909 resultados para Solid state chemistry
Resumo:
Semiconductor nanocrystals (NCs) possess high photoluminescence (PL) typically in the solution phase. In contrary, PL rapidly quenches in the solid state. Efficient solid state luminescence can be achieved by inducing a large Stokes shift. Here we report on a novel synthesis of compositionally controlled CuCdS NCs in air avoiding the usual complexity of using inert atmosphere. These NCs show long-range color tunability over the entire visible range with a remarkable Stokes shift up to about 1.25eV. Overcoating the NCs leads to a high solid-state PL quantum yield (QY) of ca. 55% measured by using an integrating sphere. Unique charge carrier recombination mechanisms have been recognized from the NCs, which are correlated to the internal NC structure probed by using extended X-ray absorption fine structure (EXAFS) spectroscopy. EXAFS measurements show a Cu-rich surface and Cd-rich interior with 46% Cu-I being randomly distributed within 84% of the NC volume creating additional transition states for PL. Color-tunable solid-state luminescence remains stable in air enabling fabrication of light-emitting diodes (LEDs).
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The solid state structure of a new seven-membered sugar oxepane derivative, namely, p-bromo phenyl 4,5,7-tri-O-benzyl-beta-D-glycero-D-talo-septanoside is discussed, as determined through single crystal X-ray structural determination and in relation to their conformational features. The molecule adopts twist-chair as the preferred conformation, with conformational descriptor (TC2,3)-T-0,1. The solid state packing of molecules is governed by a rich network of non-covalent bonding originating from O-H center dot center dot center dot O, C-H center dot center dot center dot pi, C-H center dot center dot center dot Br and aromatic pi center dot center dot center dot pi interactions that stabilize the packing of molecules in the crystal. (C) 2015 Elsevier Ltd. All rights reserved.
Resumo:
Synthesis and crystal structures of three porphyrin-based polyfunctional Lewis acids 1-3 are reported. Intermolecular HgClHgCl (linear and -type) interactions in the solid state of the peripherally ArHgCl-decorated compound 3 lead to a fascinating 3D supramolecular architecture. Compound3 shows a selective fluorescence quenching response to picric acid and discriminates other nitroaromatic-based explosives. For the first time, an electron-deficient polyfunctional Lewis acid is shown to be useful for the selective detection and discrimination of nitroaromatic explosives. The Stern-Volmer quenching constant and detection limits of compound3 for picric acid are the best among the reported small-molecular receptors for nitroaromatic explosives. The electronic structure, Lewis acidity, and selective sensing characteristics of 3 are well corroborated by DFT calculations.
Resumo:
A hitherto unseen rotation of the isopropyl group in the solid state, predicted to be forbidden based on theoretical investigations, is reported. This C-C rotation observed during the temperature dependent single-crystal-to-single-crystal transformation is attributed to the concomitant changes in molecular structure and intermolecular packing.
Resumo:
A series of binary borosilicate glasses prepared by the sol-gel method are shown to be bioactive. Tetraethyl orthosilicate (TEOS) and trimethylborate (TMB) in acidic medium are used to prepare xB(2)O(3)center dot(1-x)SiO2 glass systems for x = 0.045-0.167. The formation of a layer of apatite-like mineral on the glass surface becomes apparent after soaking in simulated body fluid for 48 h. We have measured the B-11-B-11 homonuclear second moments of the borosilicate glasses and inferred that no macroscopic phase separation occurred in our glasses. The B-11 chemical shift data also show that the formation of clustered boroxol rings is negligible in our glass system. Although the bioactivity of our borosilicate glasses is less than that of CaO-SiO2 sol-gel glasses, these simple binary systems could be taken as reference glass systems for the search of new bioactive borosilicate glasses. (C) 2008 Elsevier Ltd. All rights reserved.
