Analytical investigation of the chemical reactivity and stability of aminopropyl-grafted silica in aqueous medium

Various samples of aminopropyl-functionalized silica (APS) have been prepared by grafting an organosilane precursor 3-aminopropyl-triethoxysilane (APTES) onto the surface of silica gel. The amine group content of the materials has been adjusted by varying the amount of APTES in the reaction medium (toluene). The grafted APS solids have been characterized with using several analytical techniques (N-2 adsorption, X-ray photoelectron spectroscopy, infrared spectrometry) to determine their physico-chemical properties. Their reactivity in aqueous solutions was studied by acid-base titration, via protonation of the amine groups, and by way of complexation of these groups by Hg-II species. APS stability in aqueous medium was investigated at various pH and as a function of time, by the quantitative analysis of soluble Si- or amine-containing species that have been leached in solution upon degradation of APS. The chemical stability was found to increase when decreasing pH below the pK(a) value corresponding to the RNH3+/RNH2 couple, but very low pH values were necessary to get long-term stability because of the high local concentration of the amine groups in the APS materials. Adsorption of mercury(II) ions on APS was also performed to confirm the long-term stability of the grafted solid in acidic medium. Relationship between solution pH and APS stability was discussed. For sake of comparison, the stability of APS in ethanol and that of mercaptopropyl-grafted silica (NIPS) in water have been briefly considered and discussed with respect to practical applications of silica-based organic-inorganic hybrids, e.g., in separation science or in the field of electrochemical sensors. (C) 2003 Elsevier Science B.V. All rights reserved.