{"id":{"repo_id":"qucosa-diss","oai_identifier":"oai:qucosa:de:qucosa:24884"},"canonical_url":"https://search.dev.ndltd.org/etd/qucosa-diss/oai:qucosa:de:qucosa:24884","repository":{"repo_id":"qucosa-diss","name":"QUCOSA","base_url":"http://www.qucosa.de/oai/"},"display":{"title":"First-principles simulations of the oxidation of methane and CO on platinum oxide surfaces and thin films","abstract":"The catalytic oxidation activity of platinum particles in automobile catalysts is thought to originate from the presence of highly reactive superficial oxide phases which form under oxygen-rich reaction conditions. The thermodynamic stability of platinum oxide surfaces and thin films was studied, as well as their reactivities towards oxidation of carbon compounds by means of first-principles atomistic thermodynamics calculations and molecular dynamics simulations based on density functional theory. On the Pt(111) surface the most stable superficial oxide phase is found to be a thin layer of alpha-PtO2, which appears not to be reactive towards either methane dissociation or carbon monoxide oxidation. A PtO-like structure is most stable on the Pt(100) surface at oxygen coverages of one monolayer, while the formation of a coherent and stress-free Pt3O4 film is favoured at higher coverages. Bulk Pt3O4 is found to be thermodynamically stable in a region around 900 K at atmospheric pressure. The computed net driving force for the dissociation of methane on the Pt3O4(100) surface is much larger than on all other metallic and oxide surfaces investigated. Moreover, the enthalpy barrier for the adsorption of CO molecules on oxygen atoms of this surface is as low as 0.34 eV, and desorption of CO2 is observed to occur without any appreciable energy barrier in molecular dynamics simulations. These results, combined, indicate a high catalytic oxidation activity of Pt3O4 phases that can be relevant in the contexts of Pt-based automobile catalysts and gas sensors.","abstract_html":"The catalytic oxidation activity of platinum particles in automobile catalysts is thought to originate from the presence of highly reactive superficial oxide phases which form under oxygen-rich reaction conditions. The thermodynamic stability of platinum oxide surfaces and thin films was studied, as well as their reactivities towards oxidation of carbon compounds by means of first-principles atomistic thermodynamics calculations and molecular dynamics simulations based on density functional theory. On the Pt(111) surface the most stable superficial oxide phase is found to be a thin layer of alpha-PtO2, which appears not to be reactive towards either methane dissociation or carbon monoxide oxidation. A PtO-like structure is most stable on the Pt(100) surface at oxygen coverages of one monolayer, while the formation of a coherent and stress-free Pt3O4 film is favoured at higher coverages. Bulk Pt3O4 is found to be thermodynamically stable in a region around 900 K at atmospheric pressure. The computed net driving force for the dissociation of methane on the Pt3O4(100) surface is much larger than on all other metallic and oxide surfaces investigated. Moreover, the enthalpy barrier for the adsorption of CO molecules on oxygen atoms of this surface is as low as 0.34 eV, and desorption of CO2 is observed to occur without any appreciable energy barrier in molecular dynamics simulations. These results, combined, indicate a high catalytic oxidation activity of Pt3O4 phases that can be relevant in the contexts of Pt-based automobile catalysts and gas sensors.","abstract_has_math":false,"creators":["Seriani, Nicola"],"institution":"Technische Universität Dresden","degree_name":null,"degree_level":"thesis.doctoral","degree_discipline":null,"degree_department":null,"school":null,"contributors":["Pompe, Wolfgang","Mertens, Florian","Colombi Ciacchi, Lucio"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2006,"date_issued":"2006-07-20","date_published":"2006-07-20","updated_at":"2026-07-24T03:59:09Z","subjects":["Catalysis","carbon monoxide","methane","platinum oxide","first-principles molecular dynamics","thermodynamics","computer simulation","Katalyse","Kohlenmonoxid","Methan","Platinoxid","Ab-initio Molekulardynamik","Thermodynamik","Computersimulation"],"languages":[],"rights":[],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":null,"outbound_label":null,"outbound_source":null},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Pompe, Wolfgang","Mertens, Florian","Colombi Ciacchi, Lucio"]},{"key":"dc:creator","label":"Author","values":["Seriani, Nicola"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:publisher","label":"Institution","values":["Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden","Technische Universität