Redox Polyelectrolytes with pH-Sensitive Electroactive Functionality in Aqueous MediaClick to copy article linkArticle link copied!
- Kai-Jher TanKai-Jher TanDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by Kai-Jher Tan
- Satoshi MorikawaSatoshi MorikawaDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by Satoshi Morikawa
- Nil OzbekNil OzbekDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaDepartment of Chemical Engineering, Faculty of Chemical and Metallurgical Engineering, Istanbul Technical University, Maslak, 34469 Istanbul, TurkeyMore by Nil Ozbek
- Magdalena LenzMagdalena LenzDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by Magdalena Lenz
- Carsten-René ArltCarsten-René ArltDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by Carsten-René Arlt
- André TschöpeAndré TschöpeDepartment of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by André Tschöpe
- Matthias FranzrebMatthias FranzrebInstitute of Functional Interfaces (IFG), Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen, Baden-Württemberg 76344, GermanyMore by Matthias Franzreb
- T. Alan Hatton*T. Alan Hatton*Email: [email protected]Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States of AmericaMore by T. Alan Hatton
Abstract
A framework of ferrocene-containing polymers bearing adjustable pH- and redox-active properties in aqueous electrolyte environments was developed. The electroactive metallopolymers were designed to possess enhanced hydrophilicity compared to the vinylferrocene (VFc) homopolymer, poly(vinylferrocene) (PVFc), by virtue of the comonomer incorporated into the macromolecule, and could also be prepared as conductive nanoporous carbon nanotube (CNT) composites that offered a variety of different redox potentials spanning a ca. 300 mV range. The presence of charged non-redox-active moieties such as methacrylate (MA) in the polymeric structure endowed it with acid dissociation properties that interacted synergistically with the redox activity of the ferrocene moieties to impart pH-dependent electrochemical behavior to the overall polymer, which was subsequently studied and compared to several Nernstian relationships in both homogeneous and heterogeneous configurations. This zwitterionic characteristic was leveraged for the enhanced electrochemical separation of several transition metal oxyanions using a P(VFc0.63-co-MA0.37)-CNT polyelectrolyte electrode, which yielded an almost twofold preference for chromium as hydrogen chromate versus its chromate form, and also exemplified the electrochemically mediated and innately reversible nature of the separation process through the capture and release of vanadium oxyanions. These investigations into pH-sensitive redox-active materials provide insight for future developments in stimuli-responsive molecular recognition, with extendibility to areas such as electrochemical sensing and selective separation for water purification.
Cited By
This article is cited by 4 publications.
- Kai-Jher Tan, Laura Kuger, Matthias Franzreb, T. Alan Hatton. Physicochemical and Electrochemical Investigation of Naturally Occurring Quinones for Application toward Electrochemically Mediated Carbon Dioxide Capture. The Journal of Physical Chemistry C 2024, 128
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, 16467-16480. https://doi.org/10.1021/acs.jpcc.4c04154
- Kai-Jher Tan, Satoshi Morikawa, T. Alan Hatton. Electroactive Behavior of Adjustable Vinylferrocene Copolymers in Electrolyte Media. The Journal of Physical Chemistry B 2024, 128
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, 1748-1759. https://doi.org/10.1021/acs.jpcb.3c06140
- Nayeong Kim, Wangsuk Oh, Kyle N. Knust, Fábio Zazyki Galetto, Xiao Su. Molecularly Selective Polymer Interfaces for Electrochemical Separations. Langmuir 2023, 39
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, 16685-16700. https://doi.org/10.1021/acs.langmuir.3c02389
- Kai-Jher Tan, Satoshi Morikawa, Ali Hemmatifar, Nil Ozbek, Yayuan Liu, T. Alan Hatton. Hydrophobicity Tuned Polymeric Redox Materials with Solution-Specific Electroactive Properties for Selective Electrochemical Metal Ion Recovery in Aqueous Environments. ACS Applied Materials & Interfaces 2023, 15
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, 43859-43870. https://doi.org/10.1021/acsami.3c09321
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