Search

The local environment and dynamics of compressed carbon dioxide (CO(2)) penetration in surfactant templated silica film synthesis is interpreted from the in situ fluorescence emission spectra of pyrene (Py) and a modified pyrene probe. Pyrene emission in cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) templated silica films is monitored immediately after casting and during processing with gaseous and supercritical (sc) CO(2) (17-172 bar, 45 °C). The solvatochromic emission spectra of pyrene in CTAB templated films suggest CO(2) penetration in both the micelle interface and its interior. An anchored derivative of pyrene, 1-pyrenehexadecanoic acid (C(16)-pyr), is established for probing CPB films, where the pyrene moiety is preferentially oriented toward the micelle interior, thus limiting quenching by the pyridinium headgroup of CPB. CO(2) processing of CPB templated silica films results in an increase in the time scale for probe mobility, suggesting an increased time scale of silica condensation through CO(2) processing. The mobility of C(16)-pyr increases with pressure from gaseous to sc CO(2) processing and persists for over 5 h for sc CO(2) processing at 172 bar and 45 °C compared to about 25 min for the unprocessed film. The delivery of CO(2) soluble solutes to specific regions of surfactant templated mesoporous materials is examined via the nonradiative energy transfer (NRET) between pyrene and CO(2)-solubilized naphthalene.

Silica nanoparticles with controlled diameter (approximately 70-300 nm) and with uniform pores of 20 nm are prepared by a low temperature (10 degrees C) synthetic method in the presence of a dual surfactant system. While a triblock copolymer (Pluronic F127) acts as supramolecular template and coassembles with hydrolyzed silica species to develop a partially ordered mesophase with face-centered cubic symmetry, a fluorocarbon surfactant with high surface activity (FC-4) surrounds the silica particles through S+X-I+ interactions, thereby limiting their growth. The final textural properties of this material are achieved by means of a subsequent hydrothermal treatment to yield high pore volume mesoporous silica nanoparticles with the largest pore entrance size (17 nm) and cavity diameter (20 nm) reported up to now. After surface modification with aminopropyl groups, the nanoparticles are able to encapsulate inside the pores molecules of the firefly luciferase plasmid DNA (pGL3-Control, 5256 pb), leading to stable conjugates with up to 0.07 microg DNA m(-2), which is the highest content achieved with silica-based materials. Furthermore, plasmid DNA becomes protected from enzymatic degradation when conjugated with the mesostructured nanoparticles.

A series of WO3/SBA-15 materials with different Si/W ratios have been prepared by impregnating the host material SBA-15 with aqueous ammonium paratungstate solutions. After temperature-programmed carburization (TPC) in flowing CH4/H2 (20/80 v/v mixture), the materials are converted to the corresponding W2C/SBA-15 species. Both the oxide and carbide materials are characterized using X-ray diffraction, nitrogen adsorption-desorption, 29Si NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and TEM measurements. The XRD results show that after impregnation with different amounts of tungsten and subsequent carburization, the materials retain the mesopore structure of SBA-15. The nitrogen adsorption-desorption results indicate that a thin layer of W2C covers the internal walls of SBA-15. Quantitative 29Si single-pulse excitation MAS experiments and FTIR spectroscopy show that the incorporation of W2C in the channels of SBA-15 is correlated with the formation of Si-O-W bonds. Some Si-O-W bonds are transformed into Si-O-H bonds after carburization. The TEM results show that the thickness of the W2C thin layer is 1.7-1.9 nm in W2C/SBA-15. A model involving a discrete W2C thin layer in the channels of SBA-15 is proposed on the basis of the NMR data. The calculated thickness of the discrete W2C thin layer is consistent with value given by HRTEM.

The tailoring of porous silica thin films synthesized using perfluoroalkylpyridinium chloride surfactants as templating agents is achieved as a function of carbon dioxide processing conditions and surfactant tail length and branching. Well-ordered films with 2D hexagonal close-packed pore structure are obtained from sol-gel synthesis using the following cationic fluorinated surfactants as templates: 1-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octyl)pyridinium chloride (HFOPC), 1-(3,3,4,4,5,5,6,6,7,8,8,8-dodecafluoro-7-trifluoromethyl -octyl)pyridinium chloride (HFDoMePC), and 1-(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-decyl)pyridinium chloride (HFDePC). Processing the sol-gel film with CO2 (69-172 bar, 25 and 45 degrees C) immediately after coating results in significant increases in pore diameter relative to the unprocessed thin films (increasing from 20% to 80% depending on surfactant template and processing conditions). Pore expansion increases with CO2 processing pressure, surfactant tail length, and surfactant branching. The varying degree of CO2 induced expansion is attributed to the solvation of the "CO2-philic" fluorinated tail and is interpreted from interfacial behavior of HFOPC, HFDoMePC, and HFDePC at the CO2-water interface.

