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

• 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
• ISSN: 0044-8249; 1521-3757
• DOI: 10.1002/ange.201804661

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.