{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/23229"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/23229","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"In situ studies of the binding and reactivity of small molecules at metal electrode surfaces","abstract":"This thesis encompasses several studies of the behavior of aromatic molecules on Au(111) single crystal electrode surfaces. In the first study, the initial stages of the binding and oxidation of phenol at high pH were addressed. Phenoxide binds to the electrode surface through the oxygen atom and is tilted away from the surface normal prior to oxidation, as shown with surface infrared spectroscopy (IR). The phenoxide forms a $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). At the onset of oxidation, the molecule reorients to lie with the ring relatively parallel to the electrode surface as it polymerizes. Oligomers have been observed with scanning tunneling microscopy (STM).","abstract_html":"This thesis encompasses several studies of the behavior of aromatic molecules on Au(111) single crystal electrode surfaces. In the first study, the initial stages of the binding and oxidation of phenol at high pH were addressed. Phenoxide binds to the electrode surface through the oxygen atom and is tilted away from the surface normal prior to oxidation, as shown with surface infrared spectroscopy (IR). The phenoxide forms a $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). At the onset of oxidation, the molecule reorients to lie with the ring relatively parallel to the electrode surface as it polymerizes. Oligomers have been observed with scanning tunneling microscopy (STM).","abstract_has_math":true,"creators":["Richard, Katherine Marie"],"institution":"University of Illinois at Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Gewirth, Andrew A."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":1996,"date_issued":"1996","date_published":"1996","updated_at":"2026-07-22T22:25:21Z","subjects":["Chemistry, Analytical","Chemistry, Inorganic","Chemistry, Physical"],"languages":["eng"],"rights":["Copyright 1996 Richard, Katherine Marie"],"rights_urls":[],"identifier_entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088373","AAI9702652","(UMI)AAI9702652"],"render_values":[{"text":"9780591088373","href":null,"code":true},{"text":"AAI9702652","href":null,"code":true},{"text":"(UMI)AAI9702652","href":null,"code":true}]}]},"links":{"outbound_url":"http://hdl.handle.net/2142/23229","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Gewirth, Andrew A."]},{"key":"dc:creator","label":"Author","values":["Richard, Katherine Marie"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["1996","10000-01-01","2011-05-07T14:06:45Z"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["Dissertation"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Ph.D."]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["University of Illinois at Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry, Analytical","Chemistry, Inorganic","Chemistry, Physical"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 1996 Richard, Katherine Marie"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["9780591088373","AAI9702652","(UMI)AAI9702652","http://hdl.handle.net/2142/23229"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["This thesis encompasses several studies of the behavior of aromatic molecules on Au(111) single crystal electrode surfaces. In the first study, the initial stages of the binding and oxidation of phenol at high pH were addressed. Phenoxide binds to the electrode surface through the oxygen atom and is tilted away from the surface normal prior to oxidation, as shown with surface infrared spectroscopy (IR). The phenoxide forms a $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). At the onset of oxidation, the molecule reorients to lie with the ring relatively parallel to the electrode surface as it polymerizes. Oligomers have been observed with scanning tunneling microscopy (STM).","The continued oxidation of phenol and 2-naphthol was monitored with atomic force microscopy (AFM) and surface IR. The morphology of the growing polymer was found to depend on the constituent monomer.","The impact of ring substitution on the binding and reactivity of cyanophenols was studied using STM and surface IR. Cyanophenols substituted in the 2 or 4 position displayed an inhibition of oxidation, while 3-cyanophenol oxidized at a similar rate to phenol. Only 4-cyanophenol was found to form an ordered $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). Steric repulsions between the molecules prevented 2- and 3-cyanophenol from forming ordered adlayers.","Finally, the adsorption of uracil on Au(111) was studied while varying concentration and pH. At neutral pH values, uracil displays strongly concentration-dependent behavior. At higher concentrations, the voltammetry displays sharp peaks which are associated with phase transitions. IR data indicates that uracil binds flat to the electrode at neutral pH. In alkaline solutions, the concentration-dependence of the adsorption is less marked, but IR data indicates that the molecule binds on-edge when it is deprotonated.","Made available in DSpace on 2011-05-07T14:06:45Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702652.pdf: 4675782 bytes, checksum: f82a34528878acb421354d598855258f (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:03:03Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:30:02-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"]},{"key":"dc:title","label":"Title","values":["In situ studies of the binding and reactivity of small molecules at metal electrode surfaces"]}]}],"canonical_facts":{"dc:contributor":["Gewirth, Andrew A."],"dc:creator":["Richard, Katherine Marie"],"dc:date":["1996","10000-01-01","2011-05-07T14:06:45Z"],"dc:description":["This thesis encompasses several studies of the behavior of aromatic molecules on Au(111) single crystal electrode surfaces. In the first study, the initial stages of the binding and oxidation of phenol at high pH were addressed. Phenoxide binds to the electrode surface through the oxygen atom and is tilted away from the surface normal prior to oxidation, as shown with surface infrared spectroscopy (IR). The phenoxide forms a $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). At the onset of oxidation, the molecule reorients to lie with the ring relatively parallel to the electrode surface as it polymerizes. Oligomers have been observed with scanning tunneling microscopy (STM).","The continued oxidation of phenol and 2-naphthol was monitored with atomic force microscopy (AFM) and surface IR. The morphology of the growing polymer was found to depend on the constituent monomer.","The impact of ring substitution on the binding and reactivity of cyanophenols was studied using STM and surface IR. Cyanophenols substituted in the 2 or 4 position displayed an inhibition of oxidation, while 3-cyanophenol oxidized at a similar rate to phenol. Only 4-cyanophenol was found to form an ordered $\\rm(\\surd3\\times\\surd3)R30\\sp\\circ$ overlayer on Au(111). Steric repulsions between the molecules prevented 2- and 3-cyanophenol from forming ordered adlayers.","Finally, the adsorption of uracil on Au(111) was studied while varying concentration and pH. At neutral pH values, uracil displays strongly concentration-dependent behavior. At higher concentrations, the voltammetry displays sharp peaks which are associated with phase transitions. IR data indicates that uracil binds flat to the electrode at neutral pH. In alkaline solutions, the concentration-dependence of the adsorption is less marked, but IR data indicates that the molecule binds on-edge when it is deprotonated.","Made available in DSpace on 2011-05-07T14:06:45Z (GMT). No. of bitstreams: 2 license.txt: 4922 bytes, checksum: 910b249b4beec47e7ab768910c8f966f (MD5) 9702652.pdf: 4675782 bytes, checksum: f82a34528878acb421354d598855258f (MD5) Previous issue date: 1996","Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding (hding2@illinois.edu) on 2011-05-07T15:03:03Z Item is restricted indefinitely.","Restriction data tranferred 2014-07-01T11:30:02-05:00 Original Data Group with Access UIUC Users [automated] Release Date: none Reason: ETDs are only available to UIUC Users without author permission","ETDs are only available to UIUC Users without author permission","U of I Only"],"dc:identifier":["9780591088373","AAI9702652","(UMI)AAI9702652","http://hdl.handle.net/2142/23229"],"dc:language":["eng"],"dc:rights":["Copyright 1996 Richard, Katherine Marie"],"dc:subject":["Chemistry, Analytical","Chemistry, Inorganic","Chemistry, Physical"],"dc:title":["In situ studies of the binding and reactivity of small molecules at metal electrode surfaces"],"dc:type":["text"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois at Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:21Z"}