Luminescent properties of hybrid materials prepared by the polymeric precursor method

Rare earth complexes (RE) can be incorporated in silica matrixes, originating organic/inorganic hybrid materials with good thermal stability and high rare earth emission lines. In this work, the hybrid material was obtained by the polymeric precursor method and ultrasonic dispersed with spherical silica particles prepared by the Stöber Method. The Raman spectra indicated that the Eu3+ ions are involved in a polymeric structure formed as consequence of the chelation and polyesterification reactions of this ion with citric acid and ethylene glycol. After the ultrasonic stirring, 2-hydroxynicotinic ligand will also compose this polymeric rigid structure. The TGA/DTA analysis showed that this polymeric material was thermal decomposed at 300 °C. Moreover, this process allows the chelating process of the 2-hydroxynicotinic acid ligand to the Eu3+ ions. The 29Si NMR showed that the ultrasonic dispersion of the reactants was not able to promote the functionalization of the silica particles with the 2-hydroxynicotinic acid ligand. Moreover, heat treatment promotes the [Eu(HnicO2)3] complex particles incorporation into silica pores. At this temperature, the TGA curve showed that only the thermal degradation of ethylene glycol and citric acid used during the experimental procedure occurs. The silica and hybrid materials are composed by spherical and aggregated particles with particle size of approximately 450 nm, which can be influenced by the heat treatment. These materials also present an absorption band located at 337 nm. The photoluminescent study showed that when the hybrid samples were excited at 337 nm wavelength, the ligand absorbs the excitation light. Part of this energy is transferred to the Eu3+ ion, which main emission, 5D0→ 7F2, is observed in the emission spectrum at 612 nm. As the heating temperature increases to 300 C, the energy transfer is more favorable. The lifetime values showed that the Eu3+ emission is enhanced due to the energy transfer process in the powders. © 2013 Elsevier B.V. All rights reserved.

Synthesis and characterization of lead zirconate titanate (PZT) obtained by two chemical methods

Lead zirconate titanate (PZT) was synthesized at the ratio of Zr/Ti=52/48 using two synthesis methods: the polymeric precursor method (PPM) and the microwave-assisted hydrothermal method (MAHM). The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), particle size distribution by sedimentation, hysteresis measurements and photoluminescence (PL). The results showed that PZT powders are composed of tetragonal and rhombohedral phases. Different particle sizes and morphologies were obtained depending upon the synthesis method. From the hysteresis loop verified that PZT powders synthesized by the PPM have a typical loop of ferroelectric material and are more influenced by spatial charges while particles synthesized by the MAHM have a hysteresis loop similar to paraelectric material and are less influenced by spatial charges. Both samples showed PL behavior in the green region (525 nm) whereas the sample synthesized by the PPM showed higher intensity in spectra. © 2013 Elsevier Ltd and Techna Group S.r.l.

Synthesis, structural characterization and photophysical properties of highly photoluminescent crystals of Eu(III), Tb(III) and Dy(III) with 2,5-thiophenedicarboxylate

Lanthanide compounds of general formula [Ln2(2,5-tdc) 3(dmf)2(H2O)2] ·2dmf·H2O (Ln = Eu(III) (1), Tb(III) (2), Gd(III) (3) and Dy(III) (4), dmf = N,N′-dimethylformamide and 2,5-tdc2- = 2,5-thiophedicarboxylate anion) were synthesized and characterized by elemental analysis, X-ray powder diffraction patterns, thermogravimetric analysis and infrared spectroscopy. Phosphorescence data of Gd(III) complex showed that the triplet states (T1) of 2,5-tdc2- ligand have higher energy than the main emitting states of Eu(III), Tb(III) and Dy(III), indicating that 2,5-tdc2- ligand can act as intramolecular energy donor for these metal ions. An energy level diagram was used to establish the most relevant channels involved in the ligand-to-metal energy transfer. The high value of experimental intensity parameter Ω2 for the Eu(III) complex indicate that the europium ion is in a highly polarizable chemical environment. The emission quantum efficiency (η) of the 5D0 emitting level of Eu(III) was also determined. The complexes act as possible light conversion molecular devices (LCMDs). © 2013 Elsevier B.V. All rights reserved.

