Frequency up-conversion luminescence properties and mechanism of Tm<Superscript>3+</Superscript>/Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped oxyfluorogermanate glasses

Oxyfluoride glasses were developed with composition 60GeO 2 ·10AlF 3 ·25BaF 2 ·(1.95-x)GdF 3 · 3YbF 3 ·0.05TmF 3 ·xErF 3 (x=0.02,0.05,0.08,0.11,0.14,0.17)in mole percent.Intense blue(476 nm),green(524 and 546 nm)and red(658 nm)emissions which identified from the 1G 4 →3H 6 transition of Tm3+and the(2H 11/2 ,4S 3/2 )→4I 15/2 ,4F 9/2 →4I 15/2 transitions of Er3+,respectively,were simultaneously observed under 980 nm excitation at room temperature.The results show that multicolor luminescence including white l...     

不同组成粉煤灰吸附亚甲基蓝的性能和机理研究

从三个电厂取得三种不同组成和性质的粉煤灰,研究了粉煤灰对水溶液中亚甲基蓝的吸附性能和机理.结果表明,影响粉煤灰吸附的最重要的因素是粉煤灰粒度而不是C含量.三种粉煤灰对亚甲基蓝的吸附均符合二级吸附动力学模型,渭河、西郊和灞桥粉煤灰的二级吸附速率常数分别为5.580、4.149和2.204×10-2g.mg-1.min-1.吸附过程均由颗粒内扩散控制,渭河、西郊和灞桥粉煤灰的颗粒内扩散速率常数分别为0.067、0.109和0.160mg.g-1.min-1/2.亚甲基蓝浓度增加,粉煤灰对亚甲基蓝的吸附量增加;粉煤灰投加量增加,其对亚甲基蓝的吸附量减小;随着溶液pH值增加,粉煤灰对亚甲基蓝的吸附量先增加后略有下降.     

Synthesis of M (M=Co<Superscript>2+</Superscript>, Co<Superscript>2+</Superscript>/Ni<Superscript>2+</Superscript>)-doped FeS<Subscript>2</Subscript> Nanospheres with Enhanced Visible-light-induced Photocatalytic Activity

Nano-spherical Co²⁺-doped FeS₂ was synthesized through a simple solvothermal method. The products were investigated using XRD, FE-SEM, BET, ICP, EDS, TEM, HRTEM, XPS, and UV-vis spectroscopy. The results indicated that Co²⁺ ion could change the particle nucleation process and inhibited the particle growth of FeS₂. In addition, when the content of doped Co²⁺ was 15%, the degradation efficiency of methylene blue (MB) achieved 60.72% after 210 min irradiation, which increased by 52.01% than that of the undoped FeS₂. Moreover, comparison experiments also demonstrated that the M (M=Co²⁺, Co²⁺/Ni²⁺)-doped FeS₂ photocatalytic activity efficiency sequence was Co²⁺ > Ni²⁺>Co²⁺/Ni²⁺. This is ascribed to the fact that the Co²⁺ doping could induce the absorption edge shifting into the visible-light region and increased the surface area of the samples. The effect mechanisms of M-doping on the band gap and the photocatalytic activity of FeS₂ were also discussed.     

Orbital Calculations of Kaolinite Surface： on Substitution of Al^3＋ for Si^4＋ in the Tetrahedral Sites

The surface properties of kaolinite were determined using density functional theory discrete variational method （DFT-DVM） and Gaussian 03 program. A SiO4 tetrahedral hexagonal ring with two A1 octahedra was chosen to model the kaolinite crystal. The total density of states of the kaolinite cluster are located near the Fermi level at both sides of the Fermi level. Both the highest occupied molecular orbit （HOMO） and the lowest unoccupied molecular orbit （LUMO） of kaolinite indicate that kaolinite system can not only readily interact with electron-acceptor species, but also readily interact with electron-donor species on the edge surface and the gibbsite layer surface, and thus, shows amphoteric behavior. Substitution of Al3^＋ for Si4＋ in the tetrahedral site linking the vacant Al3^＋ octahedra does not increase the surface chemical reactivity of kaolinite, while substitution of Al3^＋ for Si^4＋ in the tetrahedral site with the apex O linking Al3^＋ octahedra increase the surface chemical reactivity of the siloxane surface of kaolinite, especially acting as electron donors. Additionally, substitution of Al3^＋. for Si^4＋ in the tetrahedral site results in the re-balance of charges, leading to the increase of negative charge of the coordinated O atoms of the AlO4 tetrahedra, and therefore favoring the formation of ionic bonds between cations and the surface O atoms in the basal plane.     

