Protein Delivery of a Ni Catalyst to Photosystem I for Light-Driven Hydrogen Production
J. Am. Chem. Soc. 2013, 135, 13246-13249, 10.1021/ja405277g
The direct conversion of sunlight into fuel is a promising means for the production of storable renewable energy. Herein, we use Nature’s specialized photosynthetic machinery found in the Photosystem I (PSI) protein to drive solar fuel production from a nickel diphosphine molecular catalyst. Upon exposure to visible light, a self-assembled PSI-[Ni(P2PhN2Ph)2](BF4)2 hybrid generates H2 at a rate 2 orders of magnitude greater than rates reported for photosensitizer/[Ni(P2PhN2Ph)2](BF4)2 systems. The protein environment enables photocatalysis at pH 6.3 in completely aqueous conditions. In addition, we have developed a strategy for incorporating the Ni molecular catalyst with the native acceptor protein of PSI, flavodoxin. Photocatalysis experiments with this modified flavodoxin demonstrate a new mechanism for biohybrid creation that involves protein-directed delivery of a molecular catalyst to the reducing side of Photosystem I for light-driven catalysis. This work further establishes strategies for constructing functional, inexpensive, earth-abundant solar fuel-producing PSI hybrids that use light to rapidly produce hydrogen directly from water.
Metal: NiLigand type: PhosphineHost protein: Flavodoxin (Fld)Anchoring strategy: SupramolecularOptimization: ---Reaction: H2 evolutionMax TON: 94ee: ---PDB: ---Notes: Recalculated TON
Metal: NiLigand type: PhosphineHost protein: Photosystem I (PSI)Anchoring strategy: UndefinedOptimization: ---Reaction: H2 evolutionMax TON: 1870ee: ---PDB: ---Notes: Recalculated TON