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Ionic liquids (ILs) containing distinct nitrogen-bearing organic cations (pyridinium, pyrrolidinium, imidazolium, ammonium, morpholinium) were first used for the preparation of 23 IL-TiO2 types of composites by ionic liquid assisted solvothermal synthesis. These 23 optimal ILs structures (i.e. compounds exhibiting an optimal combination of specific properties, functionality, and safety) for synthesis and experimental validation were selected by computational high-throughput screening from a combinatorically created library containing 836 ILs theoretically designed and characterized candidates. Then, selected IL-TiO2 structures with potential photocatalytic activity were synthesized with the use of solvothermal reaction. Then, the decomposition level, the role of the individual IL cation structure on the morphology, thermal stability, surface and photocatalytic properties of the IL-TiO2 microparticles were determined experimentally. The chemoinformatic analysis of the relationship between the structure of the ionic liquid, its thermal stability under the conditions of synthesis and photocatalytic activity was applied for the first time. The results presented here are the first step in the development of methodology (combined experimental and theoretical) that may simplify the procedure of designing safer and more efficient TiO2-based photocatalyst. The developed computational methodology makes it possible to predict properties of newly synthesized IL-TiO2 materials before synthesis and identifies structural features of ILs that influence the efficiency of IL-TiO2 system. The presented approach reduces the number and cost of necessary experiments, as well as increases the success ratio of efficient TiO2-based photocatalyst design by a selection of optimal IL structures (i.e. ionic liquid characterized by a combination of most promising physicochemical features).

Photocatalytic water splitting has great potential in solar-hydrogen production as a low-cost and environmentally friendly method. Different unique techniques used to obtain photocatalysts with various modifications to improve H2 generation have been introduced. In the present work, SrTiO3 was successfully synthesized via the solvothermal method in the presence of ionic liquid (IL) - 1-butyl-3-methylimidazolium bromide ([BMIM][Br]) followed by surface decoration with Pt particles using the photodeposition method. The effect of the noble metal content and presence of IL on the morphology, optical and surface properties of SrTiO3, thereby the effectiveness of hydrogen generation, has been thoroughly examined and presented. Unexpectedly, the presence of [BMIM][Br] at the SrTiO3 surface affected the interaction between the semiconductor surface and platinum particles formed throughout photodeposition. Platinum particles at the surface of SrTiO3_IL were found to be in the form of 2D clusters with a size of 1 nm. In comparison, Pt deposited on SrTiO3 photocatalyst without application of IL created larger, three-dimensional structures with a diameter exceeding 5 nm. This is the reason why the total amount of platinum deposited on the SrTiO3_IL sample is smaller than that on SrTiO3 and justifies a higher efficiency of hydrogen generation of Pt modified SrTiO3 photocatalyst in comparison to SrTiO3 prepared in the presence of IL. The mechanism of H2 generation in the water-splitting reaction in the presence of SrTiO3_Pt photocatalyst was discussed.

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&rsquo, 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 (&lt, 500 nm), whereas [TBA] [Cl] and [TPTZ] [Cl] ILs caused the formation of larger particles (up to 2 &mu, m). 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 &mu, mol∙g&minus, 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.

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 (&lambda, &gt, 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).

To investigate the effect of the ionic liquid (IL) chain length on the surface properties and photoactivity of TiO2, a series of TiO2 microspheres have been synthesized via a solvothermal method assisted by 1-methyl-3-octadecylimidazolium chloride ([ODMIM][Cl]) and 1-methyl-3-tetradecylimidazolium chloride ([TDMIM][Cl]). All as-prepared samples were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), scanning transmission microscopy (STEM) and the Brunauer–Emmett–Teller (BET) surface area method, whereas the photocatalytic activity was evaluated by the degradation of phenol in aqueous solution under visible light irradiation (λ > 420 nm). The highest photoefficiency (four times higher than pristine TiO2) was observed for the TiO2 sample obtained in the presence of [TDMIM][Cl] for a IL to TiO2 precursor molar ratio of 1:3. It was revealed that interactions between the ions of the ionic liquid and the surface of the growing titanium dioxide spheres results in a red-shift of absorption edge for the IL–TiO2 semiconductors. In this regard, the direct increase of the photoactivity of IL–TiO2 in comparison to pristine TiO2 was observed. The active species trapping experiments indicated that O2•− is the main active species, created at the surface of the IL–TiO2 material under visible-light illumination, and is responsible for the effective phenol degradation.

