11. Polyoxometalate Water Oxidation Catalytic Systems

  1. Antoni Llobet
  1. Jordan M. Sumliner,
  2. James W. Vickers,
  3. Hongjin Lv,
  4. Yurii V. Geletii and
  5. Craig L. Hill

Published Online: 18 APR 2014

DOI: 10.1002/9781118698648.ch11

Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes

Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes

How to Cite

Sumliner, J. M., Vickers, J. W., Lv, H., Geletii, Y. V. and Hill, C. L. (2014) Polyoxometalate Water Oxidation Catalytic Systems, in Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes (ed A. Llobet), John Wiley & Sons, Ltd, Chichester, UK. doi: 10.1002/9781118698648.ch11

Editor Information

  1. Institute of Chemical Research of Catalonia, Tarragona, Spain

Author Information

  1. Department of Chemistry, Emory University, Atlanta, GA, USA

Publication History

  1. Published Online: 18 APR 2014
  2. Published Print: 16 MAY 2014

ISBN Information

Print ISBN: 9781118413371

Online ISBN: 9781118698648

SEARCH

Keywords:

  • Water oxidation;
  • polyoxometalates;
  • visible-light-driven water oxidation;
  • stability;
  • O2 detection

Summary

Catalytic water oxidation is indispensable to solar fuel production. We have developed a family of soluble water oxidation catalysts (WOCs) based on polyoxometalates (POMs) that address many issues of concern or interest to the solar fuels research community: POM WOCs are soluble so their properties can be extensively probed experimentally and computationally, they are carbon-free and thus oxidatively resistant, thermally robust and hydrolytically stable over wide pH ranges dictated by the POM metal(s) and structure. Many POM WOCs have now been reported but truly in-depth studies of their reactivity and stability have been needed for clarity. This review addresses these issues: it elaborates pitfalls in the study of these systems, including common misinterpretations of experimental data, it discusses POM hydrolytic chemistry, and describes the many techniques used to date to probe POM WOC reactivity and stability, including some new ones that unequivocally distinguish between water oxidation by POMs versus hydrated metal cations and metal oxides that can be in equilibrium with or form from the POM.