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

Angew Chem Int Ed Engl. 2018 Dec 3;57(49):16001-16004. doi: 10.1002/anie.201808215. Epub 2018 Nov 11.

Abstract

[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.

Keywords: [NiFe]-hydrogenase; electrocatalysis; heterogeneous catalysis; hydrogen evolution; reaction mechanism.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biocatalysis
  • Catalytic Domain
  • Density Functional Theory
  • Hydrogen / chemistry
  • Hydrogen / metabolism*
  • Hydrogen-Ion Concentration
  • Hydrogenase / chemistry
  • Hydrogenase / metabolism*
  • Models, Biological*
  • Molecular Conformation
  • Solutions
  • Water / chemistry
  • Water / metabolism

Substances

  • Solutions
  • Water
  • Hydrogen
  • nickel-iron hydrogenase
  • Hydrogenase