title: Processing of surfactant templated nano-structured silica films using compressed carbon dioxide as interpreted from in situ fluorescence spectroscopy.
abstract: The local environment and dynamics of compressed carbon dioxide (CO(2)) penetration in surfactant templated silica film synthesis is interpreted from the in situ fluorescence emission spectra of pyrene (Py) and a modified pyrene probe. Pyrene emission in cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) templated silica films is monitored immediately after casting and during processing with gaseous and supercritical (sc) CO(2) (17-172 bar, 45 °C). The solvatochromic emission spectra of pyrene in CTAB templated films suggest CO(2) penetration in both the micelle interface and its interior. An anchored derivative of pyrene, 1-pyrenehexadecanoic acid (C(16)-pyr), is established for probing CPB films, where the pyrene moiety is preferentially oriented toward the micelle interior, thus limiting quenching by the pyridinium headgroup of CPB. CO(2) processing of CPB templated silica films results in an increase in the time scale for probe mobility, suggesting an increased time scale of silica condensation through CO(2) processing. The mobility of C(16)-pyr increases with pressure from gaseous to sc CO(2) processing and persists for over 5 h for sc CO(2) processing at 172 bar and 45 °C compared to about 25 min for the unprocessed film. The delivery of CO(2) soluble solutes to specific regions of surfactant templated mesoporous materials is examined via the nonradiative energy transfer (NRET) between pyrene and CO(2)-solubilized naphthalene.
authors.affiliation: Department of Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky 40506-0046, USA.
authors.forename: Kaustav
authors.initials: K
authors.lastname: Ghosh
authors.forename: Stephen E
authors.initials: SE
authors.lastname: Rankin
authors.forename: Hans-Joachim
authors.initials: HJ
authors.lastname: Lehmler
authors.forename: Barbara L
authors.initials: BL
authors.lastname: Knutson
mesh_terms: D002245:Carbon Dioxide / Q000737:chemistry*; D008823:Micelles; D008958:Models, Molecular; D015394:Molecular Structure; D049329:Nanostructures / Q000737:chemistry*; D011721:Pyrenes / Q000737:chemistry; D012822:Silicon Dioxide / Q000138:chemical synthesis / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013501:Surface-Active Agents / Q000737:chemistry*
chemical_list: D008823:Micelles; D011721:Pyrenes; D013501:Surface-Active Agents; D002245:Carbon Dioxide; D012822:Silicon Dioxide; C030984:pyrene