Preparation and Upeonversion Lumineseenee ofNanoerystailine Gd2O3： Er^3＋, Yb^3＋

Nanocrystalline Gd1.77Yb0.2Er0.03O3 samples were prepared by combustion and precipitation methods. Structures and upconversion luminescence properties of samples were studied. The results of XRD show that all samples are cubic structure, the average crystallite size could be calculated as 23 nm and 39 nm, respectively. The lattice constants were obtained. The FT-IR spectra were measured to investigate the vibrational feature of the samples. Upconversion luminescence spectra of samples under 980 nm laser excitation were investigated. The strong red emission of samples were observed, and attributed to 4F9/2→4I152 transitions of Er^3＋ ions, the emission intensity for sample synthesized by precipitation method is stronger compared to that of combustion method. The possible upconversion luminescence mechanisms in nanocrystalline Gd1.77Yb0.2Er0.03O3 were discussed.     

Measurement of refractive indices and thermal refractive index coefficients of Cr<Superscript>3+</Superscript>: Be<Subscript>3</Subscript>Al<Subscript>2</Subscript>Si<Subscript>6</Subscript>O<Subscript>18</Subscript> by auto-collimation method

The principal refractive indices and the thermal refractive index coefficients for Be₃Al₂Si₆O₁₈ crystal doped with 1.01wt% Cr₂O₃ have been accurately measured by the auto-collimation method at wavelengths of 0.488, 0.53975, 1.064, 1.0795 and 1.3414 μm, and temperatures of 308.2, 328.6, 359.1 and 395.4 K respectively. Based on the measured results of principal indices of 0.488, 0.6328, 1.0795 and 1.3414μm, the Sellmeier’s equations and the thermal refractive index coefficients have been obtained, and the result has been proven to be accurate by error analysis.     

Microstructures and fatigue-free properties of the La<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> doped Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films prepared by modified sol-gel technique

Ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) and Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) thin films were fabricated on Pt/TiO₂/SiO₂/Si (100) substrates by a modified sol-gel technique. X-ray diffraction indicated that these films were of single phase with random polycrystalline orientations. The surface morphologies of the films were observed by scanning electron microscope, showing uniform, dense films with grain size of 50–100 nm. Well-saturated hysteresis loops of the films were obtained in metal-ferroelectric-metal type capacitors with Cu top electrodes at an applied voltage of 400 kV/cm, giving the remanent polarization (2P _r) and coercive field (2E _c) values of the films of 25.1 μC/cm² and 203 kV/cm for BLT, and 44.2 μC/cm² and 296 kV/cm for BNT, respectively. Moreover, these capacitors did not show fatigue behaviors after up to 1.75×10¹⁰ switching cycles at the test frequency of 1 MHz, suggesting a fatigue-free character. The influences of the La³⁺ and Nd³⁺ doping on the properties of the films were comparatively discussed. Supported by the National Key Basic Research and Development Program of China (Grant No. 2006CB932305) and the Natural Science Foundation of Hubei Province, China (Grant No. 2004ABA082)     

Fluorescence detection for H<Subscript>2</Subscript>PO<Subscript>4</Subscript><Superscript>-</Superscript> based on carbon dots/Fe<Superscript>3+</Superscript> composite

