{"id":{"repo_id":"ohiolink","oai_identifier":"oai:etd.ohiolink.edu:case1364831283"},"canonical_url":"https://search.dev.ndltd.org/etd/ohiolink/oai:etd.ohiolink.edu:case1364831283","repository":{"repo_id":"ohiolink","name":"OhioLINK","base_url":"https://etd.ohiolink.edu/acprod/odb_etd/ws/oai/oai"},"display":{"title":"THEORETICAL PREDICTIONS OF POTENTIALS FOR INTERMEDIATE STEPS IN METHANOL AND ETHANOL ELECTROCHEMICAL OXIDATION ON Pt(111)","abstract":"The elementary steps of methanol and ethanol electrochemical oxidation on Pt(111) were investigated using quantum mechanics theory. The reversible potential for each electron-transfer step and the reaction energy for non-electron transfer steps were calculated in bulk solution using Interface 1.0. This density functional theory (DFT) code uses modified Poisson-Boltzmann theory (MPB) and the dielectric continuum model to model the solvent, and allows adding or subtracting electronic charge to the solute or the surface with considering electrolyte response. Adsorption energies for reaction intermediates were calculated and used along with reversible potentials in bulk solution to predict surface reaction reversible potentials using linear Gibbs energy relationship model (LGER). This theory is capable of predicting approximate reversible potentials of redox reactions at solid-liquid interfaces by perturbing reversible potentials in bulk solution by internal energies of adsorption. Results were analyzed and compared with available experimental data and oxidation mechanisms were proposed. The accuracy of LGER was tested by comparing reversible potential of CO reduction to formyl on Pt(111) with the one obtained by a more accurate method, the Gibbs energy curve crossing procedure. The results confirm the reliability of LGER in predicting reversible potentials for surface reactions. The Gibbs energy curve crossing procedure was also applied in predicting the cyclic voltammogram of underpotential deposited hydrogen Hupd on Pt (111). The predicted CV showed good agreement with experiment.","abstract_html":"The elementary steps of methanol and ethanol electrochemical oxidation on Pt(111) were investigated using quantum mechanics theory. The reversible potential for each electron-transfer step and the reaction energy for non-electron transfer steps were calculated in bulk solution using Interface 1.0. This density functional theory (DFT) code uses modified Poisson-Boltzmann theory (MPB) and the dielectric continuum model to model the solvent, and allows adding or subtracting electronic charge to the solute or the surface with considering electrolyte response. Adsorption energies for reaction intermediates were calculated and used along with reversible potentials in bulk solution to predict surface reaction reversible potentials using linear Gibbs energy relationship model (LGER). This theory is capable of predicting approximate reversible potentials of redox reactions at solid-liquid interfaces by perturbing reversible potentials in bulk solution by internal energies of adsorption. Results were analyzed and compared with available experimental data and oxidation mechanisms were proposed. The accuracy of LGER was tested by comparing reversible potential of CO reduction to formyl on Pt(111) with the one obtained by a more accurate method, the Gibbs energy curve crossing procedure. The results confirm the reliability of LGER in predicting reversible potentials for surface reactions. The Gibbs energy curve crossing procedure was also applied in predicting the cyclic voltammogram of underpotential deposited hydrogen Hupd on Pt (111). The predicted CV showed good agreement with experiment.","abstract_has_math":false,"creators":["ASIRI, HALEEMA AIED"],"institution":"Case Western Reserve University School of Graduate Studies","degree_name":"Doctor of Philosophy","degree_level":"doctoral","degree_discipline":"Chemistry","degree_department":null,"school":null,"contributors":["Anderson, Alfred","Burda, Clemens"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2013,"date_issued":"2013-08-16","date_published":"2013-08-16","updated_at":"2026-07-24T03:37:16Z","subjects":["Chemistry","Energy"],"languages":["English"],"rights":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://rave.ohiolink.edu/etdc/view?acc_num=case1364831283","outbound_label":"Repository record","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Anderson, Alfred","Burda, Clemens"]},{"key":"dc:creator","label":"Author","values":["ASIRI, HALEEMA AIED"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2013-08-16"]},{"key":"dc:publisher","label":"Institution","values":["Case Western Reserve University School of Graduate Studies / OhioLINK"]},{"key":"dc:type","label":"Dc Type","values":["Electronic Thesis or Dissertation"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemistry"]},{"key":"thesis:degree_level","label":"Degree Level","values":["doctoral"]},{"key":"thesis:degree_name","label":"Degree Name","values":["Doctor of Philosophy"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Case Western Reserve University School of Graduate Studies"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Chemistry","Energy"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["English"]},{"key":"dc:rights","label":"Dc Rights","values":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. 