Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles: Computational modeling, assembly and characterization

Gonghu Li, Eduardo M. Sproviero, Robert C. Snoeberger, Nobuhito Iguchi, James D. Blakemore, Robert H. Crabtree, Gary W. Brudvig, Victor S. Batista

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Abstract

Inexpensive water oxidation catalysts are needed to develop photocatalytic solar cells that mimic photosynthesis and produce fuel from sunlight and water. This paper reports the successful attachment of a dinuclear di - oxo manganese water oxidation catalyst [H2O(terpy)Mniii(-O)2 Mniv(terpy)H2O](NO3)3 (1, terpy = 2,2′:6′2″-terpyridine) onto TiO2 nanoparticles (NPs) via direct adsorption, or in situ synthesis. The resulting surface complexes are characterized by EPR and UV-visible spectroscopy, electrochemical measurements and computational modeling. We conclude that the mixed-valence (iii,iv) state of 1 attaches to near-amorphous TiO2 NPs by substituting one of its water ligands by the TiO2 NP, as suggested by low-temperature (7 K) EPR data. In contrast, the analogous attachment onto well-crystallized TiO2 NPs leads to dimerization of 1 forming Mn(iv) tetramers on the TiO2 surface as suggested by EPR spectroscopy and electrochemical studies.

Original languageEnglish
Pages (from-to)230-238
Number of pages9
JournalEnergy and Environmental Science
Volume2
Issue number2
DOIs
Publication statusPublished - Aug 31 2009

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ASJC Scopus subject areas

  • Environmental Chemistry
  • Renewable Energy, Sustainability and the Environment
  • Nuclear Energy and Engineering
  • Pollution

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