Efficient water oxidation catalysts based on readily available iron coordination complexes

Nat Chem. 2011 Sep 4;3(10):807-13. doi: 10.1038/nchem.1140.

Abstract

Water oxidation catalysis constitutes the bottleneck for the development of energy-conversion schemes based on sunlight. To date, state-of-the-art homogeneous water oxidation catalysis is performed efficiently with expensive, toxic and earth-scarce transition metals, but 3d metal-based catalysts are much less established. Here we show that readily available, environmentally benign iron coordination complexes catalyse homogeneous water oxidation to give O(2), with high efficiency during a period of hours. Turnover numbers >350 and >1,000 were obtained using cerium ammonium nitrate at pH 1 and sodium periodate at pH 2, respectively. Spectroscopic monitoring of the catalytic reactions, in combination with kinetic studies, show that high valent oxo-iron species are responsible for the O-O forming event. A systematic study of iron complexes that contain a broad family of neutral tetradentate organic ligands identifies first-principle structural features to sustain water oxidation catalysis. Iron-based catalysts described herein open a novel strategy that could eventually enable sustainable artificial photosynthetic schemes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cerium / chemistry
  • Coordination Complexes / chemistry*
  • Hydrogen-Ion Concentration
  • Iron / chemistry*
  • Kinetics
  • Nitrates / chemistry
  • Oxidation-Reduction
  • Oxides / chemistry
  • Periodic Acid / chemistry
  • Spectrophotometry, Ultraviolet
  • Water / chemistry*

Substances

  • Coordination Complexes
  • Nitrates
  • Oxides
  • cerium(IV) ammonium nitrate
  • Water
  • Periodic Acid
  • perferryl iron
  • Cerium
  • metaperiodate
  • Iron

Associated data

  • PubChem-Substance/124876633
  • PubChem-Substance/124876634
  • PubChem-Substance/124876635
  • PubChem-Substance/124876636
  • PubChem-Substance/124876637
  • PubChem-Substance/124876638
  • PubChem-Substance/124876639
  • PubChem-Substance/124876640
  • PubChem-Substance/124876641
  • PubChem-Substance/124876642
  • PubChem-Substance/124876643
  • PubChem-Substance/124876644