Search Results (118)

Combining the properties of organic and inorganic components with high surface areas and large pore volumes opens up countless possibilities for designing materials tailored to a wide range of advanced applications. As the majority of mesoporous hybrid materials are siliceous, the development of cost-effective synthetic approaches to produce water-stable hybrids with controlled porosity and functionality remains essential. Herein, we describe an original strategy for the synthesis of bridged mesoporous titania–bisphosphonate hybrids based on a one-step, template-free, non-hydrolytic sol–gel process. The reaction between Ti(OiPr)₄ and several flexible or rigid bisphosphonate esters, in the presence of acetic anhydride (Ac₂O) leads to the formation of TiO₂ anatase nanorods interconnected by fully condensed bisphosphonate groups. The general method that we depict is quantitative and low cost. All materials are mesoporous with very high specific surface areas (up to 520 m²·g⁻¹) and pore volumes (up to 0.93 cm³·g⁻¹). Full article

TiO₂ mesoporous supports were obtained by the sol–gel method from different precursors (titaniumethoxide, isopropoxide, or butoxide) in the presence of nonionic, cationic, and anionic surfactants. Among these samples, those obtained from Ti isopropoxide, Brij58 w/o activated carbon (AC), were selected as supports. Photocatalysts were obtained by modifying these supports with Ag, Fe, and AgFe (each metal around 1% mass). The characterization results showed a stronger influence of titania precursors, surfactants, and AC on the texture and an insignificant effect on the crystalline structure and morphology of the obtained materials. X-ray photoelectron spectroscopy revealed the effects of AC and Fe on the Ag⁰ concentration and of Ag on Fe-reduced species. Based on this information, the results obtained by H₂-TPR, UV–Vis, Raman, and photoluminescence spectroscopy were explained. The performance of the photocatalysts was evaluated in the degradation of Congo Red (CR) and Crystal Violet (CV) dyes under UV and visible light. The Ag-TiO₂ sample exhibited the best activity in degrading CR at acidic pH and in degrading CV under basic conditions. In visible light, we observed the significant effects of the surface plasmon resonance, AC, Ag, and Fe on the activity in CR photodegradation. The proposed kinetics and mechanisms complete the study of the reactions. Full article

The development of eco-friendly paint formulations is part of the transition process to more sustainable materials, which involves many industries such as offshore and shipbuilding, where the deterioration of steel in seawater is a key factor. This article aims to produce innovative coatings and test their protective action on DH 36 steel plates. SiO₂ and TiO₂ were modified with amino groups and iron sites to be used as filler for the design of ecological paint formulations The antimicrobial features of both NH₂ groups and iron ionic species were combined with the chemical and mechanical stability of silica and titania, with silica-based powders showing increased efficacy. The surface properties of the resulting coatings were examined by determination of thickness, water wettability, roughness, and cross-cut adhesion tests (before and after a degradation test in seawater according to ASTM D870-97 standards). Preliminary tests of the microbiological activity of the iron amino functionalized materials were carried out to monitor, as proof of concept, the growth of some bacterial strains through measurements of optical density. The findings indicate that these coatings not only provide effective corrosion protection but are promising for enhancing the durability and environmental performance of steel surfaces exposed to marine environments. Full article

The concept of using polyaniline/titanium dioxide heterostructures as efficient photocatalysts is based on the synergistic effect of conducting polymer and metal oxide semiconductors. Due to inconclusive literature reports, the effect of different polyaniline/TiO₂ ratios on photocatalytic activity under UV and visible light was investigated. In most papers, non-recommended dyes are used as model compounds to evaluate visible light activity. Therefore, colorless phenol was used instead of dyes in this study to clarify the real visible light-induced photocatalytic activity of polyaniline/TiO₂ composites. This publication also includes a discussion of whether materials derived from bulk (non-nanostructured) polyaniline and TiO₂ by the standard in situ oxidative polymerization method are suitable candidates for promising photocatalytic materials. The evaluation of photocatalytic activity was performed in both UV and visible light systems. X-ray diffraction and UV-Vis diffuse reflectance spectroscopy methods were applied to characterize the obtained samples. Obtained polyaniline (pure and in composites) was identified as emeraldine salt. In the UV system, none of the prepared samples with different polyaniline–titania ratios had activity better than reference P25 titania. It has been observed that the presence of polyaniline adversely affects the photocatalytic properties, as the polyaniline layer covering the titania surface can shield the UV light transmission by blocking the contact between the TiO₂ surface and organic molecules. In the case of using visible light, no synergies have been observed between polyaniline and titania either. The photodegradation efficiencies of the most active samples were similar to those of pure polyaniline. In conclusion, in order to obtain efficient polyaniline/titania photocatalysts active in UV and/or visible light, it is necessary to take into account the morphological and surface properties of both components. Full article

