Lanthanide complex/polymer composite optical resin with intense narrow band emission, high transparency and good mechanical performance

Novel composite resins possessing good luminescent properties have been synthesized through a free radical copolymerization of styrene, alpha-methylacrylic acid and the binary or ternary complexes of lanthanide ions (Eu3+ and Tb3+). These polymer-based composite resins not only possess good transparency and mechanical performance but also exhibit an intense narrow band emission of lanthanide complexes under UV excitation. We characterized the molecular structure, physical and mechanical performance, and luminescent properties of the composite resins. Spectra investigations indicate that alpha-methyl-acrylic acid act as both solubilizer and ligand. Photoluminescence measurements indicate that the lanthanide complexes show superior emission lines and higher intensities in the resin matrix than in the corresponding pure complex powders, which can be attributed to the restriction of molecular motion of complexes by the polymer chain networks and the exclusion of water molecules from the complex. We also found that the luminescence intensity decreased with increasing content of alpha-methylacrylic acid in the copolymer system. The lifetime of the lanthanide complexes also lengthened when they were incorporated in the polymer matrix. In addition, we found that the relationships between emission intensity and Tb (Eu) content exhibit some extent of concentration quenching.

Preparation and characterization of a layered transparent luminescent thin film of silica-CTAB-Tb(acac)(3) composite with mesostructure

A layered luminescent mesostructured thin film of silica-CTAB-Tb(acac)(3) composite has been synthesized by a dip-coating process through an in situ sol-gel method. The terbium (Tb3+) ion and beta-diketone organic ligand acetylacetone (acac) were introduced into the precursor solution, respectively. The as-synthesized composite film was transparent, colorless and possessed a layered structure. After the composite film was dried at 50 degreesC for a few minutes Tb(acac)(3) complex was synthesized in the mesostructured thin film, which can be indicated by the luminescence of the composite film under the UV lamp. The properties of the samples were characterized by XRD, absorption, Fourier transform infrared spectroscopy, and luminescent spectra.

Study on the structure change and oxygen vacation shift for Ce1-xSmxO2-y solid solution

A series of solid electrolytes Ce1-xSmxO2-y (x=0similar to0.6) were prepared by sol-gel method. XRD measurement showed that single-phase solid solution was formed in all investigated ranges at 160 degreesC, which is a significantly lower synthesis temperature compared to traditional solid state reaction. High temperature X-ray, ESR, and Raman scattering were used to characterize the samples. ESR measurement showed that ESR with sample irradiated by high-energy particle is an effective way to study the defect structure. These changes in the Raman spectrum are attributed to O vacancies, which are introduced into the lattice when tetravalent Ce4+ is substituted by trivalent Sm3+.

Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propylthiethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by H-1 NMR IR and MS, The monomer acts as a ligand for Tb3+ ion and as a sol-gel precursor. Band emission front Tb3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the D-5(4) level of Tb3+ ion falls in the exciting range to sensitize Tb3+ ion fluorescence.

A novel flow through optical fiber biosensor for glucose based on luminol electrochemiluminescence

A novel flow injection optical fiber biosensor for glucose based on luminol electrochemiluminescence (ECL) is presented. The sol-gel method is introduced to immobilize glucose oxidase (GOD) on the surface of a glassy carbon electrode. After optimization of the working conditions, glucose could be quantitated in the concentration ranges between 50 muM and 10 mM with a detection limit of around 26 muM. Signal reproducibility was about 3.62% relative standard deviation for 11 replicated measurements of 0.1 mM glucose. The ECL biosensor also showed good selectivity and operational stability. The proposed method can be applied to determination of glucose in soft drink samples.

