Synthesis of silver and sulphur codoped TiO<Subscript>2</Subscript> nanoparticles for photocatalytic degradation of methylene blue

In the present work, silver and sulphur codoped TiO₂ (Ag–S/TiO₂) photocatalysts were effectively prepared by sol–gel technique. The prepared samples were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy dispersive x-ray analysis (EDX), Fourier transform infrared (FTIR) spectroscopy, diffuse reflectance UV–Vis spectroscopy (UV-DRS) and photoluminescence (PL). The XRD patterns consisted of anatase crystalline phases and the particle size and shape of the prepared samples were observed by SEM and HR-TEM. The presence of doping ions was confirmed by EDX analysis, the decreased band-gap energy of Ag–S codoped TiO₂ nanoparticles was investigated by UV-DRS. The decreased in the intensity of Ag–S codoped TiO₂ was absorbed due to the lower separation of electron–hole pairs were confirmed by PL spectrum. The Ag–S codoped TiO₂ showed higher photocatalytic activity than pure and single-doped TiO₂ in the photodegradation of methylene blue (MB) aqueous solution under visible light irradiation. The given work was a good model to associate the considering of the synergistic effect of metal and non-metal codoped TiO₂ in the photocatalysis and photo electrochemistry.     

Structural,morphological and photocatalytic characterisations of Ag-coated anatase TiO2 fabricated by the sol–gel dip-coating method

This study reports on the synthesis, characterisation and environmental applications of immobilised Titanium dioxide (TiO₂) as photocatalyst. Nanostructured thin films have been prepared on glass substrates using a layer-by-layer dip-coating method. The crystalline phase and surface morphology of the thin films were investigated by X-ray diffraction (XRD) pattern and scanning electron microscopy (SEM), respectively. The XRD results show that the TiO₂ thin films crystallise in anatase phase and we have found that the thin films consist of titanium dioxide nanocrystals. SEM shows that the nanoparticles are sintered together to form a compact structure and TiO₂ particles coated with silver nanoclusters were observed. Ag-coated TiO₂ films demonstrated photocatalysis performance when irradiated, and the Ag carrier further showed an electron-scavenging ability to mitigate electron–hole pair recombination, which can improve the photocatalytic efficiency. With the oxidisation and electron-scavenging ability of Ag and the photocatalysis ability of TiO₂, Ag-coated TiO₂ can decolour methyl orange (MO) more than bare TiO₂. It is a new approach to form Ag-coated TiO₂ nanoparticles with a simple system and non-toxic materials. The high photocatalytic effect of Ag-coated TiO₂ nanoparticles on pollutant (MO) suggests that it may have a promising future for water and wastewater treatments.     

Oxygen-rich TiO2 decorated with C-Dots: Highly efficient visible-light-responsive photocatalysts in degradations of different contaminants

Providing novel photocatalysts with high photocatalytic efficiency is of great significance. In the present work, hydrogen peroxide and carbon dots (C-Dots) were utilized to enhance the photocatalytic performance of TiO₂ under visible light. The fabricated TiO₂-peroxo/C-Dots photocatalysts were analyzed by XRD, HRTEM, SEM, EDX, BET, FT-IR, XPS, PL, UV–Vis DRS, EIS, and photocurrent density. Photocatalytic abilities of the nanocomposites were evaluated by photocatalytic removal of RhB, MO, MB, fuchsine, and Cr (VI) upon visible-light illumination. The results demonstrated that the binary nanocomposites exhibited remarkably enhanced photocatalytic activity compared with the TiO₂ and TiO₂-peroxo photocatalysts. The best photocatalytic performance was obtained using 0.75?mL of C-Dots, which was approximately 79.2, 17.1, 71.4, and 40.5 times higher than the pure TiO₂ for degradations of RhB, MO, MB, and fuchsine, respectively. Furthermore, the TiO₂-peroxo/C-Dots nanocomposites exhibited high stability in consecutive photocatalytic processes. Based on the results, the TiO₂-peroxo/C-Dots photocatalyst is expected to become a promising photocatalyst for practical applications in water purification.     