One method for the colorimetric detection of hydrogen peroxide vapor is based on a titanium–hydrogen peroxide complex. A color changing material based on a titania hydroxypropyl cellulose thin film was initially developed. However, as this material dries, the sensitivity of the material is significantly reduced. Thus, an alternative sensing material, based on titanium(IV) oxysulfate, an ionic liquid, and in some cases, triflouromethanesulfonic acid adsorbed onto low-cost silicon thin-layer chromatography (TLC) plates, was developed. TiO₂ was heated with concentrated sulfuric acid in a controlled environment, usually at temperatures ranging from 100 °C to 250 °C. These sensors are disposable and single-use and are simple and inexpensive. When the resulting thin-film sensors are exposed to ppm levels of hydrogen peroxide vapor, they turn from a white reflective material to an intense yellow or orange. Ti(IV) oxysulfate combined with an acid catalyst and an ionic-liquid-based material provides an opportunity to enhance the sensor activity towards the peroxide vapor and decreases the detection limit. Kinetic measurements were made by the quantification of the intensity of the reflected light as a function of the exposure time from the sensor in a special cell using a low-cost web camera and a tungsten lamp. The measured rate of the color change indicates high sensitivity and first-order kinetics over a hydrogen peroxide concentration range of approximately 2 to 31 ppm. These new materials are a starting point for the preparation of more active sensor materials for hydrogen peroxide and organic peroxide vapor detection. Full article

This work focuses on the production of methane through the photocatalytic reduction of carbon dioxide using Pt-doped CdS/TiO₂ heterostructures. The photocatalysts were prepared using P25 commercial titania and CdS synthesized through a solvothermal methodology, followed by the impregnation of Pt onto the surface to enhance the physicochemical properties of the resulting photocatalysts. The pure and heterostructure-based materials were characterized using X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), ultraviolet-visible spectroscopy (UV-Vis), ultraviolet photoelectron spectroscopy (UPS), and photoluminescence spectroscopy (PL). The obtained results show the successful synthesis of the heterostructure impregnated with Pt. Moreover, the observed key role of CdS and Pt nanoparticles in the final semiconductor is to reduce the electron-hole pair recombination rate by acting as an electron sink, which slows down the recombination process and increases the photocatalyst efficiency. Thus, Pt-doped CdS/TiO₂ heterostructures with the best observed composition presents better catalytic activity than P25 titania with methane production values being 460 and 397 µmol CH₄/g·h, respectively. Full article

Photocatalytic degradation of pollutants have a high potential for sustainable and renewable uses. TiO₂ is a widely studied photocatalyst due to its high chemical and photochemical stability and wide range of applications. However, the wide band gap and low capacity of photo-induced charge separation provide lower catalytic activity; thus, improvement of these properties must be found. The doping of TiO₂ with other elements, such as carbon nanoparticles (CNP) in a quantum dot form, offers a promising pathway to improve the aforementioned properties. In addition, in situ doping methods should be investigated for practical scalability, as they offer the advantage of integrating dopants directly during material synthesis, ensuring a more uniform distribution and better interaction between the dopant and the host material, in turn leading to more consistent photocatalytic properties. Current technologies primarily involve nanoparticle combinations. This work focuses on the development of a novel in situ synthesis methodology by the introduction of three different graphene-based quantum nanodots into anodic TiO₂ and the following investigation of structural, morphological, and photocatalytic properties. Results indicate that the introduction of CNP allows for the shift of a set of parameters, such as the optical band gap, increased photo-induced charge carrier density of TiO₂/CNP composite, and, most importantly, the change of crystalline phase composition depending on added CNP material. Research indicates that not only a higher concentration of added CNP enhances higher photocatalytic activity as tested by the degradation of methylene blue dye, but also the type of CNP determines final crystalline phase. For the first time brookite and rutile phases were obtained in anodic titania synthesized in inorganic electrolyte by introducing hydrothermally treated exfoliated graphene. Full article