Luminescence properties of lanthanide complexes doped in hybrid material from tetraethoxysilane and 3-glycidyioxyropyl-trimethoxysilane

Hybrid materials, containing in-situ synthesized lanthanide complexes with intense green light, have been prepared via sol-gel process. The luminescence properties and the decay times of as-synthesized samples were investigated. The excitation spectrum of the samples indicates the formation of complexes between terbium (III) and P-Sulfosalicylic acid. The hybrid materials that contain in-situ synthesized terbium complexes exhibit the characteristic emission bands of the rare earth ions. In addition, the effect of concentration of terbium on the luminescence properties as well as the thermal stability were also studied.

Luminescence properties of transparent hybrid thin film covalently linked with lanthanide complexes

Novel hybrid thin films covalently doped with Eu3+ (Tb3+) have been prepared via direct routes involving co-condensation of tetraethoxysilane and phen-Si in the presence of Eu3+ (Tb3+) by spin-casting and their luminescence properties have been investigated in detail. Lanthanide ions can be sensitized by anchored phenanthroline in hybrid thin films. Excitation at the ligand absorption wavelength (272 nm) resulted in the strong emission of the lanthanide ions i.e. Eu3+ D-5(0)-F-7(J) (J=0, 1, 2, 3, 4) emission lines and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) due to the energy transfer from the ligands to the lanthanide ions.

Electrocatalytic performance of Pt-TiO2/C complex catalysts for oxidation of methanol

It is reported for the first time that the Pt-TiO2/C catalyst prepared with chemical reduction and sol-gel method showed the excellent electrocatalytic activity and stability for the electrooxidation of methanol. When the atom ratio of Ti to Pt in the catalysts is 1/2, the catalysts showed the best electrocatalytic properties. After the catalyst is treated at 500 degreesC, the performance is further improved. It is hopeful to use the catalyst in the pratical DMFC.

Photoluminescence of organic-inorganic hybrid SiO2 xerogels

Organic-inorganic hybrid SiO2 xerogels were prepared by the sol-gel method under various preparation conditions and compositions by using tetraethoxysilane (TEOS), (3-aminopropyl) triethoxysilane (A-PS), (3-glycidoxypropyl) trimethoxysilane (GPS), organic acid (CH3COOH) and inorganic acids (HCl, HNO3, H2SO4) as the main precursors. Luminescence and FT-IR spectra were used to characterize the resulted hybrid SiO2 xerogels. The result of FT-IR spectrum shows that the xerogels are composed of non-crystalline -Si-O-Si- networks containing some organic groups such as -NH, -CH and -OH. Under the excitation of 365 nm, all the hybrid xerogels exhibit strong luminescence in the blue region, but the emission intensity and position depend on the starting precursor compositions to a large extent. Suitable amount of polyethylene glycol (PEG500 and PEG10000) in the hybrid xerogels can enhance the emission intensity. Additionally, the emission intensity of the hybrid xerogels increases with heat treatment temperature in the range of ambient to 200degreesC, and vacuum condition is also able to enhance the emission intensity.

Synthesis and luminescence properties of oxyapatite NaY9Si6O26 doped with Eu3+, Tb3+, Dy3+ and Pb2+

Oxyapatite NaY9Si6O26 was prepared by sol-gel method. By choosing the precursors, a single phase compound was obtained. This soft chemical method lowered the reaction temperature by 100degreesC compared with the solid state method. Its morphology was studied by transmission electron microscopy (TEM). Several rare earth ions (Eu3+, Tb3+, Dy3+) and Pb2+ ion were doped in this compound. The high resolution emission spectrum of Eu3+ showed that rare earth ions occupied two yttrium sites. In spite of the charge imbalance of Pb2+ with the cations in this compound, it was found that Pb2+ could emit in UV range and transfer its excitation energy to Dy3+ ion.

Covalent grafting of luminescent rare earth complex onto MCM-41 by postsynthesis

New luminescent hybrid mesoporous material was prepared by covalent anchoring rare earth complex onto MCM-41 by a postsynthesis approach. The monomer (referred to here as PABI) which plays double roles, i.e., as a ligand for lanthanide ion and as an organic functional molecule to modify MCM-41 is synthesized and characterized by H-1 NMR and MS. The fluorescence spectra show clearly that the hybrid mesoporous material possesses excellent luminescence characteristics. The hybrid mesoporous material retains the structure of MCM-41 after modification.

