Search Results (11)

The search for effective and reliable methods of photosensitization of oxide-based semiconductor materials is of great significance for their use in photocatalytic reactions of hydrogen production and environmental remediation under natural sunlight. The present study is focused on partial substitution of titanium with manganese in the structure of layered perovskite-like titanate Na₂La₂Ti₃O₁₀, which was employed to yield a series of photocatalytically active materials, Na₂La₂Mn_xTi_3−xO₁₀ (x = 0.002–1.0), as well as their protonated forms H₂La₂Mn_xTi_3−xO₁₀ and nanosheets. It was established that the manganese cations Mn⁴⁺ are embedded in the middle sublayer of oxygen octahedra in the perovskite slabs La₂Mn_xTi_3−xO₁₀²⁻ and that the maximum achievable manganese content x in the products is ≈0.9. The partial cationic substitution in the perovskite sublattice led to a pronounced contraction of the optical band gap from 3.20 to 1.35 eV (depending on x) and, therefore, allowed the corresponding photocatalysts to utilize not only ultraviolet, but also visible and near-infrared light with wavelengths up to ≈920 nm. The materials obtained were tested as photocatalysts of hydrogen evolution from aqueous methanol, and the greatest activity in this reaction was demonstrated by the samples with low manganese contents (x = 0.002–0.01). However, the materials with greater substitution degrees may be of high interest for use in other photocatalytic processes and, especially, in thermophotocatalysis due to their improved ability to absorb the near-infrared part of solar radiation. Full article

This contribution presents a personal perspective on the development of thermo-photocatalytic schemes. It discusses several concepts focused on the common presentation of catalytic and thermo-photocatalytic data, with special emphasis on the determination of TOF (Turnover Frequency) and Quantum Efficiency parameters. The importance of including temperature profiles and photon absorption rates in the analysis for intrinsic kinetic studies, comparison of catalytic results, and the potential scaling of reactors is highlighted. Additionally, topics related to the efficiency of the use of radiation and heat transfer are discussed. Photon absorption profiles are presented for a TiO₂ catalytic surface of 20 × 20 cm (both fluorescent and LED configuration), as well as the temperature profile obtained using a thermal resistance with a diameter of 5 cm in a flat reactor. Using this example, the importance of designing thermo-photocatalytic systems to ensure an acceptable level of homogeneity in light irradiation and temperature is discussed. The discussion provides data that positions thermo-photocatalytic processes in the early stages of research. It is still necessary to advance the understanding of phenomena occurring under mixed temperature and light conditions. Additionally, new materials that meet the required characteristics for each application need to be developed, along with the design of new thermo-photocatalytic reactors. Full article

Photoinduced metal-free ATRP has been successfully applied to fabricate thermo-responsive cellulose graft copolymer (PNIPAM-g-Cell) using 2-bromoisobuturyl bromide-modified cellulose as the macroinitiator. The polymerization of N-isopropylacrylamide (NIPAM) from cellulose was efficiently activated and deactivated with UV irradiation in the presence of an organic-based photo-redox catalyst. Both FTIR and ¹³C NMR analysis confirmed the structural similarity between the obtained PNIPAM-g-Cell and that synthesized via traditional ATRP methods. When the concentration of the PNIPAM-g-Cell is over 5% in water, it forms an injectable thermos-responsive hydrogel composed of micelles at 37 °C. Since organic photocatalysis is a metal-free ATRP, it overcomes the challenge of transition-metal catalysts remaining in polymer products, making this cellulose-based graft copolymer suitable for biomedical applications. In vitro release studies demonstrated that the hydrogel can continuously release DOX for up to 10 days, and its cytotoxicity indicates that it is highly biocompatible. Based on these findings, this cellulose-based injectable, thermo-responsive drug-loaded hydrogel is suitable for intelligent drug delivery systems. Full article

The photocatalytic decomposition of ethylene was performed under UV-LED irradiation in the presence of nanocrystalline TiO₂ (anatase, 15 nm) supported on porous nickel foam. The process was conducted in a high-temperature chamber with regulated temperature from ambient to 125 °C, under a flow of reacted gas (ethylene in synthetic air, 50 ppm, flow rate of 20 mL/min), with simultaneous FTIR measurements of the sample surface. Ethylene was decomposed with a higher efficiency at elevated temperatures, with a maximum of 28% at 100–125 °C. The nickel foam used as support for TiO₂ enhanced ethylene decomposition at a temperature of 50 °C. However, at 50 °C, the stability of ethylene decomposition was not maintained in the following reaction run, but it was at 100 °C. Photocatalytic measurements conducted in the presence of certain radical scavengers indicated that a higher efficiency of ethylene decomposition was obtained due to the improved separation of charge carriers and the increased formation of superoxide anionic radicals, which were formed at the interface of the thermally activated nickel foam and TiO₂. Full article

