title: Surficial Siloxane-to-Silanol Interconversion during Room-Temperature Hydration/Dehydration of Amorphous Silica Films Observed by ATR-IR and TIR-Raman Spectroscopy.
abstract: Silica has been frequently studied using infrared and Raman spectroscopy due to its importance in many practical contexts where its surface chemistry plays a vital role. The majority of these studies have utilized chemical-vapor-deposited films in vacuo after high-temperature calcination. However, room-temperature hydration and dehydration of thin silica particle films has not been well characterized in spite of the importance of such films as substrates for polymer and surfactant adsorption. The present study has utilized ATR-IR spectroscopy and thin silica particle films exposed to varying humidity to clearly show reversible conversion between surface siloxanes and hydrogen-bonded silanols without the need for semiempirical peak deconvolution. The IR spectra from corresponding hydration experiments on deuterated silica films has confirmed the vibrational mode assignments. The variation of humidity over silica films formed from silica suspensions of differing pH gave IR spectra consistent with the change in the relative populations of siloxide to silanol surface groups. In addition, total internal reflection Raman spectroscopy has been used to provide further evidence of room-temperature dehydroxylation, with spectral evidence for the presence of three-membered siloxane rings when films are dehydrated under argon. The confirmation of room-temperature siloxane-to-silanol interconversion is expected to benefit understanding in many silica surface chemical contexts.
authors.affiliation: Department of Chemistry, University of Otago , P. O Box 56, Dunedin 9054, New Zealand.
authors.forename: Suzanne L
authors.initials: SL
authors.lastname: Warring
authors.affiliation: Future Industries Institute, University of South Australia , Mawson Lakes, Adelaide, SA 5095, Australia.
authors.forename: David A
authors.initials: DA
authors.lastname: Beattie
authors.affiliation: Department of Chemistry, University of Otago , P. O Box 56, Dunedin 9054, New Zealand.
authors.forename: A James
authors.initials: AJ
authors.lastname: McQuillan