Al3+ and H+ substitutions in TiO2 polymorphs: Structural and vibrational investigations

Sha Wang; Qingbo Wang; Yu Ye; Dan Liu; Xi Zhu; Yancheng Hu; Yunfan Miao; Zhen Wu; Yanming Pan

doi:10.2138/am-2024-9316

Article

Al³⁺ and H⁺ substitutions in TiO₂ polymorphs: Structural and vibrational investigations

Sha Wang , Qingbo Wang , Yu Ye , Dan Liu , Xi Zhu , Yancheng Hu , Yunfan Miao , Zhen Wu and Yanming Pan

Published/Copyright: February 4, 2025

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From the journal American Mineralogist Volume 110 Issue 2

Abstract

Rutile is the most common TiO₂ mineral on Earth’s surface and transforms to CaCl₂- and α-PbO₂-type structures at elevated pressures in subducted basaltic crusts. In this study, we synthesized hydrous CaCl₂- and α-PbO₂-type TiO₂ crystals with various Al³⁺ concentrations using a multi-anvil press. Al³⁺ is incorporated into the CaCl₂- and rutile-type phases mainly in the form of 3Ti⁴⁺ = 4Al³⁺, while the coupled substitution of Ti⁴⁺=Al³⁺+H⁺ is dominant in the α-PbO₂-type structure, forming Ti₁−x(AlH)x_O2 solid solutions. Consequently, the water solubility in Al-bearing α-PbO₂-type TiO₂ is at least one order of magnitude greater than those in rutile- and CaCl₂-type TiO₂ phases, making TiO₂ a significant water carrier at the pressure-temperature (P-T) conditions in the mantle transition zone (410 to 660 km depth in deep Earth’s interior), when coexisting with Al³⁺ and Fe³⁺. High-P and high-T Raman spectra were collected for these synthetic samples. The CaCl₂- and α-PbO₂-type phases irreversibly transform to a rutile-type structure at 950 K and ambient pressure. A reversible α-PbO₂→baddeleyite phase transition in TiO₂ is detected at approximately P = 10 GPa and T = 300 K, and incorporating smaller amounts of Al³⁺ cations increases the phase transition pressure. The lattice vibrational modes typically shift to lower frequencies at elevated temperature and higher frequencies with increasing pressure due to variations in Ti(Al)-O bond length with temperature or pressure. Fourier transform infrared (FTIR) spectroscopic measurements were conducted on the samples under high-T or high-P conditions. Both T- and P-dependences are negative for the OH stretching vibrations in these TiO₂ polymorphs, except that the OH bands in the α-PbO₂-type samples exhibit a blueshift at elevated temperature. A negative linear correlation can be drawn between the measured OH stretching frequencies and the incorporated M³⁺O₆ quadratic elongation, which were computed based on first-principles calculations. The local octahedral distortion can provide useful insights for understanding the M³⁺ and H⁺ incorporation mechanisms in TiO₂ and SiO₂ structures.

Keywords: TiO2 polymorphs; Al-H coupled substitution; structure refinement; OH stretching vibration; octahedral distortion

Acknowledgments and Funding

This work was supported by the National Natural Science Foundation of China (42072050, 42302040) and the National Key Research and Development Program of China (Grant No. 2018YFA0702700). We appreciate the feedback and comments from Associate Editor Charles Geiger, reviewer George Rossman, and an anonymous reviewer.

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Received: 2024-01-15

Accepted: 2024-05-26

Published Online: 2025-02-04

Published in Print: 2025-02-25

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https://doi.org/10.2138/am-2024-9316

Keywords for this article

TiO2 polymorphs; Al-H coupled substitution; structure refinement; OH stretching vibration; octahedral distortion

Al3+ and H+ substitutions in TiO2 polymorphs: Structural and vibrational investigations

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Al³⁺ and H⁺ substitutions in TiO₂ polymorphs: Structural and vibrational investigations