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

Research output: Contribution to journalArticle

63 Citations (Scopus)

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 - 2009

Fingerprint

electron spin resonance
catalyst
Nanoparticles
Paramagnetic resonance
oxidation
Oxidation
Catalysts
Water
modeling
spectroscopy
Spectroscopy
water
Dimerization
Photosynthesis
Manganese
ligand
manganese
Solar cells
photosynthesis
Ligands

ASJC Scopus subject areas

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

Cite this

Li, G., Sproviero, E. M., Snoeberger, R. C., Iguchi, N., Blakemore, J. D., Crabtree, R. H., ... Batista, V. S. (2009). Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles: Computational modeling, assembly and characterization. Energy and Environmental Science, 2(2), 230-238. https://doi.org/10.1039/b818708h

Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles : Computational modeling, assembly and characterization. / Li, Gonghu; Sproviero, Eduardo M.; Snoeberger, Robert C.; Iguchi, Nobuhito; Blakemore, James D.; Crabtree, Robert H.; Brudvig, Gary W; Batista, Victor S.

In: Energy and Environmental Science, Vol. 2, No. 2, 2009, p. 230-238.

Research output: Contribution to journalArticle

Li, Gonghu ; Sproviero, Eduardo M. ; Snoeberger, Robert C. ; Iguchi, Nobuhito ; Blakemore, James D. ; Crabtree, Robert H. ; Brudvig, Gary W ; Batista, Victor S. / Deposition of an oxomanganese water oxidation catalyst on TiO2 nanoparticles : Computational modeling, assembly and characterization. In: Energy and Environmental Science. 2009 ; Vol. 2, No. 2. pp. 230-238.
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