Anatase Samples Research Articles

Corrosion mechanisms of TiO2 photoelectrode coatings in alkaline conditions

The crystal structure of TiO2 has a significant impact on the chemical stability of the protective TiO2 thin films used in photoelectrochemical conditions. By altering the deposition temperature of atomic layer deposition method, and by post-deposition annealing treatments, amorphous, microcrystalline anatase, and Ti3+-rich nanocrystalline rutile structures can be achieved. In this paper, the chemical stability in alkaline solution and failure mechanisms of ALD grown TiO2 thin films on Si(100) were studied by SEM, XPS, EIS, and ellipsometry. The results showed that the electrically conductive Ti3+-rich nanocrystalline rutile thin film was chemically stable, whereas other samples failed within the first 10 h of the test in 1.0 M NaOH. More detailed analysis in 0.1 M NaOH revealed that the anatase sample experienced sudden failure after NaOH solution penetrated the TiO2 via grain boundaries, causing the Si substrate to dissolve. In contrast, the amorphous TiO2 films had more gradual failure as the NaOH solution permeated the TiO2 film, causing it to swell up to three times the initial thickness of the film.

Effect of Crystalline Phase and Facet Nature on the Adsorption of Phosphate Species onto TiO2 Nanoparticles.

The current use of TiO2 nanoparticles raises questions about their impact on our health. Cells interact with these nanoparticles via the phospholipid membrane and, in particular, the phosphate head. This highlights the significance of understanding the interaction between phosphates and nanoparticles possessing distinct crystalline structures, specifically anatase and rutile. It is crucial to determine whether this adsorption varies based on the exposed facet(s). Consequently, various nanoparticles of anatase and rutile TiO2, characterized by well-defined morphologies, were synthesized. In the case of the anatase samples, bipyramids, needles, and cubes were obtained. For the rutile samples, all exhibited a needle-like shape, featuring {110} facets along the long direction of the needles and facets {111} on the upper and lower parts. Phosphate adsorption experiments carried out at pH 2 revealed that the maximum adsorption was relatively consistent across all samples, averaging around 1.5 phosphate·nm-2 in all cases. Experiments using infrared spectroscopy on dried TiO2 powders showed that phosphates were chemisorbed on the surfaces and that the mode of adsorption depended on the crystalline phase and the nature of the facet: the anatase phase favors bidentate adsorption more than the rutile crystalline phase.

Structure of vanadia-titania catalysts doped with alkali metals according to solid-state NMR, ESR spectroscopies and DFT

In this work, V/M/TiO2 catalysts (M = Li, Na, K, Rb and Cs) were investigated with Solid-state nuclear magnetic resonance (SSNMR), electron paramagnetic resonance (ESR) and first-principles calculations. The total vanadium content corresponds to half monolayer (4 V atoms·nm−2 of TiO2 support surface), with V/M atomic ratio being 4/0.6. Static 51V and MAS 1H, 7Li, 51V, 23Na, 133Cs NMR spectra were acquired. Surface moieties of vanadium oxide on (001) anatase surface were modeled using density functional theory (DFT); their 51V NMR parameters were calculated with the Gauge-Including Projected Augmented Wave (GIPAW) method and compared to experimental data obtained with 51V SSNMR spectroscopy. It was found that mainly strongly bound vanadium sites (V3) are formed on anatase samples, located on TiO2 terminal oxygen atoms. Weakly bound vanadium sites (V1, V2) are formed on bridged anatase oxygen atoms. Supported alkali metals (Li, Na, K, Rb and Cs) on TiO2 were found to interact with protons located on the terminal and bridged TiO2 oxygen atoms. The relative ratio of weakly bound vanadium sites (V1, V2) increased on alkali-containing samples. Calculations performed showed lithium cation to prefer V-O-Ti or V-O-V bonds over VO, unsystematically deshielding vanadium nuclei. The presence of V3+ is likely to cause a loss of intensity in 51V NMR spectra.

