Structure and solvation control of redox-metallopolymers for electrochemically-mediated ion 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.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemical Engineering

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2023

Author dc:creator

• Chen, Raylin

Contributors dc:contributor

• Su, Xiao
• Higdon, Jonathan J. L.
• Kenis, Paul J. A.
• Gewirth, Andrew A.

• Electrochemical Separations

Statement dc:rights

• Copyright 2023 Raylin Chen

Language dc:language

en, eng

Handle dc:identifier

https://hdl.handle.net/2142/121211

OAI record oai:identifier

https://www.ideals.illinois.edu/oai-pmh?verb=GetRecord&metadataPrefix=etdms&identifier=oai%3Awww.ideals.illinois.edu%3A2142%2F121211