Green synthesis of gold nanoparticles with self-sustained natural rubber membranes

Green chemistry is an innovative way to approach the synthesis of metallic nanostructures employing eco-friendly substances (natural compounds) acting as reducing agents. Usually, slow kinetics are expected due to, use of microbiological materials. In this report we study composites of natural rubber (NR) membranes fabricated using latex from Hevea brasiliensis trees (RRIM 600) that works as reducing agent for the synthesis of gold nanoparticles. A straight and clean method is presented, to produce gold nanoparticles (AuNP) in a flexible substrate or in solution, without the use of chemical reducing reagents, and at the same time providing good size's homogeneity, reproducibility, and stability of the composites. Copyright © 2013 Flávio C. Cabrera et al.

Soft-chemical synthesis, characterization and humidity sensing behavior of WO3/TiO2 nanopowders

Tungsten oxide/titania (WO3/TiO2) nanopowders were synthesized by the polymeric precursor method which varied the WO3 content between 0 and 10 mol%. The powders were thermally treated in a conventional furnace and their structural, microstructural and electric properties were evaluated by X-ray diffraction (XRD), Raman spectrometry, N 2 physisorption, NH3 chemisorption, temperature-programmed reduction (TPR), X-ray absorption near-edge spectroscopy (XANES) in situ XANES and extended X-ray absorption fine structure spectroscopy (EXAFS) and transmission electron microscopy (TEM). XRD and Raman spectrometry confirmed the homogeneous distribution of an amorphous WO3 phase in the TiO 2 matrix which stabilized the anatase phase through the generation of [TiO5·V0] or [TiO5·V 0] complex sites. Conventional TPR-H2 (temperature programmed reduction) along with XANES TPR-H2 and XANES TPR-EtOH showed that WO3/TiO2 sample reduction occurs through the formation of these complex clusters. Moreover, the addition of WO3 promoted an increase in the surface acidity of doped samples as revealed by NH3 chemisorption. The WO3/TiO2 bulk-ceramic samples were further used to estimate their potential application in a humidity sensor in the range of 15-85% relative humidity. Probable reasons that lead to the different humidity sensor responses of samples were given based on the structural and surface characterizations. Correlation between the sensing performance of the sensor and its structural features are also discussed. Although all samples responded as a humidity sensor, the W2T sample (2 mol% added WO3) excelled for sensitivity due to the increase in acid sites, optimum mean pore size and pore size distribution. © 2013 Elsevier B.V.

Modeling of alkynes: synthesis and theoretical properties

ABSTRACT: In this paper we present the synthesis and simulation of alkynes derivatives. Semiempirical calculations were carried out for the ground and first excited states, including the spectroscopic properties of the absorption and emission (fluorescence and phosphorescence) spectra by INDO/S-CI and DNdM-INDO/S-CI methods with geometries fully optimized by PM3/CI. The fact that the theoretical spectra are in accord with the experimental absorption spectra gives us a new possible approach on how structure modifications could affect the non-linear optical properties of alkynes.

Dye incorporation in polyphosphate gels: synthesis and theoretical calculations

ABSTRACT: In this work we described theoretical calculations on the electronic structure and optical properties of the dyes crystal violet and malachite green based in semiempirical methods (Parametric Method 3 and Intermediate Neglect of Differential Overlap / Spectroscopic - Configuration Interaction) and the synthesis of a new hybrid material based upon the incorporation of these dyes in an aluminum polyphosphate gel network. The samples are nearly transparent, free-standing thick films. The optical properties of the entrapped dyes are sensitive to chemical changes within the matrix caused either by gel aging or external stimulli such as exposition to acidic and basic vapors that can percolate within the matrix. Our theoretical modeling is in good agreement with the experimental results for the dyes.

