104 mus for the metastable state (4)F(32). The branching ratio for the electronic transition from (4)F(32) to (4)I(112) is high compared to that for (4)F(32) to (4)I(132), indicating a higher emission cross section for the former transition. Laser damage threshold evaluated using 532 nm, 5 ns pulsed neodymium doped yttrium aluminum garnet laser, shows an increase by two orders of magnitude for crystals doped with 1.6 mol % Zn. Photorefractive damage threshold for these crystals shows an enhancement of four orders of magnitude due to increase in the photoconductivity.     

Structural characterization and oxidative dehydrogenation activity of V2O5/Ce(x)Zr(1-x)O2/SiO2 catalysts

The thermal stability of a nanosized Ce(x)Zr(1-x)O2 solid solution on a silica surface and the dispersion behavior of V2O5 over Ce(x)Zr(1-x)O2/SiO2 have been investigated using XRD, Raman spectroscopy, XPS, HREM, and BET surface area techniques. Oxidative dehydrogenation of ethylbenzene to styrene was performed as a test reaction to assess the usefulness of the VOx/Ce(x)Zr(1-x)O2/SiO2 catalyst. Ce(x)Zr(1-x)O2/SiO2 (1:1:2 mol ratio based on oxides) was synthesized through a soft-chemical route from ultrahigh dilute solutions by adopting a deposition coprecipitation technique. A theoretical monolayer equivalent to 10 wt % V2O5 was impregnated over the calcined Ce(x)Zr(1-x)O2/SiO2 sample (773 K) by an aqueous wet impregnation technique. The prepared V2O5/Ce(x)Zr(1-x)O2/SiO2 sample was subjected to thermal treatments from 773 to 1073 K. The XRD measurements indicate the presence of cubic Ce0.75Zr0.25O2 in the case of Ce(x)Zr(1-x)O2/SiO2, while cubic Ce0.5Zr0.5O2 and tetragonal Ce0.16Zr0.84O2 in the case of V2O5/Ce(x)Zr(1-x)O2/SiO2 when calcined at various temperatures. Dispersed vanadium oxide induces more incorporation of zirconium into the ceria lattice, thereby decreasing its lattice size and also accelerating the crystallization of Ce-Zr-O solid solutions at higher calcination temperatures. Further, it interacts selectively with the ceria portion of the composite oxide to form CeVO4. The RS measurements provide good evidence about the dispersed form of vanadium oxide and the CeVO4 compound. The HREM studies show the presence of small Ce-Zr-oxide particles of approximately 5 nm size over the surface of amorphous silica and corroborate with the results obtained from other techniques. The catalytic activity studies reveal the ability of vanadium oxide supported on Ce(x)Zr(1-x)O2/SiO2 to efficiently catalyze the ODH of ethylbenzene at normal atmospheric pressure. The remarkable ability of Ce(x)Zr(1-x)O2 to prevent the deactivation of supported vanadium oxide leading to stable activity in the time-on-stream experiments and high selectivity to styrene are other important observations.     

纳米结构Ce掺杂PbO2膜电极的电化学沉积和性质

The effect of Ce(Ⅲ) on the morphology and structure of deposited film of lead dioxide was studied by cyclic voltammetry (CV), X-ray diffractometry (XRD) and scanning tunneling microscopy (STM). The results indicated that the Ce-doped PbO2 film consisted of a mixture of α- and β-phase of PbO2. Ce doping changed the size of PbO2 crystal grains and made the crystallite size on the electrode surface in the nanometer range. Owing to the formation of nanometer-structured grains, the specific surface areas and activity sites of the electrode surface were increased, hence the catalytic activity of Ce-doped PbO2 electrode was evidently higher than that of undoped PbO2 electrode.     