Metal oxide semiconductor-based photocatalysis and advanced oxidation processes (AOPs) are effective in treating various recalcitrant pollutants such as organic dyes present in industrial wastewater streams. AOPs rely on the highly reactive hydroxyl radicals (OH^•) that facilitate the non-selective destruction of most organic pollutants. Here, we present the novel synthesis of mesoporous FeTiO₃ catalyst via a simple, hard template-free, aqueous-solution-based hydrothermal synthesis method. The surfactant, tetradecyltrimethylammonium bromide (TTAB), was used as the structure-directing agent, the removal of which led to the formation of the mesoporous structure. The catalyst was characterized by thermo-gravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), Branauer–Emette–Teller analysis (BET), X-ray diffraction (XRD), and scanning electron microscope (SEM) techniques. The obtained catalyst has been studied for its photocatalytic application in the presence of H₂O₂ towards the degradation of organic dyes as representative pollutants, namely, rhodamine B (RhB) and methylene blue (MB) under direct solar light irradiation. The various characterizations confirm the formation of mesoporous FeTiO₃ with a pore size of ≈7.5 nm and a specific surface area of 65 ± 5 m²/g. The influence of H₂O₂ oxidant on the removal of the said dyes has also been studied at various concentrations in the presence of the synthesized catalyst to determine the optimum dosage of H₂O₂. The catalyst was efficient in the complete synergistic adsorption-led photo-Fenton-like removal of MB in just 30 min of irradiation time, while the 96% RhB was degraded in 240 min. Moreover, this catalyst has also shown potential for fluoride adsorption that reaches up to more than 50% in 90 min. Full article

Acetaldehyde decomposition was performed under heating at a temperature range of 25–125 °C and UV irradiation on TiO₂ doped by metallic Ni powder and TiO₂ supported on nickel foam. The process was carried out in a high-temperature reaction chamber, “The Praying Mantis^TM”, with simultaneous in situ FTIR measurements and UV irradiation. Ni powder was added to TiO₂ in the quantity of 0.5 to 5.0 wt%. The photothermal measurements of acetaldehyde decomposition indicated that the highest yield of acetaldehyde conversion on TiO₂ and UV irradiation was obtained at 75 °C. The doping of nickel to TiO₂ did not increase its photocatalytic activity. Contrary to that, the application of nickel foam as a support for TiO₂ appeared to be highly advantageous because it increased the decomposition of acetaldehyde from 31 to 52% at 25 °C, and then to 85% at 100 °C in comparison with TiO₂ itself. At the same time, the mineralization of acetaldehyde to CO₂ doubled in the presence of nickel foam. However, oxidized nickel foam used as support for TiO₂ was detrimental. Most likely, different mechanisms of electron transfer between Ni–TiO₂ and NiO-TiO₂ occurred. The application of nickel foam greatly enhanced the separation of free carriers in TiO₂. As a consequence, high yields from the photocatalytic reactions were obtained. Full article

Synthetic organic pigments like xanthene and azo dyes from the direct discharge of textile effluents are considered colossal global issues and attract the concern of scholars. Photocatalysis continues to be a very valuable pollution control method for industrial wastewater. Incorporations of metal oxide catalysts such as zinc oxide (ZnO) on mesoporous Santa Barbara Armophous-15 (SBA-15) support to improve catalyst thermo-mechanical stability have been comprehensively reported. However, charge separation efficiency and light absorption of ZnO/SBA-15 continue to be limiting its photocatalytic activity. Herein, we report a successful preparation of Ruthenium-induced ZnO/SBA-15 composite via conventional incipient wetness impregnation technique with the aim of boosting the photocatalytic activity of the incorporated ZnO. Physicochemical properties of the SBA-15 support, ZnO/SBA-15, and Ru-ZnO/SBA-15 composites were characterized by X-ray diffraction (XRD), N₂ physisorption isotherms at 77 K, Fourier-transform infrared (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDS), and transmission electron microscopy (TEM). The characterization outcomes exhibited that ZnO and ruthenium species have been successfully embedded into SBA-15 support, andtheSBA-15 support maintains its structured hexagonal mesoscopic ordering in both ZnO/SBA-15 and Ru-ZnO/SBA-15 composites. The photocatalytic activity of the composite was assessed through photo-assisted mineralization of aqueous MB solution, and the process was optimized for initial dye concentration and catalyst dosage. 50 mg catalyst exhibited significant degradation efficiency of 97.96% after 120 min, surpassing the efficiencies of 77% and 81% displayed by 10 and 30 mg of the as-synthesized catalyst. The photodegradation rate was found to decrease with an increase in the initial dye concentration. The superior photocatalytic activity of Ru-ZnO/SBA-15 over the binary ZnO/SBA-15 may be attributed to the slower recombination rate of photogenerated charges on the ZnO surface with the addition of ruthenium. Full article

