Macromolecular Engineering of the Outer Coordination Sphere of [2Fe-2S] Metallopolymers to Enhance Catalytic Activity for H2 Production

William P. Brezinski, Metin Karayilan, Kayla E. Clary, Keelee C. McCleary-Petersen, Liye Fu, Krzysztof Matyjaszewski, Dennis H. Evans, Dennis L Lichtenberger, Richard S Glass, Dong-Chul Pyun

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Small-molecule catalysts inspired by the active sites of [FeFe]-hydrogenase enzymes have long struggled to achieve fast rates of hydrogen evolution, long-term stability, water solubility, and oxygen compatibility. We profoundly improved on these deficiencies by grafting polymers from a metalloinitiator containing a [2Fe-2S] moiety to form water-soluble poly(2-dimethylamino)ethyl methacrylate metallopolymers (PDMAEMA-g-[2Fe-2S]) using atom transfer radical polymerization (ATRP). This study illustrates the critical role of the polymer composition in enhancing hydrogen evolution and aerobic stability by comparing the catalytic activity of PDMAEMA-g-[2Fe-2S] with a nonionic water-soluble metallopolymer based on poly(oligo(ethylene glycol) methacrylate) prepared via ATRP (POEGMA-g-[2Fe-2S]) with the same [2Fe-2S] metalloinitiator. Additionally, the tunability of catalyst activity is demonstrated by the synthesis of metallocopolymers incorporating the 2-(dimethylamino)ethyl methacrylate (DMAEMA) and oligo(ethylene glycol) methacrylate (OEGMA) monomers. Electrochemical investigations into these metallo(co)polymers show that PDMAEMA-g-[2Fe-2S] retains complete aerobic stability with catalytic current densities in excess of 20 mA·cm-2, while POEGMA-g-[2Fe-2S] fails to reach 1 mA·cm-2 current density even with the application of high overpotentials (η > 0.8 V) and loses all activity in the presence of oxygen. Random copolymers of the two monomers polymerized with the same [2Fe-2S] initiator showed intermediate activity in terms of current density, overpotential, and aerobic stability.

Original languageEnglish (US)
Pages (from-to)1383-1387
Number of pages5
JournalACS Macro Letters
Volume7
Issue number11
DOIs
StatePublished - Nov 20 2018

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Catalyst activity
Polymers
Current density
Atom transfer radical polymerization
Water
Hydrogen
Monomers
Oxygen
Hydrogenase
Long Term Evolution (LTE)
Ethylene Glycol
Methacrylates
Ethylene glycol
Polyethylene glycols
Copolymers
Enzymes
Solubility
Catalysts
Molecules
poly(2-(dimethylamino)ethyl methacrylate)

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Macromolecular Engineering of the Outer Coordination Sphere of [2Fe-2S] Metallopolymers to Enhance Catalytic Activity for H2 Production. / Brezinski, William P.; Karayilan, Metin; Clary, Kayla E.; McCleary-Petersen, Keelee C.; Fu, Liye; Matyjaszewski, Krzysztof; Evans, Dennis H.; Lichtenberger, Dennis L; Glass, Richard S; Pyun, Dong-Chul.

In: ACS Macro Letters, Vol. 7, No. 11, 20.11.2018, p. 1383-1387.

Research output: Contribution to journalArticle

Brezinski, William P. ; Karayilan, Metin ; Clary, Kayla E. ; McCleary-Petersen, Keelee C. ; Fu, Liye ; Matyjaszewski, Krzysztof ; Evans, Dennis H. ; Lichtenberger, Dennis L ; Glass, Richard S ; Pyun, Dong-Chul. / Macromolecular Engineering of the Outer Coordination Sphere of [2Fe-2S] Metallopolymers to Enhance Catalytic Activity for H2 Production. In: ACS Macro Letters. 2018 ; Vol. 7, No. 11. pp. 1383-1387.
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