Highly ordered Ag–TiO<Subscript>2</Subscript> nanocomposited arrays with high visible-light photocatalytic activity

TiO₂ is active only in the ultraviolet region. To enhance the active ability, a combined method consisting of the anodic oxidation method and the hydrothermal method was developed to prepare highly ordered Ag-TiO₂ nanocomposited arrays. The anodic oxidation was used to synthesize amorphous nanotubes with high chemical activity that subsequently served as highly ordered templates in preparing the final sample. The amorphous nanotubes got converted to highly ordered Ag-TiO₂ (anatase) arrays in the silver nitrate & glucose aqueous solution via hydrothermal treatment. SEM and TEM results show that the Ag-TiO₂ nanocomposite was composed of a large number of Ag nanoparticles and anatase TiO₂ nanoparticles, and the morphology of those at the top of the arrays was found different from that of its trunk. The morphology evolution mechanism of the obtained sample was discussed. It is also revealed that the Ag-TiO₂ nanocomposite has high visible-light photocatalytic activity.     

Synthesis and characterization of Ag/TiO2-B nanosquares with high photocatalytic activity under visible light irradiation

Square-like B doped TiO₂ nanocrystals were first synthesized by a mild solvothermal method with H₃BO₄ and titanium isopropoxide as the precursors, and isopropyl alcohol as reaction medium. Then, Ag nanoparticles were deposited on TiO₂-B nanosquares by photo-deposition. The as-synthesized products have been investigated by photocatalytic reaction test and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV–vis diffuse reflectance spectra (DRS). The results showed that boron was successfully doped into TiO₂ nanosquares under solvothermal condition. The obtained Ag/TiO₂-B composite showed high efficiency in degradation of acid orange II under visible light irradiation. The high photocatalytic performance could be attributed to the synergistic effect of B doping and the plasmon photocatalysis role of the deposited silver nanoparticles over TiO₂.     

Enhanced photocatalytic activity of TiO2 by polydimethylsiloxane deposition and subsequent thermal treatment at 800 °C

A thin film of polydimethylsiloxane (PDMS) was coated on TiO₂ nanoparticles (P-25, Dagussa), and surface structures of the thin films were analyzed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Furthermore, photocatalytic activity of PDMS-coated TiO₂ samples with various annealing temperatures was determined using UV irradiation. We show that the 800 °C-annealed sample of PDMS-coated TiO₂ showed a two-fold higher photocatalytic activity with respect to the bare TiO₂. The enhanced photocatalytic activity was attributed to the greater hydrophilicity of the annealed PDMS coating.     

Photocatalytic mechanism of high-activity anatase TiO<Subscript>2</Subscript> with exposed (001) facets from molecular-atomic scale: HRTEM and Raman studies

Anatase TiO₂ with a variant percentage of exposed (001) facets was prepared under hydrothermal processes by adjusting the volume of HF, and the photocatalytic mechanism was studied from atomic-molecular scale by HRTEM and Raman spectroscopy. It was revealed that: 1) From HRTEM observations, the surface of original TiO₂ with exposed (001) facets was clean without impurity, and the crystal lattice was clear and completed; however, when mixed with methylene blue (MB) solution, there were many 1 nm molecular absorbed at the surface of TiO₂; after the photocatalytic experiment, MB molecules disappeared and the TiO₂ lattice image became fuzzy. 2) The broken path of the MB chemical bond was obtained by Raman spectroscopy, i.e., after the irradiation of the light, the vibrational mode of C-N-C disappeared due to the chemical bond breakage, and the groups containing C-N bond and carbon rings were gradually decomposed. Accordingly, we propose that the driving force for breaking the chemical bond and the disappearance of groups is from the surface lattice distortion of TiO₂ during photocatalyzation.     