ZrO₂, TiO₂, ZrO₂-TiO₂, and TiO₂-ZrO₂ were successfully prepared using the sol–gel method and fully characterized to check their physico-chemical features. X-ray diffraction showed the co-existence of monoclinic and tetragonal ZrO₂ in addition to the Anatase phase for TiO₂. The formation of mixed oxides led to a reduction in the band gap values and a modification of the textural characteristics, while the XPS evidenced an oxygen vacancy-rich surface. The ability of the synthesized materials to eliminate drug contaminants was checked using Sulfamethoxazole (SMX) as a model molecule under UV and BLUE-LED irradiation. The materials’ potential to decrease wastewater toxicity was also studied. The best photocatalyst was TiO₂-ZrO₂ with 76 and 100% conversion under visible and UV irradiation, respectively. Full article

Titanium dioxide was synthesized via hydrolysis of titanium (IV) isopropoxide using a sol–gel method, under neutral or basic conditions, and heated in the microwave-assisted solvothermal reactor and/or high-temperature furnace. The phase composition of the prepared samples was determined using the X-ray diffraction method. The specific surface area and pore volumes were determined through low-temperature nitrogen adsorption/desorption studies. The photoactivity of the samples was tested through photocatalytic reduction of carbon dioxide. The composition of the gas phase was analyzed using gas chromatography, and hydrogen, carbon oxide, and methane were identified. The influence of pH and heat treatment on the physicochemical properties of titania-based materials during photoreduction of carbon dioxide have been studied. It was found that the photocatalysts prepared in neutral environment were shown to result in a higher content of hydrogen, carbon monoxide, and methane in the gas phase compared to photocatalysts obtained under basic conditions. The highest amounts of hydrogen were detected in the processes using photocatalysts heated in the microwave reactor, and double-heated photocatalysts. Full article

Preparing high-performance oxygen evolution reaction (OER) catalysts with low precious metal loadings for water electrolysis applications (e.g., for green hydrogen production) is challenging and requires electrically conductive, high-surface-area, and stable support materials. Combining the properties of stable TiO₂ with those of active iridium oxide, we synthesized highly active electrodes for OER in acidic media. TiO₂ powders (both commercially available Degussa P-25^® and hydrothermally prepared in the laboratory from TiOSO₄, either as received/prepared or following ammonolysis to be converted to titania black), were decorated with IrO₂ by UV photodeposition from Ir(III) aqueous solutions of varied methanol scavenger concentrations. TEM, EDS, FESEM, XPS, and XRD measurements demonstrate that the optimized version of the photodeposition preparation method (i.e., with no added methanol) leads to direct deposition of well-dispersed IrO₂ nanoparticles. The electroactive surface area and electrocatalytic performance towards OER of these catalysts have been evaluated by cyclic voltammetry (CV), Linear Sweep Voltammetry (LSV), and Electrochemical Impedance Spectroscopy (EIS) in 0.1 M HClO₄ solutions. All TiO₂-based catalysts exhibited better mass-specific (as well as intrinsic) OER activity than commercial unsupported IrO₂, with the best of them (IrO₂ on Degussa P-25^® ΤiO₂ and laboratory-made TiO₂ black) showing 100 mAmg_Ir⁻¹ at an overpotential of η = 243 mV. Chronoamperometry (CA) experiments also proved good medium-term stability of the optimum IrO₂/TiO₂ electrodes during OER. Full article

One of the most significant global challenges for humans is environmental pollution. The technology to control this problem is the utilization of semiconductors as photocatalysts. In the current study, iron-doped titania nanotubes (Fe/TiNTs) with increased photocatalytic effect were synthesized via a modified hydrothermal method. The products were characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), gas adsorption, electron spin resonance (ESR) and UV–Vis diffuse reflectance spectroscopy (DRS). TEM results indicated that Fe/TiNTs have a tubular and uniform structure with an average outer diameter of 23–48 nm and length of 10–15 µm. ESR and DRS revealed that Fe³⁺ ions were successfully introduced into the TiNT structure by replacing Ti⁴⁺ ions. An enhanced light absorption in the range of 400–600 nm additionally indicated successful doping. The band gap was narrowed as iron wt% was increased. The photocatalytic activity was evaluated by the degradation of methyl orange (MO) in the presence of Fe/TiNTs and TiTNs by monitoring the degradation of MO under UV light irradiation. An acceleration on the hydration of Portland cement was observed in the presence of 2.0 wt% Fe/TiNTs. Fe/TiNTs can be used as a nanomaterial in cement-based building materials to provide self-cleaning properties to the surface of concrete even in indoor environments. Full article

