Abstract
The reaction of linear primary alcohols over CuO/ZnO/Al 2O 3 was studied under nitrogen and under carbon monoxide at 285 °C and 1 to 65 atm. The principal products for alcohols with n carbon atoms were, in addition to the corresponding aldehydes, esters with 2 n carbon atoms, ketones with 2 n carbon atoms, and ketones with 2 n−1 carbon atoms. Under nitrogen the esters predominated, but under 65 atm of carbon monoxide the principal condensation products were ketones with 2 n carbon atoms. Isotopic labeling studies showed that carbon from CO was not incorporated into the esters and ketones, that oxygen, on the other hand, was exchanged between CO and the reaction products, and that the ketones were formed by an aldol-type mechanism. The changes in selectivity observed under carbon monoxide are attributed to changes in the catalyst surface resulting from the removal of lattice oxygen by the CO and the formation of oxygen vacancies.
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