Commercial TiO2 Research Articles

Strategic defect engineering in TiO2 catalysts through electron beam irradiation: Unraveling enhanced photocatalytic pathways for multicomponent VOCs degradation

Defect engineering improves catalytic activity, electron transport efficiency, and stability by introducing defects such as oxygen vacancies, offering significant potential for applications in environmental remediation and energy conversion. Electron beam (EB) irradiation has emerged as a key technique in defect engineering, renowned for its mild reaction conditions and precise defect construction capabilities. This study synthesized defect-rich commercial TiO2 catalysts (P25) using high-energy EB irradiation to investigate the photodegradation efficiency of multicomponent VOCs. The EB irradiation technique promoted the formation of oxygen vacancies, which played a key role in the adsorption and activation of pollutant molecules. DFT calculations further confirmed the superior photocatalytic activity of the irradiated P25 catalyst. The photodegradation experiments showed that the 300P25 degraded pure ethyl acetate up to 99.05 % (40 min) and acetone up to 97.14 % (60 min), but toluene only up to 7.34 % (60 min). Interestingly, in acetone and toluene mixture, 300P25 achieved toluene removal as high as 68 % (60 min) with a rate constant (k) of 0.0181 min−1, a 12.1-fold than pure toluene (0.0015 min−1). In-situ infrared spectroscopy analysis revealed that during the simultaneous degradation of toluene and acetone, acetone significantly promoted the deep oxidation of toluene, leading to the rapid oxidation of intermediate products (benzyl alcohol and benzaldehyde) to benzoic acid and smaller molecules. This work provides important guidance for developing efficient and stable photocatalysts for degrading multicomponent VOCs.

Polyhydroxykanoate-Assisted Photocatalytic TiO2 Films for Hydrogen Production.

The photocatalytic production of hydrogen using biopolymer-immobilized titanium dioxide (TiO2) is an innovative and sustainable approach to renewable energy generation. TiO2, a well-known photocatalyst, benefits from immobilization on biopolymers due to its environmental friendliness, abundance, and biodegradability. In another way, to boost the efficiency of TiO2, its surface properties can be modified by incorporating co-catalysts like platinum (Pt) to improve charge separation. In this work, the surface of commercial TiO2 PC500 was modified with Pt nanoparticles (Pt1%@PC500) and then immobilized on glass surfaces using polyhydroxyalkanoate biopolymer poly(hydroxybutyrate-co-hydroxyhexanoate) (PHBH). The as-prepared immobilized Pt-modified TiO2 photocatalysts were fully characterized using various physicochemical techniques. The photocatalytic activity of the photocatalyst film was investigated for photocatalytic hydrogen production through water reduction using ethanol as a sacrificial donor. The impact of the film preparation conditions, e.g., PHBH concentration, PHBH:catalyst ratio, and temperature, on activity and stability was studied in detail. The application of biopolymer PHBH as a binder provides a green alternative to conventional immobilization methods, and with the application of PHBH, a stable and active photocatalyst film that showed lower activity compared to that of the suspended photocatalyst but good recyclability in six runs was prepared. A long-term photocatalytic hydrogen production experiment was carried out. In 98 h of operation, 12 mmol of hydrogen was produced in three consecutive runs with a PHBH/Pt1%@PC500 film having an area of ∼5.3 cm2. A significantly lower hydrogen productivity was observed after the first run, possibly due to a change in film structure, but thereafter, the productivity remained almost constant for the second and third runs. Hydrogen was the main product in the gas phase (90%), but carbon dioxide (4-5%) and methane (4-5%) were obtained as important byproducts. The byproducts are a consequence of the use of the sacrificial reagent ethanol. The results of the film performance are very promising, with regard to large-scale continuous hydrogen production.

