In situ SAXS study on a new mechanism for mesostructure formation of ordered mesoporous carbons: thermally induced self-assembly.

A new mechanism for mesostructure formation of ordered mesoporous carbons (OMCs) was investigated with in situ small-angle X-ray scattering (SAXS) measurements: thermally induced self-assembly. Unlike the well-established evaporation-induced self-assembly (EISA), the structure formation for organic-organic self-assembly of an oligomeric resol precursor and the block-copolymer templates Pluronic P123 and F127 does not occur during evaporation but only by following a thermopolymerization step at temperatures above 100 °C. The systems investigated here were cubic (Im3m), orthorhombic Fmmm) and 2D-hexagonal (plane group p6mm) mesoporous carbon phases in confined environments, as thin films and within the pores of anodic alumina membranes (AAMs), respectively. The thin films were prepared by spin-coating mixtures of the resol precursor and the surfactants in ethanol followed by thermopolymerization of the precursor oligomers. The carbon phases within the pores of AAMs were made by imbibition of the latter solutions followed by solvent evaporation and thermopolymerization within the solid template. This thermopolymerization step was investigated in detail with in situ grazing incidence small-angle X-ray scattering (GISAXS, for films) and in situ SAXS (for AAMs). It was found that the structural evolution strongly depends on the chosen temperature, which controls both the rate of the mesostructure formation and the spatial dimensions of the resulting mesophase. Therefore the process of structure formation differs significantly from the known EISA process and may rather be viewed as thermally induced self-assembly. The complete process of structure formation, template removal, and shrinkage during carbonization up to 1100 °C was monitored in this in situ SAXS study.

Cubic and hexagonal mesoporous carbon in the pores of anodic alumina membranes.

Cubic and circular hexagonal mesoporous carbon phases in the confined environment of the pores of anodic alumina membranes (AAM) were obtained by organic-organic self-assembly of a preformed oligomeric resol precursor and the triblock copolymer templates Pluronic F127 or P123, respectively. Casting and solvent evaporation were followed by self-assembly and the formation of a condensed wall material by thermopolymerization of the precursor oligomers, thus resulting in mesostructured phenolic resin phases. Subsequent thermal decomposition of the surfactant and carbonization were achieved through thermal treatment at temperatures up to 1000 °C under an inert atmosphere. The resulting hierarchical mesoporous composite materials were characterized by small-angle X-ray scattering and nitrogen-sorption measurements. The structural features were directly imaged in TEM cross-sections of the composite membranes. For both structures, the AAM pores were completely filled and no shrinkage was observed due to strong adhesion of the carbon-wall material to the AAM pore walls. As a consequence, the pore size of the mesophase system stays almost constant even after thermal treatment at 1000 °C.

Periodic mesoporous organosilica in confined environments.

Periodic mesoporous organosilica (PMO) mesophases based on bis(triethoxysilyl)ethane (BTSE) were synthesized within the confined tubular environment of anodic alumina membrane (AAM) channels. The resulting mesophases were investigated by transmission small angle X-ray scattering (SAXS), nuclear magnetic resonance (NMR), nitrogen sorption, and transmission electron microscopy (TEM). Two different surfactants--nonionic Brij 56 and ionic cetyltrimethylammonium bromide (CTAB)--were used in an acid-catalyzed evaporation-induced self-assembly (EISA) process. Brij 56 as the structure-directing agent (SDA) resulted in the formation of either the hexagonal circular or the cubic mesophase. While the hexagonal circular mesophase is common for such kinds of composites, the cubic mesophase has never been reported before. The template could be removed from the mesophases by template extraction and calcination after annealing the samples. When using CTAB as the SDA during EISA, the only mesophase observed was the hexagonal circular structure. This is in contrast to previous experiments and reports on pure silica mesophases, where the only mesophase formed with CTAB is hexagonal columnar.

Tuning single-molecule dynamics in functionalized mesoporous silica.

