Impact of Tetrazolium Ionic Liquid Thermal Decomposition in Solvothermal Reaction on the Remarkable Photocatalytic Properties of TiO₂ Particles

Ionic liquids (ILs) could serve as a structuring agent, a solvent, or a source of dopant during solvothermal synthesis of semiconductors particles. To understand the role of IL during formation of TiO2 particles, it is necessary to study the stability of this IL in solvothermal synthesis conditions, as well as studying the surface properties of formed TiO2 particles. In view of this, the effect of the 2,3,5-triphenyltetrazolium chloride IL ([TPTZ][Cl]) thermal decomposition during the solvothermal reaction and IL content in the reaction system on photoactivity of TiO2 microparticles has been systematically investigated. The samples obtained by using [TPTZ][Cl] exhibited remarkable photocatalytic properties in phenol degradation reaction under visible light. HPLC analysis of the solvothermal reaction medium and X-ray photoelectron spectroscopy (XPS) analysis of TiO2 particles revealed that [TPTZ][Cl] was decomposed completely and was incorporated into the TiO2 lattice. Generally, increasing the reaction time (1, 4, 12, and 24 h) promoted the TiO2 microspheres formation, as well as raising the visible light-induced photocatalytic activity of the photocatalysts. Longer reaction time was also accompanied by an increase in the efficiency of 2,3,5-triphenyltetrazolium chloride decomposition. The properties of the photocatalysts were investigated by means of UV-VIS diffuse reflectance spectroscopy (DRS), BET surface area measurements, scanning electron microscopy (SEM), X-ray powder diffraction (XRD) analysis, and XPS

Bimetallic TiO2 Nanoparticles for Lignin-Based Model Compounds Valorization by Integrating an Optocatalytic Flow-Microreactor

The challenge of improving the activity of TiO2 by modifying it with metals and using it for targeted applications in microreactor environments is an active area of research. Recently, microreactors have emerged as successful candidates for many photocatalytic reactions, especially for the selective oxidation process. The current work introduces ultrasound-assisted catalyst deposition on the inner walls of a perfluoro-alkoxy alkane (PFA) microtube under mild conditions. We report Cu-Au/TiO2 and Fe-Au/TiO2 nanoparticles synthesized using the sol–gel method. The obtained photocatalysts were thoroughly characterized by UV–Vis diffuse-reflectance spectroscopy (DRS), high-resolution scanning electron microscopy (HR-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and N2 physisorption. The photocatalytic activity under UV (375 nm) and visible light (515 nm) was estimated by the oxidation of lignin-based model aromatic alcohols in batch and fluoropolymer-based flow systems. The bimetallic catalyst exhibited improved photocatalytic selective oxidation. Herein, four aromatic alcohols were individually investigated and compared. In our experiments, the alcohols containing hydroxy and methoxy groups (coniferyl and vanillin alcohol) showed high conversion (93% and 52%, respectively) with 8% and 17% selectivity towards their respective aldehydes, with the formation of other side products. The results offer an insight into ligand-to-metal charge transfer (LMCT) complex formation, which was found to be the main reason for the activity of synthesized catalysts under visible light

Fabrication of ILs-Assisted AgTaO3 Nanoparticles for the Water Splitting Reaction: The Effect of ILs on Morphology and Photoactivity

The design of an active, stable and efficient photocatalyst that is able to be used for hydrogen production is of great interest nowadays. Therefore, four methods of AgTaO3 perovskite synthesis, such as hydrothermal, solvothermal, sol-gel and solid state reactions, were proposed in this study to identify the one with the highest hydrogen generation efficiency by the water splitting reaction. The comprehensive results clearly show that the solid state reaction (SSR) led to the obtainment of a sample with an almost seven times higher photocatalytic activity than the other methods. Furthermore, four ionic liquids, all possessing nitrogen in the form of organic cations (two imidazoliums with different anions, ammonium and tetrazolium), were used for the first time to prepare composites consisting of AgTaO3 modified with IL and Pt, simultaneously. The effect of the ionic liquids (ILs) and Pt nanoparticles’ presence on the structure, morphology, optical properties, elemental composition and the effectiveness of the hydrogen generation was investigated and discussed. The morphology investigation revealed that the AgTaO3 photocatalysts with the application of [OMIM]-cation based ILs created smaller granules (<500 nm), whereas [TBA] [Cl] and [TPTZ] [Cl] ILs caused the formation of larger particles (up to 2 μm). We found that various ILs used for the synthesis did not improve the photocatalytic activity of the obtained samples in comparison with pristine AgTaO3. It was detected that the compound with the highest ability for hydrogen generation under UV-Vis irradiation was the AgTaO3_0.2% Pt (248.5 μmol∙g−1), having an almost 13 times higher efficiency in comparison with the non-modified pristine sample. It is evidenced that the enhanced photocatalytic activity of modified composites originated mainly from the presence of the platinum particles. The mechanism of photocatalytic H2 production under UV-Vis light irradiation in the presence of an AgTaO3_IL_Pt composite in the water splitting reaction was also proposed