溶胶－凝胶法制备镶嵌在SiO2玻璃中的InAs纳米晶

以As2O3,InCl3·4H2O和正硅酸乙酯为原料,通过水解、缩聚制备了xIn2O3-xAs2O3-100SiO2(x=0.5～7.5)凝胶,在氧气中加热到450℃对凝胶热处理使其转化成凝胶玻璃,再在200～500℃与氢气反应,结果在SiO2凝胶玻璃中形成了立方相InAs,利用XRD测试了InAs纳米颗粒的大小、发现随着反应温度的升高及掺杂量的增加,InAs纳米颗粒粒径从6增大到29nm,电子衍射表明凝胶玻璃中的InAs纳米颗粒为多晶结构。     

Lanthanide‐Doped Nanocrystals: Strategies for Improving the Efficiency of Upconversion Emission and Their Physical Understanding

The fundamental understanding of lanthanide‐doped upconverted nanocrystals remains a frontier area of research because of potential applications in photonics and biophotonics. Recent studies have revealed that upconversion luminescence dynamics depend on host crystal structure, size of the nanocrystals, dopant concentration, and core–shell structures, which influence site symmetry and the distribution and energy migration of the dopant ions. In this review, we bring to light the influences of doping/co‐doping concentration, crystal phase, crystal size of the host, and core–shell structure on the efficiency of upconversion emission. Furthermore, the lattice strain, due to a change in the crystal phase and by the core–shell structure, strongly influences the upconversion emission intensity. Analysis suggests that the local environment of the ion plays the most significant role in modification of radiative and nonradiative relaxation mechanisms of overall upconversion emission properties. Finally, an outlook on the prospects of this research field is given.     

Characterization and ab initio XRPD structure determination of a novel silicate with Vierer single chains: the crystal structure of NaYSi2O6

The crystal structure of a sodium yttrium silicate with composition NaYSi2O6 has been determined from laboratory X-ray powder diffraction data by simulated annealing, and has been subsequently refined with the Rietveld technique. The compound is monoclinic with space group P2(1)/c and unit cell parameters of a=5.40787(2) A, b=13.69784(5) A, c=7.58431(3) A, and beta=109.9140(3) degrees at 23.5 degrees C (Z=4). The structure was found to be a single-chain silicate with a chain periodicity of four. The two symmetry dependent [Si4O12] chains in the unit cell are parallel to c. A prominent feature is the strong folding of the crankshaft-like chains within the b,c-plane resulting in intrachain Si-Si-Si angles close to 90 degrees. The coordination of the Y3+ ions by O2- is 7-fold in the form of slightly irregular pentagonal bipyramids, with oxygen atoms from four different chains contributing to the coordination polyhedron. Na+ ions are irregularly coordinated by 10 oxygens from two neighboring chains. No disorder of Na+ and Y3+ between the two nontetrahedral cation sites could be observed. Furthermore, micro-Raman spectra have been obtained from the polycrystalline material.     

Er3+-Yb3+共掺纳米TiO2上转换光催化杀菌作用研究

采用溶胶凝胶法合成了稀土离子Er^3＋-Yb^3＋共掺杂的纳米TiO2晶体粉末,利用XRD,UV-VIS吸收光谱及上转换发射光谱对其结构和光学特性进行了表征．以致病性嗜水气单胞菌为实验菌株,以980nm激光为激发光源,考察了室温下Er^3＋-Yb^3＋共掺杂纳米TiO2的光催化杀菌性能．结果表明,稀土离子掺杂的纳米TiO2可以通过上转换发光的途径增加TiO2对可见光的利用率,从而实现TiO2在可见光和近红外光范围的光催化氧化杀菌作用．     

Preparation, crystal structure and electrorheological performance of nano-sized particle materials containing ZrO2

A series of nano-sized particle materials containing ZrO₂ was prepared and their compositions were determined by elemental analysis and thermogravimetric analysis (TGA). The effect of particle size and crystal structure type (lattice and space group) on the ER performance of these materials was investigated by X-ray diffraction (XRD) analysis, Raman spectra, the particle size analysis and rheological measurement. Their electrorheological (ER) effects show that the ER activities of the ZrO₂ materials doped with rare earth (RE=Y, La, Ce, Gd, Tb), whose grain sizes were less than that of pure ZrO₂, were lower than that of pure ZrO₂, which belongs to the tetragonal crystal system. The ER activity of Y₂O₃-ZrO₂ is the strongest among all the RE-doped ZrO₂ materials. The ER activity of the tetragonal phase ZrO₂ is higher than that of the monoclinic phase ZrO₂.     

