[FeFe]‐Hydrogenase Mimetic Metallopolymers with Enhanced Catalytic Activity for Hydrogen Production in Water. Issue 37 (19th August 2018)

• Record Type: Journal Article
• 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
• Is Part Of: Angewandte Chemie international edition. Volume 57:Issue 37(2018)
• Page Start: 11898
• Page End: 11902
• Publication Date: 2018-08-19
• Subjects: electrocatalysis -- enzymes -- hydrogen -- metallopolymers -- polymerization; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201804661
• Languages: English
• ISSNs: 1433-7851

Abstract

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. Abstract : Splitting water : An organometallic [2Fe‐2S] mimic of the active site of an [FeFe]‐hydrogenase enzyme was incorporated into a metallopolymer. The electrocatalytic performance for hydrogen production in water at pH 7 by the [2Fe‐2S]‐metallopolymer was found to greatly exceed the performance of the enzyme, and approaches the performance of platinum. Unlike the enzyme, the [2Fe‐2S]‐metallopolymer catalyst operates in the presence of air.