A novel fluorescent probe for H₂PO₄ ^- was designed and fabricated based on the carbon dots/Fe³⁺ composite. The carbon dots were synthesized by an established one-pot hydrothermal method and characterized by transmission electron microscope, X-ray diffractometer, UV-Vis absorption spectrometer and fluorescence spectrophotometer. The carbon dots/Fe³⁺ composite was obtained by aqueous mixing of carbon dots and FeCl₃, and its fluorescence property was characterized by fluorescence spectrophotometer. The fluorescence of carbon dots was quenched by aqueous Fe³⁺ cations, resulting in the low fluorescence intensity of the carbon dots/Fe³⁺ composite. On the other hand, H₂PO₄ ^- reduced the concentration of Fe³⁺ by chemical reaction and enhanced the fluorescence of the carbon dots/Fe³⁺ composite. The Stern-Volmer equation was introduced to describe the relation between the relative fluorescence intensity of the carbon dots/Fe³⁺ composite and the concentration of H₂PO₄ ^-, and a fine linearity (R ²=0.997) was found in the range of H₂PO₄ ^- concentration of 0.4-12 mM.     

Roles of Eu^2＋, Dy^3＋ Ions in Persistent Luminescence of Strontium Aluminates Phosphors

The polycrystalline Eu^2＋ and Dy ^3＋ co-doped strontium aluminates SrAl2O4： Eu^2＋, Dy^3＋ with different compositions were prepared by solid state reactions. The UV-excited photoluminescence, persistent luminescence and thermo-luminescence were studied and compared. Results show that the doped Eu^2＋ ion in SrAl2O4： Eu^2＋, Dy^3＋ phosphors works as not only the UV-excited luminescent center but also the persistent luminescent center. The doped Dy^3＋ ion can hardly yield any luminescence under UV-excitation, but effectively enhance the persistent luminescence and thermo-luminescence of SrAl2O4： Eu^2＋. Dy^3＋ co-doping can help form electron traps with appropriate depth due to its suitable electro-negativity, and increase the density and depth of electron traps. Based on above observations, a persistent luminescence mechanism, electron transfer model, is proposed and illustrated.     

Preparation of nanometer Nd<Superscript>3+</Superscript>, Y<Superscript>3+</Superscript> co-doped CaF<Subscript>2</Subscript> powder by coprecipitation-azeotropic distillation technique

The synthesis of Nd³⁺, Y³⁺:CaF₂ nanopowder was conducted by azeotropic distillation method, which effectively dehydrated hydrous CaF₂ and prevented forming hard agglomerates. X-ray diffraction (XRD), scanning electron microscopy (SEM), scanning calorimetries-thermalgravimetry (DSC-TG), Fourier transform infrared spectroscopy (FT-IR) and absorption spectroscopy were performed to characterize the powder properties. The experimental results showed that products obtained by azeotropic distillation were single phased, rather monodispersed, successfully prevented the hard agglomerate formation and effectively removed the residual water inside the as-prepared precipitate than that of the direct drying. The absorption spectra showed a wider and stronger absorption bands around 792 nm, which should be profitable for LD pumping.     

Phase transition and photoluminescence properties of Eu<Superscript>3+</Superscript>-doped ZnMoO<Subscript>4</Subscript> red phosphors

Eu³⁺-doped ZnMoO₄ with different doping concentrations were synthesized by a hydrothermal method. The effects of Eu³⁺ doping on the phase structure and photoluminescence (PL) properties of ZnMoO₄ were investigated. The result showed that the introduction of Eu3+ could lead to phase transition of ZnMoO₄. With the increase of Eu³⁺ doping amount, β-ZnMoO₄ was transformed to α phase gradually, which led to different photoluminescence performances. The optimized doping concentration of Eu³⁺ was 6 mol% for the highest emission intensity at 615 nm. Its CIE chromaticity coordinates were (0.667, 0.331), which were very close to the values of standard chromaticity (0.67, 0.33) for National Television Standards Committee (NTSC) system. Therefore, Eu³⁺-doped ZnMoO₄ is considered to be a promising red-emitting phosphor for white LED applications.     

