Anisotropy of photocatalytic properties of MoO3/TiO2–SiO2 core–shell polycrystalline composites

• Published in: Inorganic chemistry communications 2024-02, Vol.160, p.112005, Article 112005
• Main Authors: Kuznetsova, Svetlana A., Khalipova, Olga S., Averina, Galina A., Malchik, Alexandra G., Chen, Yu-Wen
• Format: Article
• Language: English
• Subjects: Molybdenum trioxide; Organic dye destruction; Orientations of single crystals in polycrystallites; Photocatalysis; Titanium dioxide
• ISSN: 1387-7003; 1879-0259
• DOI: 10.1016/j.inoche.2023.112005

[Display omitted] •Spherical MoO3/TiO2–SiO2 core–shell materials were prepared by sol–gel and template methods at different temperatures.•The anisotropy of photocatalytic properties of MoO3/TiO2–SiO2 depends on the number of MoO3 crystals oriented in the layer growth plane (l00).•The predominance of MoO3 crystallites oriented in the growth plane (l00) leads to the formation of less defective MoO3 in the anion sublattice (MoO2.951) and more defective in the cation sublattice, forming the Mo5+ cation ([Mo5+O5]), that influences the recombination of charge carriers in the MoO3/TiO2–SiO2 material. In this work, the effect of the preferred orientation of MoO3 crystals in polycrystalline MoO3/TiO2–SiO2 composites on their optical properties and photocatalytic activities in the decomposition reaction of organic dyes was investigated. The anisotropy of the photocatalytic properties was shown. The MoO3/TiO2–SiO2 core–shell spherical composites were prepared using TOKEM-320Y anion exchange resin as a template by the combined method, including template and sol–gel methods. The XRD, XPS, EDS, SEM, Raman, IR, DRS, N2 sorption, and PL techniques were used to characterize the elemental and phase compositions, textural and optical properties of the MoO3/TiO2–SiO2 spherical particles. The MoO3/TiO2–SiO2 composites prepared at 600 °C were characterized by the lowest anisotropy coefficient (1.23) of the crystals growth rate in the plane (l00) relative to the crystals growth rate in the plane (lll) and the highest concentration of oxygen vacancies. High temperature treatment of MoO3/TiO2–SiO2 samples up to 700 °C leads to a change in the degree of their texture, which is due to the growth of the anisotropy coefficient up to 1.38 and crystallites in the (l00) plane, which was confirmed by increasing the Lotgering factor. The content of Mo5+ in the surface and subsurface layers of such composites is the highest. The MoO3/TiO2 − SiO2 composites prepared at 600 °C exhibited a much higher photocatalytic activity (the rate constant is 0.0319 min-1). This work demonstrates that the predominant orientation of MoO3 crystals in the (l00) plane negatively affects the oxygen defect (the value decreases to 0.0486) and MoO3/TiO2 − SiO2 polycrystalline composites photocatalytic activity.