Synthesis, structure and optical properties of new organic-inorganic haloplumbates complexes (C5H10N3)PbX4 (X = Br, Cl), (C2H2N4)PbBr3

Layered organic-inorganic composite materials (C5H10N3)PbX4 (X = Br 1, Cl 2) containing histaminium dications were grown via a solution-cooling process, and their structure and optical properties were determined. The organic ligand-histaminium introduced into the corner-sharing octahedra of the 'PbX4- layer' contains both primary ammonium and imidazolium different from the traditionally primary amine found in this system. As comparison, another analogous amine of 3-amino-1,2,4-triazol was used as ligand to coordinate with PbBr2 in acid solution. A novel complex (C2H2N4)PbBr3 (3) was obtained with zigzag PbBr2 chains different from the PbX4 layer in compound as 1 and 2. The hybrid (C5H10N3)PbX4 show exciton absorption at 339 nm for X = Cl and 419 nm for X = Br with the corresponding emission at 360 and 436 nm, respectively. The different PbBr2 chain structure of compound 3 does not show photo luminescence.

Sonochemical synthesis and photoluminescent property of YVO4 : Eu nanocrystals

YVO4 nanocrystals doped with 10.0 mol% Eu3+ have been synthesized from an aqueous solution of ( Y, Eu)( NO3) (3) and NH4VO3 with or without ultrasonic irradiation. The ultrasonic irradiation has a strong effect on the morphology of the YVO4: Eu particles. The spindle-like particles with an equatorial diameter of 90 - 150 nm and a length of 250 - 300 nm could be obtained with ultrasonic irradiation, whereas only nanoparticles were produced without ultrasonic irradiation. The photoluminescence intensity of YVO4: Eu of the spindle-like particles was largely improved compared with that of the nanoparticles. The possible formation mechanism of the spindle-like particles of YVO4: Eu with the application of ultrasonic irradiation was discussed in this paper.

Preparation and luminescence properties of in situ formed lanthanide complexes covalently grafted to a silica network

Lanthanide-doped sol-gel-derived materials are an attractive type of luminescent materials that can be processed at ambient temperatures. However, the solubility of the lanthanide complexes in the matrix is a problem and it is difficult to obtain a uniform distribution of the complexes. Fortunately, these problems can be solved by covalently linking the lanthanide complex to the sol-gel-derived matrix. In this study, luminescent Eu3+ and Tb3+ bipyridine complexes were immobilized on sol-gel-derived silica. FT-IR, DTA-TG and luminescence spectra, as well as luminescence decay analysis, were used to characterize the obtained hybrid materials. The organic groups from the bipyridine-Si moiety were mostly destroyed between 220 and 600 degreesC. The luminescence properties of lanthanide bipyridine complexes anchored to the backbone of the silica network and the corresponding pure complexes were comparatively investigated, which indicates that the lanthanide bipyridine complex was formed during the hydrolysis and co-condensation of TEOS and modified bipyridine. Excitation at the ligand absorption wavelength (336 nm for the hybrid materials and 350 nm for the pure complexes) resulted in strong emission of the lanthanide ions: Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4) and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) emission lines due to efficient energy transfer from the ligands to the lanthanide ions.

Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We have investigated the inverted phase formation and the transition from inverted to normal phase for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer in solution-cast films with thickness about 300 nm during the process of the solution concentrating by slow solvent evaporation. The cast solvent is 1, 1,2,2-tetrachloroethane (Tetra-CE), a good solvent for both blocks but having preferential affinity for the minority PMMA block. During such solution concentrating process, the phase behavior was examined by freeze-drying the samples at different evaporation time, corresponding to at different block copolymer concentrations, phi. As phi increases from similar to 0.1 % (nu/nu), the phase structure evolved from the disordered sphere phase (DS), consisting of random arranged spheres with the majority PS block as I core and the minority PMMA block as a corona, to ordered inverted phases including inverted spheres (IS), inverted cylinders (IC), and inverted hexagonally perforated lamellae (IHPL) with the minority PMMA block comprising the continuum phase, and then to the lamellar (LAM) phase with alternate layers of the two blocks, and finally to the normal cylinder (NC) phase with the majority PS block comprising the continuum phase. The solvent nature and the copolymer solution concentration are shown to be mainly responsible for the inverted phase formation and the phase transition process.

Core-shell structured SiO2@YVO4 : Dy3+/Sm3+ phosphor particles: Sol-gel preparation and characterization

Spherical SiO2 particles have been coated with YVO4:Dy3+/Sm3+ phosphor layers by a Pechini sol-gel process, leading to the formation of core-shell structured SiO2@YVO4:Dy3+/Sm3+ particles. X-ray diffraction (XRD), Fourier-transform IR spectroscopy, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO2 @YVO4:Dy3+/Sm3+ core-shell phosphors. The obtained core-shell phosphors have perfect spherical shape with narrow size distribution (average size ca. 300 nm), smooth surface and non-agglomeration. The thickness of shells could be easily controlled by changing the number of deposition cycles (20 nm for one deposition cycle). The core-shell particles show strong characteristic emission from Dy3+ for SiO2@YVO4:Dy3+ and from Sm3+ for SiO2@YVO4:Sm3+ due to an efficient energy transfer from YVO4 host to them. The PL intensity of Dy3+ and Sm3+ increases with raising the annealing temperature and the number of coating cycles.

