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.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 11898-11902 |
| Number of pages | 5 |
| Journal | Angewandte Chemie - International Edition |
| Volume | 57 |
| Issue number | 37 |
| DOIs | |
| State | Published - Sep 10 2018 |
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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 journal › Article
}
TY - JOUR
T1 - [FeFe]-Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water
AU - Brezinski, William P.
AU - Karayilan, Metin
AU - Clary, Kayla E.
AU - Pavlopoulos, Nicholas G.
AU - Li, Sipei
AU - Fu, Liye
AU - Matyjaszewski, Krzysztof
AU - Evans, Dennis H.
AU - Glass, Richard S
AU - Lichtenberger, Dennis L
AU - Pyun, Dong-Chul
PY - 2018/9/10
Y1 - 2018/9/10
N2 - 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.
AB - 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.
KW - electrocatalysis
KW - enzymes
KW - hydrogen
KW - metallopolymers
KW - polymerization
UR - http://www.scopus.com/inward/record.url?scp=85052402022&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85052402022&partnerID=8YFLogxK
U2 - 10.1002/anie.201804661
DO - 10.1002/anie.201804661
M3 - Article
VL - 57
SP - 11898
EP - 11902
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 37
ER -