Abstract
dc:description.abstractThe reaction of methanol with the nearly-stoichiometric and oxygen-terminated surfaces of Cr₂O₃ (101̅2) was studied using thermal desorption spectroscopy and x-ray photoelectron spectroscopy. Dissociative adsorption of methanol occurs on the nearly-stoichiometric surface and is attributed to the presence of cation/anion site-pairs. An array of products including CH₄, CH₂O, CO, CO₂, and H₂ are produced above 550 K on the nearly-stoichiometric surface. Monolayer coverage of methanol yields a 58% conversion to products. Of these products, selectivity to CO is the highest (41%), followed by CH₂O (28%), CH₄ (24%), and CO₂ (7%). At higher temperatures methoxides reversibly undergo dehydrogenation and nucleophilic from lattice oxygen to form dioxymethylene. Hydrogenation of methoxides leads to the formation of CH₄ and CH₃OH above 550 K. Formate is formed as a surface intermediate by reversible dehydrogenation of dioxymethylene. Formaldehyde is produced via C-O bond cleavage of dioxymethylene, and the decomposition of formate yields CO, CO₂, and H₂. The oxygen-terminated surface is unreactive for methanol dissociation due cation site blocking by terminal chromyl oxygen.
Degree
thesis:*- Name thesis:degree_name
- Master of Science
- Level thesis:degree_level
- masters
- Discipline thesis:degree_discipline
- Chemical Engineering
- Department dc:contributor.department
- Chemical Engineering
- Grantor dc:publisher
- Virginia Tech
- Year dc:date.issued
- 2003
Author and committee
dc:creator, dc:contributor.*- Author dc:creator
-
- Mensch, Michael W.
- Chair dc:contributor.committeechair
-
- Cox, David F.
- Committee members dc:contributor.committeemember
-
- Davis, Richey M.
- Oyama, Shigeo Ted
Subjects
dc:subject × 4Rights
dc:rights- Statement dc:rights
-
- In Copyright
- Licence dc:rights.uri
Identifiers
dc:identifier.*- Dc Identifier Other
- etd-03262003-111044
- OAI identifier oai:identifier
- oai:vtechworks.lib.vt.edu:10919/31546