Synthesis and characterization of zeolite NaP using kaolin waste as a source of silicon and aluminum

The synthesis of zeolite NaP using kaolin waste, from the Amazon region, as a predominant source of silicon and aluminum has been studied. The zeolitisation process occurred in hydrothermal conditions using static autoclaving and the effects of time, temperature, and the Si/Al ratio were investigated. The starting material and the phases formed as reaction products were characterized by XRD, SEM and FTIR. The results showed that pure zeolite NaP is hydrothermally synthesized, at 100 °C for 20 hours, using metakaolin waste material in alkaline medium in presence of additional silica. The XRD and SEM analyses indicate that the synthesized zeolite presents good crystallinity.

Synthesis and photocatalytic properties of bismuth titanate with different structures via oxidant peroxo method (OPM)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Towards controlled synthesis and better understanding of blue shift of the CaS crystals

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Role of the reactive atmosphere during the sol-gel synthesis on the enhancing of the emission quantum yield of urea cross-linked tripodal siloxane-based hybrids

Transparent monoliths and films of urea cross-linked tripodal siloxane-based hybrids (named tri-ureasils) were prepared by the sol-gel process, under controlled atmosphere (inside a glove box) and ambient conditions and their structure and optical features were compared. X-ray diffraction data point out that all the materials are essentially amorphous and Si-29 NMR reveal an increase in the condensation degree (0.97) for the hybrids prepared under controlled atmosphere relatively to that found for those prepared under ambient conditions (0.84-0.91). The tri-ureasils are white light emitters under UV/Visible excitation (from 250 to 453 nm) being observed for the composites prepared inside the glove box a significant enhancement (60-80 %) of the absorption coefficient and higher emission quantum yield values (similar to 0.27 and similar to 0.20 for monoliths and films, respectively) relatively to those synthesized under ambient condition.

Direct Synthesis of Ag Nanoparticles Incorporated on a Mesoporous Hybrid Material as a Sensitive Sensor for the Simultaneous Determination of Dihydroxybenzenes Isomers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Er3+-doped Y2O3 obtained by polymeric precursor: Synthesis, structure and upconversion emission properties

The relentless pursuit for materials containing rare earth ions with photoluminescent properties has led to several studies with applications in the development of new technologies. The main focus of this work is the preparation of Er3+-doped polycrystalline Y2O3 with photoluminescent properties using PEG as an organic precursor and heat-treated at different temperatures. The methodology used in this synthesis is highly attractive due to its high feasibility for improved technology and low cost for preparing materials. The behavior of the viscous resin has been evaluated and the final compounds exhibited the formation of a cubic polycrystalline phase, which is able to support variations in Er3+ doping concentrations up to 10 mol%, without significant changes in the polycrystalline parameters. The values of the nanocrystallite size calculated by Scherrer's equation showed direct dependence on the heat-treatment temperature as well as the Er3+ concentration. Intense emission in the visible region under excitation at 980 nm was attributed to an upconversion phenomenon assigned to the intraconfigurational f-f transitions of Er3+ ions. The upconversion mechanism was investigated and it was demonstrated that the higher intense emission in the red region in comparison to the emission in the green region is related to the crystallite size. The studies about the intensity showed the dependence of upconversion emission of power source, indicating that two-photon are responsible for the green and red photoluminescence. These polycrystalline materials exhibit properties that make them promising for use in solar energy systems, C-telecom band or solid-state laser devices. (C) 2014 Elsevier B.V. All rights reserved.

Sugarcane bagasse cellulose fibres and their hydrous niobium phosphate composites: synthesis and characterization by XPS, XRD and SEM

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Microwave-assisted hydrothermal synthesis of magnetite nanoparticles with potential use as anode in lithium ion batteries

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)