Theoretical and Experimental Studies on the Visible Light Activity of TiO2 Modified with Halide-Based Ionic Liquids

Formation of a surface complex between organic molecules and TiO2 is one of the possible strategies for the development of visible light-induced TiO2 photoactivity. Herein, three ionic liquids (ILs) with the same cation and different anions (1-butylpirydynium chloride/bromide/iodide) have been applied for the surface modification of TiO2 and to understand the role of anions in visible light-induced activity of ILs-TiO2 systems. Photocatalytic screening tests (the measurements of phenol photodegradation reaction rate) revealed that anion type affected visible light activity (λ > 420 nm) of TiO2 obtained by the ILs-assisted solvothermal method. Density functional theory (DFT) calculations demonstrated that interactions between halogen anions and oxygen vacancies (OV) on the surface of the TiO2 particles could be responsible for the specific wavelength-induced excitation and finally for the observed photoactivity of titania under visible light. Finally, our theoretical calculations have been proven by experiments using monochromatic light (the apparent quantum efficiency was measured) and the properties of obtained samples were characterized using scanning electron microscopy (SEM), X-ray powder diffraction analysis (XRD), UV-Vis spectroscopy and X-ray photoelectron spectroscopy (XPS)

Dependence between Ionic Liquid Structure and Mechanism of Visible-Light-Induced Activity of TiO₂ Obtained by Ionic-Liquid-Assisted Solvothermal Synthesis

Because of the tremendous structural diversity of ionic liquids (ILs), simple transfer of observations performed for one IL used for IL-TiO₂ preparation on different samples is not possible. Therefore, four ionic liquids, all containing distinct nitrogen-bearing organic cations (pyridinium, pyrrolidinium, ammonium, imidazolium), were used for the first time for the preparation of IL-TiO₂ composites. The role of the individual IL cation in the synthesis of TiO₂ microspheres, as well as the effect of the IL structure on the mechanism of the visible-light (Vis)-induced photoactivity of IL-TiO₂ was presented and discussed in regard to structure, morphology, absorption properties, elemental composition, and reactive species involved in the photocatalytic reaction of phenol degradation. The successful modification of the TiO₂ with organic IL species including possible interactions between IL and TiO₂ surface, as well as the TiO₂ matrix (doping with N), were confirmed. The sample that exhibited the highest photoactivity under Vis irradiation (58%) was TiO₂ prepared in a presence of 1-butylpyridinium chloride with a IL:precursor molar ratio of 1:3. For this sample, the highest partial decomposition of cationic species of IL was observed resulting in interaction of N atoms with deeper sites of TiO₂ (Ti-N_<i>x</i>) as well as the highest surface defects in a form of Ti³⁺. The superoxide radical species O₂^• – were found to be main active species responsible for high efficiency of degradation under Vis irradiation

Highly Active TiO2 Microspheres Formation in the Presence of Ethylammonium Nitrate Ionic Liquid

Spherical microparticles of TiO2 were synthesized by the ionic liquid-assisted solvothermal method at different reaction times (3, 6, 12, and 24 h). The properties of the prepared photocatalysts were investigated by means of UV-VIS diffuse-reflectance spectroscopy (DRS), Brunauer&ndash;Emmett&ndash;Teller (BET) surface area measurements, scanning electron microscopy (SEM), X-ray diffraction analysis (XRD), and X-ray photoelectron spectroscopy (XPS). The results indicated that the efficiency of the phenol degradation was related to the time of the solvothermal synthesis, as determined for the TiO2_EAN(1:1)_24h sample. The microparticles of TiO2_EAN(1:1)_3h that formed during only 3 h of the synthesis time revealed a really high photoactivity under visible irradiation (75%). This value increased to 80% and 82% after 12 h and 24 h, respectively. The photoactivity increase was accompanied by the increase of the specific surface area, thus the poresize as well as the ability to absorb UV-VIS irradiation. The high efficiency of the phenol degradation of the ionic liquid (IL)&ndash;TiO2 photocatalysts was ascribed to the interaction between the surface of the TiO2 and ionic liquid components (carbon and nitrogen)