ZnO clusters encapsulated inside micropores of zeolites studied by UV Raman and laser-induced luminescence spectroscopies

Using microporous zeolites as host, sub-nanometric ZnO clusters were prepared in the micropores of the host by the incipient wetness impregnation method. A small amount of sub-nanometric ZnO clusters were introduced into the channels of HZSM-5 zeolite, whereas a large quantity of sub-nanometric ZnO clusters can be accommodated in the supercages of HY zeolite and no macrocrystalline ZnO exists on the extra surface of the HY material. The vibrations of the zeolite framework and ZnO were characterized by UV Raman spectroscopy. The optical properties of these ZnO clusters were studied by UV-visible absorption spectroscopy and laser-induced luminescence spectroscopy. It is found that there are strong host-guest interactions between the framework oxygen atoms of zeolite and ZnO clusters influencing the motions of the framework oxygen atoms. The interaction may be the reason why ZnO clusters are stabilized in the pores of zeolites. Different from bulk ZnO materials, these sub-nanometric ZnO clusters exhibit their absorption onset below 265 nm and show a purple luminescence band (centered at 410-445 nm) that possesses high quantum efficiency and quantum size effect. This purple luminescence band most likely originates from the coordinatively unsaturated Zn sites in sub-nanometric ZnO clusters. On the other hand, the differences in the pore structure between HZSM-5 and HY zeolites cause the absorption edge and the purple luminescence band of ZnO clusters in ZnO/HZSM-5 show a red shift in comparison with those of ZnO clusters in ZnO/HY.

Crystallization and Si incorporation mechanisms of SAPO-34

In this study of the synthesis of SAPO-34 molecular sieves, XRD, SEM, XRF, IR and NMR techniques were applied to monitor the crystalloid, structure and composition changes of the samples in the whole crystallization process in order to get evidence for the crystallization as well as Si incorporation mechanism of SATO-34. XRD results revealed that the crystallization contained two stages. In the first 2.5 h (the earlier stage), high up to similar to80% of relative crystallinity could be achieved and the crystal size of SAPO-34 was almost the same as that of any longer time, indicating a fast crystallization feature of the synthesis. In this stage, IR revealed that the formation of SAPO-34 framework structure was accompanied by the diminution of hydroxyls, suggesting that crystal nuclei of SAPO-34 may arise from the structure rearrangement of the initial gel and the condensation of the hydroxyls. NMR results reveal that the template and the ageing period are crucial for the later crystallization of SAPO-34. Preliminary structure units similar to the framework of SAPO-34 have already formed before the crystallization began (0 h and low temperature). Evidence from IR, NMR, and XRF shows that the formation of the SAPO-34 may be a type of gel conversion mechanism, the solution support and the appropriate solution circumstance are two important parameters of the crystallization of SAPO-34. Meanwhile, NMR measurements demonstrated that about 80% of total Si atoms directly take part in the formation of the crystal nuclei as well as in the growth of the crystal grains in the earlier stage (<2.5 h). Evidence tends to support that Si incorporation is by direct participation mechanism rather than by the Si substitution mechanism for P in this stage (<2.5 h). In the later stage (>2.5 h), the relative content of Si increased slightly with a little decrease of Al and P. The increase of Si(4Al) and the appearance of the Si(3Al), Si(2Al), Si(1Al) and Si(OAl) in this stage suggest that substitution of the Si atoms for the phosphorus and for the phosphorus and aluminum pair takes place in the crystallization. The relationship among structure, acidity and crystallization process is established, which suggests a possibility to improve the acidity and catalytic properties by choosing a optimum crystallization time, thus controlling the number and distribution of Si in the framework of SAPO-34. (C) 2002 Elsevier Science Inc. All rights reserved.

Diagnostic experiments for transport mechanisms of suspended sediment discharged from the Yellow River in the Bohai Sea

Five diagnostic experiments with a 3D baroclinic hydrodynamic and sediment transport model ECOMSED in couple with the third generation wave model SWAN and the Grant-Madsen bottom boundary layer model driven by the monthly sediment load of the Yellow River, were conducted to separately diagnose effects of different hydrodynamic factors on transport of suspended sediment discharged from the Yellow River in the Bohai Sea. Both transport and spatio-temporal distribution of suspended sediment concentration in the Bohai Sea were numerially simulated. It could be concluded that suspended sediment discharged from the Yellow River cannot be delivered in long distance under the condition of tidal current. Almost all of sediments from the Yellow River are deposited outside the delta under the condition of wind-driven current, and only very small of them are transported faraway. On the basis of wind forcing, sediments from the Yellow River are mainly transported north-northwestward, and others which are first delivered to the Laizhou Bay are continuously moved northward. An obvious 3D structure characteristic of sediment transport is produced in the wind-driven and tide-induced residual circulation condition. Transport patterns at all layers are generally consistent with circulation structure, but there is apparent deviation between the depth-averaged sediment flux and the circulation structure. The phase of temporal variation of sediment concentration is consistent with that of the bottom shear stress, both of which are proved to have a ten-day cycle in wave and current condition.

Synthesis and luminescence properties of hybrid organic-inorganic transparent titania thin film activated by in-situ formed lanthanide complexes

Stable transparent titania thin films were fabricated at room temperature by combining thenoyltrifluoroacetone (TTFA)-modified titanium precursors with amphiphilic triblock poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, P123) copolymers. The obtained transparent titania thin films were systematically investigated by IR spectroscopy, PL emission and excitation spectroscopy and transmission electron microscopy. IR spectroscopy indicates that TTFA coordinates the titanium center during the process of hydrolysis and condensation. Luminescence spectroscopy confirms the in-situ formation of lanthanide complexes in the transparent titania thin film.