TiO2 Nanoparticles with Adjustable Phase Composition Prepared by an Inverse Microemulsion Method: Physicochemical Characterization and Photocatalytic Properties.

Titania nanoparticles (NPs) find wide application in photocatalysis, photovoltaics, gas sensing, lithium batteries, etc. One of the most important synthetic challenges is maintaining control over the polymorph composition of the prepared nanomaterial. In the present work, TiO2 NPs corresponding to anatase, rutile, or an anatase/rutile/brookite mixture were obtained at 80 °C by an inverse microemulsion method in a ternary system of water/cetyltrimethylammonium bromide/1-hexanol in a weight ratio of 17:28:55. The only synthesis variables were the preparation of the aqueous component and the nature of the Ti precursor (Ti(IV) ethoxide, isopropoxide, butoxide, or chloride). The materials were characterized with X-ray diffraction, scanning/transmission electron microscopy, N2 adsorption-desorption isotherms, FTIR and Raman vibrational spectroscopies, and diffuse reflectance spectroscopy. The synthesis products differed significantly not only in phase composition, but also in crystallinity, textural properties, and adsorption properties towards water. All TiO2 NPs were active in the photocatalytic decomposition of rhodamine B, a model dye pollutant of wastewater streams. The mixed-phase anatase/rutile/brookite nanopowders obtained from alkoxy precursors showed the best photocatalytic performance, comparable to or better than the P25 reference. The exceptionally high photoactivity was attributed to the advantageous electronic effects known to accompany multiphase titania composition, namely high specific surface area and strong surface hydration. Among the single-phase materials, anatase samples showed better photoactivity than rutile ones, and this effect was associated, primarily, with the much higher specific surface area of anatase photocatalysts.

Water Structure in the First Layers on TiO2: A Key Factor for Boosting Solar-Driven Water-Splitting Performances.

The water hydrogen-bonded network is strongly perturbed in the first layers in contact with the semiconductor surface. Even though this aspect influences the outer-sphere electron transfer, it was not recognized that it is a crucial factor impacting the solar-driven water-splitting performances. To fill this gap, we have selected two TiO2 anatase samples (with and without B-doping), and by extensive experimental and computational investigations, we have demonstrated that the remarkable 5-fold increase in water-splitting photoactivity of the B-doped sample cannot be ascribed to effects typically associated to enhanced photocatalytic properties, such as band gap, heterojunctions, crystal facets, and other aspects. Studying these samples by combining FTIR measurements under controlled humidity with first-principles simulations sheds light on the role and nature of the first-layer water structure in contact with the photocatalyst surfaces. It turns out that the doping hampers the percolation of tetrahedrally coordinated water molecules while enhancing the population of topological H-bond defects forming approximately linear H-bonded chains. This work unveils how doping the semiconductor surface affects the local electric field, determining the water splitting rate by influencing the H-bond topologies in the first water layers. This evidence opens new prospects for designing efficient photocatalysts for water splitting.

Laser‐Crystallization of TiO2 Nanotubes for Photocatalysis: Influence of Laser Power and Laser Scanning Speed

AbstractTitanium dioxide (TiO2) nanotubes have raised significant attention in the field of photocatalysis. However, achieving locally‐confined, tunable, and efficient crystallization remains challenging. Laser crystallization that enables surface‐confined, fast, and localized annealing has emerged as an alternative to calcination of TiO2 nanotubes. Nonetheless, questions regarding crystallization parameters and mechanism remain open. In this work, amorphous TiO2 nanotubes are synthesized by a two‐step anodization process and laser exposed (515 nm, 1 MHz, 250 fs, 256–569 mW, 1–200 mm s−1) to study the impact of laser parameters and the mechanism of laser crystallization. A thorough analysis via Raman spectroscopy, X‐ray diffraction, scanning electron microscopy, UV–vis spectroscopy, transmission electron microscopy, and degradation of methylene blue is performed and the influence of laser processing parameters on the crystallization are studied and discussed. As laser power increases, a gradual transition from amorphous to anatase and rutile phase takes place, consistent with a thermal crystallization mechanism. Contrary, with increasing laser scanning speeds, thus lower pulse numbers, anatase is converted to rutile and melting occurs. The degradation of methylene blue with anatase samples crystallized by laser and calcination exhibits equal kinetic degradation constants of 0.013 s−1cm−2. This study enhances the understanding of laser crystallization of TiO2 nanotubes.

