Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 116, Issue 12, Pages 7219-7226Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp212577g
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Funding
- Netherlands Organization for Scientific Research (NWO)
- Shell-TU Delft
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The incorporation of Fe as a dopant in anatase TiO2 nanoparticles has been systematically investigated with the aim of changing the coordination geometry of Ti via the formation of oxygen vacancies. Although Fe3+ ions are present in the solution during growth of the nanoparticles, a high-temperature heat treatment is found to be necessary to incorporate Fe3+ as a substituent for Ti4+ in the bulk of the TiO2 nanoparticles. The Fe3+ acceptors are found to be charge-compensated by oxygen vacancies, up to dopant concentrations as high as 10%. The surprisingly high solubility of Fe is attributed to the very similar radii of Ti4+ and Fe3+ and to the energetically favorable Coulomb attraction between the negatively charged Fe acceptor and the positively charged oxygen vacancies. A combined EXAFS/XANES study reveals that part of the Ti4+ ions changes their coordination number from 6 to 4 at high oxygen vacancy concentrations. The deliberate use of oxygen vacancies to modify the coordination geometry of metal ions represents a new strategy that offers exciting possibilities to tune the selectivity of photocatalytically active metal oxide nanoparticles.
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