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

机译:金属掺杂的聚氧钛钛笼的光学性质及其与金属掺杂的二氧化钛关系的研究

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摘要

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). © 2014 the Partner Organisations.
机译:过渡金属离子的存在可以在多大程度上影响结构明确的金属掺杂的聚氧钛(POT)笼的光学性能,这是关于这些物种对技术上重要的金属掺杂的TiO2建模的紧密程度的一个关键问题。这也直接暗示了这些有机可溶性无机笼作为光催化氧化还原系统在化学转化中的潜在应用。一系列紧密相关的多氧钛钛笼[MnTi14(OEt)28O14(OH)2](1),[FeTi14(OEt)28O14(OH)2](2)和[GaTi14(OEt)28O15( OH)](3)包含间隙性Mn(ii),Fe(ii)和Ga(iii)掺杂离子,表明仅过渡金属掺杂不会降低带隙,使其低于TiO2或相应的金属掺杂TiO2。相反,这些笼的带隙在先前发现的过渡金属掺杂的TiO2纳米粒子的值范围内。先前报道的1和最近报道的相关Mn掺杂POT笼的低带隙似乎是低带隙杂质(很可能是非晶态Mn掺杂的TiO2)的结果。 ©2014合作伙伴组织。

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