Photocatalytic destruction of organic dyes by titanium dioxide particles doped with gold

Nanocomposites based on titanium dioxide doped with gold in concentrations of 0.2 and 0.8 wt.% were obtained by the sol-gel method using titanium tetraisopropoxide and chlorauric acid. Thermal treatment of precipitates at T = 600 °C led to the formation of highly dispersed anatase powders and increasing the temperature to 1000-1200 °C contributed to the formation of well-crystallized rutile particles. The gold in the structure of the powders is heterogeneously distributed. The size of the primary particles of anatase did not exceed 10 nm, and that of rutile reached 35-46 nm, gradually increasing with increasing processing temperature. The photocatalytic properties of TiO2&Au structures were studied during the decolorization of solutions of organic dyes (Methylene Blue, Rhodamine B, Methyl Orange, Orange G) with a concentration of 20 mg/dm3. The resulting structures did not show significant sorption activity, and visible light caused a slight desorption of the dyes. At the same time, under the influence of UV irradiation for 60 minutes, the decolorization process took place effectively and was subject to a pseudo-first-order reaction. The biggest photocatalytic activity was shown by the sample of anatase with a gold content of 0.8 wt.%. When it was added into the solution, the degree of decolorization of Rhodamine B reached up to 50%, Methyl Orange - up to 81.5%, Methylene Blue - up to 91%, and Orange G - up to 95.2%. Increasing the efficiency of the destruction of dyes can be achieved by supplementing the photo-catalytic process with a catalytic one.
 
 Аcknowledgements : Olena Lavrynenko is supported by the PAUSE program, a national emergency program for scientists and artists in exile, run by the Collège de France

Revealing the role of defect-induced trap levels in sol–gel-derived TiO2 samples and the synergistic effect of a mixed phase in photocatalytic degradation of organic pollutants

Sol–gel-derived TiO2 samples were synthesized by annealing a xerogel at three different temperatures, namely 350, 550, and 750 °C, which resulted in near-pure anatase, an anatase/rutile mixed phase, and a pure rutile phase, respectively. With the increase in annealing temperature, the average crystallite size increased from ca. 9–48 nm, while the specific surface area decreased from 110.9 to 2.3 m2/g. The mixed-phase sample with a rutile-rich outer layer showed the highest photocatalytic activity, even though the specific surface area of this sample (7.4 m2/g) was much lower than that of the anatase sample (110.9 m2/g). In solar photocatalytic degradation of Methylene Blue dye, the rate constant over this sample (6.25 × 10−2 min−1) was more than three times that over the commercially available photocatalyst Degussa P25 (1.97 × 10−2 min−1). The synergistic increase in the photodegradation performance is attributed to interfacial charge transfer between the anatase and rutile phases. The photocatalytic performances of the anatase and rutile phases can be correlated to the presence of different types of defects. The majority of defects in the anatase sample are shallow levels associated with Vo+, while rutile contains shallow levels related to Ti3+ as well as deep levels corresponding to Vo++.

