Abstract
On the basis of Langmuir–Hinshelwood mechanism, with density functional theory method, all the dehydrogenation reactions in both Samanos mechanism and Moiseev mechanism in acetoxylation of ethylene to vinyl acetate, i.e., the dehydrogenation of ethylene, acetic acid and hydrogenated vinyl acetate (VAH), on Pd/Au(100) surface consisting of two diagonal Pd atoms were taken into consideration to examine the influence of surface oxygen atoms and hydroxyl groups on these dehydrogenation reactions. Besides, the corresponding adsorption of relevant species was investigated and the energetics of the dehydrogenation reactions was compared. Our calculations show that the surface Os kinetically facilitate ethylene dehydrogenation, but surface OHs kinetically inhibit ethylene dehydrogenation; the surface Os and OHs can kinetically facilitate acetic acid dehydrogenation, while they are kinetically unpreferable for VAH dehydrogenation; both surface Os and OHs are thermodynamically favored for the dehydrogenation of ethylene, acetic acid and VAH.
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References
Rase HF (2000) Handbook of commercial catalysts: heterogeneous catalysts. Boca Raton: CRC Press LLC
Moiseev I, Vargaftik M, Syrhim YK (1960) About the mechanism of the reaction between palladium and alkenes in hydroxyl containing solvents. Dokl Akad Nauk USSR 133:377–380
Abel R, Collins P, Eichler K, Nicolau I, Peters D (1997) Ocyacetylation: vinyl acetate from ethylene. In: Ertl G, Knozinger H, Weitkamp J (eds) Handbook of heterogeneous catalysis. Wiley-VCH, Weinheim, pp 2298–2301
Macleod N, Keel JM, Lambert RM, (2004) Appl Catal A 261:37–46
Dowden DA, Reynolds PW (1950) Discuss Faraday Soc 8:184–190
Schwab GM (1950) Discuss Faraday Soc 8:166–171
Sinfelt JH (1983) Bimetallic catalysts: discoveries, concepts, and applications. Wiley, New York
Han YF, Kumar D, Sivadinarayana C, Clearfield A, Goodman DW (2004) Catal Lett 94:131–134
Nakamura S, Yasui T (1970) J Catal 17:366–374
Provine WD, Mills PL, Lerou JJ (1996) Discovering the role of Au and KOAc in the catalysis of vinyl acetate synthesis. In: Joe WNDEI, Hightower W, Alexis TB (eds) Studies in surface science and catalysis, vol 101. Elsevier, Amsterdam, pp 191–200
Neurock M, Tysoe WT (2013) Top Catal 56:1314–1332
Calaza F, Mahapatra M, Neurock M, Tysoe WT (2014) J Catal 312:37–45
Han Y F, Wang JH, Kumar D, Yan Z, Goodman DW, (2005) J Catal 232:467–475
Han YF, Kumar D, Sivadinarayana C, Goodman DW (2004) J Catal 224:60–68
Chen M S, Kumar D, Yi CW, Goodman DW (2005) Science 310:291–293
Kumar D, Chen MS, Goodman DW, (2007) Catal Today 123:77–85
Baiker A, Blaser HU, Ertl G, Knözinger H, Weitkamp J (1997) Handbook of heterogeneous catalysis. Wiley-VCH, Weinheim, pp 974–980
Samanos B, Boutry P, Montarnal R, (1971) J Catal 23:19–30
Neurock M (2003) J Catal 216:73–88
Stacchiola D, Calaza F, Burkholder L, Schwabacher AW, Neurock M, Tysoe WT (2005) Angew Chem Int Ed 44:4572–4574
Li ZJ, Gao F, Tysoe WT (2008) Surf Sci 602:416–423
Calaza F, Stacchiola D, Neurock M, Tysoe WT (2010) J Am Chem Soc 132:2202–2207
Kumar D, Han YF, Chen MS, Goodman DW (2006) Catal Lett 106:1–5
Hammer B, Hansen LB, Nørskov JK (1999) Phys Rev B 59:7413–7421
Monkhorst HJ, Pack JD (1976) Phys Rev B 13:5188–5192
Govind N, Petersen M, Fitzgerald G, King-Smith D, Andzelm J (2003) Comput Mater Sci 28:250–258
Yuan D, Gong X, Wu R (2008) J Phys Chem C 112:1539–1543
Garcia-Mota M, Lopez N (2008) J Am Chem Soc 130:14406–14407
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Huang, Y., Dong, X. & Yu, Y. The Influence of Surface Oxygen and Hydroxyl Groups on the Dehydrogenation of Ethylene, Acetic Acid and Hydrogenated Vinyl Acetate on Pd/Au(100): A DFT Study. Catal Lett 146, 2516–2533 (2016). https://doi.org/10.1007/s10562-016-1886-3
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DOI: https://doi.org/10.1007/s10562-016-1886-3