Cu/Zr-modified TiO₂ photocatalysts were prepared in the form of nanopowders and characterized by photothermal spectrometry, UV–Vis spectrophotometry and X-ray diffraction (XRD) to investigate the effect of Cu/Zr content on their thermo-optical and transport properties. Adding Cu (0.05%) caused a change in the light absorption range limit, which reduced from 3.25 eV for pure TiO₂ to 2.85 eV for Cu-modified TiO₂. The decrease in energy band gap was accompanied by a 19.5% decrease in the charge carrier lifetime, which is not favorable for photocatalysis. The decrease in charge carrier lifetime can be minimized by additional modification of TiO₂ with Zr (1%), which showed insignificant effects on the energy band gap of the investigated materials. Furthermore, modification of TiO₂ with Zr affected the material’s structure and increased its specific surface area, which improved the adsorption of degraded compounds as well as the absorption of light. Altogether, these effects resulted in higher photocatalytic degradation rate constants of the investigated TiO₂-based photocatalyst. It was also found that modification of TiO₂ with Cu and/or Zr increases both the material’s thermal diffusivity and conductivity due to changes in the band gap and structure of material. Beam deflection spectrometry (BDS) has demonstrated high potential in materials’ characterization which stems from its high sensitivity and precision. Full article

The photodehydrogenation of ethanol is a sustainable and potentially cost-effective strategy to produce hydrogen and acetaldehyde from renewable resources. The optimization of this process requires the use of highly active, stable and selective photocatalytic materials based on abundant elements and the proper adjustment of the reaction conditions, including temperature. In this work, Cu₂O-TiO₂ type-II heterojunctions with different Cu₂O amounts are obtained by a one-pot hydrothermal method. The structural and chemical properties of the produced materials and their activity toward ethanol photodehydrogenation under UV and visible light illumination are evaluated. The Cu₂O-TiO₂ photocatalysts exhibit a high selectivity toward acetaldehyde production and up to tenfold higher hydrogen evolution rates compared to bare TiO₂. We further discern here the influence of temperature and visible light absorption on the photocatalytic performance. Our results point toward the combination of energy sources in thermo-photocatalytic reactors as an efficient strategy for solar energy conversion. Full article

The current work focused on the sunlight-driven thermo-photocatalytic reduction of carbon dioxide (CO₂), the primary greenhouse gas, by ethane (C₂H₆), the second most abundant element in shale gas, aiming at the generation of ethanol (EtOH), a renewable fuel. To promote this process, a hybrid catalyst was prepared and properly characterized, comprising of strontium titanate (SrTiO₃) co-doped with ruthenium oxide (RuO₂) and nickel oxide (NiO). The photocatalytic activity towards EtOH production was assessed in batch-mode and at gas-phase, under the influence of different conditions: (i) dopant loading; (ii) temperature; (iii) optical radiation wavelength; (vi) consecutive uses; and (v) electron scavenger addition. From the results here obtained, it was found that: (i) the functionalization of the SrTiO₃ with RuO₂ and NiO allows the visible light harvest and narrows the band gap energy (ca. 14–20%); (ii) the selectivity towards EtOH depends on the presence of Ni and irradiation; (iii) the catalyst photoresponse is mainly due to the visible photons; (iv) the photocatalyst loses > 50% efficiency right after the 2nd use; (v) the reaction mechanism is based on the photogenerated electron-hole pair charge separation; and (vi) a maximum yield of 64 μmol EtOH g_cat⁻¹ was obtained after 45-min (85 μmol EtOH g_cat⁻¹ h⁻¹) of simulated solar irradiation (1000 W m⁻²) at 200 °C, using 0.4 g L⁻¹ of SrTiO₃:RuO₂:NiO (0.8 wt.% Ru) with [CO₂]:[C₂H₆] and [Ru]:[Ni] molar ratios of 1:3 and 1:1, respectively. Notwithstanding, despite its exploratory nature, this study offers an alternative route to solar fuels’ synthesis from the underutilized C₂H₆ and CO₂. Full article

The photocatalytic activities of reduced titanium dioxide (TiO₂) materials have been investigated by measuring their ability to produce hydroxyl radicals under UV and visible light irradiation. Degussa P25 TiO₂ was doped with nitrogen (N), fluorine (F), and/or phosphorus (P) and then subjected to surface modification employing a thermo-physicochemical process in the presence of reducing agent sodium borohydride (NaBH₄). The reduced TiO₂ materials were characterized by a number of X-ray, spectroscopic and imaging methods. Surface doping of TiO₂ was employed to modulate the band gap energies into the visible wavelength region for better overlap with the solar spectrum. Hydroxyl radical generation, central to TiO₂ photocatalytic water purification applications, was quantitated using coumarin as a trap under UV and visible light irradiation of the reduced TiO₂ materials. At 350 nm irradiation, the yield of hydroxyl radicals generated by the reduced forms of TiO₂ was nearly 90% of hydroxyl radicals generated by the Degussa P25 TiO₂. Hydroxyl radical generation by these reduced forms of TiO₂ was also observed under visible light irradiation (419 and 450 nm). These results demonstrated that simple surface modification of doped TiO₂ can lead to visible light activity, which is important for more economical solar-driven applications of TiO₂ photocatalysis. Full article