[FeFe]-Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water

William P. Brezinski, Metin Karayilan, Kayla E. Clary, Nicholas G. Pavlopoulos, Sipei Li, Liye Fu, Krzysztof Matyjaszewski, Dennis H. Evans, Richard S Glass, Dennis L Lichtenberger, Dong-Chul Pyun

Research output: Contribution to journalArticle

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Abstract

Electrocatalytic [FeFe]-hydrogenase mimics for the hydrogen evolution reaction (HER) generally suffer from low activity, high overpotential, aggregation, oxygen sensitivity, and low solubility in water. By using atom-transfer radical polymerization (ATRP), a new class of [FeFe]-metallopolymers with precise molar mass, defined composition, and low polydispersity, has been prepared. The synthetic methodology introduced here allows facile variation of polymer composition to optimize the [FeFe] solubility, activity, and long-term chemical and aerobic stability. Water soluble functional metallopolymers facilitate electrocatalytic hydrogen production in neutral water with loadings as low as 2 ppm and operate at rates an order of magnitude faster than hydrogenases (2.5×105 s−1), and with low overpotential requirement. Furthermore, unlike the hydrogenases, these systems are insensitive to oxygen during catalysis, with turnover numbers on the order of 40 000 under both anaerobic and aerobic conditions.

LanguageEnglish (US)
Pages11898-11902
Number of pages5
JournalAngewandte Chemie - International Edition
Volume57
Issue number37
DOIs
StatePublished - Sep 10 2018

Fingerprint

Hydrogenase
Hydrogen production
Catalyst activity
Water
Solubility
Oxygen
Molar mass
Atom transfer radical polymerization
Polydispersity
Chemical analysis
Catalysis
Hydrogen
Polymers
Agglomeration

Keywords

  • electrocatalysis
  • enzymes
  • hydrogen
  • metallopolymers
  • polymerization

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

[FeFe]-Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water. / Brezinski, William P.; Karayilan, Metin; Clary, Kayla E.; Pavlopoulos, Nicholas G.; Li, Sipei; Fu, Liye; Matyjaszewski, Krzysztof; Evans, Dennis H.; Glass, Richard S; Lichtenberger, Dennis L; Pyun, Dong-Chul.

In: Angewandte Chemie - International Edition, Vol. 57, No. 37, 10.09.2018, p. 11898-11902.

Research output: Contribution to journalArticle

Brezinski, William P. ; Karayilan, Metin ; Clary, Kayla E. ; Pavlopoulos, Nicholas G. ; Li, Sipei ; Fu, Liye ; Matyjaszewski, Krzysztof ; Evans, Dennis H. ; Glass, Richard S ; Lichtenberger, Dennis L ; Pyun, Dong-Chul. / [FeFe]-Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water. In: Angewandte Chemie - International Edition. 2018 ; Vol. 57, No. 37. pp. 11898-11902.
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