In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst
Millar, Graeme J., Metson, James B., Bowmaker, Graham A., & Cooney, Ralph P. (1995) In situ Raman studies of the selective oxidation of methanol to formaldehyde and ethene to ethylene oxide on a polycrystalline silver catalyst. Journal of the Chemical Society, Faraday Transactions, 91(22), pp. 4149-4159.
The combined techniques of in situ Raman microscopy and scanning electron microscopy (SEM) have been used to study the selective oxidation of methanol to formaldehyde and the ethene epoxidation reaction over polycrystalline silver catalysts. The nature of the oxygen species formed on silver was found to depend critically upon the exact morphology of the catalyst studied. Bands at 640, 780 and 960 cm-1 were identified only on silver catalysts containing a significant proportion of defects. These peaks were assigned to subsurface oxygen species situated in the vicinity of surface dislocations, AgIII=O sites formed on silver atoms modified by the presence of subsurface oxygen and O2 - species stabilized on subsurface oxygen-modified silver sites, respectively. The selective oxidation of methanol to formaldehyde was determined to occur at defect sites, where reaction of methanol with subsurface oxygen initially produced subsurface OH species (451 cm-1) and adsorbed methoxy species.
Two distinct forms of adsorbed ethene were identified on oxidised silver sites. One of these was created on silver sites modified by the interaction of subsurface oxygen species, and the other on silver crystal planes containing a surface coverage of atomic oxygen species. The selective oxidation of ethene to ethylene oxide was achieved by the reaction between ethene adsorbed on modified silver sites and electrophilic AgIII=O species, whereas the combustion reaction was perceived to take place by the reaction of adsorbed ethene with nucleophilic surface atomic oxygen species. Defects were determined to play a critical role in the epoxidation reaction, as these sites allowed the rapid diffusion of oxygen into subsurface positions, and consequently facilitated the formation of the catalytically active AgIII=O sites.
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|Item Type:||Journal Article|
|Keywords:||silver, catalyst, formaldehyde, ethylene oxide, Raman|
|Subjects:||Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000) > PHYSICAL CHEMISTRY (INCL. STRUCTURAL) (030600) > Catalysis and Mechanisms of Reactions (030601)|
|Divisions:||Current > Schools > School of Chemistry, Physics & Mechanical Engineering
Current > Institutes > Institute for Future Environments
Current > QUT Faculties and Divisions > Science & Engineering Faculty
|Deposited On:||25 Aug 2013 23:32|
|Last Modified:||25 Aug 2013 23:32|
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