The effect of the ionic liquid's (IL) anion type ([BIMIM][X], where X= [Br], [PF6] or [OctSO4]) and content on the morphology, surface properties and photoactivity of TiO2 obtained by solvothermal method has been systematically investigated. Our results revealed that the presence of [Br], [OctSO4] anions favor formation of anatase phase, while presence of [PF6] anion causes formation of mixture of anatase and Ti(OH)PO4 phases. The highest photocatalytic activity under visible radiation (approximately four times higher than pristine TiO2) was observed for the TiO2 sample grown in a presence of 1-butyl-3-methylimidazolium bromide for ionic liquid to TiO2 precursor molar ratio 1:2. Visible light induced phenol degradation was found to be realized mainly by oxygen radical anions, whereas the contributions of the other processes, involving reactions with trapped electrons, holes and hydroxyl radical, are limited in the overall reaction mechanism. Quantum chemical calculations concerning model of anatase vacancy suggest that charge transfer between the bromide anion and molecular oxygen interacting with the vacancy is a source of photoreactivity induced by visible photons.

Most efforts in heterogeneous photocatalysis are focused on development of new and stable photoactive materials efficient in degradation of various pollutants under visible-light irradiation. In this regard, the wide-bandgap perovskite semiconductors, i.e., SrTiO3 (titanate), SrSnO3 (stannate) and AgTaO3 (tantalate), were prepared by a solvothermal method, and then modified with carbon quantum dots (CQDs) or graphene quantum dots (GQDs) co-modified with erbium. The photocactivity was investigated for: (i) toluene degradation (gas phase), (ii) phenol decomposition (aqueous phase), and (iii) inactivation of Escherichia coli K12 bacteria. It has been found that the morphology of semiconductors depends on the synthesis conditions, resulting in the formation of spherical particles, rods and faceted particles for SrTiO3, SnSrO3 and AgTaO3, respectively. Additionally, deposition of CQDs and GQDs/erbium has resulted in an enhancement of light harvesting, thus improved photoactivity under visible-light irradiation. Samples modified with both erbium and GQDs revealed much higher photoactivity than corresponding pristine and CQDs-modified samples. Moreover, all photocatalyst modified with GQDs and Er exhibited a significant antibacterial properties under visible light irradiation (λ > 420 nm). Accordingly, it has been proposed that obtained semiconductors modified with QDs and Er are promising candidates as sustainable, clean and cheap materials for environmental purification under solar radiation.

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).

Spherical microparticles of TiO2 were synthesized by the ionic liquid-assisted solvothermal method at different reaction time (3, 6, 12 and 24h). The properties of the prepared photocatalysts were investigated by means of UV-vis diffuse-reflectance spectroscopy (DRS), 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 phenol degradation was related with a time of the solvothermal synthesis as determined for TiO2_EAN(1:1)_24h sample. Microparticles of TiO2_EAN(1:1)_3h formed during the only 3h of synthesis time revealed really high photoactivity under visible irradiation – 75%. This value increased to 80% and 82% after 12h and 24h, respectively. The photoactivity increase was accompanied by the increase of the specific surface area thus pores size, as well as ability to absorb UV-vis irradiation. The high efficiency of phenol degradation of IL-TiO2 photocatalysts was ascribed to the interaction between the surface of TiO2 and ionic liquid components (carbon and nitrogen).

Efficient and stable photocatalysts must satisfy some critical requirements: (1) the semiconductor must have a bandgap large enough to provide energetic electrons, but small enough to allow for efficient absorption overlap with the solar spectrum (1.23 eV ≤ E g ≤ 3.0 eV, typically E g > 2.0 eV); (2) there must be a mechanism to efficiently drive the charge separation and transportation processes. From this viewpoint, it is important to obtain photocatalysts with high photoefficiency. This chapter describes the synthetic methods of unitary metal oxide semiconductors (TiO 2 , WO 3 , ZnO, Fe 3 O 3 , Ta 2 O 5 , and CuO), heterojunction photocatalysts, and composite-based materials. Their structure, surface properties, and photocatalytic activity are also discussed.

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 photo...