Dresden"]},{"key":"dc:type","label":"Dc Type","values":["doctoralThesis"]},{"key":"thesis:degree_level","label":"Degree Level","values":["thesis.doctoral"]},{"key":"thesis:institution_name","label":"Thesis Institution Name","values":["Technische Universität Dresden"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Catalysis","carbon monoxide","methane","platinum oxide","first-principles molecular dynamics","thermodynamics","computer simulation","Katalyse","Kohlenmonoxid","Methan","Platinoxid","Ab-initio Molekulardynamik","Thermodynamik","Computersimulation"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description.abstract","label":"Abstract","values":["The catalytic oxidation activity of platinum particles in automobile catalysts is thought to originate from the presence of highly reactive superficial oxide phases which form under oxygen-rich reaction conditions. The thermodynamic stability of platinum oxide surfaces and thin films was studied, as well as their reactivities towards oxidation of carbon compounds by means of first-principles atomistic thermodynamics calculations and molecular dynamics simulations based on density functional theory. On the Pt(111) surface the most stable superficial oxide phase is found to be a thin layer of alpha-PtO2, which appears not to be reactive towards either methane dissociation or carbon monoxide oxidation. A PtO-like structure is most stable on the Pt(100) surface at oxygen coverages of one monolayer, while the formation of a coherent and stress-free Pt3O4 film is favoured at higher coverages. Bulk Pt3O4 is found to be thermodynamically stable in a region around 900 K at atmospheric pressure. The computed net driving force for the dissociation of methane on the Pt3O4(100) surface is much larger than on all other metallic and oxide surfaces investigated. Moreover, the enthalpy barrier for the adsorption of CO molecules on oxygen atoms of this surface is as low as 0.34 eV, and desorption of CO2 is observed to occur without any appreciable energy barrier in molecular dynamics simulations. These results, combined, indicate a high catalytic oxidation activity of Pt3O4 phases that can be relevant in the contexts of Pt-based automobile catalysts and gas sensors."]},{"key":"dc:title","label":"Title","values":["First-principles simulations of the oxidation of methane and CO on platinum oxide surfaces and thin films"]}]}],"canonical_facts":{"dc:contributor":["Pompe, Wolfgang","Mertens, Florian","Colombi Ciacchi, Lucio"],"dc:creator":["Seriani, Nicola"],"dc:description.abstract":["The catalytic oxidation activity of platinum particles in automobile catalysts is thought to originate from the presence of highly reactive superficial oxide phases which form under oxygen-rich reaction conditions. The thermodynamic stability of platinum oxide surfaces and thin films was studied, as well as their reactivities towards oxidation of carbon compounds by means of first-principles atomistic thermodynamics calculations and molecular dynamics simulations based on density functional theory. On the Pt(111) surface the most stable superficial oxide phase is found to be a thin layer of alpha-PtO2, which appears not to be reactive towards either methane dissociation or carbon monoxide oxidation. A PtO-like structure is most stable on the Pt(100) surface at oxygen coverages of one monolayer, while the formation of a coherent and stress-free Pt3O4 film is favoured at higher coverages. Bulk Pt3O4 is found to be thermodynamically stable in a region around 900 K at atmospheric pressure. The computed net driving force for the dissociation of methane on the Pt3O4(100) surface is much larger than on all other metallic and oxide surfaces investigated. Moreover, the enthalpy barrier for the adsorption of CO molecules on oxygen atoms of this surface is as low as 0.34 eV, and desorption of CO2 is observed to occur without any appreciable energy barrier in molecular dynamics simulations. These results, combined, indicate a high catalytic oxidation activity of Pt3O4 phases that can be relevant in the contexts of Pt-based automobile catalysts and gas sensors."],"dc:publisher":["Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden","Technische Universität Dresden"],"dc:subject":["Catalysis","carbon monoxide","methane","platinum oxide","first-principles molecular dynamics","thermodynamics","computer simulation","Katalyse","Kohlenmonoxid","Methan","Platinoxid","Ab-initio Molekulardynamik","Thermodynamik","Computersimulation"],"dc:title":["First-principles simulations of the oxidation of methane and CO on platinum oxide surfaces and thin films"],"dc:type":["doctoralThesis"],"thesis:degree_level":["thesis.doctoral"],"thesis:institution_name":["Technische Universität Dresden"]},"updated_at":"2026-07-24T03:59:09Z"}