Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

能源化学(英文) ›› 2013, Vol. 22 ›› Issue (4): 671-679.

• Articles • 上一篇

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Bin Xing^a, Zizhang Wei^b, Guichang Wang^a

a. Department of Chemistry and the Center of Theory and Computational Chemistry, Nankai University, Tianjin 300071, China;
b. Tianjin Enviromental Engineering Assessment Center, Tianjin 300191, China

收稿日期:2012-04-25 修回日期:2012-06-05 出版日期:2013-07-20 发布日期:2013-07-27
通讯作者: Guichang Wang

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Bin Xing^a, Zizhang Wei^b, Guichang Wang^a

a. Department of Chemistry and the Center of Theory and Computational Chemistry, Nankai University, Tianjin 300071, China;
b. Tianjin Enviromental Engineering Assessment Center, Tianjin 300191, China

Received:2012-04-25 Revised:2012-06-05 Online:2013-07-20 Published:2013-07-27

摘要/Abstract

摘要： 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 DFT results showed that for VA synthesis, the ‘Samanos’ reaction mechanism (i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent β-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.

关键词: VA synthesis, Pd/Au(100), Pd/Au(111), acetate coverage effect, reaction mechanism, DFT calculations

Abstract: 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 DFT results showed that for VA synthesis, the ‘Samanos’ reaction mechanism (i.e., direct coupling of coadsorbed ethylene and acetate species and subsequent β-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.

Key words: VA synthesis, Pd/Au(100), Pd/Au(111), acetate coverage effect, reaction mechanism, DFT calculations

Bin Xing, Zizhang Wei, Guichang Wang. Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces[J]. 能源化学(英文), 2013, 22(4): 671-679.

Bin Xing, Zizhang Wei, Guichang Wang. Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces[J]. Journal of Energy Chemistry, 2013, 22(4): 671-679.

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Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

Acetate coverage effect on the reactivity of vinyl acetate synthesis on Pd/Au alloy surfaces

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