Bogna E. Grabicka

Effective method for removal of polymeric template from SBA-16 silica combining extraction and temperature-controlled calcination

An effective method for the removal of polymeric template, which combines extraction and temperature-controlled calcination, is proposed to obtain high pore volume and large pore size ordered mesoporous silicas, SBA-16 (Im3m symmetry group), synthesized in the presence of sodium chloride at low acid concentrations using poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (Pluronic F127) as a structure directing agent and tetraethylorthosilicate as a silica source. The aforementioned materials were characterized by small angle X-ray powder diffraction, nitrogen adsorption, high resolution thermogravimetry and elemental analysis.

Effect of polymer-to-silica ratio on the formation of large three-dimensional cage-like mesostructures

This work shows the influence of polymer-to-silica ratio on the formation of cage-like ordered mesoporous silica, FDU1, having a three-dimensional face-centered cubic symmetry. The FDU1 samples studied were synthesized from tetraethyl orthosilicate (TEOS) under acidic conditions in the presence of poly(ethylene oxide)–poly(butylene oxide)–poly(ethylene oxide) (EO39BO47EO39) triblock copolymer. The molar ratio of triblock copolymer to TEOS in the reaction mixture was varied from 0.0037 to 0.0148. Small angle X-ray scattering, argon adsorption–desorption and high resolution thermogravimetry studies indicate that an optimal EO39BO47EO39/TEOS ratio, which led to a high-quality FDU1 material with uniform cage openings, narrow pore size distribution and high specific surface area, was about 0.0074. The FDU1 silicas obtained for lower and higher ratios than the aforementioned value possessed non-uniform cage entrances, broader pore size distributions, lower BET specific surface areas and smaller mesopore diameters.

Post-synthesis surface-modified silicas as adsorbents for heavy metal ion contaminants Cd(II), Cu(II), Cr(III), and Sr(II) in aqueous solutions.

To analyze the influence of silica surface modification and confined space effects on specific interactions of divalent and trivalent metal cations with surface functionalities, three different high surface area silicas with different pore size distributions were modified with the following organosilanes: 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, 3-(trimethoxysilylpropyl)diethylenetriamine, N-(triethoxysilylpropyl)ethylenediaminetriacetic acid (EDTrA), and 3-(2,4-dinitrophenylamino)propyltriethoxysilane. The silicas were characterized by N(2) adsorption and reflectance FTIR spectroscopy before and after surface modification. N(2) adsorption and pore size distributions showed an increase in the pore width for all EDTrA-modified silicas, opposite to what occurred with the other organosilanes. Adsorption isotherms of Cd(II), Cr(III), Cu(II), and Sr(II) obtained from aqueous solutions were compared and analyzed by silica type, organosilane functional group, and metal adsorbed. Reflectance FTIR spectroscopy was used to probe the acetate functionality in EDTrA as a function of adsorbed metal content. A band shift to higher energy for Cr(III) on the wide pore silica studied indicated that the interaction with the acetate groups can be probed in this manner. In general, the wider pore distribution silica provided larger adsorption maxima, whereas the narrower pore distribution silica provided more favorable ΔG because of stronger binding of the cations. Cr(III) and Cu(II) exhibited larger adsorption maxima compared to Cd(II) and Sr(II), with the grafted organosilanes studied since the first cations have a greater charge/radius ratio than the second ones that provide a greater binding energy.

Effects of Hydrothermal Treatment and Template Removal on the Adsorption and Structural Properties of SBA-16 Mesoporous Silica

The evolution of the adsorption and structural properties of large-pore SBA-16 silica samples was studied in relation to hydrothermal treatment and template removal procedures. These samples were synthesized using the poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer Pluronic F127 as the structure-directing agent and tetraethyl orthosilicate as the silica source in the presence of hydrochloric acid (low concentration) and sodium chloride under various hydrothermal treatment conditions. The concomitant use of the recently reported two-step template removal procedure, which combines solvent extraction and low-temperature calcination, afforded the SBA-16 samples with large pore volumes, high surface areas, uniform cages and uniform cage openings as demonstrated by nitrogen and argon adsorption isotherms measured at −196°C. Small-angle X-ray diffraction spectra confirmed the existence of the Im3m symmetry group (body-centred cubic pore structure) for the samples studied. The efficiency of the aforementioned template removal method was confirmed via thermogravimetric analysis.

Tailoring cage-like organosilicas with multifunctional bridging and surface groups

Monofunctional and bifunctional cubic silicas with cage-like structure (FDU-1) containing surface and bridging groups were prepared by one-pot synthesis route using various organosilanes such as tetraethyl orthosilicate (TEOS) along with ureidopropyltrimethoxysilane (UP), 3-mercaptopropylsilane (MP) and bis(triethoxysilylpropyl)disulfide (DS). The aforementioned mesostructures were characterized by X-ray diffraction, N 2 adsorption and elemental analysis.