A critical review of adsorption methods that are currently used in the characterization of ordered organic−inorganic nanocomposite materials is presented, and the adsorption methodology that is potentially useful for this characterization, but has not yet been applied, is discussed. The ordered organic−inorganic nanocomposites include surface-functionalized ordered mesoporous materials (OMMs) with siliceous frameworks (synthesized either via postsynthesis surface modification or via direct co-condensation method), periodic mesoporous organosilicas, and surfactant-containing OMMs. This review covers the methods for determination of the specific surface area and pore volume. The available methods for mesopore size analysis are critically compared and evaluated, with special emphasis on the recent developments related to the application of advanced computational methods for studying adsorption in porous media and to the direct modeling of adsorption using highly ordered surface-functionalized OMMs as model a...

Gas adsorption characterization of ordered organic-inorganic nanocomposite materials

A review was presented to demonstrate a historical description of the synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. Electroluminescence (EL) was first reported in poly(para-phenylene vinylene) (PPV) in 1990 and researchers continued to make significant efforts to develop conjugated materials as the active units in light-emitting devices (LED) to be used in display applications. Conjugated oligomers were used as luminescent materials and as models for conjugated polymers in the review. Oligomers were used to demonstrate a structure and property relationship to determine a key polymer property or to demonstrate a technique that was to be applied to polymers. The review focused on demonstrating the way polymer structures were made and the way their properties were controlled by intelligent and rational and synthetic design.

Synthesis of Light-Emitting Conjugated Polymers for Applications in Electroluminescent Devices

Nanostructured carbon materials are potentially of great technological interest for the development of electronic1,2, catalytic3,4 and hydrogen-storage systems5,6. Here we describe a general strategy for the synthesis of highly ordered, rigid arrays of nanoporous carbon having uniform but tunable diameters (typically 6 nanometres inside and 9 nanometres outside). These structures are formed by using ordered mesoporous silicas as templates, the removal of which leaves a partially ordered graphitic framework. The resulting material supports a high dispersion of platinum nanoparticles, exceeding that of other common microporous carbon materials (such as carbon black, charcoal and activated carbon fibres). The platinum cluster diameter can be controlled to below 3 nanometres, and the high dispersion of these metal clusters gives rise to promising electrocatalytic activity for oxygen reduction, which could prove to be practically relevant for fuel-cell technologies. These nanomaterials can also be prepared in the form of free-standing films by using ordered silica films as the templates.

Ordered nanoporous arrays of carbon supporting high dispersions of platinum nanoparticles

On the Controllable Soft-Templating Approach to Mesoporous Silicates

In this review, the progress made in the last ten years concerning the synthesis of porous carbon materials is summarized. Porous carbon materials with various pore sizes and pore structures have been synthesized using several different routes. Microporous activated carbons have been synthesized through the activation process. Ordered microporous carbon materials have been synthesized using zeolites as templates. Mesoporous carbons with a disordered pore structure have been synthesized using various methods, including catalytic activation using metal species, carbonization of polymer/polymer blends, carbonization of organic aerogels, and template synthesis using silica nanoparticles. Ordered mesoporous carbons with various pore structures have been synthesized using mesoporous silica materials such as MCM-48, HMS, SBA-15, MCF, and MSU-X as templates. Ordered mesoporous carbons with graphitic pore walls have been synthesized using soft-carbon sources that can be converted to highly ordered graphite at high temperature. Hierarchically ordered mesoporous carbon materials have been synthesized using various designed silica templates. Some of these mesoporous carbon materials have successfully been used as adsorbents for bulky pollutants, as electrodes for supercapacitors and fuel cells, and as hosts for enzyme immobilization. Ordered macroporous carbon materials have been synthesized using colloidal crystals as templates. One-dimensional carbon nanostructured materials have been fabricated using anodic aluminum oxide (AAO) as a template.

Recent Progress in the Synthesis of Porous Carbon Materials

Molecular sieves with uniform large pores are desirable for chemical reactions and for use in separations involving large molecules.1 Periodic cubic and hexagonal mesoporous silica phases with uniform large pores have been synthesized by using nonionic triblock and star diblock copolymers as templates.2 Control over the pore size is achieved by adjusting the hydrophobic volumes of the self-assembled aggregates.2,3 In this paper, we describe how adding a sufficiently large amount of an organic cosolvent induces a phase transformation from the highly ordered p6mm mesostructure of SBA-15-type mesoporous silicas to remarkable mesostructured cellular foams (mesocellular foams, MCFs) composed of uniformly sized, large spherical cells that are interconnected by uniform windows to create a continuous 3-D pore system. The interconnected nature of the large uniform pores makes these new mesostructured silicas promising candidates for supports for catalysts and in separations involving large molecules, and they may be of interest in low-dielectric applications. The MCFs have been synthesized in aqueous acid by using dilute Pluronic P123 solutions in the presence of 1,3,5-trimethylbenzene (TMB) as organic cosolvent.4 X-ray diffraction (XRD) experiments5 reveal well-resolved peaks at small angles, as shown in Figure 1 for a sample with a cell diameter of 33 nm. Careful analyses of the scattering data for MCFs show that the higher order peaks cannot be indexed to any plane or space group (e.g., p6mm) or to a lamellar diffraction pattern. In fact, after subtraction of the background,6 the X-ray data are in good agreement with simulated scattering7 due to monodisperse spheres (cells) of diameter D (see Table 1), while attempts to fit the X-ray data to

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Mesocellular siliceous foams with uniformly sized cells and windows

Siliceous mesostructured cellular foams (MCFs) with well-defined ultralarge mesopores and hydrothermally robust frameworks are described. The MCFs are templated by oil-in-water microemulsions and are characterized by small-angle X-ray scattering, nitrogen sorption, transmission electron microscopy, scanning electron microscopy, thermogravimetry, and differential thermal analysis. The MCFs consist of uniform spherical cells measuring 24−42 nm in diameter, possess BET surface areas up to 1000 m2/g and porosities of 80−84%, and give, because of their pores with small size distributions, higher-order scattering peaks even in the absence of long-range order. Windows with diameters of 9−22 nm and narrow size distribution interconnect the cells. The pore size can be controlled by adjusting the amount of the organic swelling agent that is added and by varying the aging temperature. Adding ammonium fluoride selectively enlarges the windows by 50−80%. In addition, the windows can be enlarged by postsynthesis treatm...

