Preparation and luminescence properties of the mesoporous MCM-41s intercalated with rare earth complex

Rare earth complex Eu(DBM)(3)phen (DBM: dibenzoylmethane, phen: 1.10-phenanthroline) hits been incorporated into unmodified MCM-41 and modified MCM-41s by aminopropyltriethoxysilane (APTES) or N-[(3-triethoxysilyl)propyl]ethylenediamine(TEPED). Thus, the assemblies of unmodified or modified MCM-41s with rare earth (RE) complex have been obtained. XRD spectra. NMR spectra. diffuse reflectance spectra. and the luminescence spectra were used to characterize the pure RE complex and the corresponding assemblies. The assemblies have better luminescence properties under UV irradiation. and their fluorescence lifetimes on the excited state are longer than that of the corresponding pure complex. The possible mechanisms are also discussed in the context.

Nanocluster-containing mesoporous magnetoceramics from hyperbranched organometallic polymer precursors

Pyrolysis of hyperbranched poly[1,1'-ferrocenylene(methyl)silyne] (5) yields mesoporous, conductive, and magnetic ceramics (6). Sintering at high temperatures (1000-1200 degrees C) under nitrogen and argon converts 5 to 6N and 6A, respectively, in similar to 48-62% yields. The ceramization yields of 5 are higher than that (similar to 36%) of its linear counterpart poly[1,1'-ferrocenylene(dimethyl)silylene] (1), revealing that the hyperbranched polymer is superior to the linear one as a ceramic precursor. The ceramic products 6 are characterized by SEM, XPS, EDX, XRD, and SQUID. It is found that the ceramics are electrically conductive and possess a mesoporous architecture constructed of tortuously interconnected nanoclusters. The iron contents of 6 estimated by EDX are 36-43%, much higher than that (11%) of the ceramic 2 prepared from the linear precursor 1. The nanocrystals in 6N are mainly alpha-Fe2O3 whereas those in 6A are mainly Fe3Si. When magnetized by an external field at room temperature, 6A exhibits a high-saturation magnetization (M-s similar to 49 emu/g) and near-zero remanence and coercivity; that is, 6A is an excellent soft ferromagnetic material with an extremely low hysteresis loss.

Preparation, characterization and luminescent properties of MCM-41 type materials impregnated with rare earth complex

Hybrid materials incorporating Eu-(TTA)(3). 2H(2)O (7hereafter designated as Eu-TTA, with TTA: thenoyltrifluoroacetone) in unmodified or modified MCM-41 by 3-aminopropyl-triethoxysilane (APTES) were prepared by impregnation method. The obtained materials were characterized using X-ray diffraction (XRD), IR and diffuse reflectance spectroscopy and luminescence spectra. All the hybrid samples exhibited the characteristic emission bands of EU3+ under UV light excitation at room temperature, and the excitation spectra showed significant blue-shifts compared to the pure rare-earth complex. Although the red emission intensity in the modified hybrid was almost the half of the red emission intensity in the pure Eu-TTA complex at room temperature, the hybrid showed a much higher thermal stability due to the shielding character of the MCM-41 host.

Encapsulation of fluorescein into MCM-41 mesoporous molecular sieve by a sol-gel method

MCM-41-hosted fluorescein mesophase was prepared by addition of the dye into the sol-gel mixture for the synthesis of MCM-41 mesoporous molecular sieve under microwave radiation. The as-synthesized organo-silica-surfactant material possessed hexagonal mesostructure with short-range symmetry and a uniform nanosize of about 30 nm. Furthermore, fluorescence spectrum, increase in lifetime and lack of aggregation at high concentration were discussed in terms of the effect of the host-guest interaction on these properties. (C) 2001 Published by Elsevier Science B.V.

Stable tetrahedral aluminum sites in hexagonal mesoporous aluminosilicates

A unique templating approach for the synthesis of hexagonal mesoporous aluminosilicates via self-assembly of pre-formed aluminosilcate nanoclusters with the templating micella formed by cetyltrimethylammonium bromide (CTAB) is described. The obtained materials of MAS-5 are hydrothermally stable, which is shown by X-ray diffraction (XRD) analysis. Furthermore, as characterized by NMR technique, MAS-5 has stable tetrahedral aluminum sites that is the major contributions to the acidity of aluminosilicate molecular sieve, and on non-framework aluminium species in the samples was observed.

Direct synthesis and characterization of titanium-substituted mesoporous molecular sieve SBA-15

Ti-substituted mesoporous SBA-15 (Ti-SBA-15) materials have been synthesized by using a new approach in which the hydrolysis of the silicon precursor (tetramethoxysilane, TMOS) is accelerated by fluoride. These materials were characterized by powder X-ray diffraction patterns (XRD), X-ray fluorescence spectroscopy (Y-RF), N-2 sorption isotherms, diffuse-reflectance UV-visible (UV-vis) and UV-Raman spectroscopy, Si-29 MAS NMR, and the catalytic epoxidation reaction of styrene. Experiments show that Ti-SBA-15 samples of high quality can be obtained under the following conditions: F/Si greater than or equal to 0.03 (molar ratio), pH less than or equal to 1.0, aging temperature less than or equal to 80 degreesC, and Ti/Si less than or equal to 0.01. It was found that the hydrolysis rate of TMOS was remarkably accelerated by fluoride, which was suggested to play the main role in the formation of Ti-SBA-15 materials of high quality. There is no stoichiometric incorporation of Ti, and the Ti contents that are obtained are quite low in the case of the approach that is proposed. The calcined Ti-SBA-15 materials show highly catalytic activity in the epoxidation of styrene.