Harnessing natural light: Novel nanoheterojunction photocatalyst NaGdF4:Yb,Tm@TiO2/Cu2(OH)2CO3 for actual wastewater remediation

This study introduces NaGdF4:Yb,Tm@TiO2/Cu2(OH)2CO3 (UTCu), an innovative nanophotocatalyst designed to address global energy crises and water contamination issues. Our developed photocatalyst, NaGdF4:Yb,Tm@TiO2/0.5mol%Cu2(OH)2CO3 (UTCu0.5), demonstrated exceptional efficiency, degrading 96.3% of malachite green (MG) within 2 h under Xenon lamp irradiation. The photocatalytic degradation rate of UTCu0.5 surpassed those of UT, Cu2(OH)2CO3, and P25 (Commercial TiO2) by 3.3, 9, and 2.8 times, respectively. The process effectively mineralized MG into less harmful compounds, marking its potential for eco-friendly wastewater treatment. Furthermore, UTCu0.5 exhibited robust degradation capabilities across various organic dyes and maintained its efficacy in mixed dye systems. Detailed mechanistic analysis revealed that the ·OH and ·O2− radicals play pivotal roles in the degradation process, facilitated by the formation of heterojunctions that enhance carrier separation and photocatalytic performance. Theoretical studies supported the significance of S-scheme heterojunctions in boosting the photocatalytic activity of UTCu0.5. Additionally, the catalyst was effective in degrading organic pollutants in different water matrices under both Xenon lamp irradiation and direct sunlight. Remarkably, it achieved a 77.4% removal rate of NH4⁺-N in real municipal wastewater under natural sunlight, with a selective conversion rate of 95.3% to N2, underscoring its practical applicability in environmental remediation. This research not only progresses photocatalysis technology but also provides vital insights for enhancing natural condition wastewater treatment strategies.

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles.

A commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid-state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub-surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster-type energy transfer from excited sub-surface Ti3+ centers.

Singlet Oxygen Photocatalytic Generation by Silanized TiO2 Nanoparticles

AbstractA commercial TiO2 sample, used as received or hydrothermally treated to increase surface hydroxylation, has been functionalized by surface modification with hexadecyltrimethoxysilane. The anchoring of the silane has been characterized by means of FTIR and solid‐state NMR spectroscopies, and the grafting density was determined by thermogravimetric and N2 physisorption analyses. The silane moieties induce a partial decrease of the shielding of the valence electrons of the Ti ions at the surface, and a local modification of their crystal field, as demonstrated by XPS and UV/Vis spectroscopy, respectively. The changes in coordination and the produced oxygen vacancies result in the formation of Ti3+ defects localized in the sub‐surface region, as revealed by EPR spectroscopy. These paramagnetic centers are stabilized in the silanized samples, as the electron transfer to O2 is efficiently inhibited even under UV irradiation. However, the amount of Ti3+ centers appears to be correlated with the singlet oxygen (1O2) formation rate. Accordingly, epoxidation of limonene under UV light, chosen as a model photocatalytic reaction triggered by 1O2, occurred with higher selectivity when TiO2 was silanized and upon simultaneous NIR irradiation. These evidences suggest that in the silanized sample 1O2 may be generated through Förster‐type energy transfer from excited sub‐surface Ti3+ centers.

Layer-by-Layer Deposition of Hollow TiO2 Spheres with Enhanced Photoelectric Conversion Efficiency for Dye-Sensitized Solar Cell Applications.

Fabricating photoanodes with a strong light-scattering effect can improve the photoconversion efficiency of dye-sensitized solar cells (DSSCs). In this work, a facile microwave hydrothermal process was developed to prepare Au@TiO2 core-shell nanostructures, and then the Au core was removed by etching, resulting in hollow TiO2. Morphological characterizations such as field emission scanning and transmission electron microscopy measurements have been used for the successful formation of core-shell and hollow TiO2 nanostructures. Next, we attempted to deposit the different-sized hollow TiO2-based microspheres simultaneously on the surface of small-sized TiO2 nanoparticles-based compact film as light-scattering layers via electrophoretic deposition. The deposited hollow TiO2 microspheres constitute bi- and tri-layers that not only improve the light-harvesting properties but also speed up the photogenerated charge transfer. Compared to commercial TiO2 compact film (4.75%), the resulting bi-layer and tri-layered films-based DSSCs displayed power conversion efficiencies of 6.33% and 8.08%, respectively. It is revealed that the deposited bi- and tri-layered films can enhance the light absorption ability via multiple photon reflection. This work validates a novel and controllable strategy to develop light-scattering layers with increased light-harvesting properties for highly efficient dye-sensitized solar cells.

