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

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...

Full description

Saved in:
Bibliographic Details
Published in:Angewandte Chemie 2018-09, Vol.130 (37), p.12074-12078
Main Authors: 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, Jeffrey
Format: Article
Language:English
Subjects:
Aerobic conditions
Anaerobic conditions
Catalysis
Catalytic activity
Chemical activity
Chemistry
Composition
Elektrokatalyse
Enzyme
Hydrogen
Hydrogen evolution reactions
Hydrogen production
Hydrogen storage
Hydrogenase
Metallopolymere
Organic chemistry
Oxygen
Polydispersity
Polymerisationen
Polymerization
Solubility
Wasserstoff
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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. Wasserspaltendes Polymer: Ein metallorganisches [2Fe‐2S]‐Mimetikum des aktiven Zentrums einer [FeFe]‐Hydrogenase wurde in ein Metallopolymer eingebaut. Bei der elektrokatalytischen Wasserstofferzeugung in Wasser bei pH 7 übertraf das [2Fe‐2S]‐Metallopolymer das Enzym deutlich; es war fast so leistungsfähig wie Platin. Anders als das Enzym kann das [2Fe‐2S]‐Metallopolymer auch an Luft eingesetzt werden.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201804661