Functionalization of porous siliceous materials, Part 2: Surface characterization by inverse gas chromatography

Abstract

Surface modification of porous glass beads by ethanol-based 3-mercaptopropyltrimethoxysilane (MPTMS) grafting solutions is directly evidenced by nitrogen adsorption, elemental analysis, thermogravimetry, infrared and ²⁹Si CP MAS NMR spectroscopy. Furthermore, the energetic characterization of the surface is essential to understand comprehensively the physico-chemical interactions between the pristine and MPTMS-modified surface and its gas/liquid-phase environment. In this study, inverse gas chromatography (IGC) is used to characterize the surface properties of porous glass (PG). By means of IGC at infinite dilution (IGC-ID), the dispersive component of the surface energy (γ_s^d), the enthalpy and entropy of adsorption of C₆-C₁₀ hydrocarbon probes were determined at temperatures between 30 and 120 °C. The specific component of the surface energy (γ_s^sp) at the temperature of 120 °C has been obtained via the Van Oss theory and a least-squares procedure evaluating the IGC data of 8 polar probe molecules collectively. After surface silylation, the total surface energy (γ_s^t) decreased from 402 to 255 mJ/m² indicating both a reduced wettability and an increased hydrophobicity of the MPTMS-modified PG. Moreover, the acidity/basicity parameters according to the Van Oss and the Gutmann approach indicated that the acidity of the PG surface decreases by MPTMS grafting. Using n-octane and isopropanol probes, IGC at finite concentration (IGC-FC) was applied to obtain their adsorption isotherms and subsequently the BET specific surface areas. In addition, the surface heterogeneity of the studied PGs was also computed. The energy distribution functions of adsorption sites were monomodal (peak maximum at about 22 kJ/mol) for the n-octane probe, while isopropanol revealed a bimodal distribution function (maxima at about 18 and 25 kJ/mol) on both pristine and MPTMS-modified PG. Furthermore, the proportion of high energy sites (apparently assigned to SiOH groups) has been reduced by surface modification from 65% to only 35% despite a high surface coverage of ˜10 MPTMS species/nm². These findings are in agreement with the results of ²⁹Si CP MAS NMR measurements and are supported by DFT calculations on the adsorption of isopropanol and n-octane on the surface of a silica cluster model.

Keywords: 3-Mercaptopropyltrimethoxysilane; Inverse gas chromatography; Porous glass; Surface heterogeneity; Surface modification; Surface properties.