Photoadsorption of Cr(VI) on titanium dioxide modified by high-energy milling

Microcrystalline powders of rutile and anatase were milled in a high-energy planetary mill down to obtain nanosized TiO2 powders (the size of coherent scattering region (CSR) about 30 nm and 60 nm, respectively). The resulting powders were characterized by HRTEM, Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and the ξ-potential of the aqueous suspensions was determined. High-energy milling made it possible to significantly increase the ability of TiO2 to remove chromium from aqueous solutions. The effectiveness of the powders for not only Cr(VI) removing but also total chromium adsorption under UV-irradiation and short wavelength visible light has been shown. This is important, since Cr(III) does not remain in the aqueous medium and cannot be oxidized back to Cr(VI) under the influence of some environmental factors. It is possible to remove more than 99.9% of total chromium and 100 % of chromium hexavalent from a 50 mg·L-1 solution of Cr(VI) using milled anatase. XPS showed that, upon the photoadsorption, Cr(VI) is reduced to Cr(III). The presence of an acetate buffer in the solution promotes the most efficient removal of chromium. This work shows a simple way to obtain a highly effective material with potential applications for the removal of high toxic hexavalent chromium from industrial wastewater. The milled anatase sample was successfully tested to remove Cr (VI) from a real wastewater sample.

A Sol-Gel/Solvothermal Synthetic Approach to Titania Nanoparticles for Raman Thermometry.

The accurate determination of the local temperature is one of the most important challenges in the field of nanotechnology and nanomedicine. For this purpose, different techniques and materials have been extensively studied in order to identify both the best-performing materials and the techniques with greatest sensitivity. In this study, the Raman technique was exploited for the determination of the local temperature as a non-contact technique and titania nanoparticles (NPs) were tested as nanothermometer Raman active material. Biocompatible titania NPs were synthesized following a combination of sol-gel and solvothermal green synthesis approaches, with the aim of obtaining pure anatase samples. In particular, the optimization of three different synthesis protocols allowed materials to be obtained with well-defined crystallite dimensions and good control over the final morphology and dispersibility. TiO2 powders were characterized by X-ray diffraction (XRD) analyses and room-temperature Raman measurements, to confirm that the synthesized samples were single-phase anatase titania, and using SEM measurements, which clearly showed the nanometric dimension of the NPs. Stokes and anti-Stokes Raman measurements were collected, with the excitation laser at 514.5 nm (CW Ar/Kr ion laser), in the temperature range of 293-323 K, a range of interest for biological applications. The power of the laser was carefully chosen in order to avoid possible heating due to the laser irradiation. The data support the possibility of evaluating the local temperature and show that TiO2 NPs possess high sensitivity and low uncertainty in the range of a few degrees as a Raman nanothermometer material.

Photocatalytic Degradation of Paracetamol under Simulated Sunlight by Four TiO2 Commercial Powders: An Insight into the Performance of Two Sub-Micrometric Anatase and Rutile Powders and a Nanometric Brookite Powder

The photocatalytic degradation of the emerging contaminant paracetamol in aqueous solution has been studied under 1 SUN (~1000 W m−2) in the presence of four commercial TiO2 powders, namely sub-micrometric anatase and rutile, and nanometric brookite and P25 (the popular anatase/rutile mixture used as a benchmark in most papers). The rutile powder showed low activity, whereas, interestingly, the anatase and the brookite powders outperformed P25 in terms of total paracetamol conversion to carboxylic acids, which, according to the literature, are the final products of its degradation. To explain such results, the physicochemical properties of the powders were studied by applying a multi-technique approach. Among the physicochemical properties usually affecting the photocatalytic performance of TiO2, the presence of some surface impurities likely deriving from K3PO4 (used as crystallization agent) was found to significantly affect the percentage of paracetamol degradation obtained with the sub-micrometric anatase powder. To confirm the role of phosphate, a sample of anatase, obtained by a lab synthesis procedure and having a “clean” surface, was used as a control, though characterized by nanometric particles and higher surface area. The sample was less active than the commercial anatase, but it was more active after impregnation with K3PO4. Conversely, the presence of Cl at the surface of the rutile did not sizably affect the (overall poor) photocatalytic activity of the powder. The remarkable photocatalytic activity of the brookite nanometric powder was ascribed to a combination of several physicochemical properties, including its band structure and nanoparticles size.

