title: Photolysis of dibenzyl ketones sorbed on MFI zeolites in the presence of spectator molecules: cage effects, kinetics, and external surface sites characterization.
abstract: Over the past two decades, the photolytic reactions of dibenzyl ketones sorbed on zeolites have been investigated. The reported results are consistent with a supramolecular model that takes into account the physical and chemical nature of the structure of the zeolites and their effect on the reactive radical intermediates produced by photolysis of adsorbed molecules. The model incorporates various phenomena such as surface coverage, external and internal sorption, surface diffusion, radical sieving, and the resulting product distributions. This account reports direct evidence for the validation of the model through FT-IR spectroscopy and through a new method for "titrating" the binding sites via EPR spectroscopy. It is shown that it is possible to adjust and modulate the photolytic product distribution by varying the parameters of the system. The effects of co-adsorbed spectator molecules with different polarities, namely water, pyridine, and benzene, on the photolysis of o-methyldibenzyl ketone and dibenzyl ketone sorbed on MFI zeolites is examined. This study provides insights into a displacement mechanism caused by spectator molecules and further demonstrates how the product distribution of photolysis of sorbed ketones can be controlled. The kinetics of persistent radicals formed by photolysis of ketones sorbed on zeolites is directly monitored over time by EPR, providing a measure of the lifetime of these reactive organic intermediates. Finally, measurement of Langmuir isotherms was employed to provide classical evidence for the model.
authors.affiliation: Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Alberto
authors.initials: A
authors.lastname: Moscatelli
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Liu
authors.forename: Xuegong
authors.initials: X
authors.lastname: Lei
authors.forename: Joanne
authors.initials: J
authors.lastname: Dyer
authors.forename: Lloyd
authors.initials: L
authors.lastname: Abrams
authors.forename: M Francesca
authors.initials: MF
authors.lastname: Ottaviani
authors.forename: Nicholas J
authors.initials: NJ
authors.lastname: Turro
mesh_terms: D000327:Adsorption; D001593:Benzyl Compounds / Q000737:chemistry / Q000528:radiation effects; D001665:Binding Sites; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals / Q000737:chemistry; D007659:Ketones / Q000737:chemistry / Q000528:radiation effects; D007700:Kinetics; D008954:Models, Biological; D010782:Photolysis; D017550:Spectroscopy, Fourier Transform Infrared; D017641:Zeolites / Q000737:chemistry*
chemical_list: D001593:Benzyl Compounds; D005609:Free Radicals; D007659:Ketones; D017641:Zeolites