Resumo:
We have prepared single crystalline SnO2 and ZnO nanowires and polycrystalline TiO2 nanotubes (1D networks) as well as nanoparticle-based films (3D networks) from the same materials to be used as photoanodes for solid-state dye-sensitized solar cells. In general, superior photovoltaic performance can be achieved from devices based on 3-dimensional networks, mostly due to their higher short circuit currents. To further characterize the fabricated devices, the electronic properties of the different networks were measured via the transient photocurrent and photovoltage decay techniques. Nanowire-based devices exhibit extremely high, light independent electron transport rates while recombination dynamics remain unchanged. This indicates, contrary to expectations, a decoupling of transport and recombination dynamics. For typical nanoparticle-based photoanodes, the devices are usually considered electron-limited due to the poor electron transport through nanocrystalline titania networks. In the case of the nanowire-based devices, the system becomes limited by the organic hole transporter used. In the case of polycrystalline TiO2 nanotube-based devices, we observe lower transport rates and higher recombination dynamics than their nanoparticle-based counterparts, suggesting that in order to improve the electron transport properties of solid-state dye-sensitized solar cells, single crystalline structures should be used. These findings should aid future design of photoanodes based on nanowires or porous semiconductors with extended crystallinity to be used in dye-sensitized solar cells. © 2013 The Royal Society of Chemistry.
Resumo:
The power-conversion efficiency of solid-state dye-sensitized solar cells can be optimized by reducing the energy offset between the highest occupied molecular orbital (HOMO) levels of dye and hole-transporting material (HTM) to minimize the loss-in-potential. Here, we report a study of three novel HTMs with HOMO levels slightly above and below the one of the commonly used HTM 2,2′,7,7′- tetrakis(N,N-di-p-methoxyphenylamino)-9,9′- spirobifluorene (spiro-OMeTAD) to systematically explore this possibility. Using transient absorption spectroscopy and employing the ruthenium based dye Z907 as sensitizer, it is shown that, despite one new HTM showing a 100% hole-transfer yield, all devices based on the new HTMs performed worse than those incorporating spiro-OMeTAD. We further demonstrate that the design of the HTM has an additional impact on the electronic density of states present at the TiO2 electrode surface and hence influences not only hole- but also electron-transfer from the sensitizer. These results provide insight into the complex influence of the HTM on charge transfer and provide guidance for the molecular design of new materials. © 2013 American Chemical Society.
Resumo:
In this article, the ZnO quantum dots-SiO2 (Z-S) nanocomposite particles were first synthesized. Transparent Z-S/epoxy super-nanocomposites were then prepared by introducing calcined Z-S nanocomposite particles with a proper ratio of ZnO to SiO2 into a transparent epoxy matrix in terms of the filler-matrix refractive index matching principle. It was shown that the epoxy super-nanocomposites displayed intense luminescence with broad emission spectra. Moreover, the epoxy super-nanocomposites showed the interesting afterglow phenomenon with a long phosphorescence lifetime that was not observed for ZnO-QDs/epoxy nanocomposites. Finally, the transparent and light-emitting Z-S/epoxy super-nanocomposites were successfully employed as encapsulating materials for synthesis of highly bright LED lamps.
Resumo:
Electrochemiluminescence (ECL) of tris(2,2'-bipyridyl) ruthenium [Ru(bpy)(3)(2+)] has received considerable attention. By immobilizing Ru(bpy)(3)(2+) on an e electrode surface, solid-state ECL provides several advantages over solution-phase ECL, such as reducing consumption of expensive reagent, simplifying experimental design and enhancing the ECL signal.This review presents the state of the art in solid-state ECL of Ru(bpy)(3)(2+).
Resumo:
A novel cemented carbides (W0.7Al0.3)C-0.65-Co with different cobalt contents were prepared by solid-state reaction and hot-pressing technique. Hot-pressing technique as a novel technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have superior mechanical properties compared with WC-Co. The density, operate cost of the novel material were lower than WC-Co system. The novel materials were easy to process nanoscale sintering and get the rounded particles in the bulk materials. There is almost no eta-phase in the (W0.7Al0.3)C-0.65-Co cemented carbides system although the carbon deficient get the astonished 35% value.