Mesoporous silica materials are promising host structures for diverse applications in nanoscience. Many applications can profit significantly from the ability to influence guest dynamics in the host matrix. To this end, we introduce covalently attached organic functionalization into the walls of mesoporous silica networks. Using single-molecule fluorescence microscopy, we study the diffusion behavior of single terrylene diimide dye molecules in functionalized mesoporous silica films. We show that, through variation of the chemical nature and density of the functional groups, the diffusion dynamics of the dye molecules, in the presence of the surfactant template, can be controlled precisely. The mean diffusion coefficient of the dye molecules increases or decreases depending on the functional group attached to the silica wall. This allows fine-tuning of the diffusion dynamics of the dye by approximately one order of magnitude. The observed changes in the mean diffusion coefficients can be explained by shielding of hydroxyl groups on the silica surface in combination with changes in the rigidity of the micellar packing in the film, as well as direct interactions between the functional groups and the dye molecules.

Vertical columnar block-copolymer-templated mesoporous silica via confined phase transformation.

An efficient method is described for the preparation of phase-pure columnar mesoporous silica nanosystems within the channels of anodic alumina membranes (AAM) via evaporation-induced self-assembly (EISA). Upon the basis of a systematic investigation of the effects of interfacial interactions and different synthesis parameters on the resulting hierarchical mesophase, a salt-induced phase transformation was developed for efficient structural control. Samples with a columnar hexagonal 2D structure along the vertical channels of the AAM can be produced with ionic CTAB as template. However, when nonionic surfactants (Pluronic P123 and Brij 56) are used, samples with a circular hexagonal 2D structure perpendicular to the channels or phase mixtures of circular and columnar orientations are obtained. The behavior of ionic CTAB can be mimicked by adding inorganic salt to the nonionic template precursor solution, thus leading to a phase transformation toward columnar orientation. The distribution between the orientations was determined by means of small-angle X-ray scattering (SAXS) experiments. The effects of other synthesis parameters were also investigated, including temperature, surfactant: silica ratio, and salt composition. Strikingly, calcination-stable mesoporous materials with a columnar orientation exhibiting high mesoporosity and specific surface area were obtained for the first time with such structure directors. The salt-induced phase transformation is an efficient means for achieving a desired hierarchical mesostructure in the confined space of the AAM channels.

Formation mechanism of mesostructured silica in confined space: an in situ GISAXS study.

The structural evolution of periodic mesoporous material within the channels of anodic alumina membranes (AAMs) by evaporation-induced self-assembly (EISA) is investigated by a combination of in situ grazing-incidence small-angle X-ray scattering (GISAXS) with parallel detection of solvent evaporation and ex situ transmission electron microscopy (TEM). Kinetically controlled and equilibrium-controlled structural evolution can be distinguished for these EISA processes. A new mechanism for formation of mesostructures in the confined environment of AAMs is proposed. Data are presented for samples synthesized with nonionic surfactants at various surfactant:silica ratios and relative humidities. The formation of and transformations between circular or columnar 2D hexagonal and tubular lamellar structures are observed. The circular hexagonal phase is kinetically favored over the columnar hexagonal orientation. The TEM images provide evidence that phase transformations, depending on their type, either start preferentially at the channel wall or in the center of the mesostructured fibers.

Nanocrystalline mesoporous palladium activated tin oxide thin films as room-temperature hydrogen gas sensors.

A unique nanocrystalline, mesoporous PdO-SnO(2) film exhibiting high sensitivity and selectivity to hydrogen gas at room temperature has been developed.

Visualization of the self-assembly of silica nanochannels reveals growth mechanism.

