Abstract
Lewis acidic Sn centers isolated within Beta zeolite frameworks catalyze bimolecular ethanol dehydration to diethyl ether, yet with kinetic behavior sensitive to the hydrophobic character of their confining microporous voids. Sn sites in open ((HO)-Sn-(OSi)3) and closed (Sn-(OSi)4) configurations, quantified from infrared spectra of adsorbed CD3CN before and after reaction, convert to structurally similar intermediates during ethanol dehydration catalysis (404 K) and revert to their initial configurations after regenerative oxidation treatments (21% O2, 803 K). Dehydration rate data (404 K, 0.5–35 kPa C2H5OH, 0.1–50 kPa H2O) measured on ten low-defect (Sn-Beta-F) and high-defect (Sn-Beta-OH) zeolites were described by a rate equation that was derived from mechanisms identified previously by density functional theory calculations and simplified using microkinetic modeling to identify kinetically-relevant pathways and intermediates. Polar hydroxyl defect groups located in the microporous environments that confine Sn sites preferentially stabilize reactive (ethanol-ethanol) and inhibitory (ethanol-water) dimeric intermediates over monomeric ethanol intermediates. As a result, equilibrium constants (404 K) for ethanol-water and ethanol-ethanol dimer formation are 3–4× higher on Sn-Beta-OH than on Sn-Beta-F, consistent with insights from single-component (302 K) and two-component (303 K, 403 K) ethanol and water adsorption measurements. Intrinsic dehydration rate constants (404 K) were identical, within error, among Sn-Beta-OH and Sn-Beta-F zeolites; thus, measured differences in dehydration turnover rates solely reflect differences in prevalent surface coverages of inhibitory and reactive dimeric intermediates at active Sn sites. The confinement of Lewis acidic binding sites within secondary microporous environments of different defect density confers the ability to discriminate surface intermediates on the basis of polarity, providing a design strategy to accelerate turnover rates and suppress inhibition by water.
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