Effect of protons on the redox chemistry of colloidal zinc oxide nanocrystals

J Am Chem Soc. 2013 Jun 12;135(23):8492-5. doi: 10.1021/ja4035945. Epub 2013 May 29.

Abstract

Electron transfer (ET) reactions of colloidal 3-5 nm diameter ZnO nanocrystals (NCs) with molecular reagents are explored in aprotic solvents. Addition of an excess of the one-electron reductant Cp*2Co (Cp* = pentamethylcyclopentadienyl) gives NCs that are reduced by up to 1-3 electrons per NC. Protons can be added stoichiometrically to the NCs by either a photoreduction/oxidation sequence or by addition of acid. The added protons facilitate the reduction of the ZnO NCs. In the presence of acid, NC reduction by Cp*2Co can be increased to over 15 electrons per NC. The weaker reductant Cp*2Cr transfers electrons only to ZnO NCs in the presence of protons. Cp*2M(+) counterions are much less effective than protons at stabilizing reduced NCs. With excess Cp*2Co or Cp*2Cr, the extent of reduction increases roughly linearly with the number of protons added. Some of the challenges in understanding these results are discussed.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Colloids / chemistry
  • Nanoparticles / chemistry*
  • Oxidation-Reduction
  • Protons*
  • Zinc Oxide / chemistry*

Substances

  • Colloids
  • Protons
  • Zinc Oxide