Photoluminescent properties of sol-gel derived (La, Gd)MgB5O10 : Ce3+/Tb3+ nanocrystalline thin films

Ce3+ and/or Tb3+-doped (La,Gd)MgB5O10 nanocrystalline thin films were deposited on silica glass substrates by a sol-gel dip-coating process using triethyl borate B(OC2H5)(3) as the boron source. The results of XRD indicated that the films have fully crystallized after annealing at 800 degrees C. The films are transparent, uniform and crack free with a thickness of about 300 nm, consisting of particles with an average grain size of 50 nm. The luminescence and energy transfer properties of Ce3+ and Tb3+ have been studied in the films. It is confirmed that the excitation energy of Ce3+ transfers to the Gd3+, migrates over the Gd3+ sublattices, trapped by the Tb3+ and resulted in its characteristic green emission (D-5(4)-F-7(5) at 543 nm) in GdMgB5O10 nanocrystalline films as in the powder phosphors.

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.

Phenanthroline-functionalized MCM-41 doped with europium ions

Organo-functionalized MCM-41 containing non-covalently linked 1,10-phenanthroline (denoted as Phen-MCM-41) was synthesized by template-directed co-condensation of tetraethoxysilane and the modified phenanthroline (denoted as Phen-Si). XRD, FTIR, UV/VIS spectroscopy as well as luminescence spectroscopy were employed to characterize Phen-MCM-41. No disintegration or loss of the Phen-Si during the solvent extraction procedure could be observed. When monitored by the ligand absorption wavelength (272 nm), the undoped MCM-41 produces a broad band emission centered at 450 run, whereas europium (III) doped Phen-MCM-41 displays the emission of the Eu3+, i.e., D-5(0) --> F-7(J) (J = 0, 1, 2, 3, 4) transition lines due to the energy transfer from the ligands to Eu3+ as well as a broad band emission centered at 442 nm.

Preparation and luminescence properties of hybrid materials containing europium(III) complexes covalently bonded to a silica matrix

A new kind of luminescent organic-inorganic hybrid material (denoted Hybrid I) consisting of europium 1,10-phenanthroline complexes covalently attached to a silica-based network was prepared by a sol-gel process. 1,10-Phenanthroline grafted to 3-(triethoxysilyl)propyl isocyanate was used as one of the precursors for the preparation of an organic-inorganic hybrid materials. For comparison purposes, the hybrid material (denoted Hybrid II) in which phenanthroline was not grafted onto the silica backbone of the frameworks was also prepared. Elemental analysis; NMR, FT-IR, UV/vis absorption, and luminescence spectroscopies, and luminescence decay analysis were used to characterize the obtained hybrid materials. It is shown that the homogeneity of Hybrid I is superior to that of Hybrid II, and a higher concentration europium can be incorporated into Hybrid I than Hybrid II. Excitation at the ligand absorption wavelength (283 nm) resulted in the strong emission of the Eu3+ D-5(0)-F-7(J) (J = 0-4) transition lines as a result of the efficient energy transfer from the ligands to the EU3+ in Hybrid I. The number of water molecules coordinated to the europium ion was estimated, and the structure of the as-synthesized Hybrid I was predicted on the basis of the experimental results.

Lasing behavior in DCM-doped PVK microcavity

A surface emitting microcavity was formed by sandwiching a polymer film containing PVK, Alq(3) and DCM between a distributed Bragg reflector (DBR) with a reflectivity of 99% and a silver film (300 nm). The lasing phenomenon was observed in DCM-doped PVK microcavity. The full width at half maximum (FWHM) was 0.6 nm with the peak wavelength at 603 nm. The threshold energy for lasing was estimated to be about 2.5 mu J per pulse. (C) 2000 Published by Elsevier Science S.A. All rights reserved.

Geophysical evaluation methods for buried hill reservoirs in the Jiyang superdepression of the Bohai Bay basin, eastern China

The Jiyang superdepression is one of the richest hydrocarbon accumulations in the Bohai Bay basin, eastern China. Comprehensive seismic methods have been used in buried hill exploration in Jiyang to describe these fractured reservoirs better. Accurate seismic stratigraphic demarcation and variable-velocity mapping were applied to reveal the inner structure of the buried hills and determine the nature of the structural traps more precisely. Based on the analysis of rock properties and the characteristics of well-developed buried hill reservoirs, we have successfully linked the geology and seismic response by applying seismic forward technology. Log-constrained inversion, absorption coefficient analysis and tectonic forward-inversion with FMI loggings were applied to analyse and evaluate the buried hill reservoirs and gave satisfying results. The reservoir prediction was successful, which confirmed that the comprehensive utilization of these methods can be helpful in the exploration of buried hill reservoirs.

