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[FeFe]‐Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water
Author(s) -
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
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201804661
Subject(s) - overpotential , hydrogenase , catalysis , chemistry , dispersity , hydrogen production , hydrogen , solubility , atom transfer radical polymerization , oxygen evolution , water splitting , photochemistry , polymerization , combinatorial chemistry , polymer , chemical engineering , organic chemistry , electrochemistry , photocatalysis , electrode , engineering
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 (2.5×10 5 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.