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, Jeffrey
N1 - Funding Information:
D.L.L., R.S.G., and J.P. gratefully acknowledge support of this work by NSF (CHE-1664745), Dr. Andrei Astachkine for his assistance with the X-ray crystallographic structural analysis, Dr. Michael L. Heien and his group members for electrochemical consultation. KM acknowledges support of this work by NSF (DMR 1501324).
Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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
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U2 - 10.1002/anie.201804661
DO - 10.1002/anie.201804661
M3 - Article
C2 - 30053346
AN - SCOPUS:85052402022
VL - 57
SP - 11898
EP - 11902
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 37
ER -