Resumo:
Tris(2,2'-bipyridine)ruthenium(II) ((Ru(bpy)(3)](2+)) is one of the most extensively studied and used electrochemiluminescent (ECL) compounds owing to its superior properties, which include high sensitivity and stability under moderate conditions in aqueous solution. In this paper we present a simple method for the preparation of [Ru(bpy)(3)](2+)-containing microstructures based on electrostatic assembly The formation of such micro-structures occurs in a single process by direct mixing of aqueous solutions of [Ru(bpy)(3)]Cl-2 and K-3[Fe(CN)(6)] at room temperature. The electrostatic interactions between [Ru(bpy)(3)]Cl-2 cations and [Fe(CN)(6)](3-) anions cause them to assemble into the resulting microstructures. Both the molar ratio and concentration of reactants were found to have strong influences on the formation of these microstructures. Most importantly, the resulting [Ru(bpy)(3)](2+)- containing microstructures exhibit excellent ECL behavior and, therefore, hold great promise for solid-state ECL detection in capillary electrophoresis (CE) or CE microchips.
Resumo:
Highly ordered, vertically oriented TiO2 nanotube arrays were prepared by potentiostatic anodization of titanium on FTO-coated glass substrate and for the first time successfully applied in the fabrication of solid-state dye sensitized solar cells (SSDSCs), giving a power conversion efficiency of 1.67% measured under an irradiation of air mass 1.5 global (AM 1.5 G) full sunlight. Furthermore, 3.8% efficiency was reached with a 2.8 mu m thin TiO2 nanotube array film based on a metal free organic dye using ionic liquid electrolyte.
Resumo:
In this correspondence, we report on the first preparation of novel, robust Ru(bpy)(3)(2+)-containing supramolecular microstructures via a solution-based self-assembly strategy, carried out by directly mixing H2PtCl6 and Ru(bpy)(3)Cl-2 aqueous solutions at room temperature. It reveals that both the molar ratio and concentration of reactants have a heavy influence on the morphologies of such microstructures. The electrochemical behavior of the Ru(bpy)(3)(2+) components contained in the solid film of the microstructures formed on the electrode surface is also studied and found to exhibit a diffusion-controlled voltammetric feature. Most importantly, such microstructures exhibit excellent electrochemiluminescence (ECL) behaviors and therefore hold great promise as new luminescent materials for solid-state ECL detection in capillary electrophoresis (CE) or CE microchip.
Resumo:
The new compounds La2-xCaxMo1.7W0.3O9-delta (0 <= x <= 0.2) in which La3+ substituted with Ca2+ were synthesized by dry-chemistry techniques based on the oxygen Ionic conductor La2Mo1.7W0.3O9. The new series were characterized by X-ray Diffraction (XRD), Raman and X-ray Photoelectron Spectroscopy (XPS) and the electrical conductivity of samples were investigated by AC impedance spectroscopy. The lattice parameters were reduced due to the smaller atomic radius of the Ca2+ compared with that of the La3+. Furthermore, Additional oxygen vacancies were introduced into La2Mo1.7W0.3O9 lattice by substitution, and then the oxygen ionic conductivity was increased. At 550 degrees C, the conductivity increased 89.9%, that is, from 0.79 x 10(-4) S center dot cm(-1) (x=0) to 1.5 X 10(-4)S center dot cm(-1) (x=0.16, 0.2).
Resumo:
A simple thermal process for the preparation of small Pt nanoparticles is presented, carried out by heating a H-2-PtCl6/3- thiophenemalonic acid aqueous solution. The following treatment of such colloidal Pt solution with Ru( bpy)(3)(2+) causes the assembly of Pt nanoparticles into aggregates. Most importantly, directly placing such aggregates on bare solid electrode surfaces can produce very stable films exhibiting excellent electrochemiluminescence behaviors.