Following Electroenzymatic Hydrogen Production by Rotating Ring-Disk Electrochemistry and Mass Spectrometry*

Angew Chem Int Ed Engl. 2021 Apr 26;60(18):10001-10006. doi: 10.1002/anie.202100863. Epub 2021 Mar 22.

Abstract

Gas-processing metalloenzymes are of interest to future bio- and bioinspired technologies. Of particular importance are hydrogenases and nitrogenases, which both produce molecular hydrogen (H2 ) from proton (H+ ) reduction. Herein, we report on the use of rotating ring-disk electrochemistry (RRDE) and mass spectrometry (MS) to follow the production of H2 and isotopes produced from deuteron (D+ ) reduction (HD and D2 ) using the [FeFe]-hydrogenase from Clostridium pasteurianum, a model hydrogen-evolving metalloenzyme. This facilitates enzymology studies independent of non-innocent chemical reductants. We anticipate that these approaches will be of value in resolving the catalytic mechanisms of H2 -producing metalloenzymes and the design of bioinspired catalysts for H2 production and N2 fixation.

Keywords: [FeFe]; enzymatic electrochemistry; hydrogen; kinetic isotope effect; metalloenzymes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Clostridium / enzymology
  • Electrochemical Techniques
  • Electrodes
  • Hydrogen / chemistry
  • Hydrogen / metabolism*
  • Hydrogenase / chemistry
  • Hydrogenase / metabolism*
  • Iron-Sulfur Proteins / chemistry
  • Iron-Sulfur Proteins / metabolism*
  • Mass Spectrometry

Substances

  • Iron-Sulfur Proteins
  • Hydrogen
  • iron hydrogenase
  • Hydrogenase

Supplementary concepts

  • Clostridium pasteurianum