Vinyl acetate （VA） synthesis on Pd/Au（111） and Pd/Au（100） surfaces has been systematically investigated through first-principles density functional theory （DFT） calculations. The DFr results showed that for VA...Vinyl acetate （VA） synthesis on Pd/Au（111） and Pd/Au（100） surfaces has been systematically investigated through first-principles density functional theory （DFT） calculations. The DFr results showed that for VA synthesis, the ＇Samanos＇ reaction mechanism （i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent/%hydride elimination to form VA） is more favorable than the ＇Moiseev＇ mechanism （i.e., ethylene first dehydrogenates to form vinyl species which then couple with the coadsorbed acetate species to form VA）. More importantly, it was found the surface coverage of acetate has a significant effect on the reactivity of VA synthesis, and the activation energy of the rate- controlling step on Pd/Au（100） surface is smaller than that on Pd/Au（111） surface （0.88 vs. 0.95 eV）, indicating the former is more active than the latter.展开更多
基金supported by the State Key Program of Natural Science of Tianjin (Grant No. 13JCZDJC26800)the foundation of State Key Laboratory of Coal Conversion (Grant No. J13-14-908)
文摘Vinyl acetate （VA） synthesis on Pd/Au（111） and Pd/Au（100） surfaces has been systematically investigated through first-principles density functional theory （DFT） calculations. The DFr results showed that for VA synthesis, the ＇Samanos＇ reaction mechanism （i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent/%hydride elimination to form VA） is more favorable than the ＇Moiseev＇ mechanism （i.e., ethylene first dehydrogenates to form vinyl species which then couple with the coadsorbed acetate species to form VA）. More importantly, it was found the surface coverage of acetate has a significant effect on the reactivity of VA synthesis, and the activation energy of the rate- controlling step on Pd/Au（100） surface is smaller than that on Pd/Au（111） surface （0.88 vs. 0.95 eV）, indicating the former is more active than the latter.
