Facile synthesis of PbWO4: Applications in photoluminescence and photocatalytic degradation of organic dyes under visible light

Stolzite polymorph of PbWO4 catalyst was prepared by the facile room temperature precipitation method. Structural parameters were refined by the Rietveld analysis using powder X-ray data. PbWO4 was crystallized in the scheelite-type tetragonal structure with space group I4(1)/a (No. 88). Field emission scanning electron microscopy revealed leaf like morphology. Photoluminescence spectra exhibit broad blue emission (425 nm) under the excitation of 356 nm. The photocatalytic degradation of Methylene blue, Rhodamine B and Methyl orange dyes were measured under visible illumination. The 100% dye degradation was observed for MB and RhB dyes within 60 and 105 min. The rate constant was found to be in the decreasing order of MB > RhB > MO which followed the 1st order kinetic mechanism. Therefore, PbWO4 can be a potential candidate for blue component in white LEDs and also acts as a catalyst for the treatment of toxic and non-biodegradable organic pollutants in water. (C) 2014 Elsevier B.V. All rights reserved.

Synthesis and characterization of high-spin organic materials: prototypes for the polaronic ferromagnet

The design, synthesis and magnetic characterization of thiophene-based models for the polaronic ferromagnet are described. Synthetic strategies employing Wittig and Suzuki coupling were employed to produce polymers with extended π-systems. Oxidative doping using AsF_5 or I_2 produces radical cations (polarons) that are stable at room temperature. Magnetic characterization of the doped polymers, using SQUID-based magnetometry, indicates that in several instances ferromagnetic coupling of polarons occurs along the polymer chain. An investigation of the influence of polaron stability and delocalization on the magnitude of ferromagnetic coupling is pursued. A lower limit for mild, solution phase I_2 doping is established. A comparison of the variable temperature data of various polymers reveals that deleterious antiferromagnetic interactions are relatively insensitive to spin concentration, doping protocols or spin state. Comparison of the various polymers reveals useful design principles and suggests new directions for the development of magnetic organic materials. Novel strategies for solubilizing neutral polymeric materials in polar solvents are investigated.

The incorporation of stable bipyridinium spin-containing units into a polymeric high-spin array is explored. Preliminary results suggest that substituted diquat derivatives may serve as stable spin-containing units for the polaronic ferromagnet and are amenable to electrochemical doping. Synthetic efforts to prepare high-spin polymeric materials using viologens as a spin source have been unsuccessful.

Imidazolium-Based Organic Structure Directing Agents for the Synthesis of Microporous Materials

The central theme of this thesis is the use of imidazolium-based organic structure directing agents (OSDAs) in microporous materials synthesis. Imidazoliums are advantageous OSDAs as they are relatively inexpensive and simple to prepare, show robust stability under microporous material synthesis conditions, have led to a wide range of products, and have many permutations in structure that can be explored. The work I present involves the use of mono-, di-, and triquaternary imidazolium-based OSDAs in a wide variety of microporous material syntheses. Much of this work was motivated by successful computational predictions (Chapter 2) that led me to continue to explore these types of OSDAs. Some of the important discoveries with these OSDAs include the following: 1) Experimental evaluation and confirmation of a computational method that predicted a new OSDA for pure-silica STW, a desired framework containing helical pores that was previously very difficult to synthesize. 2) Discovery of a number of new imidazolium OSDAs to synthesize zeolite RTH, a zeolite desired for both the methanol-to-olefins reaction as well as NOX reduction in exhaust gases. This discovery enables the use of RTH for many additional investigations as the previous OSDA used to make this framework was difficult to synthesize, such that no large scale preparations would be practical. 3) The synthesis of pure-silica RTH by topotactic condensation from a layered precursor (denoted CIT-10), that can also be pillared to make a new framework material with an expanded pore system, denoted CIT-11, that can be calcined to form a new microporous material, denoted CIT-12. CIT-10 is also interesting since it is the first layered material to contain 8 membered rings through the layers, making it potentially useful in separations if delamination methods can be developed. 4) The synthesis of a new microporous material, denoted CIT-7 (framework code CSV) that contains a 2-dimensional system of 8 and 10 membered rings with a large cage at channel intersections. This material is especially important since it can be synthesized as a pure-silica framework under low-water, fluoride-mediated synthesis conditions, and as an aluminosilicate material under hydroxide mediated conditions. 5) The synthesis of high-silica heulandite (HEU) by topotactic condensation as well as direct synthesis, demonstrating new, more hydrothermally stable compositions of a previously known framework. 6) The synthesis of germanosilicate and aluminophosphate LTA using a triquaternary OSDA. All of these materials show the diverse range of products that can be formed from OSDAs that can be prepared by straightforward syntheses and have made many of these materials accessible for the first time under facile zeolite synthesis conditions.

Hydrothermal Synthesis and Study of Inorganic-Organic Hybrid Vanadate of Nickel(II) Coordination Complex with Pyrazine, Ni3(C4H4N2)3(V8O23)

Artículo científico: postprint

π-Conjugated molecules with fused rings for organic field-effect transistors: design, synthesis and applications

π-Conjugated molecular materials with fused rings are the focus of considerable interest in the emerging area of organic electronics, since the combination of excellent charge carrier mobility and high stability may lead to their practical applications. This tutorial review discusses the synthesis, properties and applications of π-conjugated organic semiconducting materials, especially those with fused rings. The achievements to date, the remaining problems and challenges, and the key research that needs to be done in the near future are all discussed.

