Abstract
A photochemical system utilizing the semisynthetic biomolecular catalyst acetylated cobalt microperoxidase-11 (CoMP11-Ac) along with [Ru(bpy)(3)](2+) as a photosensitizer and ascorbic acid as an electron donor is shown to generate hydrogen from water in a visible light-driven reaction. The reductive quenching pathway facilitated by photoexcited [Ru(bpy)(3)](2+) overcomes the high overpotential observed for CoMP11-Ac in electrocatalysis, yielding turnover numbers ranging from 606 to 2390 (2 μM - 0.1 μM CoMP11-Ac). The longevity of CoMP11-Ac in the photochemical system, sustaining catalysis for over 20 h, is in contrast to its previously reported behavior in an electrochemical system where catalysis slows after 15 min. Proton reduction turnover number and rate are highest at a neutral pH, a rare feature among cobalt catalysts in similar photochemical systems, which typically function best under acidic conditions. Incorporating biomolecular components into the design of catalysts for photochemical systems may address the need for hydrogen generation from neutral-pH water sources.