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Adsorption energies for reaction intermediates were calculated and used along with reversible potentials in bulk solution to predict surface reaction reversible potentials using linear Gibbs energy relationship model (LGER). This theory is capable of predicting approximate reversible potentials of redox reactions at solid-liquid interfaces by perturbing reversible potentials in bulk solution by internal energies of adsorption. Results were analyzed and compared with available experimental data and oxidation mechanisms were proposed. The accuracy of LGER was tested by comparing reversible potential of CO reduction to formyl on Pt(111) with the one obtained by a more accurate method, the Gibbs energy curve crossing procedure. The results confirm the reliability of LGER in predicting reversible potentials for surface reactions. The Gibbs energy curve crossing procedure was also applied in predicting the cyclic voltammogram of underpotential deposited hydrogen Hupd on Pt (111). The predicted CV showed good agreement with experiment."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf","p.116","1.43 MB"]},{"key":"dc:title","label":"Title","values":["THEORETICAL PREDICTIONS OF POTENTIALS FOR INTERMEDIATE STEPS IN METHANOL AND ETHANOL ELECTROCHEMICAL OXIDATION ON Pt(111)"]}]}],"canonical_facts":{"dc:contributor":["Anderson, Alfred","Burda, Clemens"],"dc:creator":["ASIRI, HALEEMA AIED"],"dc:date":["2013-08-16"],"dc:description":["The elementary steps of methanol and ethanol electrochemical oxidation on Pt(111) were investigated using quantum mechanics theory. The reversible potential for each electron-transfer step and the reaction energy for non-electron transfer steps were calculated in bulk solution using Interface 1.0. This density functional theory (DFT) code uses modified Poisson-Boltzmann theory (MPB) and the dielectric continuum model to model the solvent, and allows adding or subtracting electronic charge to the solute or the surface with considering electrolyte response. Adsorption energies for reaction intermediates were calculated and used along with reversible potentials in bulk solution to predict surface reaction reversible potentials using linear Gibbs energy relationship model (LGER). This theory is capable of predicting approximate reversible potentials of redox reactions at solid-liquid interfaces by perturbing reversible potentials in bulk solution by internal energies of adsorption. Results were analyzed and compared with available experimental data and oxidation mechanisms were proposed. The accuracy of LGER was tested by comparing reversible potential of CO reduction to formyl on Pt(111) with the one obtained by a more accurate method, the Gibbs energy curve crossing procedure. The results confirm the reliability of LGER in predicting reversible potentials for surface reactions. The Gibbs energy curve crossing procedure was also applied in predicting the cyclic voltammogram of underpotential deposited hydrogen Hupd on Pt (111). The predicted CV showed good agreement with experiment."],"dc:format":["application/pdf","p.116","1.43 MB"],"dc:identifier":["http://rave.ohiolink.edu/etdc/view?acc_num=case1364831283"],"dc:language":["English"],"dc:publisher":["Case Western Reserve University School of Graduate Studies / OhioLINK"],"dc:rights":["unrestricted","This thesis or dissertation is protected by copyright: all rights reserved. It may not be copied or redistributed beyond the terms of applicable copyright laws."],"dc:subject":["Chemistry","Energy"],"dc:title":["THEORETICAL PREDICTIONS OF POTENTIALS FOR INTERMEDIATE STEPS IN METHANOL AND ETHANOL ELECTROCHEMICAL OXIDATION ON Pt(111)"],"dc:type":["Electronic Thesis or Dissertation"],"thesis:degree_discipline":["Chemistry"],"thesis:degree_level":["doctoral"],"thesis:degree_name":["Doctor of Philosophy"],"thesis:institution_name":["Case Western Reserve University School of Graduate Studies"]},"updated_at":"2026-07-24T03:37:16Z"}