The interplay between dopant and a surface structure of the photocatalyst – The case study of Nb-doped faceted TiO2

Anatase nanoparticles, exposing the majority of the {0 0 1}, {1 0 0} and {1 0 1} facets were synthesized and doped with different niobium amount to investigate the self-trapping of the excess electrons and resulting photocatalytic activity. Photocatalyst structure and presence of excess electrons inside the obtained Nb-doped anatase samples was confirmed by the combination of structural and spectroscopic analyses. Only for the {1 0 1} facets, introduced electrons were found to localize on the surface titanium sites, as long as the analysis was performed in the ambient environment. The photocatalytic activity data, studied in the reaction of 4-nitrophenol reduction and phenol oxidation, show that the dopant-introduced electrons might increase photocatalytic activity only for the anatase structures exposing {0 0 1} and {1 0 0} facets. Ultimately, the dopant effect on the photocatalytic activity depends on the exposed facet, which might be investigated for other systems to increase their applicability.

Reduced TiO2 with prolonged electron lifetime for improving photocatalytic water reduction activity

The reduction of anatase TiO2 with NaBH4 under argon atmosphere at a high temperature resulted in a longer electron lifetime and a larger electron population. The reduced gray anatase sample with disorder layer showed a higher evolution rate of H2 (130.2 μmol h−1 g−1) compared to pristine TiO2 (24.1 μmol h−1 g−1) in the presence of Pt co-catalyst in an aqueous glucose solution under exposure to ultraviolet light (λ ⩽ 400 nm). Ti3+ and oxygen vacancy defects were proposed to exist in the reduced TiO2. A continuum tail forms above the valence band edge top as a result of these two defects, which contribute to the lattice disorder. This is presumably also the case with the conduction band, which has a continuum tail composed of mid-gap states as a result of the defects. The Ti3+ and oxygen vacancy defects operate as shallow traps for photoexcited electrons, thereby preventing recombination. Since the defects are primarily located at the surface, i.e. in the disorder layer, the photoexcited electrons in shallow traps hence become readily available for the reduction of H3O+ into H2. The prolonged electron lifetime increases the photoexcited electron population in the reduced TiO2, resulting in enhanced water reduction activity.

Fabrication and In Vitro Drug Delivery Evaluation of Cephalexin Monohydrate-Loaded PLA:PVA/HAP:TiO2 Fibrous Scaffolds for Bone Regeneration.

Owing to the excellent osteoconductive property of hydroxyapatite, we aimed to design a cephalexin monohydrate-loaded PLA:PVA/HAP:TiO2 nanofibrous scaffold to improve the drug delivery efficiency toward bone regenerative applications. In this study, HAP:TiO2 (anatase and rutile phases) samples were prepared by a coprecipitation method, which were later blended with PLA:PVA polymeric solution (with and without the drug) to fabricate a nanofibrous matrix via the electrospinning technique. All the prepared samples were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, contact angle, porosity, and tensile strength tests. Further, in vitro biodegradation and the drug-releasing ability were examined by varying the concentration of cephalexin monohydrate in the composite matrix. Deposition of the apatite layer on the scaffolds was examined after incubation in simulated body fluid solution to confirm the bioactivity of the prepared nanofibers. Biocompatibility by the MTT assay and osteogenic differentiation by ARS staining were evaluated by culturing MG63 cells on PLA:PVA/HAP:TiO2 nanofibers, which could ensue better support for cell proliferation. Consequently, the sustained release profile and better biocompatibility of the scaffolds revealed a strong potential use in bone regenerative applications.

