The development of methods to synthesize and study the properties of dark titania is of the utmost interest due to prospects for its use, primarily in photocatalysis when excited by visible light. In this work, the dark titania powder was prepared by pulsed laser ablation (Nd:YAG laser, 1064 nm, 7 ns) in water and dried in air. To study the changes occurring in the material, the thermal treatment was applied. The structure, composition, and properties of the obtained powders were studied using transmission electron microscopy, low-temperature N2 adsorption/desorption, X-ray diffraction, thermogravimetry/differential scanning calorimetry, X-ray photoelectron, Raman and UV-vis spectroscopies, and photoluminescence methods. The processes occurring in the initial material upon heating were studied. The electronic structure of the semiconductor materials was investigated, and the nature of the defects providing the visible light absorption was revealed. The photocatalytic and antibacterial activities of the materials obtained were also studied. Dark titania obtained via laser ablation in liquid was found to exhibit catalytic activity in the phenol photodegradation process under visible light (>420 nm) and showed antibacterial activity against Staphylococcus aureus and bacteriostatic effect towards Escherichia coli.
3 April 2024 in Transactions of Tianjin University
The development of visible-light active titanium dioxide is one of the key challenges in photocatalysis that stimulates the development of TiO2-based composite materials and methods for their synthesis. Here, we report the use of pristine and Pt-modified dark titanium dioxide prepared via pulsed laser ablation in liquid (Nd:YAG laser, 1064 nm, 7 ns) for photocatalytic hydrogen evolution from alcohol aqueous solutions. The structure, textural, optical, photoelectrochemical, and electrochemical properties of the materials are studied by a complex of methods including X-ray diffraction, low-temperature nitrogen adsorption, electrophoretic light scattering, diffuse reflection spectroscopy, photoelectrochemical testing, and electrochemical impedance spectroscopy. Both the thermal treatment effect and the effect of modification with platinum on photocatalytic properties of dark titania materials are studied. Optimal compositions and experimental conditions are selected, and high photocatalytic efficiency of the samples in the hydrogen evolution reaction (apparent quantum yield of H2 up to 0.38) is demonstrated when irradiated with soft UV and blue LED, i.e., 375 and 410 nm. The positive effect of low platinum concentrations on the increase in the catalytic activity of dark titania is explained.
Laser methods are successfully used to prepare complex functional nanomaterials, especially for biomedicine, optoelectronics, and heterogeneous catalysis. In this paper, we present complex oxide and composite nanomaterials based on Bi and Si produced using laser ablation in liquid followed by subsequent powder annealing. Two synthesis approaches were used, with and without laser post-treatment of mixed (in an atomic ratio of 2:1) laser-generated Bi and Si colloids. A range of methods were used to characterize the samples: UV-Vis diffusion reflection, IR and Raman spectroscopy, synchronous thermal analysis, X-ray diffraction, transmission electron microscopy, as well as specific surface-area evaluation. We also followed the dynamics of phase transformations, as well as composition, structure and morphology of annealed powders up to 800 °C. When heated, the non-irradiated series of samples proceeded from metallic bismuth, through β-Bi2O3, and resulted in bismuth silicates of various stoichiometries. At the same time, in their laser-irradiated counterparts, the formation of silicates proceeded immediately from the amorphous Bi2SiO5 phase formed after laser treatment of mixed Bi and Si colloids. Finally, we show their ability to decompose persistent organic molecules of Rhodamine B and phenol under irradiation with a soft UV (375 nm) source.
Hydrosphere pollution by organic pollutants of different nature (persistent dyes, phenols, herbicides, antibiotics, etc.) is one of the urgent ecological problems facing humankind these days. The task of water purification from such pollutants can be effectively solved with the help of modern photocatalytic technologies. This article is devoted to the study of photocatalytic properties of composite catalysts based on ZnO modified with plasmonic Ag nanoparticles. All materials were obtained by laser synthesis in liquid and differed by their silver content and preparation conditions, such as additional laser irradiation and/or annealing of produced powders. The prepared ZnO-Ag powders were investigated by electron microscopy, X-ray diffraction and UV-Vis spectroscopy. Photocatalytic tests were carried out with well- known test molecules in water (persistent dye rhodamine B, phenol and common antibiotic tetracycline) using LED light sources with wavelengths of 375 and 410 nm. The introduction of small concentrations (up to 1%) of plasmonic Ag nanoparticles is shown to increase the efficiency of the ZnO photocatalyst by expanding its spectral range. Both the preparation conditions and material composition were optimized to obtain composite photocatalysts with the highest efficiency. Finally, the operation mechanisms of the material with different distribution of silver are discussed.
In this work, we studied the catalytic performance of a β-Bi2O3/Bi12SiO20 nanocomposite material in the reactions involving the photodecomposition of rhodamine B and selective photooxidation of 5-hydroxymethylfurfural (HMF). The semiconductor composite nanomaterial was obtained by means of the mechanical grinding of a mixture of nanopowders of β-Bi2O3 and sillenite, both individually produced via pulsed laser ablation. The crystal structure of the prepared composite particles was confirmed by means of X-ray diffraction, while the optical properties of both individual components and their composite (with different ratios of Bi2O3 and Bi12SiO20) were also studied. The photocatalytic activity of the composite particles was studied in the course of their decomposition of rhodamine B under LED excitation at wavelengths of 375, 410 and 470 nm. It was shown that the optimal β-Bi2O3/Bi12SiO20 ratio in the composite particles resulted in their photocatalytic activity exceeding those of both single-phase β-Bi2O3 and Bi12SiO20, as well as that of their mixtures (by ~2.3 times for the excitation of an LED with λ = 375 nm). The novel composite particles were also found to perform better in the selective photocatalytic oxidation of HMF: at a conversion of ~5%, the selectivity toward DFF of the nanocomposite was significantly higher (10.3%) than that of sample Bi2O3 (−4.2%). A model was proposed that explains the increase in activity of the newly prepared photocatalyst due to the formation of a type II heterojunction in its particles.