The nature of the active site for vinyl acetate synthesis over Pd–Au

• Published in: Catalysis today 2006-09, Vol.117 (1), p.37-45
• Main Authors: Chen, M.S., Luo, K., Wei, T., Yan, Z., Kumar, D., Yi, C.-W., Goodman, D.W.
• Format: Article
• Language: English
• Subjects: Acetic acid; Active ensemble; Bimetal; Catalysis; Chemistry; Ethylene; Exact sciences and technology; General and physical chemistry; Gold; Palladium; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Vinyl acetate
• ISSN: 0920-5861; 1873-4308
• DOI: 10.1016/j.cattod.2006.05.001

The surface composition of a Pd–Au alloy was determined using low energy ion scattering spectroscopy (LEISS). A stable surface composition was found between 700 and 1000 K with substantial enrichment in Au compared to the bulk. Infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) were used to investigate the surface adsorption sites and ensembles. The isolated Pd sites, PdAu 6 for Pd–Au on Mo(1 1 0) and for Pd/Au(1 1 1), and PdAu 4 for Pd/Au(1 0 0), were observed by controlling the Pd amount and the annealing temperature. Acetoxylation of ethylene to vinyl acetate (VA) was used to investigate the mechanism of the promotional effect of Au in a Pd–Au alloy catalyst. The enhanced rates of VA formation for low Pd coverages relative to high Pd coverages on Au single crystal surfaces demonstrate that the critical reaction site for VA synthesis consists of two, non-contiguous, suitably spaced Pd monomers. The results show that the role of Au is to isolate single Pd sites that facilitate the coupling of critical surface species to product while inhibiting the formation of undesirable reaction by-products.