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

Journal Article (Journal Article)

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.

Full Text

Duke Authors

Cited Authors

  • Brezinski, WP; Karayilan, M; Clary, KE; Pavlopoulos, NG; Li, S; Fu, L; Matyjaszewski, K; Evans, DH; Glass, RS; Lichtenberger, DL; Pyun, J

Published Date

  • September 2018

Published In

Volume / Issue

  • 57 / 37

Start / End Page

  • 11898 - 11902

PubMed ID

  • 30053346

Electronic International Standard Serial Number (EISSN)

  • 1521-3773

International Standard Serial Number (ISSN)

  • 1433-7851

Digital Object Identifier (DOI)

  • 10.1002/anie.201804661


  • eng