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. 2019 Sep 29;12(19):3195.
doi: 10.3390/ma12193195.

Trinuclear Oxo-Titanium Clusters: Synthesis, Structure, and Photocatalytic Activity

Maciej Janek  1 , Tadeusz M Muzioł  2 , Piotr Piszczek  3
Affiliations

Trinuclear Oxo-Titanium Clusters: Synthesis, Structure, and Photocatalytic Activity

Maciej Janek et al. Materials (Basel). .

Abstract

The interest in titanium (IV) oxo-complexes is due to their potential application in photodegradation processes and environmental pollutants reduction. Titanium (IV) oxo-complexes (TOCs) of the general formula [Ti3O(OiPr)8(OOCR')2] (R' = -C13H9 (1), -p-PhCl (2), -m-PhNO2 (3), -C4H7 (4)) were synthesized and structurally characterized. The use of the different carboxylate ligands allowed modulating the optical band gaps of the produced microcrystals, which were measured via diffuse reflectance ultraviolet and visible spectroscopy (UV-Vis-DRS) and calculated using the density functional theory (DFT) method. The dispersion of TOCs (1-3) in the poly (methyl methacrylate) matrix (PMMA) led to the formation of polymer/TOCs composites, which in the next stage of our works have been applied in the photocatalytic activity estimation of synthesized trinuclear Ti(IV) oxo-complexes. Studies of the photocatalytic degradation of methylene blue (MB) induced by UV irradiation exhibit that the PMMA-TOCs composite containing (1) oxo-clusters is the most active, followed by the system containing the complex (3).

Keywords: DFT calculations; Titanium (IV) oxo-clusters; bandgap modification; photocatalytic activity; polymer/inorganic composite systems; structure.

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Conflict of interest statement

The authors declare no conflicts of interest. The sponsors had no role in the design, execution, interpretation, or writing of the study.

Figures

Figure 1
Figure 1
Structure of {Ti3O} core, which was found in [Ti3O(OR)8(O2CR’)2] (R = iPr, R’ = PhCl (2), PhNO2 (3) complexes (crystallographic ball-stick scheme). For clarity, the terminal alkoxide groups are omitted.
Figure 2
Figure 2
IR (a) and Raman (b) spectra of (1–4) complexes, registered in the range of appearance of bands coming from vibrations of {Ti3O} bridges.
Figure 3
Figure 3
UV-Vis-DRS spectra of (1–4) complexes (a) and Kubelka–Munk function versus light energy plot for the band gap determination (b).
Figure 4
Figure 4
Plots calculated with B3LYP/6-31G(d) level of theory for optimized geometries of [Ti3O(OMe)8(O2CC13H9)2], [Ti3O(OMe)8(O2CC6H4-Cl)2], [Ti3O(OMe)8(O2CC6H4-NO2)2], and [Ti3O(OMe)8(O2CC4H7)2] clusters.
Figure 4
Figure 4
Plots calculated with B3LYP/6-31G(d) level of theory for optimized geometries of [Ti3O(OMe)8(O2CC13H9)2], [Ti3O(OMe)8(O2CC6H4-Cl)2], [Ti3O(OMe)8(O2CC6H4-NO2)2], and [Ti3O(OMe)8(O2CC4H7)2] clusters.
Figure 5
Figure 5
Scanning electron microscopy (SEM) images of PMMA/TOCs composite foils (PMMA = poly(methyl methacrylate); TOCs = (1), (2), (3)) used in photocatalytic experiments.
Figure 6
Figure 6
Changes in the concentration of methylene blue (MB) solution under photocatalysis experiment conditions for studied PMMA/{Ti3O} (1–3) composite foils.
Figure 7
Figure 7
Pseudo-first order fitting of the methylene blue photocatalysis on PMMA foils with selected complexes.
See this image and copyright information in PMC

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