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• W2057112488 endingPage "10037" @default.
• W2057112488 startingPage "10029" @default.
• W2057112488 abstract "Layered titanium phosphates (TiPs) have many potentially important applications in ion exchange, catalysis, intercalation, and sorption. Characterization of metal local environments by solid-state 47/49Ti NMR has been difficult due to many unfavorable 47/49Ti NMR properties. In this work, we have directly characterized the local structures around Ti in several representative layered TiPs, including α-, β-, and γ-TiP, by examining the 47/49Ti static NMR spectra of these materials at an ultrahigh magnetic field of 21.1 T. The 47/49Ti chemical shielding and electric field gradient (EFG) tensors have been extracted from spectral analysis. The observed 47/49Ti spectra are mainly determined by the second-order quadrupolar interactions. The quadrupole coupling constants (CQ) are sensitive to the distortion of the TiO6 octahedron in this series of layered TiPs. Quantum mechanical calculations have been performed on several model clusters as well as periodic systems. The results indicate that, in addition to the oxygens in the first coordination sphere of Ti, the atoms in the second and third coordination spheres and beyond also have significant effects on the EFG at the metal center, and this long-range effect contributes substantially to the CQ. A relationship between observed CQ and the Ti−O bond length distortion parameter appears to exist, and this empirical correlation is also confirmed by theoretical calculations. Using sodium-exchanged α-TiP (α-Na-TiP) with an unknown structure as an example, we show that the 47/49Ti NMR spectra can provide partial information on the local environment of the metal center. For this material, the ion exchange does not affect the Ti local environment significantly. It appears that the layer in α-TiP is more robust compared to that of the zirconium analogue." @default.
• W2057112488 created "2016-06-24" @default.
• W2057112488 creator A5008557264 @default.
• W2057112488 creator A5022187815 @default.
• W2057112488 creator A5029489804 @default.
• W2057112488 creator A5060635954 @default.
• W2057112488 date "2009-05-13" @default.
• W2057112488 modified "2023-10-17" @default.
• W2057112488 title "A ^47/49Ti Solid-State NMR Study of Layered Titanium Phosphates at Ultrahigh Magnetic Field" @default.
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• W2057112488 doi "https://doi.org/10.1021/jp901235w" @default.
• W2057112488 hasPublicationYear "2009" @default.
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