A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania

Yaokang Lv, Jun Cheng (Corresponding Author), Peter D Matthews, Juan Pedro Holgado, Janina Willkomm, Michal Leskes, Alexander Steiner, Dieter Fenske, Timothy C King, Paul T Wood, Lihua Gan, Richard M. Lambert, Dominic S Wright

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Abstract

To what extent the presence of transition metal ions can affect the optical properties of structurally well-defined, metal-doped polyoxotitanium (POT) cages is a key question in respect to how closely these species model technologically important metal-doped TiO2. This also has direct implications to the potential applications of these organically-soluble inorganic cages as photocatalytic redox systems in chemical transformations. Measurement of the band gaps of the series of closely related polyoxotitanium cages [MnTi14(OEt)28O14(OH)2] (1), [FeTi14(OEt)28O14(OH)2] (2) and [GaTi14(OEt)28O15(OH)] (3), containing interstitial Mn(II), Fe(II) and Ga(III) dopant ions, shows that transition metal doping alone does not lower the band gaps below that of TiO2 or the corresponding metal-doped TiO2. Instead, the band gaps of these cages are within the range of values found previously for transition metal-doped TiO2 nanoparticles. The low band gaps previously reported for 1 and for a recently reported related Mn-doped POT cage appear to be the result of low band gap impurities (most likely amorphous Mn-doped TiO2).
Original languageEnglish
Pages (from-to)8679-8689
Number of pages11
JournalDalton Transactions
Volume43
Issue number23
Early online date15 Apr 2014
DOIs
Publication statusPublished - 21 Jun 2014

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Lv, Y., Cheng, J., Matthews, P. D., Holgado, J. P., Willkomm, J., Leskes, M., ... Wright, D. S. (2014). A study of the optical properties of metal-doped polyoxotitanium cages and the relationship to metal-doped titania. Dalton Transactions, 43(23), 8679-8689. https://doi.org/10.1039/C4DT00555D