Preparation of Ce‐doped TiO2 Hollow Fibers and Their Photocatalytic Degradation Properties for Dye Compound

Cerium‐doped titanium dioxide (TiO₂) with a hollow fiber structure was successfully prepared using ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fiber as the template. The effects of cerium (Ce)‐doping on the crystallite sizes, crystal pattern, and optical property of the prepared catalysts were investigated by means of techniques such as scanning electron microscopy (SEM), X‐ray diffraction (XRD), BET surface area, and UV‐vis diffuse absorption spectroscopy. SEM observation showed that the prepared TiO₂ fibers possessed fibrous shape inherited from the cotton fiber and had a hollow structure. As confirmed by XRD and UV‐vis diffuse absorption spectroscopy examinations, Ce‐doping restrained the growth of grain size and extended the photoabsorption edge of TiO₂ hollow fiber into the visible light region. The present photocatalyst showed higher photocatalytic reactivity in photodegradation of highly concentrated methylene blue (MB) solutions than pure TiO₂ under UV and visible light, and the amount of Ce‐doped significantly affected the catalytic property. In the experiment condition, the photocatalytic activity of 0.5 mol% Ce‐doped TiO₂ fiber was optimal of all the prepared samples. In addition, the possibility of cyclic usage of the photocatalyst was also confirmed. The material was easily removed by centrifugal separation. Therefore, using the template method and by doping with cerium, TiO₂ may hopefully become a low‐energy consuming, high activity and green environmentally friendly catalytic material.     

Catalytic properties of Ni/ceria-yttria electrode materials for partial oxidation of methane

The catalytic properties of electrode materials Ni/Ce1-xYxO2-δ (x = 0.05, 0.10, 0.15 and 0.20) were investigated for partial oxidation of methane (POM). The CeO2-Y2O3 solid solutions were prepared by co-precipitaion method. The Ni-based catalysts supported on the solid solutions were obtained using the impregnation method. Structural, surface and redox characteristics of the prepared catalysts were systematically examined by means of X-ray diffraction (XRD), N2 adsorption-desorption (Brunauer-Emmet-Teller BET method), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS) methods. The results indicated that yttria doped in the ceria system, forming a good solid solution, readily induced more defects and oxygen vacancies that favored the improvement of catalytic activity and coking resistance. In the temperature range of 600-850 ℃, Ni/Ce0.90Y0.10O1.95 catalyst exhibited the best catalytic activity among the four tested catalysts, with the CH4 conversion, CO selectivity and H2 selectivity of 78.8%, 90.6% and 89.8%, respectively, at 850 ℃. And the H2/CO molar ratio in products of Ni/Ce0.90Y0.10O1.95 catalyst was closer to the theoretical value of 2.0. The excellent coking resistant behaviors for all catalysts were clearly manifested by Thermal Analysis.     

Y掺杂纳米TiO2的合成及晶型转变过程

溶胶-凝胶;锐钛型;金红石型;Y掺杂纳米TiO2的合成及晶型转变过程     

Tuning of the structure and emission spectra of upconversion nanocrystals by alkali ion doping

Recently, lanthanide based nanocrystals with upconversion fluorescence emission have attracted a lot of interest and the nanocrystals have been used for bioimaging, biodetection, and therapeutic applications. Use of the nanocrystals for multiplexed detection has also been explored; however, nanocrystals with multicolor emission are required. Some efforts have been made to tune the emission spectra of the nanocrystals based on manipulation of upconverting lanthanide ions doped in the crystals or creation of core/shell structures. In this work, alkali ions with an ionic radius slightly larger or smaller than Na such as Li and K were doped into NaYF(4):Yb,Er nanocrystals and their effect on the crystal structure and subsequently the upconversion emission spectra were studied. It was found that the phase transition occurs in the nanocrystals when a different amount of Li and K was doped. Furthermore, the intensity ratios between the blue, green, and red emission peaks changed accordingly, and make it possible to tune the upconversion fluorescence of the nanocrystals by Li and K doping.