Sunlight-activated composite TiO2-F-V-Mo materials for photodegradation of the organic pollutant methylene blue

F-doped TiO2 photocatalyst materials were prepared using solid-state and sol-gel synthesis with varying weight percentages of LiF or NH4F. Subsequently, molybdate and vanadium oxide were added to the prepared powders to create composite photocatalysts with reduced bandgap energy, enhancing light absorption in the visible region of the spectrum, which is essential for effective photocatalytic activity using sunlight. The synthesized powders were characterized by thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and specific surface area using the BET method. The crystallization and anatase-to-rutile phase transformation of the powders were verified by X-ray diffraction (XRD), and the composite nanoparticles were further investigated by transmission electron microscopy (TEM). The photocatalytic activity of the F-doped commercial TiO2, sol-gel synthesized TiO2, and prepared composite powders was evaluated through the photocatalytic degradation of methylene blue (MB) in water under ultraviolet (UV), UV–visible, and sunlight irradiation. The results indicated that the incorporation of Molybdenum and Vanadium significantly influenced the photocatalytic efficiency by substantially reducing the bandgap of this composite photocatalyst. The LiF-doped TiO2 powders synthesized by sol-gel using TTIP, and doped with vanadium and molybdenum, activated by sunlight, exhibited high performance in MB degradation compared to commercial TiO2 and undoped synthesized TiO2 powders, achieving an optimal degradation rate of 7.26 × 10⁻⁹ mol per gram of photocatalyst.

Cu surface plasmon resonance promoted charge transfer in S-scheme system enhanced visible light photocatalytic hydrogen evolution

Reasonably constructing nanocomposite photocatalysts with fast charge transfer and broad solar response capabilities is significant for efficiently converting solar energy into chemical energy. Cu modifies P25/CeO2 heterojunctions prepared by photodeposition (P25 is commercial TiO2). The local surface plasmon resonance (LSPR) effect caused by Cu nanoparticles broadens the spectral response range and generates significant photothermal effects. After 90 s of irradiation, the temperature of 9.5 %Cu-P25/CeO2 increases to 148.1 °C. The photocatalytic hydrogen evolution rate (HER) of 9.5 %Cu-P25/CeO2 under visible light (λ = 400 nm) reaches 1538.2 μmol h−1 g−1, which is 158.6 times, 17.7 times, and 2.5 times higher than that of Cerium dioxide (CeO2), P25, and P25/CeO2, respectively. This catalyst has stronger light absorption, easier carrier transfer, and separation. This study guides the construction of efficient hydrogen evolution photocatalysts.

Facile modification of TiO2 as S-Scheme multifunctional materials for environmental protection and energy-storage applications

This paper reports a simple one-step modification of commercial TiO2 with a conducting polytrimethoxyslilypropyl aniline (PTMSPA, a polyaniline derivative having silyl networks) to have multi-functional (photocatalytic, optical, pseudocapacitive, hydrophobic, porous, antibacterial, and electromagnetic interference shielding (EMI)) properties and demonstrates associated applications. We present the S-Scheme heterojunction (SHJ) formation between TiO2 and PTMSPA through band position alignments and designate the resultant TiO2 - TiO2- based SHJ multifunctional materials as MF-TSSM. The internal electric field that is generated at the interface facilitates the transportation of the photogenerated electron transfer . The XRD pattern of MF-TSSM exhibits mainly the peaks of anatase TiO2. The TEM image of MF-TSSM indicates that the TiO2 particles are spherical in shape with sizes showing variations in diameters ranging from 60 nm to 250 nm depending on the experimental conditions of preparation and TiO2 particles are homogeneously distributed within the PTMSPA matrix. The optical energy band gap of MF-TSSM is 1.60 eV, a much lower value than PTMSPA (3.02 eV), suggesting that the composite formation between TiO2 and PTMSPA. The contact angle of MF-TSSM is significantly increased to 47.1 ° from 8.0 of TiO2, informing the increase of hydrophobic characteristics. The rate constant (k) for methylene blue photodegradation was 0.030 min-1, and 0.010 min-1 for MF-TSSM and pristine TiO2, respectively, The MF-TSSM composite exhibits a higher specific capacitance value (28.7 F/g) than TMSPA (21.1 F/g). At a frequency of 0.42 THz, MF-TSSM and PTMSPA exhibit return loss features indicating good EMI shielding performance. The MF-TSSM has been tested against two different Gram-positive and Gram-negative bacterial strains. The nanoparticles were evaluated at doses of 10, 20, 40, and 80 µg/ml. The results indicated that Klebsiella pneumoniae demonstrated a greater zone of inhibition, ranging from 9 mm at 10 µg/ml to 23 mm at 80 µg/ml, indicating increased susceptibility. Pseudomonas aeruginosa exhibited reduced inhibition zones, ranging from 10 mm at 10 µg/ml to 14 mm at 80 µg/ml, indicating increased resistance. The excellent effectiveness of MF-TSSM against various Gram-positive and Gram-negative pathogenic bacteria is explained by the interaction between reactive oxygen species and the cellular components of the bacteria as well the electrostatic interaction arising between positive charges in TMSPA and negative charges in the cell components, resulting in notable cytotoxicity and damage to the bacterial cells. The research underscores the capability of these modified TiO₂ nanoparticles in addressing bacterial infections, with efficiency differing by bacterial strain.

