Enhanced Hydrogen Evolution in Neutral Water Catalyzed by a Cobalt Complex with a Softer Polypyridyl Ligand
Abstract
To explore the structure–function relationships of cobalt complexes in the catalytic hydrogen evolution reaction (HER), we studied the substitution of a tertiary amine with a softer pyridine group and the inclusion of a conjugated bpy unit in a Co complex with a new pentadentate ligand, 6-[6-(1,1-di-pyridin-2-yl-ethyl)-pyridin-2-ylmethyl]-[2,2′]bipyridinyl (Py3Me-Bpy). These modifications resulted in significantly improved stability and activity in both electro- and photocatalytic HER in neutral water. [Co(Py3Me-Bpy)(OH2)](PF6)2 catalyzes the electrolytic HER at −1.3 V (vs. SHE) for 20 hours with a turnover number (TON) of 266 300, and photolytic HER for two days with a TON of 15 000 in pH 7 aqueous solutions. The softer ligand scaffold possibly provides increased stability towards the intermediate CoI species. DFT calculations demonstrate that HER occurs through a general electron transfer/proton transfer/electron transfer/proton transfer pathway, with H2 released from the protonation of CoII−H species.
Publication Title
Angewandte Chemie - International Edition
Recommended Citation
Wang, P., Liang, G., Smith, N., Hill, K., Donnadieu, B., Webster, C., & Zhao, X. (2020). Enhanced Hydrogen Evolution in Neutral Water Catalyzed by a Cobalt Complex with a Softer Polypyridyl Ligand. Angewandte Chemie - International Edition, 59 (31), 12694-12697. https://doi.org/10.1002/anie.202002640