Self-assembled mesoporous structures with well-ordered nanoscale channels could be used in applications such as molecular separation, nano-optics, molecular electronics, nanomedicine and catalysis. However, the domain sizes that can be created in such systems are limited by our lack of a detailed understanding of the relevant growth processes. Here we report the real-time observation of domain growth in the self-assembly of silica nanochannels using fluorescence polarization imaging and atomic force microscopy. We show that transient lamellar structures precede the formation of hexagonal layers, and that the layer growth follows two distinct pathways. In addition, the domains are grown on a mesoporous film substrate, which acts as a sieve and allows control of the delivery of the reactive species. We use these insights and capabilities to grow layers of well-ordered silica nanochannels with domain sizes of up to ∼0.3 mm.

Crystalline nanoporous metal oxide thin films by post-synthetic hydrothermal transformation: SnO2 and TiO2.

Nanostructured and nanoporous metal oxide thin films are rarely accessible by standard synthetic approaches but highly desired for many applications, e.g. as electrodes, transparent conducting coatings, sensors or surface catalysts. Template based sol­gel chemistry combined with post-synthetic hydrothermal treatment allows now the synthesis of nanocrystalline mesostructured porous thin films of metal oxides, e.g. tin oxide and titania. Even in cases where the crystallization cannot be induced highly stable thin films can be achieved, e.g. niobium oxide thin films. We demonstrate how the size of the nanocrystallites influences and stabilizes the mesostructure at temperatures as low as 100 C and thereby in the case of titania or tin dioxide even prevents it from deterioration at higher temperatures up to 400­600 C.

Characterization of lipid-templated silica and hybrid thin film mesophases by grazing incidence small-angle X-ray scattering.

The nanostructure of silica and hybrid thin film mesophases templated by phospholipids via an evaporation-induced self-assembly (EISA) process was investigated by grazing-incidence small-angle X-ray scattering (GISAXS). Diacyl phosphatidylcholines with two tails of 6 or 8 carbons were found to template 2D hexagonal mesophases, with the removal of lipid from these lipid/silica films by thermal or UV/O3 processing resulting in a complete collapse of the pore volume. Monoacyl phosphatidylcholines with single tails of 10-14 carbons formed 3D micellular mesophases; the lipid was found to be extractable from these 3D materials, yielding a porous material. In contrast to pure lipid/silica thin film mesophases, films formed from the hybrid bridged silsesquioxane precursor bis(triethoxysilyl)ethane exhibited greater stability toward (both diacyl and monoacyl) lipid removal. Ellipsometric, FTIR, and NMR studies show that the presence of phospholipid suppresses siloxane network formation, while actually promoting condensation reactions in the hybrid material. 1D X-ray scattering and FTIR data were found to be consistent with strong interactions between lipid headgroups and the silica framework.

In situ GISAXS study of the formation of mesostructured phases within the pores of anodic alumina membranes.

The formation and subsequent transformations of mesostructured silica within the confined tubular environment of anodic alumina membrane (AAM) channels [porous alumina membrane (PAM) channels] were investigated for the first time in situ with grazing incidence small-angle X-ray scattering (GISAXS) techniques, in combination with ex situ transmission electron microscopy (TEM) of the same samples. A better understanding of the mesostructure formation mechanism within the confined space of the AAM pores is a direct result of this study. Three different surfactants were used as the structure-directing agents in acid-catalyzed silica synthesis solutions. With ionic cetyltrimethylammonium bromide acting as the structure-directing agent, a columnar hexagonal structure with mesopores oriented parallel to the AAM channels was observed to form directly from the beginning of the synthesis. In samples synthesized with the nonionic surfactants Brij 56 and Pluronic P123, a circular hexagonal structure was found to form first; here, the mesopores are aligned around the circumference of the AAM channels. The circular structure subsequently transforms directly into a columnar hexagonal (P123 surfactant), or a mixture of columnar hexagonal and a new curved lamellar phase with lamellae oriented parallel to the walls of the AAM channels (Brij 56 surfactant). These transformations occur after complete solvent evaporation and therefore differ from a simple evaporation-induced phase formation. The existence of a previously postulated lamellar phase could be proven by GISAXS and TEM investigations.