Photocatalysis of Adsorbed Catechol on Degussa P25 TiO2 at the Air-Solid Interface.

Semiconductor photocatalysis with commercial TiO2 (Degussa P25) has shown significant potential in water treatment of organic pollutants. However, the photoinduced reactions of adsorbed catechol, a phenolic air pollutant from biomass burning and combustion emissions, at the air-solid interface of TiO2 remain unexplored. Herein we examine the photocatalytic decay of catechol in the presence of water vapor, which acts as an electron acceptor. Experiments under variable cut-off wavelengths of irradiation (λcut-off ≥ 320, 400, and 515 nm) distinguish the mechanistic contribution of a ligand-to-metal charge-transfer (LMCT) complex of surface chemisorbed catechol on TiO2. The LMCT complex injects electrons into the conduction band of TiO2 from the highest occupied molecular orbital of catechol by visible light (≥2.11 eV) excitation. The deconvolution of diffuse reflectance UV-visible spectral bands from LMCT complexes of TiO2 with catechol, o-semiquinone radical, and quinone and the quantification of the evolving gaseous products follow a consecutive kinetic model. CO2(g) and CO(g) final oxidation products are monitored by gas chromatography and Fourier-transform infrared spectroscopy. The apparent quantum efficiency at variable λcut-off are determined for reactant loss (Φ- TiO2/catechol = 0.79 ± 0.19) and product growth ΦCO2 = 0.76 ± 0.08). Spectroscopic and electrochemical measurements reveal the energy band diagram for the LMCT of TiO2/catechol. Two photocatalytic mechanisms are analyzed based on chemical transformations and environmental relevance.

Toward a green economy: Lignin-based hybrid materials as functional additives in flame-retardant polymer coatings

This study describes the combination of unique properties of lignin with TiO2 as an innovative and effective preparation method for high-performance flame-retardant additives that may be utilized as polymer coatings. The use of lignin resulted in numerous advantages including an increased number of functional groups, satisfactory biocompatibility, low toxicity, and high carbon content. The major benefit of lignin is associated with the reduced carbon footprint of the manufactured product. Lignin can be classified as a natural flame-retardant agent owing to the high amount of char formed during combustion. In turn, TiO2 exhibits high chemical stability and low operating costs and is considered a non-toxic and environmentally friendly material. During the experiments, commercial TiO2 in anatase crystallographic form, TiO2 synthesized from titanyl sulfate hydrate, and kraft lignin as well as organic–inorganic hybrid materials composed of these materials were evaluated as functional additives in epoxy-resin-based polymer coatings (Epidian 601) and their properties were investigated in detail. The cone colorimetry test confirmed that the obtained hybrids are effective flame-retardant additives for polymer coatings, with a notable fire hazard reduction observed for samples containing a synergistic system of titanium oxide and lignin. The coating with lignin was the most effective in fire suppression processes. The conducted thermal and mechanical investigations confirmed good performance properties of the coatings indicating thermal resistance up to 360 °C and Shore D hardness in a range of 80.36–86.28°Sh, accordingly. Optical profilometry investigations show that the lignin/TiO2 hybrids exhibit a stable topological surface shape as well as good dispersion and uniformity in the polymer matrix. All the conducted tests allowed confirmation that the presence of functional additives in polymer coatings in the form of lignin and TiO2 can be a promising alternative to non-biodegradable synthetic materials which improve flame-retardant properties.

