Titanyl Sulphate, an Inorganic Polymer: Structural Studies and Vibrational Assignment

Abstract

In this work, anhydrous titanyl sulfate (TiOSO 4) was synthesized and characterized by elemental analyses and vibrational spectroscopy by the first time. In order to verify the stability of the crystallographic structure reported in the literature, an optimization calculation of the unit cell geometry was done with the CRYSTAL17 software, and the agreement with the experimental results was very good. Raman, infrared and far infrared spectra were obtained, the bands having been tentatively assigned, based on literature data for similar systems. Essentially, the spectra exhibit the vibrational modes of the sulfate anion splitted by the low local symmetry along with the bands of the TiO 6 skeleton. The Raman spectra shows two intense bands, tentatively assigned to Ti-O modes.

Investigating the activation of passive metals by a combined in-situ AFM and Raman spectroscopy system: a focus on titanium

“…10 ) indicating TiOSO 4 ·2H 2 O as the main constituent. The Raman lines at 192 cm −1 and 391 cm −1 , collected inside the concentration cell and in regions covered by the black corrosion product, coincide with the vibrations of the TiO 6 octahedra composing an oxy-sulphate crystal structure 44 . Moreover, depending on the hydration level of the sulphonated film doublet and triplet may arise from the ν 2 -SO 4 2− and ν 4 -SO 4 2− vibrational mode according to the symmetry lowering occurring when passing from the liquid to the solid state 41 .…”

Anomalous Deformation Behavior in ULE Glass upon Microindentation: A Vibrational Spectroscopic Investigation in the Induced Structural Changes of a Ti-Silicate Glass

“…In amorphous and crystalline fresnoite BaTiSi 2 O 8 , a broad band at 825 cm –1 or narrower bands at 854 and 873 cm –1 , respectively, dominate the spectra. , This apical short Ti–O bond of the square-planar pyramid of a fivefold coordinated titanium is written as Ti–O* in the literature to distinguish it from the bridging or charge-bearing nonbridging Ti–O bonds, without designating it as a TiO double bond. The latter seems to be elusive in solids, where, however, long and short Ti–O bonds have been confirmed . Those titanyl compounds for which a real double bond has been confirmed show a Raman band at 950 cm –1 or at higher frequency. ,, A band at lower frequencies, between 800 and 900 cm –1 , is typical for this apical short Ti–O* bond of [5] Ti and is also known for silica-free K 2 Ti 2 O 5 crystals, where it peaks at 905 cm –1 .…”

“…The latter seems to be elusive in solids, where, however, long and short Ti−O bonds have been confirmed. 60 Those titanyl compounds for which a real double bond has been confirmed show a Raman band at 950 cm −1 or at higher frequency. 56,60,61 A band at lower frequencies, between 800 and 900 cm −1 , is typical for this apical short Ti−O* bond of [5] Ti and is also known for silica-free K 2 Ti 2 O 5 crystals, where it peaks at 905 cm −1 .…”

“…60 Those titanyl compounds for which a real double bond has been confirmed show a Raman band at 950 cm −1 or at higher frequency. 56,60,61 A band at lower frequencies, between 800 and 900 cm −1 , is typical for this apical short Ti−O* bond of [5] Ti and is also known for silica-free K 2 Ti 2 O 5 crystals, where it peaks at 905 cm −1 . 56 In silicate-titanates, this band is overlaid by the activity of silicate tetrahedra with nonbridging oxygen atoms that are charge-balanced by a modifier cation, as the − [O 3 Si−O] δ− [TiO 4 ] δ+ linkage in fresnoite, which from the frequency around 850 cm −1 would correspond to Q 2 silicate groups (see Figure 4b,c).…”

Novel Method for Preparing Amorphous Titanyl Sulfate from Hydrous Titanium Oxide

“…Titanyl sulfate (TiOSO 4 ) has various applications in the industrial and scientific fields, including pigment preparation, photocatalysts, battery materials, ceramic materials, wastewater treatment, and electroplating materials. − Currently, the majority of titanyl sulfate produced in the chemical industry serves as an intermediate in the sulfate TiO 2 process. In this process, ilmenite is dissolved in sulfuric acid solution through acidolysis and leaching, resulting in a black viscous solution containing titanyl sulfate, ferrous sulfate, and sulfuric acid. − The solution also contains various impurity ions, such as calcium, magnesium, aluminum, chromium, vanadium, nickel, and other soluble impurities.…”