Bioinspired catalyst/electrode system for hydrogen production

Using First-Principles Molecular-Dynamics simulations we have investigated the cycle of H₂ production by the [FeFe]_H cluster of the active site of the di-iron hydrogenases linked to a supporting FeS₂ surface electrode both in vacuo and in an acidic water environment. We focus on the [FeFe]H cluster because of the established high efficiency of di-iron hydrogenases in the hydrogen evolution reaction. The choice of pyrite as the electrode material is motivated by the central role of the iron sulfur bonding in the enzyme's active site, and by the important role of this material in many redox geochemical and biogeochemical processes. We show that a modification of the [FeFe]_H cluster forms a stable link with the pyrite electrode and is catalytically active for H₂ production.