title: Specificity of sites within eight-membered ring zeolite channels for carbonylation of methyls to acetyls.
abstract: The acid-catalyzed formation of carbon-carbon bonds from C1 precursors via CO insertion into chemisorbed methyl groups occurs selectively within eight-membered ring (8-MR) zeolite channels. This elementary step controls catalytic carbonylation rates of dimethyl ether (DME) to methyl acetate. The number of O-H groups within 8-MR channels was measured by rigorous deconvolution of the infrared bands for O-H groups in cation-exchanged and acid forms of mordenite (M,H-MOR) and ferrierite (H-FER) after adsorption of basic probe molecules of varying size. DME carbonylation rates are proportional to the number of O-H groups within 8-MR channels. Na+ cations selectively replaced protons within 8-MR channels and led to a disproportionate decrease in carbonylation turnover rates (per total H+). These conclusions are consistent with the low or undetectable rates of carbonylation on zeolites without 8-MR channels (H-BEA, H-FAU, H-MFI). Such specificity of methyl reactivity upon confinement within small channels appears to be unprecedented in catalysis by microporous solids, which typically select reactions by size exclusion of bulkier transition states.
authors.affiliation: Department of Chemical Engineering, University of California at Berkeley, Berkeley, California 94720, USA.
authors.forename: Aditya
authors.initials: A
authors.lastname: Bhan
authors.forename: Ayman D
authors.initials: AD
authors.lastname: Allian
authors.forename: Glenn J
authors.initials: GJ
authors.lastname: Sunley
authors.forename: David J
authors.initials: DJ
authors.lastname: Law
authors.forename: Enrique
authors.initials: E
authors.lastname: Iglesia