Hydrogen Evolution from Aqueous Solutions Mediated by a Heterogenized [NiFe]‐Hydrogenase Model: Low pH Enables Catalysis through an Enzyme‐relevant Mechanism

: [NiFe]-hydrogenase enzymes are efficient catalysts for H2 evolution but their synthetic models have not been reported to be active under aqueous conditions so far. Here we show that a close model of the [NiFe]-hydrogenase active site can work as a very active and stable heterogeneous H2 evolution catalyst under mildly acidic aqueous conditions. Entry in catalysis is a NiI FeII complex, with electronic structure analogous to the Ni-L state of the enzyme, corroborating the mechanism modification recently proposed for [NiFe]-hydrogenases.