{"id":{"repo_id":"buffalo","oai_identifier":"oai:ubir.buffalo.edu:10477/80916"},"canonical_url":"https://search.dev.ndltd.org/etd/buffalo/oai:ubir.buffalo.edu:10477/80916","repository":{"repo_id":"buffalo","name":"Buffalo","base_url":"https://ubir.buffalo.edu/oai/request"},"display":{"title":"Surface Chemistry and Charge Transfer Dynamics in Cadmium Chalcogenide Quantum Dots Tethered to Linker Functionalized Metal Oxides and Redox-Active Molecules","abstract":"Ph.D.","abstract_html":"Ph.D.","abstract_has_math":false,"creators":["Rivera-Gonzalez, Natalia; 0000-0002-6683-0993"],"institution":"State University of New York at Buffalo","degree_name":null,"degree_level":null,"degree_discipline":null,"degree_department":null,"school":null,"contributors":["Watson, David","Chemistry"],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2019,"date_issued":"2019-10-29T16:48:07Z","date_published":"2019-10-29T16:48:07Z","updated_at":"2026-07-27T19:05:25Z","subjects":["chemistry","inorganic chemistry","materials science"],"languages":["eng"],"rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"http://hdl.handle.net/10477/80916","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Watson, David","Chemistry"]},{"key":"dc:creator","label":"Author","values":["Rivera-Gonzalez, Natalia; 0000-0002-6683-0993"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2019-10-29T16:48:07Z","2019","2019-08-09 09:47:29"]},{"key":"dc:publisher","label":"Institution","values":["State University of New York at Buffalo"]},{"key":"dc:type","label":"Dc Type","values":["Text","Dissertation"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["chemistry","inorganic chemistry","materials science"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["http://hdl.handle.net/10477/80916"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Ph.D.","In this dissertation, I report on the assembly and excited-state charge-transfer reactivity of heterostructures consisting of cadmium chalcogenide quantum dots (QDs) interfaced with molecular or materials-based acceptors via amine-bearing ligands. Chapters 2 and 3 report on the synthesis and characterization of QD-molecule-metal oxide heterostructures using amine-bearing ligands prepared by linker-assisted assembly (LAA), via both in-situ and ex-situ approaches. Chapter 4 reports on heterostructures of QDs and a redox-active ferrocene derivative as a molecular acceptor. For the various heterostructures, we studied charge-transfer dynamics using steady-state emission and time-resolved emission. In LAA, a bifunctional linker molecule is used as the bridge to bind QDs to the metal oxide. The nature and strength of the interaction between the ligands and the surface of QDs determined the stability of the QD-ligand complexes. Thiolate linkers such as 3-mercaptopropionic acid (MPA) have been widely used for this purpose and have shown efficient electron transfer (ET). However, adsorbed thiolates accept valence band holes which reduces (1) the oxidizing potentials of the photogenerated holes and (2) the distance between electrons and holes in the charge-separated state. Amines, on the contrary, can bind to cadmium chalcogenide QDs without accepting holes, as long as they have sufficiently positive oxidation potentials. Amines have shown enhancement of band-edge emission and shift of trap states to higher energies, which can promote an increase in driving force and elimination of electron-hole recombination pathways. Amines are thus attractive alternatives to thiol-bearing ligands for LAA and for tethering redox-active molecular acceptors to surfaces.In in-situ LAA, linear aminoalkanoic acids (AAAs) and linear mercaptoalkanoic acids (MAAs) were used to tether CdSe QDs to nanocrystalline TiO2 thin films. The adsorption of CdSe QDs to linker-functionalized films to followed the Langmuir adsorption isotherm and kinetics. Steady-state and time-resolved spectroscopy measurements showed evidence of electrons being transferred from band-edge and trap states of the CdSe QDs to TiO2 with rate constant on the order of 107 s-1."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Surface Chemistry and Charge Transfer Dynamics in Cadmium Chalcogenide Quantum Dots Tethered to Linker Functionalized Metal Oxides and Redox-Active Molecules"]}]}],"canonical_facts":{"dc:contributor":["Watson, David","Chemistry"],"dc:creator":["Rivera-Gonzalez, Natalia; 0000-0002-6683-0993"],"dc:date":["2019-10-29T16:48:07Z","2019","2019-08-09 09:47:29"],"dc:description":["Ph.D.","In this dissertation, I report on the assembly and excited-state charge-transfer reactivity of heterostructures consisting of cadmium chalcogenide quantum dots (QDs) interfaced with molecular or materials-based acceptors via amine-bearing ligands. Chapters 2 and 3 report on the synthesis and characterization of QD-molecule-metal oxide heterostructures using amine-bearing ligands prepared by linker-assisted assembly (LAA), via both in-situ and ex-situ approaches. Chapter 4 reports on heterostructures of QDs and a redox-active ferrocene derivative as a molecular acceptor. For the various heterostructures, we studied charge-transfer dynamics using steady-state emission and time-resolved emission. In LAA, a bifunctional linker molecule is used as the bridge to bind QDs to the metal oxide. The nature and strength of the interaction between the ligands and the surface of QDs determined the stability of the QD-ligand complexes. Thiolate linkers such as 3-mercaptopropionic acid (MPA) have been widely used for this purpose and have shown efficient electron transfer (ET). However, adsorbed thiolates accept valence band holes which reduces (1) the oxidizing potentials of the photogenerated holes and (2) the distance between electrons and holes in the charge-separated state. Amines, on the contrary, can bind to cadmium chalcogenide QDs without accepting holes, as long as they have sufficiently positive oxidation potentials. Amines have shown enhancement of band-edge emission and shift of trap states to higher energies, which can promote an increase in driving force and elimination of electron-hole recombination pathways. Amines are thus attractive alternatives to thiol-bearing ligands for LAA and for tethering redox-active molecular acceptors to surfaces.In in-situ LAA, linear aminoalkanoic acids (AAAs) and linear mercaptoalkanoic acids (MAAs) were used to tether CdSe QDs to nanocrystalline TiO2 thin films. The adsorption of CdSe QDs to linker-functionalized films to followed the Langmuir adsorption isotherm and kinetics. Steady-state and time-resolved spectroscopy measurements showed evidence of electrons being transferred from band-edge and trap states of the CdSe QDs to TiO2 with rate constant on the order of 107 s-1."],"dc:format":["application/pdf"],"dc:identifier":["http://hdl.handle.net/10477/80916"],"dc:language":["eng"],"dc:publisher":["State University of New York at Buffalo"],"dc:rights":["Users of works found in University at Buffalo Institutional Repository (UBIR) are responsible for identifying and contacting the copyright owner for permission to reuse. University at Buffalo Libraries do not manage rights for copyright-protected works and cannot assist with permissions.","Copyright retained by author."],"dc:subject":["chemistry","inorganic chemistry","materials science"],"dc:title":["Surface Chemistry and Charge Transfer Dynamics in Cadmium Chalcogenide Quantum Dots Tethered to Linker Functionalized Metal Oxides and Redox-Active Molecules"],"dc:type":["Text","Dissertation"]},"updated_at":"2026-07-27T19:05:25Z"}