Viologen-Radical-Driven Hydrogen Evolution from Water Catalyzed by Co-NHC Catalysts: Radical Scavenging by Nitrate and Volmer-Heyrovsky-like CPET Pathway.

The factors controlling the catalytic activity in photochemical hydrogen evolution reaction (HER) are studied in detail for two macrocyclic cobalt compounds bearing two N-heterocyclic carbenes and two pyridyl donors ( and , where has a methoxy substituent on each pyridyl ligand). The present study adopts an aqueous photosystem consisting of EDTA, [Ru(bpy)] (bpy = 2,2'-bipyridine), and MV (MV = methylviologen) at pH = 5. Both catalysts are shown to promote HER in a similar efficiency (TON = 12-13 in 6 h), revealing a minor contribution of the electron-donating methoxy substituents. The catalyst degradation is shown to proceed during the photocatalysis, leading to afford [Co(edta)] (EDTA = Hedta) as a dead-end species. The lack of any heterogeneous species was evidenced by DLS (dynamic light scattering). It was also found that nitrate involved as a counteranion in the photocatalysis components substantially inhibits the photocatalytic HER, giving rise to a large diminishment in TON from 12.7 to 7.2. The Griess test was used to confirm that NO serves as a scavenger deactivating the reduced form of MV (i.e., MV·). The detailed spectroscopic study reveals that the radical dimer (MV·) plays a key role in promoting the one-step two-electron process: (MV·) + NO + 2H → 2MV + NO + HO. Experimental and DFT results also reveal that a unique double CPET (concerted proton-electron transfer) pathway is taken to evolve H by the Co-NHC catalysts with substantially minimized reorganization energies: Co(II)-NHC Co(III)(H)-NHC Co(II)-NHC + H. This pathway can be viewed as related to the so-called Volmer-Heyrovsky mechanism adopted by some metals and is quite unique to the Co-NHC catalysts.