In this paper, we developed a facile way to synthesize highly ordered optically active MCM-48 at room temperature, by using mixtures of hemicyanine dye N-alkyl-2-[p-(N,N-diethylamino)-o-(alkyloxy)]pyridinium bromide (denoted as o-CnPOCm, Scheme 1) and cetyltrimethylammonium bromide (CTAB) as the structure-directing agents. The mesoporous materials were systematically characterized by powder X-ray diffraction, transmission electron microscopy, nitrogen sorption, and thermogravimetry. The resultant MCM-48 exhibits unusually high thermal stability. For example, in the case of o-C(2)POC(14), it can retain its cubic structure even under calcinations at 900 degrees C for 5 h, although the pore size is shifted to the micropore region because of shrinkage of the framework. The typical surface area and pore volume are 980 m(2)/g and 0.44 cm(3)/g, respectively, for the powder calcined under such a high temperature. This is the first report of room-temperature synthesis of MCM-48 with such good thermal stability using cationic-cationic mixed surfactant as the structure-directing agent. The fluorescence lifetimes of the as-synthesized mesostructured MCM-48 were also measured, and the result showed that the incorporated dye molecules have a 1 order of magnitude longer lifetime than that of free species in solution, showing that the hemicyanine dye molecules are well dispersed within the CTAB surfactant matrix. Furthermore, we compared eight other dye congeners (Scheme 1) to fully investigate the mesophase resulting from the dye-CTAB system. The results show that, upon addition of the dye surfactant to the starting mixtures, the mesostructured silica undergoes an intrinsic phase-transition process; however, specific dye geometry is required to obtain MCM-48 at room temperature. Those functionalities as well as the designed synthesis of this novel mesostructured MCM-48 material promise a bright future in multifunctional optical and electric nano- and microdevices (e.g., waveguides, laser, light-emitting diodes, etc.) and also shed light on the self-assembly behavior in complex colloidal system.

In this article, we report the synthesis of methylene-bridged periodic mesoporous organosilicas (PMOs) of the SBA-15 type. The materials were characterized by SAXS, BET, NMR, FESEM, and TEM. It was found that the synthesis of methylene-bridged SBA-15 PMOs requires more rigorous conditions than that of SBA-15 PMOs bearing organic bridges other than methylene. A mild acidic environment, which slows down the hydrolysis and condensation rates of the precursor, with the assistance of a salt, which enhances precursor-template interaction, should be used to synthesize high-quality large-pore methylene-bridged PMOs. We attributed this to the fast hydrolysis and condensation rates and the rigid backbone of precursor 1,2-bis(triethoxysilyl)methylene. By examining and comparing the synthesis of three large-pore PMOs with different bridges, we concluded that the inductive, bridging, and conformation effects of the organic bridging group play an important role in the synthesis of large-pore PMO materials.

An effective approach has been demonstrated for the synthesis of novel composite architectures, SiO2 nanowires (NWs) growing on hexagonally arranged circular patterns surrounded by TiO2 films on Si substrate. First, a solution-dipping template strategy is used to create TiO2 films with hexagonally arranged pores on Au-coated Si substrate, resulting in hexagonally arranged circular patterns of catalysts surrounded by TiO2 films. Then the patterned catalysts guide the growth of SiO2 NWs with the original TiO2 films preserved, realizing the composite structures. Such composite architectures combine the photoluminescence (PL) properties of the two components, and also present more favorable PL property, laying a foundation for future advanced nano-optoelectronic devices.

The initial stages of SBA-15 synthesis have been studied by using in situ time-resolved small-angle X-ray scattering with a synchrotron radiation source. The quantitative analysis of X-ray scattering and diffraction intensities allows the structures of intermediates to be identified at the different stages of SBA-15 synthesis. Following tetraethylorthosilicate (TEOS) addition, an intense small-angle scattering and an associated secondary maximum are observed, which are attributed to non-interacting surfactant template micelles encrusted with silicate species. After 25-30 min of the reaction, the broad scattering disappears and narrow Bragg diffraction peaks typical of hexagonally ordered structure are observed. The cylindrical micelles identified from X-ray scattering data appear to be the direct precursors of 2D hexagonal SBA-15 structure. Just after the formation of the SBA-15 hexagonal phase, the cylindrical micelles are only weakly linked in the hexagonal structure. As the synthesis proceeds, the solvent in the void volume between the cylindrical micelles is gradually replaced by more dense silicate species. The unit cell parameter of SBA-15 is progressively decreasing during the SBA-15 synthesis, which can be related to the condensation and densification of silicate fragments in the spaces between the cylinders. The volume fraction of the 2D hexagonally ordered phase is sharply growing during the first 2 h of the reaction. The inner core radius of SBA-15 material remains almost constant during the whole synthesis and is principally affected by the size of the poly(propylene oxide) inner core in the original cylindrical micelles.

