Abstract
The rates of reaction of acetate species adsorbed on a range of Au/Pd(111) alloys with gas-phase ethylene to form vinyl acetate monomer (VAM) were explored by monitoring the time dependence of the adsorbate coverages using infrared spectroscopy. It was found that the acetate species react directly to form VAM since the decrease in the coverage of acetate species correlates directly with the rate of VAM formation. The VAM was retained on the surface, in accord with the stronger binding of VAM on Au/Pd(111) alloys than on the metal as found in previous surface science studies. In addition, the formation of ethylidyne species from ethylene, previously found on Pd(111), was suppressed on alloys for gold coverages ≥0.37 monolayers. A substantial increase in the rate of VAM formation was found with increasing gold coverage in the alloy. In addition to the strengthening of the binding of VAM on the alloy, the binding of the reactants decreased with increasing gold content in the alloy, leading to an overall increase in the exothermicity of the reaction. This is expected to lead to a decrease in reaction activation energies, rationalizing the observed increase in reactions rate. However, it has also been found previously that the reactant coverages influence the elementary step activation energies on Pd(111). Increasing the gold coverage in the alloy also decreases the coverages of the reactants and may therefore also influence the VAM formation activity.
Graphical Abstract
Similar content being viewed by others
References
Colling PM, Johnson LR, Nicolau I (1996) Palladium-gold catalyst for vinyl acetate production. In: U.S.P. Office (ed), Hoechst Celanese Corporation, United States
Horning L, Wunder F, Quadflieg T (1967) Process for preparing vinyl acetates. In: F.H.A.V.M.L. Bruning (ed), United States
Chen M, Kumar D, Yi C-W, Goodman DW (2005) Science 310:291–293
Han YF, Kumar D, Goodman DW (2005) J Catal 230:353–358
Stacchiola D, Calaza F, Burkholder L, Tysoe WT (2004) J Am Chem Soc 126:15384–15385
Stacchiola D, Calaza F, Burkholder L, Schwabacher AW, Neurock M, Tysoe WT (2005) Angew Chem Int Edit 44:4572–4574
Samanos B, Boutry P, Montarnal R (1971) J Catal 23:19–30
Calaza F, Stacchiola D, Neurock M, Tysoe WT (2010) J Am Chem Soc 132:2202–2207
Calaza F, Stacchiola D, Neurock M, Tysoe WT (2010) Catal Lett 138:135–142
Calaza F, Stacchiola D, Neurock M, Tysoe WT (2005) Surf Sci 598:263–275
Sinfelt JH (1983) Bimetallic catalysts: discoveries, concepts, and applications. Wiley, New York
Dowden DA, Reynolds PW (1950) Discuss Faraday Soc 8:184–190
Schwab G-M (1950) Discuss Faraday Soc 8:166–171
Sinfelt JH, Carter JL, Yates DJC (1972) J Catal 24:283–296
Woodruff DP (2002) Surface alloys and alloy surfaces. Elsevier, Amsterdam
Rodriguez J (1996) Surf Sci Rep 24:223–287
Gao F, Goodman DW (2012) Chem Soc Rev 41:8009–8020
Li Z, Furlong O, Calaza F, Burkholder L, Poon HC, Saldin D, Tysoe WT (2008) Surf Sci 602:1084–1091
Li Z, Gao F, Wang Y, Calaza F, Burkholder L, Tysoe WT (2007) Surf Sci 601:1898–1908
Boscoboinik JA, Plaisance C, Neurock M, Tysoe WT (2008) Phys Rev B 77
Calaza F, Gao F, Li Z, Tysoe WT (2007) Surf Sci 601:714–722
Yuan D, Gong X, Wu R (2008) J Phys Chem C 112:1539–1543
Yuan D, Gong X, Wu R (2007) Phys Rev B 75:233401
Calaza F, Li Z, Gao F, Boscoboinik J, Tysoe WT (2008) Surf Sci 602:3523–3530
Bowker M, Morgan C, Couves J (2004) Surf Sci 555:145–156
Bowker M, Morgan C, Zhdanov VP (2007) Phys Chem Chem Phys 9
Calaza F, Tysoe WT, Stacchiola DJ (2011) Adsorpt Sci Technol 29:603–611
Li Z, Gao F, Tysoe WT (2008) Surf Sci 602:416–423
Li Z, Calaza F, Gao F, Tysoe WT (2007) Surf Sci 601:1351–1357
Boscoboinik JA, Calaza FC, Garvey MT, Tysoe WT (2010) J Phys Chem C 114:1875–1880
Baddeley CJ, Tikhov M, Hardacre C, Lomas JR, Lambert RM (1996) J Phys Chem 100:2189–2194
Ormerod RM, Baddeley CJ, Lambert RM (1991) Surf Sci 259:L709–L713
James J, Saldin DK, Zheng T, Tysoe WT, Sholl DS (2005) Catal Today 105:74–77
Koestner RJ, Van Hove MA, Somorjai GA (1983) J Phys Chem 87:203–213
Kesmodel LL, Dubois LH, Somorjai GA (1978) Chem Phys Lett 56:267–271
Cremer PS, Su X, Shen YR, Somorjai GA (1996) J Am Chem Soc 118:2942–2949
Zaera F, Somorjai GA (1984) J Am Chem Soc 106:2288–2293
Stacchiola D, Tysoe WT (2009) J Phys Chem C 113:8000–8001
Moskaleva LV, Chen Z-X, Aleksandrov HA, Mohammed AB, Sun Q, Rösch N (2009) J Phys Chem C 113:2512–2520
Conrad H, Ertl G, Latta EE (1974) Surf Sci 41:435–446
Bligaard T, Nørskov JK, Dahl S, Matthiesen J, Christensen CH, Sehested J (2004) J Catal 224:206–217
Loffreda D, Delbecq F, Vigné F, Sautet P (2009) Angew Chem Int Ed 48:8978–8980
Logadottir A, Rod TH, Nørskov JK, Hammer B, Dahl S, Jacobsen CJH (2001) J Catal 197:229–231
van Santen RA, Neurock M (2006) Molecular heterogeneous catalysis: a conceptual and computational approach. Wiley-VCH, Weinheim
van Santen RA, Neurock M, Shetty SG (2009) Chem Rev 110:2005–2048
Rivalta I, Mazzone G, Russo N, Sicilia E (2009) J Chem Theory Comput 5:1350–1360
García-Mota MN, López NR (2008) J Am Chem Soc 130:14406–14407
G. Mazzone, I. Rivalta, N. Russo, E. Sicilia, Chem Commun, 0 (2009) 1852-1854
Acknowledgments
We gratefully acknowledge the support of this work by the National Science Foundation, under Grant number CHE-1109377.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Calaza, F., Li, Z., Garvey, M. et al. Reactivity and Selectivity in the Au/Pd(111) Alloy-Catalyzed Vinyl Acetate Synthesis. Catal Lett 143, 756–762 (2013). https://doi.org/10.1007/s10562-013-1042-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10562-013-1042-2