Studying Some of Physical Properties of a Lead Doping Titanium Dioxide TiO₂: Pb with Different Ratios

Titanium dioxide TiO2 has witnessed great interest in international research laboratories due to its excellent properties. To study the changes in its physical properties, the structural properties of pure and lead-doped titanium dioxide powder samples were examined with different ratios (x = 0.2 - 0.5 - 0.7 - 0.9 g). The results of X-ray diffraction showed the participation of samples of anatase and rutile of the tetragonal crystal system and brookite of the orthorhombic crystal system based in the titanium dioxide compound with the peaks corresponding to the crystalline levels (110), (012), (040), (111), (211), (123), (112)The preferred orientation is (110) in all pure and doped samples. The relative intensities, distance between crystalline planes (d), crystal size (D), lattice parameters (a), (b) and (c), Initial cell size (V), dislocation density (δ), and theoretical density of the X-ray diffraction spectrum for the powders (ρX-ray) were determined, and the number of atoms of a substance per unit volume (n) and the average distance between atoms (L).

Is Black Titania a Promising Photocatalyst?

Five different (commercial and self-synthesized) titania samples were mixed with NaBH4 and then heated to obtain black titania samples. The change in synthesis conditions resulted in the preparation of nine different photocatalysts, most of which were black in color. The photocatalysts were characterized by various methods, including X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), photoacoustic and reverse-double beam photoacoustic spectroscopy (PAS/RDB-PAS). The photocatalytic activity was tested for oxidative decomposition of acetic acid, methanol dehydrogenation, phenol degradation and bacteria inactivation (Escherichia coli) under different conditions, i.e., irradiation with UV, vis, and NIR, and in the dark. It was found that the properties of the obtained samples depended on the features of the original titania materials. A shift in XRD peaks was observed only in the case of the commercial titania samples, indicating self-doping, whereas faceted anatase samples (self-synthesized) showed high resistance towards bulk modification. Independent of the type and degree of modification, all modified samples exhibited much worse activity under UV irradiation than original titania photocatalysts both under aerobic and anaerobic conditions. It is proposed that the strong reduction conditions during the samples’ preparation resulted in the partial destruction of the titania surface, as evidenced by both microscopic observation and crystallographic data (an increase in amorphous content), and thus the formation of deep electron traps (bulk defects as oxygen vacancies) increasing the charge carriers’ recombination. Under vis irradiation, a slight increase in photocatalytic performance (phenol degradation) was obtained for only four samples, while two samples also exhibited slight activity under NIR. In the case of bacteria inactivation, some modified samples exhibited higher activity under both vis and NIR than respective pristine titania, which could be useful for disinfection, cancer treatment and other purposes. However, considering the overall performance of the black titania samples in this study, it is difficult to recommend them for broad environmental applications.

Structural and photoelectrochemical dynamics of in-situ hydrogenated anatase TiO2 thin films grown by DC reactive magnetron sputtering

Hydrogenation has become one of the most used strategies to improve the photoactive properties of titanium dioxide nanomaterials, n-TiO2. To obtain more information about the hydrogenated process on anatase TiO2 thin films and the improvement of the photoactivity of this material, we report a study on the structural changes of hydrogenated anatase thin films produced by direct-current reactive magnetron sputtering. In the first stage of the hydrogenation process, the obtained polycrystalline anatase films present an increment of the {001} facet according to the amount of hydrogen used in the plasma reaction. At higher hydrogen concentrations, amorphous and rutile phases start to appear. The photoactivity of the hydrogenated anatase samples, H:TiO2, presents a redshift of the photoelectrochemical onset and an increase of the reactivity in the UV region. Both results were experimentally and theoretically related to the formation of the {001} facet and the TiH/TiOH bonds at the surface of the hydrogenated thin films.