Effects of dissolved organic matter on the growth and pigments synthesis of Spirulina platensis (Arthrospira)

Excessive accumulation of dissolved organic matter (DOM) in the culture ponds of Spirulina platensis is usually considered to be one of the potential factors affecting the production of S. platensis, however, we are not quite aware of effects of DOM on the growth and pigments synthesis of S. platensis. In the present study, S. platensis was grown in batch or semi-continuous cultures using the filtrate in the culture ponds that had not been renewed for years. It was found that disssolved organic carbon up to 60 mg/L did not bring about an inhibitory effect on the growth of S. platensis, but increased the contents of chlorophyll a and phycocyanin instead. However, further accumulation of dissolved organic matter could decrease the content of chlorophyll a.

Synthesis and characterization of well-aligned Zn1-xMgxO nanorods and film by metal organic chemical vapor deposition

Well-aligned Zn1-xMgxO nanorods and film with Mg-content x from 0 to 0.051 have been successfully synthesized by metal organic chemical vapor deposition (MOCVD) without any catalysts. The characterization results showed that the diameters and lengths of the nanorods were in the range of 20-80 nm and 330-360 nm, which possessed wurtzite structure with a c-axis growth direction. As the increase of Mg precursor flows into the growth chamber, the morphology of Zn1-xMgxO evolves from nanorods to a film with scale-like surface and the height of the nanorods and the film was almost identical, it is suggested that the growth rate along the c-axis was hardly changed while the growth of six equivalent facets of the type {1 0 (1) over bar 0} of the Zn1-xMgxO has been improved. Photoluminescence and Raman spectra show that the products have a good crystal quality with few oxygen vacancies. With the Mg incorporation, multiple-phonon scattering become weak and broad, and the intensities of all observed vibrational modes decrease. And the ultraviolet near-band-edge emission shows a clear blueshift (x=0.051, as much as 90 meV) and slightly broadening compared with that of pure ZnO nanorods. (C) 2008 Elsevier B.V. All rights reserved.

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.

Controlled synthesis of organic-inorganic hybrid nanofibers by a wet-chemical route

Organic-inorganic hybrid nanofibers are successfully synthesized by incorporating 3,3 ',5,5 '-tetramethylbenzidine (TMB) and H2PtCl6 at room temperature. The morphology and size can be simply controlled by tuning the molar ratio and initial concentration of reactants. A possible formation mechanism was suggested on the basis of the experimental results. The optical properties were investigated and the as-obtained product displays a strong fluorescence emission at room temperature that may be promising for applications in the fabrication of photoelectric materials. (C) 2008 Elsevier B.V. All rights reserved.

Solution-Processible Red Iridium Dendrimers based on Oligocarbazole Host Dendrons: Synthesis, Properties, and their Applications in Organic Light-Emitting Diodes

A series of novel red-emitting iridium dendrimers functionalized with oligocarbazole host dendrons up to the third generation (red-G3) have been synthesized by a convergent method, and their photophysical, electrochemical, and electroluminescent properties have been investigated. In addition to controlling the intermolecular interactions, oligocarbazole-based dendrons could also participate in the electrochemical and charge-transporting process. As a result, highly efficient electrophosphorescent devices can be fabricated by spin-coating from chlorobenzene solution in different device configurations.

Hydrothermal Synthesis, Structures, and Luminescent Properties of Seven d(10) Metal-Organic Frameworks Based on 9,9-Dipropylfluorene-2,7-Dicarboxylic Acid (H(2)DFDA)

A series of Zn(II) and Cd(II) metal-organic frameworks, namely, [Zn(DFDA)] (1), [Cd(DFDA)(C2H5OH)] (2), [Zn-2(DFDA)(2)(L-1)(2)](2) center dot 3H(2)O (3), [Cd-2(DFDA)(2)(L-1)(2)] (4), [Zn(DFDA)(L-2)] (5), [Cd(DFDA)(L-2)(DMF)] (6), and [Zn(DFDA)(L-3)] (7) (where DFDA = 9,9-dipropylfluorene-2,7-dicarboxylate anion, L-1 = 1,4-bis(imidazol-1-ylmethyl)benzene, L-2 = 1,1'-(1,4-butanediyl) bis(imidazole), L-3 = 2,2'-bipyridine) have been synthesized under hydrothermal conditions and structurally characterized. Compound 1 exhibits a three-dimensional (3D framework containing one-dimensional (1D) Zn(II)-O clusters, with (4(8).6(7)) topology. Compound 2 contains hydrophobic channels built from infinite 1D Cd(II)-O clusters, with (4(8).5(4).6(3)) topology.

Synthesis and Application of Thiadiazoloquinoxaline-Containing Chromophores as Dopants for Efficient Near-Infrared Organic Light-Emitting Diodes

series of a donor-acceptor-donor type of near-infrared (NIR) fluorescent chromophores based on [1,2,5]thiadiazolo[3,4-g]quinoxaline (TQ) as an electron acceptor and triphenylamine as an electron donor are synthesized and characterized. By introducing pendent phenyl groups or changing the pi-conjugation length in the TQ core, we tuned tile energy levels of these chromophores, resulting in the NIR emission in a range from 784 to 868 nm. High thermal stability and glass transition temperatures allow these chromophores to be used as dopant emitters, which can be processed by vapor deposition for the fabrication of organic light-emitting diodes (OLEDs) having the multilayered structure of ITO/MoO3/NPB/Alq(3):dopant emitter/BCP/Alq(3)/LiF/Al. The electroluminescence spectra of the devices based on these new chromophores cover a range from 748 to 870 nm. With 2 wt % of dopant 1, the LED device shows an exclusive NIR emission at 752 nm with the external quantum efficiency (EQE) as high as 1.12% over a wide range of current density (e.g., around 200 mA cm(-2)).