Effects of Heat-treatment Temperature on Eu^3＋ and Li^＋ Co-doped ZnO Photoluminescence by Sol-gel Process

The photoluminescence （PL） characteristics of Eu^3＋ and Li^＋ co-doped ZnO PL materials against heat-treatment temperature were discussed. The PL xerogel and powder samples were prepared by solgel process. The emission spectra of all samples showed two broad bands peaking at 590 nm and 620 nm under UV-Vis excitation. But the relative intensity of red PL （620 nm） was much greater than that of green PL （590 nm） of the same sample, that s to say, the red color was the main luminescence. With heat-treatment temperature increase, the two kinds of colors PL intensity decreased, and both the red and green PL intensity of the xerogel samples was much greater than those of powder samples respectively. The XRD patterns revealed that Eu^3＋ ions were successfully incorporated in ZnO crystals in xerogel samples. When heat-treatment temperature reached 350 ℃, the Eu^3＋ began to separate out of the ZnO crystals and Eu2O3 crystals came into being. When the powder sample was subjected to UV-Vis excitation, the energy transfered from the host ZnO emission to Eu^3＋ became weaker than the xerogel sample.     

Sensitization and intra-molecular energy transfer of Eu<Superscript>3+</Superscript> by Tb<Superscript>3+</Superscript> in Eu-Tb binuclear complexes/PMMA

A series of Eu0.5Tb0.5(TTA)3Phen/PMMA (TTA=thenoyltrifluoroacetone,Phen=phenanthroline) and Eu0.5Tb0.5(TTA)3Dipy/PMMA (Dipy=2,2’-dipyridyl) were prepared by in-situ polymerization.The structures of the composites were characterized by IR spectra and electron spectrum.Photoluminescence properties were investigated by UV-Vis spectra and fluorescence spectra.Meanwhile,the energy transfer models were set up.The results indicated that polymer parts were attached with the rare-earth molecular parts in the composi...     

Interaction of rare earth ions in Sr<Subscript>2</Subscript>MgSi<Subscript>2</Subscript>O<Subscript>7</Subscript>: Eu<Superscript>2+</Superscript>, Dy<Superscript>3+</Superscript> material

To discuss the function of Eu and Dy and their interaction in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ long afterglow material, the Eu and Dy single doped and their co-doped Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ were prepared. The samples were characterized by X-ray diffraction (XRD), decay curves, photoluminescence (PL), and thermoluminescence (TL). The results indicate that Sr₂MgSi₂O₇: Eu has afterglow properties, and the doping of Eu ion in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ can lower the depth of traps. Eu ion can not only serve as luminescence center, but also produce traps in the matrix, meanwhile, it also exerts certain influences on the traps produced by Dy in Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺. The Dy ion can not act as luminescence center but relates to the change of the traps in the Sr₂MgSi₂O₇ matrix.     

Combustion synthesis and luminescent properties of CaO: Eu<Superscript>3+</Superscript>, M<Superscript>+</Superscript> (M=Li,Na, K) phosphor

Li⁺, Na⁺, or K⁺ co-doped CaO: Eu³⁺ phosphors were prepared by the combustion synthesis method and characterized by X-ray diffraction (XRD), photoluminescence and photoluminescence excitation (PL-PLE) spectra. The experimental results show that, upon excitation with 250 nm xenon light, the emission spectrum of the CaO: Eu³⁺ consists of 4f-4f emission transitions from the ⁵ D ₀ excited level to the ⁷ F _J (J=1, 2, 3) levels with the mainly electric dipole transition ⁵ D ₀→⁷ F ₂ of Eu³⁺, indicating that the Eu³⁺ occupies a low symmetry. The charge-transfer band (CTB) shows somewhat red shift with the decreasing ionic radii of co-doped alkali metal ions. The PL and PLE intensities are significantly enhanced, especially the strongest intensity of luminescent is CaO: Eu³⁺, Li⁺ phosphor, when alkali metal ions are incorporated. The strongest peak of emission is slightly shifted from 614 to 593 nm, indicating that the Eu³⁺ ion locates in a symmetric position (O _h ) when alkali metal ions are incorporated.     

