Sensitized layered metal oxide semiconductor particles for photochemical hydrogen evolution from nonsacrificial electron donors

Yeong Il Kim, Stephen J. Atherton, Elaine S. Brigham, Thomas E. Mallouk

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Abstract

Layered alkali-metal titanates (Na 2 Ti 3 O 7 and K 2 Ti 4 O 9 ), niobates (KNb 3 O 8 and K 4 Nb 6 O 17 ), and titanoniobates (KTiNbO 5 and CsTi 2 NbO 7 ) were internally platinized, acid-exchanged, sensitized with ruthenium polypyridyl complexes, and studied as photocatalysts for the production of H 2 and I 3 - from acidic alkali-metal iodide solutions. The titanates were inactive as photocatalysts, whereas the niobates and titanoniobates were active with quantum efficiencies up to 0.3% for HI photolysis with visible light. Calculations based on electronegativity showed that the conduction band edge potentials of the acid-exchanged titanates were too positive to prevent semiconductor-mediated recombination of photogenerated H 2 and I 3 - . Laser flash photolysis/transient diffuse reflectance spectra established that iodide reduces the oxidized sensitizer, forming I 2 •- , which subsequently decays in a bimolecular reaction to form I 3 - . The inefficiency of HI photolysis can be attributed to charge recombination between I 3 - and conduction band electrons for the niobates and titanoniobates. Modulation of the layer spacing in the hexaniobate, A 4-x H x Nb 6 O 17 , by exchange with different alkali metals (A), showed that the hydrogen evolution rate decreased sharply as the average layer spacing increased. This result suggests that the competition between charge recombination and electron tunneling between layers determines the efficiency of the HI photolysis reaction.

Original languageEnglish (US)
Pages (from-to)11802-11810
Number of pages9
JournalJournal of physical chemistry
Volume97
Issue number45
DOIs
StatePublished - Jan 1 1993

All Science Journal Classification (ASJC) codes

  • Engineering(all)
  • Physical and Theoretical Chemistry

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