Two-dimensional P1 approximation (P1-2D) for the evaluation of the radiant field in annular and tubular photocatalytic reactors

The local volumetric rate of photon absorption (LVRPA) was formulated by solving the radiative transfer equation (RTE) in two dimensions using the P1 approximation approach (P1-2D) to describe the radiant field in annular and tubular photocatalytic reactors. The radiant sources employed were assumed to be periodic when applying the boundary conditions to facilitate the determination of the integration constants in the RTE solution. Three different systems were considered: S1 and S2 consisted of annular reactors, while S3 consisted of a tubular reactor. Simulations were conducted using commercial TiO2 P25 and anatase TiO2 as photocatalyst models, with their optical properties sourced from the literature. The linear source spherical emission (LSSE), Gaussian emission (GE), and uniform emission (UE) models were used as radiant sources. The LVRPA was found to decrease from the inner to the outer wall of the reactor for S1 and S2, and from the wall to the center of the reactor for S3; it was close to the values obtained using the Monte Carlo (MC) procedure in S2. The overall volumetric rate of photon absorption (OVRPA) increased exponentially with catalyst loading until a point where no significant increase was observed for each reactor. The apparent optical thickness τ App 1 ​formulated was a more reliable optimization parameter than the optical thickness.

A novel lanthanum-modified polytitanium chloride coagulant: Efficient algae removal and enhanced photocatalytic ability of recycled algal sludge

The removal of harmful cyanobacterial blooms (HCBs) and reuse of the resulting algal sludge are pressing issues in current environmental governance and ecological conservation. Aiming at tackling the above-mentioned challenges, titanium (Ti)-based coagulants are promising candidates. However, most of them suffer from poor stability and weak actual algal removal ability, and recycling of the algal sludge usually produces titanium dioxide (TiO2) with low photocatalytic ability. In this work, a lanthanum (La)-modified polytitanium chloride (La-PTC) coagulant is reported. La in the La-PTC coagulant serves a "kill two birds with one stone" strategy in algae removal and algae sludge reuse. Owing to the introduction of La ions, the La-PTC coagulant exhibits ultra-high stability and excellent algae removal capability with an efficiency of 98.71%, which is 7.25% higher than that of PTC coagulant. Moreover, recycling algae sludge can prepare high catalytic (2.45 times the commercial P25 TiO2) La/C-TiO2, where the presence of La enhances its visible light response range and inhibits electron hole recombination. The strategy of this La modified coagulant can not only achieve efficient removal of HCBs, but also transform the recovered algal sludge into photocatalysts with higher catalytic capacity.

Application of TiO2 Photocatalyst for Improving Ozone Generation Efficiency

ABSTRACT With a strong oxidizing capability, ozone (O3) is widely used in industry. However, ozone generators on the market are expensive and require a lot of energy to operate, which remains the bottleneck for the wide applications. In this study, a novel and energy-efficient ozone generation system is developed via the combination of black-TiO2 photocatalyst and plasma system. Black-TiO2 catalyst is prepared by calcining commercial TiO2 catalyst at 550 °C under a nitrogen atmosphere to extend the absorption spectrum to visible light range to improve catalytic activity. The experimental results show that ozone generation efficiency can be greatly increased to 415 g O3/kWh via combined black-TiO2 catalyst and plasma with O2 as the feeding gas. This can be attributed to the fact that black-TiO2 catalyst with a smaller energy gap is more efficiently activated to form electron–hole pairs in plasma, which can enhance ozone generation. On the other hand, black-TiO2 catalyst can provide abundant active sites for active O atoms and O2 molecules to promote O3 generation. Black-TiO2 catalyst prepared in this study reveals good stability. Overall, combination of black-TiO2 catalyst with plasma reveals good ozone generation efficiency and has a good potential for practical applications.

