{"id":{"repo_id":"uiuc","oai_identifier":"oai:www.ideals.illinois.edu:2142/130146"},"canonical_url":"https://search.dev.ndltd.org/etd/uiuc/oai:www.ideals.illinois.edu:2142/130146","repository":{"repo_id":"uiuc","name":"University of Illinois - Urbana-Champaign","base_url":"https://www.ideals.illinois.edu/oai-pmh"},"display":{"title":"Understanding molecular interactions and design of selective electrochemical processes for water treatment","abstract":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-08-01","abstract_html":"Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-08-01","abstract_has_math":false,"creators":["Roman Santiago, Anaira"],"institution":"University of Illinois Urbana-Champaign","degree_name":"Ph.D.","degree_level":"Dissertation","degree_discipline":"Chemical Engineering","degree_department":null,"school":null,"contributors":["Su, Xiao","Cusick, Roland D","Yang, Hong","Kong, Hyun J."],"advisors":[],"committee_chairs":[],"committee_members":[],"year":2025,"date_issued":"2025-07-08","date_published":"2025-07-08","updated_at":"2026-07-22T22:25:06Z","subjects":["Electrochemistry","Water Treatment","Pfas","Rare Earth Elements"],"languages":["en","eng"],"rights":["Copyright 2025 Anaira Roman Santiago"],"rights_urls":[],"identifier_entries":[]},"links":{"outbound_url":"https://hdl.handle.net/2142/130146","outbound_label":"Handle","outbound_source":"dc:identifier"},"metadata_groups":[{"id":"people","label":"People","entries":[{"key":"dc:contributor","label":"Contributor","values":["Su, Xiao","Cusick, Roland D","Yang, Hong","Kong, Hyun J."]},{"key":"dc:creator","label":"Author","values":["Roman Santiago, Anaira"]}]},{"id":"academic_context","label":"Academic Context","entries":[{"key":"dc:date","label":"Dc Date","values":["2025-07-08","2025-08"]},{"key":"dc:type","label":"Dc Type","values":["text"]},{"key":"thesis:degree_discipline","label":"Discipline","values":["Chemical Engineering"]},{"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 Urbana-Champaign"]}]},{"id":"subjects_keywords","label":"Subjects and Keywords","entries":[{"key":"dc:subject","label":"Dc Subject","values":["Electrochemistry","Water Treatment","Pfas","Rare Earth Elements"]}]},{"id":"language_rights","label":"Language and Rights","entries":[{"key":"dc:language","label":"Dc Language","values":["en","eng"]},{"key":"dc:rights","label":"Dc Rights","values":["Copyright 2025 Anaira Roman Santiago"]}]},{"id":"identifiers","label":"Identifiers","entries":[{"key":"dc:identifier","label":"Identifier","values":["https://hdl.handle.net/2142/130146"]}]},{"id":"additional","label":"Additional Metadata","entries":[{"key":"dc:description","label":"Description","values":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-08-01","The student, Anaira Roman Santiago, accepted the attached license on 2025-07-07 at 10:16.","The student, Anaira Roman Santiago, submitted this Dissertation for approval on 2025-07-07 at 16:34.","This Dissertation was approved for publication on 2025-07-08 at 15:03.","DSpace SAF Submission Ingestion Package generated from Vireo submission #22425 on 2025-10-25 at 15:53:07","Water scarcity, resource depletion, and exposure to anthropogenic contaminants have been major drivers for the development of efficient technologies for water remediation. Recently electrochemical separations have emerged as a promising solution due to their modularity, scalability, and potential for net-zero emissions when powered by renewable energy. However, their broader adaptation is limited by poor ion selectivity, which increases energy demands. This challenge is largely dependent on the electrode materials used in electrochemical systems. Developing tailored materials with molecular-level selectivity can help achieve energy-efficient separations. For my doctoral thesis, I investigated the molecular-level interactions and interface morphology governing electrochemical separations of per- and polyfluoroalkyl substances (PFAS), phosphates, and rare earth elements (REE) from water, aiming to enhance selectivity and efficiency in pollutant removal and resource recovery. By designing and characterizing redox-active polymers and ligands, we identified key interactions─ electrostatic, redox, fluorophilic and non-covalent interactions—that drive selective binding and release of target species. For PFAS, we demonstrate that electrostatic interactions predominantly govern capture, while fluorophilic groups selectively enhance uptake of short-chain PFAS. Polymer structure and porosity, influenced by fluorinated monomer content, were shown to further modulate PFAS selectivity via steric effects. Furthermore, integration of electrosorption with electrodegradation enabled energy-efficient PFAS destruction by concentrating contaminants in wastewater prior to oxidation. To recover phosphorus, we developed ferrocene-based polymers which achieved high selectivity