Interaction of Silanol Species on Silica Surface with Hydrogen Bonding Agents Studied by Photoacoustic Spectroscopy

"The interaction of amorphous silica particles with several hydrogen bonding agents (H2O,, C2H,OH, C,H,NO) was investigated by monitoring the changes in the bulk and surface IR vibrational modes of silica using photoacoustic spectroscopy, It is argued that the intensity of the silanol band at 3747 cm-1 provides (an inverse) quantitative measure of the interaction of surface groups, along with the shift in the broad hydroxyl band, the interaction following the order C,H,NO > C2H2OH > H2O.The use of IR spectroscopy to study the adsorption on solid surfaces is well documented in the literature,"" For example, hydroxylation of a clean silica surface results in the formation of the free silanol group Si-OH, with a sharp IR band near 3747 cm-1. Further hydroxylation produces a broad band near 3500 cm-1, which is believed to result from various hydrogen-bonded silanol bands leading to a multilayered surface structure of few nm.3-6 Earlier studies had indicated a relationship between the surface silanol band and various chemical activities of silica such as cytotoxicity,7-9 catalysis,10-12 and others.13 Recent studies from our group14-in which the intensity of the silanol band and cytotoxicity of silica, heat-treated at various temperatures up to 1095°C, were investigated-have provided a strong correlation between cytotoxicity and intensity of the silanol band.Coating of silica by PVPNO (polyvinyl-2-pyridine N-oxide with the empirical formula C7H8N0), a strong hydrogen bonding agent, is known to reduce the cytotoxicity of silica, presumably by chemically blocking the silanol groups from phospholipids.15 This interaction of the hydrogen bonding agents with the silica can be studied by IR spectroscopy, and Knozinger16 and Rouxlet and Semples17 have used transmission IR spectroscopy to study the effect of various chemicals on the surface IR modes of silica. However, one of the major disadvantages of transmission IR spectroscopy is that the sample preparation (grinding and mixing with KBr and pelletizing) usually distorts the surface modes (see, e.g., Ref. 14) and there is always a doubt about the effect of the sample preparation on the measured properties, In recent years, photoacoustic (PA) spectroscopy has become the technique of choice for studying the IR spectra of samples in their natural state, since no sample preparation is necessary.18,19 Moreover, according to a recent paper,20 the relative intensity of the surface modes in PA spectroscopy of silica particles is much higher than that in transmission FT-IR spectroscopy. Consequently PA spectroscopy is ideal for studying the surface chemistry, In this work, we have used PA spectroscopy to investigate the interaction of three hydrogen bonding agents (C7H8NO, C2H5OH, and H20) with the silica surface by monitoring changes in the surface IR modes, Our results show that the surface IR modes get perturbed to a larger extent than the bulk IR modes in interaction with the hydrogen bonding agents, Moreover, whereas in the earlier studies, the shift of the broad silanol band near 3500 cm-1 was used as a measure of the interaction with hydrogen bonding agents,16,17 here we show that the relative decrease in the intensity of the sharp silanol band near 3747 cm-1 also serves as a quantitative parameter for the relative surface coverage and surface modification, Details of this work are given below,The Cab-O-Sil samples of silica used here were obtained from the Cabot Corporation of Tuscola, IL, In our earlier studies,14,20 we have shown these particles to be amorphous and about 0.05 am in size, For coverage of these particles with H20 and C2H50H, the following procedure was employed. About 5 mg of silica was mixed with 50 mL of the liquid (H2O or C2H5OH) and refluxed for one hour, The remaining liquid was allowed to evap¬orate to dryness and 1 mg of the treated sample was used to collect the PA spectra. In the case of PVPNO, the amount that binds to Cab-O-Sil is taken from the data on quar"