2026-09-23T15:08:28Z https://www.ideals.illinois.edu/oai-pmh

oai:www.ideals.illinois.edu:2142/121211 2023-12-11 col_2142_5131 col_2142_11615 com_2142_5130 com_2142_9130 com_2142_8903

Su, Xiao Su, Xiao Higdon, Jonathan J. L. Kenis, Paul J. A. Gewirth, Andrew A. 2023-08 application/pdf en text Submission published under a 24 month embargo labeled 'Closed Access', the embargo will last until 2025-08-01 The student, Raylin Chen, accepted the attached license on 2023-06-29 at 15:57. The student, Raylin Chen, submitted this Dissertation for approval on 2023-06-29 at 16:07. This Dissertation was approved for publication on 2023-07-05 at 16:07. DSpace SAF Submission Ingestion Package generated from Vireo submission #19486 on 2023-12-04 at 17:30:33 Structure and solvation control of redox-metallopolymers for electrochemically-mediated ion separations Chen, Raylin 2023-07-05 Electrochemical Separations Electroresponsive polymer materials have garnered interest as selective and electrically switchable adsorbent materials. The improved selectivity of these materials would allow for the increased efficiency of existing adsorption separation processes and electrically switchable nature of these materials could greenify adsorption separations processes by reducing the need for chemical elution. This thesis presents some work on elucidating the underlying physicochemical mechanisms that govern the selectivity of ferrocene polymers toward target anion species. After a critical review of the current state of the art literature, the results are summarized in two parts. First, we demonstrated that a change in the ferrocene polymer structure, from a pendant ferrocene to a main-chain ferrocene, resulted in different ion selectivity towards a range of transition metal oxyanions. Through electronic structure calculations, we showed that the addition of a electron donation silane substituent on ferrocene can change ion binding energies with the ferrocenium binding cite based on the the ionization energy of the ion. Second, through copolymerization of a ferrocene moiety with another hydrophilic moiety, we could change the hydrophilicity of the polymer, independent of the ferrocene cite charge transfer. This change in hydrophilicity resulted in different ion selectivity as well. Overall, these results may provide for future metallopolymer design for targeted ion capture in aqueous systems. Text eng https://hdl.handle.net/2142/121211 Copyright 2023 Raylin Chen Ph.D. Dissertation Chemical Engineering University of Illinois at Urbana-Champaign Chemical & Biomolecular Engr