Synthesis and Upconversion Luminescence Properties of GdF3:Er3+, Yb3+

GdF3:Er3+,Yb-3 with Er3+ ion of 3% and Yb3+ ion concentration of 10%, 20% have been prepared by a hydrothermal method. The results of XRD show that all the samples are of an orthorhombic structure. The average crystallite sizes estimated by Scherrer formula are 28 and 26 nm for Gd0.87Yb0.10Er0.03F3 and Gd0.77Yb0.20Er0.03F3, respectively. The Upconversion luminescence spectra of the samples have been studied under 980 run laser excitation. The results show that the green and red upconversion emission can be attributed to the H-2(11/2),S-4(3/2) -> 4I(15/2) and 4F(9/2) -> 4I(15/2) transitions of Er3+, respectively.

Preparation and characterization of Gd2O3:Eu3+ luminescence nanotubes

The size controllable Gd2O3:Eu3+ luminescence nanotubes were successfully prepared using a simple method by coating gadolinium compounds on the carbon nanotubes and then firing the carbon nanotubes. The morphology of the obtained Gd2O3:Eu3+ nanotubes was determined by transmission electron microscopy (TEM). It was found that the obtained nanotubes have the outer diameters of similar to 100 nm, the inner diameters of similar to 50 nm, and the lengths of several tens of microns. The sizes of Gd2O3:Eu3+ nanotubes can be easily controlled by changing the reaction times and the concentration of reactants.

Preparation and upconversion luminescence of nanocrystalline Gd2O3 : Er3+, Yb3+

Nanocrystalline Gd1.77Yb0.2 Er0.03O3 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 of Y2O3 : Er3+, Yb3+ nanoparticles prepared by a homogeneous precipitation method

Y2O3: Er3+, Yb3+ nanoparticles were synthesized by a homogeneous precipitation method without and with different concentrations of EDTA 2Na. Upconversion luminescence spectra of the samples were studied under 980 nm laser excitation. The results of XRD showed that the obtained Y2O3:Er3+,Yb3+ nanoparticles were of a cubic structure. The average crystallite sizes calculated were in the range of 28-40 nm. Green and red upconversion emission were observed, and attributed to H-2(11/2), S-4(3/2) -> I-4(15/2) and F-4(9/2) -> I-4(15/2) transitions of the Er3+ ion, respectively.

Red and green upconversion luminescence of Gd2O3 : Er3+, Yb3+ nanoparticles

Gd2O3:Er3+, Yb3+ nanoparticles have been synthesized by a homogeneous precipitation method with EDTA 2Na of two different concentrations. Upconversion luminescence spectra of the samples have been studied under 980 nm laser excitation. The results of XRD show that obtained Gd2O3:Er3+, Yb3+ nanoparticles are of a cubic structure. The average crystallite sizes could be calculated as 22 and 29 nm, respectively. The strong green and red upconversion emission were observed, and attributed to the H-2(11/2), S-4(3/2) -> I-4(15/2) and F-4(19/2) -> I-4(15/2) transitions of Er3+ ion, respectively.

Synthesis and Luminescence Properties of CdS Nanoparticles

CdS nanoparticles were successfully prepared by polyol method with PVP-K30 as a surfactant. The microstructure, size and morphology of the products were investigated in detail by XRD, TEM and SEM. The results indicate that uniform CdS nanospheres were achieved. Photoluminescence properties of the resulted nanoparticles (S1 and S3) were investigated, and the results indicate that the CdS nanoparticles could be used as a potential blue light emitting material.

Near-infrared luminescence from sol-gel materials doped with holmium(III) and thulium(III) complexes

A series of ternary Ln(tta)(3)L complexes (Ln = Ho, Tm; Htta = 2-thenoyltrifluoroacetone; L = 1,10-phenanthroline, 2,2'-bipyridine, or triphenyl phosphate oxide) and their corresponding sol-gel hybrid materials formed via the in situ synthesis process (designated as Ln-T-L gel) were reported. The complexes and the gels were studied in detail, which suggest the complexes have been successfully synthesized in the corresponding gels.

1.54 mu m near-infrared photoluminescent and electroluminescent properties of a new Erbium (111) organic complex

The crystal structure of Er(PM)(3)(TP)(2) [PM = 1-Phenyl-3-methyl-4-isobutyryl-5-pyrazoloiie, TP = triphenyl phosphine oxide] was reported and its photoluminescence properties were studied by UV-vis absorption, excited, and emission spectra. The Judd-ofelt theory was introduced to calculate the radiative transition rate and the radiative decay time of 3.65 ms for the I-4(13/2) -> I-4(15/2) transition of Er3+ ion in this complex.

Luminescence functionalization of mesoporous silica with different morphologies and applications as drug delivery systems

Ordered mesoporous silica (MCM-41) particles with different morphologies were synthesized through a simple hydrothermal process. Then these silica particles were functionalized with luminescent YVO4:EU3+ layers via the Pechini sol-gel process. The obtained YVO4:Eu3+ and MCM-41 composites, which maintained the mesoporous structure of MCM-41 and the red luminescence property of YVO4:Eu3+ were investigated as drug delivery systems using ibuprofen (IBU) as model drug. The physicochemical properties of the samples were characterized by X-ray diffraction (XRD), Fourier transform-infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N-2 adsorption, and photoluminescence (PL) spectra, respectively.