Preparation and luminescence properties of ormosil material doped with Eu(TTA)(3)phen complex

The europium complex, Eu(TTA)(3)phen (TTA = thenoyltrifluoroacetone, phen = 1,10-phenanthroline) was successfully doped into organically modified silicate (ormosil) matrix-SiO2/(VTMOS+PMMA) (VTMOS = vinyltrimethoxysilane, PMMA = polymethylmethacrylate) via sol-gel process, and the luminescence properties of the resultant ormosil composite phosphors [ormosil: Eu(TTA)(3)phen were investigated compared with those of the pure Eu(TTA)(3)phen complex powder. The ormosil composite materials incorporated with Eu(TTA)(3)phen show the characteristic red emission of Eu3+ ion. The Eu3+ possesses fewer emission lines and longer lifetime in the hybrid phosphor than in the pure Eu(TTA)(3)phen complex. This has been explained from the viewpoint of the surrounding environment where the Eu3+ ion lies. (C) 2000 Elsevier Science B.V. All rights reserved.

Synthesis and luminescence properties of organic-inorganic hybrid thin films doped with Eu(III)

In this study, silica-based transparent organic-inorganic hybrid films were prepared by the sol-gel method. Tetraethoxysilane and 3-(trimethoxysilyl)propyl methacrylate were used as the inorganic and organic compounds, respectively. Lanthanide complexes [Eu(phen)(2)]Cl-3 were incorporated into the organically modified silicates (ORMOSIL) and the luminescence properties of the resultant hybrid films (ORMOSIL:[Eu(phen)(2)]Cl-3) were characterized. The relative quantum efficiency was observed higher and the lifetimes were longer in hybrid films than those in pure silica films. Furthermore, thermal stability of hybrid films incorporating various concentration of Eu(III) complex was studied. (C) 2001 Elsevier Science B.V. All rights reserved.

Preparation of poly(4-vinylpyridine)/silica hybrids supported cyclopentadienyltitanium trichloride (CpTiCl3) catalyst and styrene polymerization

Poly(4 - vinylpyridine)/silica( PVP/SiO2) organic - inorganic nanoscale hybrid was prepared using sol - gel method, in which PVP was used as an organic component and TEOS as a SiO2 precusor, This hybrid was used as CpTiCl3 support. The XPS and IR measurements showed that two kinds of catalytic active site were formed through analyzing the interaction mode between support and CpTiCl3. The results of styrene polymerization showed that syndiotactic was the highest at 50 degreesC. The catalytic activity was 1.09 x 10(6) g PS/ (mol Ti . h) at 70 degreesC when n(Al)/n(Ti) = 1500. GPC results showed a bimodal molecular weight distribution.

Preparation and properties of nanocrystalline Yb2O3

Nanocrystalline Yb2O3 of various particle sizes was prepared using sol-gel method. XRD analysis shows that the prepared nanocrystalline Yb2O3 is cubic in structure with space group Ia3. TEM photographs indicate that Yb2O3 nanoparticles are basically spherical in shape. Calculation of crystallite size indicates that the average crystallite size of Yb2O3 increases with increasing calcination temperature, but the average crystal lattice distortion rate decreases with increasing calcination temperature and crystallite size. This result shows that the smaller the crystallite size, the bigger the crystal lattice distortion, and the worse crystal growth. Solubility test of Yb2O3 in nitric acid shows that the surface activity of Yb2O3 increases with decreasing crystallite size. Fourier Transform Infrared Spectrometer (FTIR) spectra reveal that nanocrystalline Yb2O3 has higher surface activity; than that of ordinary Yb2O3. Absorbance intensity of Yb-O bond of nanocrystalline Yb2O3 is weaker than that of ordinary Yb2O3, and the absorbance of Yb-O bond of nanocrystalline Yb2O3 is small blue-shifted.