Advanced oxidation processes stand as green alternatives for the decontamination of waste waters. Photocatalysis is an advanced oxidation process in which a semiconductor material absorbs photon energy and triggers redox reactions capable of degrading organic pollutants. Titanium dioxide (TiO₂, titania) represents one of the most popular choices of photocatalytic materials, however the UV-activation of its anatase phase and its high charge recombination rate decrease its photocatalytic activity and weaken its potential. Graphene oxide is a 2D carbon nanomaterial consisting of exfoliated sheets of hexagonally arranged carbons decorated with oxygen- and hydrogen- functional groups. Composite nanomaterials consisting of titania nanoparticles and graphene oxide have proven to enhance the photocatalytic activity of pure TiO₂. In this review, we present a thorough literature review of ternary nanocomposites based on synthesized or commercial titania nanoparticles and GO (or reduced GO) particularly used for the photodegradation of dyes. GO/TiO₂ has been enriched primarily with metals, semiconductors and magnetic nanomaterials, proving a superior dye degradation performance and reusability compared to bare TiO₂. Ongoing challenges and perspectives are outlined. Full article

This study presents a relatively low-cost method for modifying TiO₂-based materials for photocatalytic bacterial inactivation. The photocatalytic inactivation of Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus epidermidis) bacteria using modified sulphated TiO₂ was studied. The modification focused on the reduction of TiO₂ by ammonia agents and hydrogen at 400–450 °C. The results showed a high impact of sulphate species on the inactivation of E. coli. The presence of these species generated acid sites on TiO₂, which shifted the pH of the reacted titania slurry solution to lower values, around 4.6. At such a low pH, TiO₂ was positively charged. The ammonia solution caused the removal of sulphate species from TiO₂. On the other hand, hydrogen and ammonia molecules accelerated the removal of sulphur species from TiO₂, as did heating it to 450 °C. Total inactivation of E. coli was obtained within 30 min of simulated solar light irradiation on TiO₂ heat-treated at 400 °C in an atmosphere of Ar or NH₃. The S. epidermidis strain was more resistant to photocatalytic oxidation. The contact of these bacteria with the active titania surface is important, but a higher oxidation force is necessary to destroy their cell membrane walls because of their thicker cell wall than E. coli. Therefore, the ability of a photocatalyst to produce ROS (reactive oxidative species) will determine its ability to inactivate S. epidermidis. An additional advantage of the studies presented is the inactivation of bacteria after a relatively short irradiation time (30 min), which does not often happen with photocatalysts not modified with noble metals. The modification methods presented represent a robust and inexpensive alternative to photocatalytic inactivation of bacteria. Full article

The esterification of oleic acid was applied in order to screen the suitability of a series of phosphotungstic-based Wells-Dawson types of compounds as potential catalysts in the heterogeneous transesterification of sunflower waste cooking oil. This test reaction indicated that the phosphotungstic Wells-Dawson heteropolyacid H₆P₂W₁₈O₆₂·xH₂O, dispersed on titania oxide in a loading of 15 mg per m² of oxide support (named 42% HPA/TiO₂) and possessing exclusively Brønsted acid sites, was the most promising among the screened materials. In addition, the application of a nonlinear analysis methodology to find a surface that fits the specific activity of the oleic acid esterification with methanol at various temperatures, weights of catalyst, molar ratios of substrates, and stirring speeds, and also considering the active phase desorption out of the catalyst’s surface, allowed determining the optimum operative conditions that were applied in the transesterification of the waste cooking oil afterwards. The transesterification of the waste cooking oil at 60 °C and 1:9 WCO: methanol molar ratio in a batch reactor under stirring at 650 rpm for 3 h, catalyzed with 0.25 wt% of 42% HPA/TiO₂ (20.0 g of oil and 49.6 mg of catalyst), presents 74.6% of conversion of glycerides and 74.4% yield towards fatty acid methyl esters. The catalyst was recovered and reused several times, maintaining a fairly constant catalytic performance. Full article

The method of micro-arc oxidation has been utilized to synthesize a protective biocompatible coating for a bioresorbable orthopedic Mg implant. This paper presents the results of comprehensive research of micro-arc coatings based on diatomite—a biogenic material consisting of shells of diatom microalgae. The main focus of this study was the functionalization of diatomite-based micro-arc coatings by incorporating particles of titania (TiO₂) into them. Various properties of the resulting coatings were examined and evaluated. XRD analysis revealed the formation of a new magnesium orthosilicate phase—forsterite (Mg₂SiO₄). It was established that the corrosion current density of the coatings decreased by 1–2 orders of magnitude after the inclusion of TiO₂ particles, depending on the coating process voltage. The adhesion strength of the coatings increased following the particle incorporation. The processes of dissolution of both coated and uncoated samples in a sodium chloride solution were studied. The in vitro cell viability was assessed, which showed that the coatings significantly reduced the cytotoxicity of Mg samples. Full article