Fluorescence Characterization of Dissolved Organic Matter in East China Sea

Sea water samples were collected in the East China Sea in March and April, 2005, and three-dimensional fluorescence of dissolved organic matter was measured by fluorescence excitation-emission matrix spectroscopy. The position, number and intensity of fluorescence peak in the spectra and the relations of the peaks were analyzed to determine the type, distribution and origin of the fluorescence dissolved organic matter. Seven types of fluorescence peaks were detected from the samples. There are protein-like fluorescence peaks B with Ex(max)/Em(max) = 275/300 nm, D with Ex(max)/Em(max) = 225/295-305 nm, T with Ex(max)/Em(max) = 280/345 nm, and S with Ex(max)/Em(max) = 225-240/320-350 nm, two humic-like peaks A with Ex(max)/Em(max) = 250-255/410-455 nm and C 335-345/410-440 ran, and marine humic peak M with Ex(max)/Em(max) = 305 nm/400-420 nm. Peaks B, S and A appeared in all surveyed area. Peaks T and D appeared in the north of the surveyed area. Peaks M and C only appeared in a few stations. In the surface layer, the source of the fluorescence dissolved organic matter might be the fresh water outflow of the Yangtze River, while the fluorescence dissolved organic matter in the middle layer had double sources from the Yangtze River and the phytoplankton. The good correlationships of different fluorescence peaks showed the same source or some relationship between the protein-like and the humic-like fluorescence dissolved organic matter.

可见光响应光催化剂K4Ce2M10O30（M=Ta, Nb）及其光解水特性的研究

氢能已被广泛认为是最具有潜力解决能源危机和环境问题的理想替代能源之一，其开发备受各个领域科学家的重视，更是从根本上解决环境地球化学工作者的主要目标：对已被破坏的环境和生态进行修复以及对可能破坏环境与生态的人类活动进行干预和指导。在众多的氢能开发手段中，利用太阳能光催化分解水制取氢气是一种兼顾能耗、资源和环境的最为理想和最有前途的氢能开发手段之一。在光催化分解水过程中，最为首要的研究内容就是开发具有适宜能带结构能响应可见光，稳定地、高量子效率地光解水的固相半导体光催化剂。 本论文中，通过高温固相反应合成了呈四方晶系钨青铜结构的半导体光催化剂K4Ce2M10O30(M=Ta, Nb)，吸收边分别达到580 nm (M＝Ta) 和690 nm (M＝Nb)，对应带隙为2.2 eV和1.8 eV。可见光下（λ> 420 nm）光催化分解H2O产生H2和O2的活性表明它们不仅有适宜的带隙响应可见光，并且其价带和导带位置能满足完全分解水的电化学电位需要。在担载Pt、RuO2以及NiO（NiOx）等助催化剂对产氢性能有显著的提高。同时以乙醇钽和草酸铌可溶性前驱体，分别通过溶胶凝胶法（Sol-gel）和聚合物络合法(Polymerizable Complex)制备了K4Ce2Ta10O30和K4Ce2Nb10O30。通过湿法化学合成的光催化剂显示了更高的光催化活性，并且通过PC法制备的K4Ce2Nb10O30更是实现了在大于300 nm 的光辐射下完全分解纯水产生摩尔比为约2:1 的H2和O2。 通过高温固相反应得到Nb取代K4Ce2Ta10O30中部分晶格Ta形成的单相无限固溶体系列K4Ce2Ta10-xNbxO30（x=0~10）是结构一致的同系物，吸收边介于540 nm～710 nm 之间，并且随着x的增加，吸收边依次红移，光催化产氢活性依次降低，但是x=2，5，8时的产氧活性比x=0和10的高，光催化活性的差异主要源于它们光吸收特性和能带结构的差异。基于密度范函理论DFT的第一性原理计算结果表明，光催化剂K4Ce2M10O30(M=Ta, Nb)的能带结构为：导带主要由Ta 5d (Nb 4d)组成，处于高能级的电子未占据态的Ce 4f 与其有很明显的重迭，但由于其高度局域特性，不能很好地参与光生电子在导带的传导，从而其对光催化活性的贡献很小，而价带则由O 2p与Ta 5d (Nb 4d)以及电子占据态的Ce 4f杂化轨道组成。同时通过高温固相反应合成了系列含稀土元素的光催化剂K4Re2M10O30(Re=La, Ce, Nd, Sm, Y; M=Ta, Nb)，通过对它们及其前驱体氧化物的光吸收特性以及电子结构的第一性原理计算研究，合理的解释了只有当Ln＝Ce时才具有可见光响应特性的微观机理。