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Sulfinato iron(III) complex for electrocatalytic proton reduction.

Andrew C Cavell1, Carolyn L Hartley1, Dan Liu1

  • 1†Department of Chemistry, College of William and Mary, 540 Landrum Drive, Williamsburg, Virginia 23185, United States.

Inorganic Chemistry
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Summary

This study introduces a novel sulfinato iron(III) complex as a highly active electrocatalyst for proton reduction. This iron complex shows promise for future aqueous proton reduction catalyst development.

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Area of Science:

  • Inorganic Chemistry
  • Electrochemistry
  • Catalysis

Background:

  • Proton reduction electrocatalysis is crucial for sustainable energy technologies.
  • Developing efficient and robust molecular catalysts remains a significant challenge.
  • Sulfinate ligands offer unique coordination properties for metal complexes.

Purpose of the Study:

  • To report the first sulfinato iron(III) complex as an electrocatalyst for proton reduction.
  • To investigate the catalytic mechanism and activity of the sulfinato Fe(III) complex.
  • To assess the potential of sulfinate groups in aqueous catalysis.

Main Methods:

  • Synthesis and characterization of a sulfinato Fe(III) complex.
  • Electrochemical evaluation of the complex for proton reduction in acetonitrile.
  • Kinetic studies to determine reaction orders and rate constants.

Main Results:

  • The sulfinato Fe(III) complex demonstrated high activity for proton reduction at -1.57 V vs Fc/Fc(+).
  • Catalysis exhibited first-order dependence on catalyst concentration and second-order dependence on trifluoroacetic acid.
  • An 11% increase in activity was observed in the presence of water, indicating potential for aqueous applications.

Conclusions:

  • Sulfinato iron(III) complexes are effective electrocatalysts for proton reduction.
  • The hemilabile nature of the sulfinate ligand likely plays a role in catalysis.
  • Sulfinate moieties show promise as functional groups for designing aqueous proton reduction catalysts.