Michael Grün

Novel pathways for the preparation of mesoporous MCM-41 materials: control of porosity and morphology

Two novel synthesis routes for the preparation of mesoporous MCM-41 materials are introduced. Both methods use tetra-n-alkoxysilanes such as tetraethoxysilane (TEOS) or tetra-n-propoxysilane (TPS) as a silica source which are added to an aqueous solution of a cationic surfactant in the presence of ammonia as catalyst. In this study, n-alkyltrimethylammonium bromides and n-alkylpyridinium chlorides were employed as templates. The addition of an alcohol (e.g. ethanol or isopropanol) leads to a homogeneous system which allows the formation of spherical MCM-41 particles. The main advantages of these methods are short reaction times, excellent reproducibility and easy preparation of large batches.

Comparison of an ordered mesoporous aluminosilicate, silica, alumina, titania and zirconia in normal-phase high-performance liquid chromatography

This paper investigates the behaviour of silica, alumina, titania, zirconia and the novel mesoporous aluminosilicate MCM-41 in normal-phase high-performance liquid chromatography under comparable conditions. The physicochemical properties of the oxides and MCM-41 are described. MCM-41 is an ordered mesoporous material with a regular pore structure composed of an assembly of hexagonal tubes with a pore diameter of 4 nm. In chromatography MCM-41 exhibits acid and basic properties and proves to be suitable for the separation of acid, neutral and basic compounds.

Synthesis of spherical porous silicas in the micron and submicron size range: challenges and opportunities for miniaturized high-resolution chromatographic and electrokinetic separations

Classical silica technology has reached its limit with respect to an ultimate minimum particle size of about 2 microm in diameter. Here, a novel process is presented which allows one to synthesize porous silica beads and control their particle diameter in situ, within the range of 0.2-2.0 microm. As a result, no sizing is required and losses of silica are avoided. Furthermore, the process enables one to control in situ the pore structural parameters and the surface chemistry of the silica beads. Even though surface funtionalized silicas made according to this process can principally be applied in fast HPLC the column pressure drop will be high even for short columns. In addition, the column efficiency, expressed in terms of the theoretical plate height is about H-2d(p) in the best case and limited by the A and C term of the Van Deemter equation. In other words the gain in total plate number when using 1-2 microm silica beads in short columns is minimal as compared to longer columns packed with 5 microm particles. Capillary electrochromatography (CEC) as a hybrid method enables the application of micron size as well as submicron size particles. This consequently enhances column efficiency by a factor of 5-10 when compared to HPLC. The use of short CEC columns packed with submicron size silicas provides the basis for fast and efficient miniaturized systems. The most significant feature of CEC as compared to HPLC is that the former allows one to resolve polar and ionic analytes in a single run. An alternative method for miniaturization is capillary electrophoresis (CE) which generates extremely high efficiencies combined with fast analysis. Its application, however, is limited to ionic substances.

Tailored syntheses of nanostructured silicas: Control of particle morphology, particle size and pore size

Ordered mesoporous silicas with spherical morphology and average particle size in the range between 100 nm and 2 μm were synthesised according to two novel routes. Both synthesis routes used tetraethoxysilane, water, alcohol and aqueous ammonia for producing spherical silica beads. The porosity was created by adding two different kinds of pore structure directing agents to the starting solution: one was an n-alkyltrialkoxysilane which was covalently bonded to the silica framework, the other was an n-alkylamine which acted as a nonionic template. After calcination and post treatment the resulting particles showed a specific surface area up to 1000 m2 g-1, a specific pore volume of up to 0.8 cm3g-1 and an average pore diameter between 2 and 6 nm.

Critical Appraisal of the Pore Structure of MCM-41

Purely siliceous and aluminosilicate types of MCM-41 were synthesized and characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen sorption (NS) and size exclusion chromatography (SEC).