Microfluidic assisted low-temperature and speedy synthesis of TiO2/ZnO/GOx with bio/photo active cites for amoxicillin degradation

For the first time, a bio-photo-catalyst is synthesized in a microfluidic platform. The microchannel, which is wall-coated by in situ synthesized bio-photo-catalyst is used as an opto-fluidic reactor for amoxicillin degradation. Analyses including SEM, XRD, FTIR, Raman, UV–Vis spectra, and DLS have been used to characterize samples. The structure and morphology of TiO2 in microfluidic assisted synthesis are studied at 70–120 °C. The results show that both single-crystalline anatase sample and two-phase samples of anatase and rutile can be attained. According to SEM images, the smallest size and the narrowest particle size distribution (0.86 nm pm hspace{0.17em}0.14) is achieved by synthesis at 70 °C. Elemental mapping of Ti shows a uniform coating layer on inner walls. Raman signals besides the primary amines in FTIR results show the biological activity of the cross-linked Glucose oxidase (GOx), which is aimed for situ generation of H2O2. FTIR comparison of bulk and spiral microfluidic synthesized ZnO indicates identical bonds. SEM-coupled with performance experimentation reveal that by regulating the flowrate of spiral micromixer for ZnCl2 at 25 µl/min and NaOH at 50 µl/min, the narrowest size distribution and best the bio-photo-catalytic performance of ZnO nanoparticles is observed.

Surface and Trapping Energies as Predictors for the Photocatalytic Degradation of Aromatic Organic Pollutants

In this study, anatase samples enclosed by the majority of three different crystal facets {0 0 1}, {1 0 0}, and {1 0 1} were successfully synthesized. These materials were further studied toward photocatalytic degradation of phenol and toluene as model organic pollutants in water and gas phases. The obtained results were analyzed concerning their surface structure, reaction type, and surface development. Moreover, the regression model was created to find the correlation between the possible predictors and the photodegradation rate constants (k). From the studied factors, the trapping energy of charge carriers at the surface was found to be the most significant one, exponentially affecting the observed k. This resulted in the overall per-surface activity between the samples being in the order {1 0 1} > {1 0 0} > {0 0 1}. Further introduction of the surface energy (Esurf) to the regression model and the number of possible trapping centers per number of pollutant’s molecules (ntrap·n–1) improved the model accuracy, simultaneously showing the dependence on the reaction type. In the case of phenol photocatalytic degradation, the best accuracy was observed for the model including Esurf ·(ntrap·n–1)1/2 relation, while for the toluene degradation, it included Esurf2 and the S·n–1 ratio, where S is the simple surface area. Concerning different surface features which influence photocatalytic performance and are commonly discussed in the literature, the results presented in this study suggest that trapping is of particular importance.

Visible-Light-Active Black TiO2 Nanoparticles with Efficient Photocatalytic Performance for Degradation of Pharmaceuticals.

Special attention has recently been paid to surface-defective titanium dioxide and black TiO2 with advanced optical, electrical, and photocatalytic properties. Synthesis of these materials for photodegradation and mineralization of persistent organic pollutants in water, especially under visible radiation, presents interest from scientific and application points of view. Chemical reduction by heating a TiO2 and NaBH4 mixture at 350 °C successfully introduced Ti3+ defects and oxygen vacancies at the surface of TiO2, with an increase in the photocatalytic degradation of amoxicillin—an antibiotic that is present in wastewater due to its intense use in human and animal medicine. Three TiO2 samples were prepared at different annealing temperatures to control the ratio between anatase and rutile and were subjected to chemical reduction. Electron paramagnetic resonance investigations showed that the formation of surface Ti3+ defects in a high concentration occurred mainly in the anatase sample annealed at 400 °C, contributing to the bandgap reduction from 3.32 eV to 2.92 eV. The reduced band gap enhances visible light absorption and the efficiency of photocatalysis. The nanoparticles of ~90 m2/g specific surface area and 12 nm average size exhibit ~100% efficiency in the degradation of amoxicillin under simulated solar irradiation compared with pristine TiO2. Mineralization of amoxicillin and by-products was over 75% after 48 h irradiation for the anatase sample, where the Ti3+ defects were present in a higher concentration at the catalyst’s surface.