D-band center modulated water molecule adsorption and activation towards highly photocatalytic toluene mineralization

Photocatalysis is a promising strategy for deep purification of low-concentration toluene, driving by hydroxyl radicals (•OH) with potent oxidation capacity. Unfortunately, •OH evolution from H2O activation is a thermodynamically unfavorable process and suffers from the low utilization efficiency of photoexcited holes. Herein, a novel strategy to tailor the d-band center of perovskite BaSnO3 via heteroatom Zn substitution is proposed, aiming at optimizing the H2O adsorption configuration and efficiently activating H2O to yield •OH. The upshifted d‐band center mediated by the incorporation of Zn improves the adsorption capacity of H2O molecule, and directly determines the H2O adsorption configuration. Meanwhile, the dual transport channels of electron-hole accelerate O-H band fracture and lower the energy barrier for hole transfer to OH, allowing for efficient H2O activation. The optimized catalyst shows a 3-fold activity in toluene mineralization compared to commercial TiO2. This work sheds substantial light on H2O activation and environmental catalyst design.

Innovative fabrication of highly efficient CeO2 ceramic nanomaterials for enhanced photocatalytic degradation of toxic contaminants under sunlight

In this research, we report an innovative sonochemical technique for synthesizing cerium oxide (CeO2) nanoparticles utilizing glucose as a capping agent, significantly boosting their photocatalytic performance under visible light. Through meticulous optimization, our CeO2 nanoparticles demonstrated exceptional degradation efficiencies: 97.2 % for Acid Red 14, 99.1 % for Captopril, 98.7 % for Malachite Green, and 98.3 % for Amlodipine, substantially outstripping performance metrics of commercial TiO2 and untreated samples. Our kinetic analyses, based on the Langmuir-Hinshelwood model, indicated a superior rate constant of 0.0701 min⁻1 for Acid Red 14 degradation—reflecting a stark enhancement over other catalysts tested. Furthermore, mechanistic insights revealed that the significant improvement in photocatalytic activity was predominantly due to the generation of hydroxyl radicals and effective utilization of electron vacancies, with the role of these reactive species validated by detailed scavenger tests. This enhancement in photocatalytic efficiency is attributed to the sonochemical synthesis paired with glucose modification, which optimizes the nanoparticles' surface characteristics crucial for reactivity. Moreover, the nanoparticles showcased remarkable stability and reusability, maintaining an 87.8 % degradation rate after 11 cycles, evidencing minimal loss in activity and underscoring their potential for long-term applications in environmental remediation. This study not only paves the way for the practical application of CeO2 nanoparticles in pollutant degradation but also illustrates the broader applicability of sonochemically synthesized nanomaterials in sustainable environmental management, offering a promising solution to the challenge of complex organic pollutants in aquatic environments.

Hydrothermal synthesis of bare TiO2 nanowires and polystyrene (PS)-TiO2 nanowires used for selective photocatalytic oxidation of 3-pyridinemethanol in water and PS photodegradation in solid state

In the present work, nanowire (NW) structured TiO2 nanoparticles were prepared using the hydrothermal method and characterized by X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and BET specific surface area techniques. They were obtained in the anatase phase and presented a high surface area (ca. 300 m2/g). A commercial TiO2 (anatase, Merck) was used for comparison. The TiO2 catalysts were tested for photocatalytic oxidation of 3-pyridinemethanol to 3-pyridinemethanal and vitamin B3 in water under UVA irradiation. The effects of acid treatment and subsequent calcination for TiO2 catalysts after the hydrothermal synthesis were also investigated. The sample, subjected to acid treatment and calcined at 300 °C (NW-HCl-300), showed the highest photocatalytic activity and selectivity towards the products. Consequently, this sample and Merck TiO2 were used to prepare polystyrene (PS)/TiO2 composites using the hydrothermal method. They were characterized by XRD, SEM–EDX, Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FT-IR), Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), UV–Vis, Gel Permeation Chromatography (GPC), and contact angle measurements and tested for PS (present in the composite) photodegradation. The results indicated that NW-HCl-300 had a high surface area, and was highly hydroxylated, favouring a good distribution of PS in the composite. The composite presented high thermal stability, but under UVA irradiation the polymer underwent solid-state photocatalytic degradation due to the contact with TiO2. The composite photodegradation was investigated using gravimetric, GPC, FT-IR, UV–Vis, and SEM techniques.