Synthesis of ordered mesoporous carbons composed of nanotubes via catalytic chemical vapor deposition

Ordered mesoporous carbons composed of arrays of nanotubes have been synthesized using ordered mesoporous silica templates via catalytic chemical vapor deposition. The ordered carbons possess bimodal pores, namely, the pores arise from the "replica" of frameworks of the template and the pores correspond to carbon nanotubes formed in the channels of the template (see Figure).

Sol-gel derived oxides and mixed oxides catalysts with narrow mesoporous distribution

A novel sol-gel process for preparing oxides and mixed oxides sols from precipitation and peptization process is reported in this article. Inorganic salts are used as raw materials in this study. It is found that the amount of acid has great influence on the stability and particle diameter distribution of the precursor sols. Ultrasonic treatment is used to prepare alumina sol at room temperature. The result of Al-27 NMR shows that there exist Al-13(7+) species in the sol. By controlling the sol particles with narrow particle diameter distribution, alumina, titania and silica-alumina (SA) materials with narrow mesoporous distribution are formed by regular packing of sol particles during gelation without using any templates. The results also show that the structure and particle diameter distribution of precursor sol determine the final materials' texture.

Highly ordered periodic mesoporous ethanesilica synthesized under neutral conditions

Highly ordered mesoporous ethanesilica (MES) with 2D hexagonal structure was synthesized from 1,2-bis(trimethoxysilyl) ethane under neutral conditions for the first time. Divalent salts, such as NiCl2, MgCl2, ZnCl2, ZnSO4 and Zn(NO3)(2), were used to help the formation of the ordered mesostructure. The MES samples were characterized by powder X-ray diffraction, nitrogen sorption, transmission electron microscopy, FT-IR, C-13 and Si-29 solid-state NMR and thermal gravimetric analysis. A phase transition from a disordered wormhole-like structure to an ordered P6mm structure was observed upon the addition of inorganic salts. The pore size of the MES decreases from 4.7 to 3.9 nm with increasing content of the inorganic salts. Fluoride was also found to be important for the formation of ordered MES under neutral conditions.

Dibenzodioxin adsorption on inorganic materials

Dibenzodioxin adsorption/desorption on solid surfaces is an important issue associated with the formation, adsorption, and emission of dioxins. Dibenzodioxin adsorption/desorption behaviors on inorganic materials (amorphous/mesoporous silica, metal oxides, and zeolites) were investigated using in situ FT-IR spectroscopy and thermogravimetric (TG) analysis. Desorption temperatures of adsorbed dibenzodioxin are very different for different kinds of inorganic materials: similar to 200 degrees C for amorphous/mesoporous silica, similar to 230 degrees C for metal oxides, and similar to 450 degrees C for NaY and mordenite zeolites. The adsorption of dibenzodioxin can be grouped into three categories according to the red shifts of the IR band at 1496 cm(-1) of the aromatic ring for the adsorbed dibenzodioxin: a shift of 6 cm-1 for amorphous/mesoporous silica, a shift of 10 cm(-1) for metal oxides, and a shift of 14 cm(-1) for NaY and mordenite, suggesting that the IR shifts are proposed to associated with the strength of the interaction between adsorbed dibenzodioxin and the inorganic materials. It is proposed that the dibenzodioxin adsorption is mainly via the following three interactions: hydrogen bonding with the surface hydroxyl groups on amorphous/mesoporous silica, complexation with Lewis acid sites on metal oxides, and confinement effect of pores of mordenite and NaY with pore size close to the molecular size of dibenzodioxin.

Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

Selectivity control in hydrogenation reactions by nanoconfinement of polymetallic nanoparticles in mesoporous thin films

A one-pot sol-gel synthesis method has been developed for the incorporation of metal nanoparticles into mesoporous oxide thin films deposited on various plane substrates by spin-coating and on the inner surface of fused silica capillaries by dip-coating. The size, the metal loading and the stoichiometry of the metal nanoparticles could be precisely controlled by following this methodology. In the first step, polymer stabilized Pt50Sn50 and Pt90Sn10 nanoparticles were obtained by a solvent-reduction method. Then, the nanoparticles were added to a metal oxide precursor sol, which was destabilized by solvent evaporation. After calcination, the obtained materials were tested in the hydrogenation of citral in both batch and continuous modes. The highest selectivity of 30% towards the unsaturated alcohols was obtained over supported Pt90Sn10 nanoparticles with a preferential formation of the cis-isomer (nerol) due to a unique confinement of the bimetallic nanoparticles in the mesoporous framework. The selectivity towards the unsaturated alcohols was further improved to 56% over the PtRu5Sn nanoparticles supported by impregnation onto mesoporous silica films. (C) 2009 Elsevier B.V. All rights reserved.