over competing ions such as chloride. In-situ neutron reflectometry revealed solvation-driven ion selectivity under dynamic redox modulation, providing insights into polymer design and separation treatment trains. For REE extraction, we demonstrated how the design of ligands can be accelerated via integration with artificial intelligence and chemical language models to yield selective chemistries that lower separation costs. Across all systems, the interplay of interfacial morphology, hydration, and chemical functionality was shown to be critical for efficient separations. The findings of this dissertation provide a framework for designing advanced interfaces for selective separations, with broader implications for sustainable water treatment and applications in industries requiring precise molecular selectivity."]},{"key":"dc:format","label":"Dc Format","values":["application/pdf"]},{"key":"dc:title","label":"Title","values":["Understanding molecular interactions and design of selective electrochemical processes for water treatment"]}]}],"canonical_facts":{"dc:contributor":["Su, Xiao","Cusick, Roland D","Yang, Hong","Kong, Hyun J."],"dc:creator":["Roman Santiago, Anaira"],"dc:date":["2025-07-08","2025-08"],"dc:description":["Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2027-08-01","The student, Anaira Roman Santiago, accepted the attached license on 2025-07-07 at 10:16.","The student, Anaira Roman Santiago, submitted this Dissertation for approval on 2025-07-07 at 16:34.","This Dissertation was approved for publication on 2025-07-08 at 15:03.","DSpace SAF Submission Ingestion Package generated from Vireo submission #22425 on 2025-10-25 at 15:53:07","Water scarcity, resource depletion, and exposure to anthropogenic contaminants have been major drivers for the development of efficient technologies for water remediation. Recently electrochemical separations have emerged as a promising solution due to their modularity, scalability, and potential for net-zero emissions when powered by renewable energy. However, their broader adaptation is limited by poor ion selectivity, which increases energy demands. This challenge is largely dependent on the electrode materials used in electrochemical systems. Developing tailored materials with molecular-level selectivity can help achieve energy-efficient separations. For my doctoral thesis, I investigated the molecular-level interactions and interface morphology governing electrochemical separations of per- and polyfluoroalkyl substances (PFAS), phosphates, and rare earth elements (REE) from water, aiming to enhance selectivity and efficiency in pollutant removal and resource recovery. By designing and characterizing redox-active polymers and ligands, we identified key interactions─ electrostatic, redox, fluorophilic and non-covalent interactions—that drive selective binding and release of target species. For PFAS, we demonstrate that electrostatic interactions predominantly govern capture, while fluorophilic groups selectively enhance uptake of short-chain PFAS. Polymer structure and porosity, influenced by fluorinated monomer content, were shown to further modulate PFAS selectivity via steric effects. Furthermore, integration of electrosorption with electrodegradation enabled energy-efficient PFAS destruction by concentrating contaminants in wastewater prior to oxidation. To recover phosphorus, we developed ferrocene-based polymers which achieved high selectivity over competing ions such as chloride. In-situ neutron reflectometry revealed solvation-driven ion selectivity under dynamic redox modulation, providing insights into polymer design and separation treatment trains. For REE extraction, we demonstrated how the design of ligands can be accelerated via integration with artificial intelligence and chemical language models to yield selective chemistries that lower separation costs. Across all systems, the interplay of interfacial morphology, hydration, and chemical functionality was shown to be critical for efficient separations. The findings of this dissertation provide a framework for designing advanced interfaces for selective separations, with broader implications for sustainable water treatment and applications in industries requiring precise molecular selectivity."],"dc:format":["application/pdf"],"dc:identifier":["https://hdl.handle.net/2142/130146"],"dc:language":["en","eng"],"dc:rights":["Copyright 2025 Anaira Roman Santiago"],"dc:subject":["Electrochemistry","Water Treatment","Pfas","Rare Earth Elements"],"dc:title":["Understanding molecular interactions and design of selective electrochemical processes for water treatment"],"dc:type":["text"],"thesis:degree_discipline":["Chemical Engineering"],"thesis:degree_level":["Dissertation"],"thesis:degree_name":["Ph.D."],"thesis:institution_name":["University of Illinois Urbana-Champaign"]},"updated_at":"2026-07-22T22:25:06Z"}