Ce3+/Ce4+–TiO2 Nano‐Octahedra as Active Photocatalysts for Ciprofloxacin Photodegradation Under Solar Light

AbstractCerium‐containing titania nano‐octahedra (CeTNOh) are obtained by ultrasonication‐hydrothermal synthesis of Ce‐containing titanate nanowires (0.35, 0.46, and 0.70 Ce mol %) from commercial TiO2 (Degussa P25). CeTNOh are tested as photocatalysts to degrade a target pollutant (ciprofloxacin) under simulated solar light and at mild conditions. CeTNOh are anatase polymorphs with increasing crystallite size as Ce content increases. Hydrothermal treatments enhance the specific surface area (SSA) compared to P25, although Ce addition slightly reduces SSA while increasing crystallite size. Electron Microscopy confirms the morphology, although higher Ce levels hinder a full transformation. X‐ray photoemission spectroscopy (XPS) shows the presence of Ce3+/Ce4+ redox pair, promoting electron mobility and Ti‐Ce interactions. Optical and electronic spectroscopy reveals that Ce loading reduces the bandgap from 3.20 to 2.74 eV, extending light absorption into the visible range, thus enhancing the photocatalytic activity. The best sample, CeTNOh0.35, achieved 83% degradation of ciprofloxacin after 360 minutes under solar irradiation, with poor adsorption in the dark period. Higher Ce loadings negatively affect photoactivity by partially covering titania active sites. Reusability tests confirm the stability and efficiency of CeTNOh0.35 over three cycles, highlighting the importance of octahedral morphology in Ce‐containing systems to boost the final photoactivity for water remediation.

Formic Acid Dehydration Using Mechanochemically Prepared TiO2‐Graphite Composites

AbstractCommercial high surface area graphite (HSAG300) and commercial TiO2 were used to produce composite materials through a simple mechanochemical method involving milling and ultrasonic treatments. The acid and basic sites exposed on the surfaces of these materials were characterized by temperature‐programmed desorption (TPD) of ammonia and carbon dioxide. The catalytic materials were tested in the dehydration reaction of formic acid to produce hydrogen‐free CO. While HSAG300 is practically inactive under reaction conditions (continuous gas flow at temperatures in the range of 100–250 °C), all samples containing TiO2 are active, exhibiting high selectivity to CO without significant deactivation at moderate reaction temperatures. It is demonstrated that the presence of graphite in the catalysts enhances the specific catalytic activity of TiO2. Assuming that the dehydration reaction is catalyzed by acid sites on the TiO2 surfaces, a comparative evaluation of the surface sites reveals that the graphite‐TiO2 interactions not only change the density of surface sites but also modify the strength of the acid centers of TiO2. In summary, the interaction of HSAG300 with TiO2 modulates the surface properties of the prepared composite catalysts, decreasing the total number of basic surface sites and increasing the strength of acidic sites compared to bare TiO2.

Influence of the Structure of Hydrothermal-Synthesized TiO2 Nanowires Formed by Annealing on the Photocatalytic Reduction of CO2 in H2O Vapor.

The present study investigates the photocatalytic properties of hydrothermally synthesized TiO2 nanowires (NWs) for CO2 reduction in H2O vapor. It has been demonstrated that TiO2 NWs, thermally treated at 500-700 °C, demonstrate an almost tenfold higher yield of products compared to the known commercial powder TiO2 P25. It has been found that the best material is a combination of anatase, TiO2-B and rutile. The product yield increases with increasing heat treatment temperature of TiO2 NWs. This is associated with an increase in the degree of crystallinity of the material. It is shown that the best product yield of the CO2 reduction in H2O vapor is achieved when the TiO2 NW photocatalyst is heated to 100 °C.