Crystallization and luminescence properties of Sm<Superscript>3+</Superscript>-doped SrO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

The Sm³⁺-doped SrO-Al₂O₃-SiO₂ (SAS) glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian (SrAl₂Si₂O₈) and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm³⁺-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the ⁴G_5/2→⁶ H _j/2 (j=5, 7, 9, 11) transitions of Sm³⁺, respectively. Besides, by increasing the crystallization temperature or the concentration of Sm³⁺, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that the Sm³⁺-doped SAS glass-ceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.     

Preparation and characterization of antibacterial Zn<Superscript>2+</Superscript>-exchanged montmorillonites

Zn-montmorillonites(Zn-MMTs) as antibacterial compounds were prepared by an ion-exchange reaction. The reaction time, initial pH value and molar ratios of CEC influencing zinc content in Zn-MMTs were investigated, and Zn-MMTs were characterized by means of EDX, XRD, XPS, and SEM. The results of bacterial growth tests were confirmed by determination of the minimum inhibition concentrations (MICs) and minimum bactericidal concentrations (MBCs). The experimental results show that the zinc is confirmed as bivalent zinc state, the d ₀₀₁ basal spacing of Zn-MMTs is enlarged with the enhancement of the zinc content, and the particles of Zn-MMTs are formed with irregular shape. Moreover, the antibacterial activity of Zn-MMTs increases with increasing the zinc content, and Zn-MMT-3 containing 6.76 mass% of zinc exhibits optimum antibacterial activity against Escherichia coli and Staphylococcus aureus. The intercalated zinc ions act as very effective antibacterial substances in the long term.     

Optimized photoluminescence of red phosphor K<Subscript>2</Subscript>LiAlF<Subscript>6</Subscript>:Mn<Superscript>4+</Superscript> synthesized by a cation-exchange method

Red phosphor K₂LiAlF₆:Mn⁴⁺ has been synthesized by a cation-exchange method in HF solution. To optimize their optical properties, phosphors were synthesized using different reaction conditions. The K₂LiAlF₆:0.5%Mn⁴⁺ synthesized at 20°C for 4 h shows the highest luminescence intensity. The temperature-dependent emission intensity of the phosphor was investigated, and it was found to exhibit good thermal stability, making it a promising red phosphor candidate for warm WLEDs.     

Chemial Bond and Stability of Adsorption of [Au（ AsS3 ）]^2- on the Surface of Kaolinite

Density function theory and discrete variation method (DFT-DVM) were used to study the adsorption of [Au( AsS3 )]^2- on the surface of kaolinite. The correlation among structure, chemical bond and stability was discussed. Several models were selected with [ Au( AsS3)]^2- in different directions and sites. The results show that the models with gold on the edge of kaolinite basal layer contain pincerlike bond among gold and several oxygen atoms and form strong Au - 0 covalent bond, so these models are more stable than those with gold above or under the layer. The models with gold near to [ AlO2(OH)4] octahedra are more stable than those with gold near to the vacancy withont aluminium. These two stable tendencies in kaolinite- [ Au( AsS3)]^2- are stronger than that in kaolinite-Au systems. The interaction between [ Au( AsS3 )]^2- and kaolinite is stronger than that between gold and kaolinite, and this interaction is strong enough to form the surface complexes.     

Preparation and optical properties of Er<Superscript>3+</Superscript>: Na<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> transparent glass-ceramics

Na₂O-Al₂O₃-SiO₂ glass-ceramics doped with Er³⁺ ions were synthesized by the conventional melt quenching technique at a low melting temperature. The samples were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-vis-NIR scanning spectrophotometry, and fluorescence spectrometry. The results show that the main crystalline phase of glass-ceramics is nepheline.The best heat-treatment process is at 520 °C for 2 h. Because the up-conversion luminescence and near infrared luminescence properties of glass doped with Eu³⁺ are studied in detail.