Microemulsion Templating of Siliceous Mesostructured Cellular Foams with Well-Defined Ultralarge Mesopores

The diameters of primary mesopores in materials with well-defined cylindrical pores can be accurately determined by the 4V/A method when the volume and surface area are determined by a standard adsorption method and 13.5 A2 is used as the molecular area of adsorbed nitrogen. A simple method for determining standard adsorption using the statistical thickness of the adsorbed gas layer defined by Frenkel−Halsey−Hill (FHH) theory is described. For materials in which the pores are not cylindrical or well-defined, a simplified Broekhoff−de Boer method can be used to determine pore dimensions. The use of Hill's approximation for the thickness of the adsorbed gas layer in the Broekhoff−de Boer method simplifies its use. The results of these methods on small pore MCM-41 materials, large pore SBA-15 materials, and spherical pore mesocellular foams are reported.

Evaluating Pore Sizes in Mesoporous Materials: A Simplified Standard Adsorption Method and a Simplified Broekhoff−de Boer Method

We have investigated the phase transition between two distinct mesoporous silicas:  SBA-15, comprising a hexagonally packed arrangement of cylindrical pores (6−12 nm in diameter), and mesocellular silica foams (MCF), consisting of spherical voids (22−42 nm in diameter) interconnected by “windows” of ∼10 nm. Both SBA-15 and MCF are formed using an amphiphilic triblock copolymer (Pluronic P123) as a template. The synthesis conditions for the two materials are identical, except substantial trimethylbenzene is added to form MCF. We find that the phase transition occurs at an oil−polymer mass ratio of 0.2−0.3. Although the pore structures and pore sizes change dramatically, the mean surface curvature of the system remains essentially the same throughout the transition.

Hexagonal to Mesocellular Foam Phase Transition in Polymer-Templated Mesoporous Silicas

The acid-catalyzed synthesis of highly ordered mesostructured materials has led to a variety of twoand three-dimensional periodic symmetries, and has proven to be an effective route for the generation of fibers, spheres, thin films, and other monolithic forms of mesoporous materials. Zhao et al. recently used non-ionic poly(alkylene oxide) block copolymers, under acidic conditions, to prepare well-ordered, hexagonal mesoporous silica, denoted SBA-15, featuring uniform and adjustable large pore sizes combined with thick hydrothermally stable walls. The catalytic effect of fluoride in the synthesis of mesoporous silica at neutral to basic pH has been described by Voegtlin et al. Fluoride has been successfully used to extend the pH range over which anionic silica precursors can be utilized to create organized periodic structures; it has been used to diminish framework defects in zeolites, and to improve the organization in MCM-41 molecular sieves and MSU-X materials. However, to the best of our knowledge, no studies have been reported on the role of fluoride on cationic silica species in the aqueous acid-synthesis of ordered porous silica. In this communication, we describe the hierarchical ordering effects induced by small amounts of fluoride added during the synthesis of SBA-15-type mesoporous silica under acidic aqueous conditions. The non-ionic poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer EO20PO70EO20 (Pluronic P123) has been employed as the structure-directing agent. At low pH, remarkably well-ordered, hydrothermally stable, large hexagonal mesoporous silica rods with uniform channels extending over micrometer-sized length scales, and with few defects, have been synthesized. The fluoride-induced enhancement of order has enabled the preparation of SBA-15 materials at moderate acidity (~ pH 2.5±3) without compromising the long-range hexagonal symmetry. The mesoporous silicas possess narrow pore-size distributions, hydrothermally stable frameworks, large surface areas, and pore volumes of up to 0.92 cm/g. This work has been motivated by our interest in i) the patterning of mesoporous materials ranging from mesoscopic to macroscopic length scales while retaining molecular-level structural control and ii) understanding the underlying mechanism for the acid-catalyzed mesoporous silica synthesis. Addition of small amounts of fluoride (F:Si molar ratios of 0.008 and 0.03; fluoride source: NH4F or (NH4)2SiF6) during the aqueous acidic SBA-15-type silica synthesis induces substantial ordering that is manifested on different length scales: both the mesoscopic structure and the macroscopic morphology of the mesoporous silicas are significantly improved. Scanning electron microscopy (SEM) has revealed that small amounts of fluoride bring about the formation of large mesoporous silica rods (Fig. 1a) when pre-

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Patrick Schmidt-Winkel

Papers

Mesocellular siliceous foams with uniformly sized cells and windows

Microemulsion Templating of Siliceous Mesostructured Cellular Foams with Well-Defined Ultralarge Mesopores

Evaluating Pore Sizes in Mesoporous Materials: A Simplified Standard Adsorption Method and a Simplified Broekhoff−de Boer Method

Hexagonal to Mesocellular Foam Phase Transition in Polymer-Templated Mesoporous Silicas

Fluoride-Induced Hierarchical Ordering of Mesoporous Silica in Aqueous Acid-Syntheses