The surface hydrophobicity of colloidal silica (SiO2) nanospheres is manipulated by a chemical graft of alkyl chains with silane coupling agents or by physical adsorption of a cationic surfactant. The surface-modified SiO2 spheres can be transferred from the aqueous phase to organic solvents and readily self-assemble at the water-air interface to form two-dimensional (2D) particle arrays. Closely packed particle monolayers are obtained by adjusting the hydrophilic/hydrophobic balance of the synthesized SiO2 spheres and may further be transferred onto solid substrates layer by layer to form three-dimensional (3D) ordered particle arrays with a hexagonal close-packed (hcp) crystalline structure. The 2D monolayer and 3D multilayer SiO2 films exhibit photonic crystal properties, which were determined by the UV-visible spectroscopic analysis in transmission mode. In the multilayer films, the Bragg diffraction maxima increased with an increase in thickness of the particle layers. The experimentally observed diffraction positions are in good agreement with those that were theoretically calculated.

We report on the synthesis, structural characterization, physical properties, and lasing action of two organic dyes, Rhodamine 6G (Rh6G) and Pyrromethene 597 (PM597), incorporated into new hybrid organic-inorganic materials, where the organic component was either poly(2-hydroxyethyl-methacrylate) (PHEMA) or copolymers of HEMA with methyl methacrylate (MMA), and the inorganic counterpart consisted of silica derived from hydrolysis-condensation of methyltriethoxysilane (TRIEOS) in weight proportion of up to 30%. Lasing efficiencies of up 23% and high photostabilities, with no sign of degradation in the initial laser output after 100 000 pump pulses at 10 Hz, were demonstrated when pumping the samples transversely at 534 nm with 5.5 mJ/pulse. A direct relationship could be established between the structure of the hybrid materials, analyzed by solid-state NMR, and their laser behavior. An inorganic network dominated by di-/tri- substituted silicates in a proportion approximately 35:65, corresponding to samples of HEMA with 15 and 20 wt % proportion of TRIEOS, optimizes the lasing photostability. The thermal properties of these materials, together with the high homogeneity revealed by atomic force microscopy (AFM) images, even in compounds with high silica content, indicate their microstructure to be a continuous phase, corresponding to the polymer matrix, which "traps" the silica components at molecular level via covalent bonding, with few or no silica islands.

The properties of the silica layer during the formation of the mesoporous material MCM-41 were investigated by electron paramagnetic resonance (EPR) experiments carried out on a specifically designed, organo(trialkoxy)silane spin probe, SL1SiEt. Minute amounts of the spin probe were co-condensed with the silica source, tetraethyl orthosilicate (TEOS), in the synthesis of MCM-41 with cetyltrimethylammonium bromide (CTAB) under basic conditions. The mobility and location of the spin probe were followed in the CTAB micellar solution before the reaction, in the reaction mixture and in the final ordered material. It was found that the EPR spectra of hydrolyzed SL1SiEt throughout the room temperature part of the reaction are characteristic of a fast tumbling species, indicating that the silica is highly fluid prior to drying. After filtering, a slow motion type spectrum was observed, showing that the spin-label experiences considerable motional hindrance. The liquidlike behavior could be restored upon stirring the material in water. When the reaction is performed with a hydrothermal stage, the spectrum of SL1SiEt in the final product is the same as that of the room temperature synthesized material, but the addition of water did not restore the high mobility, due to a higher degree of silica cross-linking. The location of SL1SiEt throughout the formation process was obtained from electron spin-echo envelope modulation (ESEEM) measurements on MCM-41 prepared with CTAB deuterated either at the N-methyl or the alpha position and in a reaction carried out in D2O. Comparing the deuterium modulation depth, k(2H), induced by CTAB-alpha-d2, CTAB-d9, or D2O in CTAB micellar solutions of a number of reference spin probes with those of SL1SiEt revealed that the hydrolyzed SL1SiEt is located near the polar heads of the surfactant in the absence of base and TEOS. This supports the postulation of charge matching at the interface as a driving force for the formation of the mesostructure. Similar experiments carried out on reaction mixtures containing SL1SiEt showed a decrease of k(2H) from CTAB-alpha-d2 and CTAB-d9 compared to the micellar solution, exhibiting practically no time dependence. This indicates that the spin probe is pulled away from the micelle-water interface into the loosely linked, forming silica network. After drying, the modulation depth induced by CTAB-alpha-d2 and CTAB-d9 increases, showing that, once the water is removed, the silica walls contract around the micelles, pushing the silica-linked spin probe into the organic phase within the mesopores.

We studied the optical properties of sol-gel synthesized porous silica excited by synchrotron radiation in the 4-10 eV range. The spectral and temporal characteristics of the ultraviolet photoluminescence at about 3.7 eV are reported. The UV emission results from the contribution of two different centers: the first one centered at 3.7 eV with a decay time of 2.0 ns and the second one peaked at 3.9 eV with a decay time of 20 ns. We propose to assign the observed luminescence to different interacting surface silanols.