Visible-light-responsive Ag–Si codoped anatase TiO2 photocatalyst with enhanced thermal stability

To utilize visible light more efficiently and enhance the photocatalytic performance of TiO₂, Ag–Si/TiO₂ photocatalyst was synthesized via a two-step method. The obtained materials were characterized by XRD, Raman, TEM, HRTEM, BET, TG–DTA, XPS, ICP as well as UV–vis DRS. All photocatalyst materials held an anatase phase confirmed by XRD, Raman and HRTEM. The Ag–Si/TiO₂ photocatalysts possessed high thermal stability and the phase transformation was retarded to about 900 °C revealed by XRD and TG–DTA. The Ag–Si/TiO₂ particles synthesized via the nonaqueous method were highly monodispersed and the particles size became smaller compared to the un-doped TiO₂, resulting in the enlargement of surface area. In addition, UV–vis light absorption shifted to visible region after Ag doping. XPS results demonstrated that Si weaved into the matrix of TiO₂ and enriched in the surface layer, while Ag dispersed on the surface of TiO₂ particles. The Ag dopant suppressed the recombination of photogenerated electrons and holes, Si enlarged the surface of photocatalysts. Silver and silicon co-doping improved the visible photocatalytic activity, which was evaluated by Rhodamine B (RhB) degradation. The photocatalytic activity of the obtained Ag–Si/TiO₂ sample was much more higher than those of pure TiO₂ and Ag/TiO₂, reaching the maximum at the Ag and Si content of 0.5 mol% and 20.0 mol%, respectively. The improved visible photocatalytic activity may be attributed to the synergetic effects of codoping by silver and silicon.     

Highly stable visible‐light photocatalytic properties of black rutile TiO2 hydrogenated in ultrafast flow

The hydrogenation and introducing oxygen vacancies (V_O) can lead to surface lattice disorder in TiO₂, which is a new form of TiO₂ named black TiO₂, with excellent visible-light photocatalytic activity, but this TiO₂ is easy to failure because oxidation makes the concentration of surface V_O decrease rapidly in a short time. In this work, black TiO₂ nanoparticles with V_O almost concentrated inside nanoparticles were fabricated under ultrafast hydrogen flow. These bulk V_O shortened the bandgaps of black TiO₂, enhanced its visible light absorption, and meanwhile provided extremely strong stability. The location of V_O in black TiO₂ was evident from EPR, XPS with HRTEM investigation, and other characteristics of black TiO₂ were obtained by XRD, UV-Vis, SEM, PL, and photocurrent techniques. The degradation experiments on Cr⁶⁺ or rhodamine B demonstrated the good visible-light photocatalytic performance of our material. After 18 months of natural aging treatment (in the air), our samples showed no discoloration and maintained 89.5% photocatalytic efficiency, and further study exhibited that this black TiO₂ also contained excellent acid resistance and moderate alkaline resistance. This work could help design lattice disorder to obtain more stable and practical black TiO₂.

     

Preparation N-F-codoped TiO2 nanorod array by liquid phase deposition as visible light photocatalyst

An efficient method for the preparation of N-F-codoped visible light active TiO₂ nanorod arrays is reported. In the process, simultaneous nitrogen and fluorine doped TiO₂ nanorod arrays on the glass substrates were achieved by liquid phase deposition method using ZnO nanorod arrays as templates with different calcination temperature. The as-prepared samples were characterized by Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-vis absorption spectra measurements. It was found that calcination temperature is an important factor influencing the microstructure and the amount of N and F in TiO₂ nanorod arrays samples. The visible light photocatalytic properties were investigated using methylene blue (MB) dye as a model system. The results showed that N-F-codoped TiO₂ nanorod arrays sample calcined at 450 °C demonstrated the best visible light activity in all samples, much higher than that of TiO₂ nanoparticles and P25 particles films.     

Visible-light photocatalytic activity of semiconductor composites supported by electrospun fiber

The preparation and photocatalysis of TiO₂–ZnS/fluoropolymer fiber composites were investigated. The fluoropolymer nanofiber mats with carboxyl groups were prepared by electrospinning, and then titanium and zinc ions were introduced onto the fiber surfaces by the coordinating of carboxyl of fluoropolymer in solution. The TiO₂–ZnS composites with diameters 15 nm to 1 μm were immobilized on the surface of fluoropolymer electrospun fiber using hydrothermal synthesis. The Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis reveal that some chemical interaction exists between TiO₂–ZnS composites and fluoropolymer fibers, so the semiconductor composites were immobilized tightly on the surface of fluoropolymer fibers. The ultraviolet–visible absorption spectra show the TiO₂–ZnS/fluoropolymer fiber composites have low band gap and good visible-light response ability. The degradation rate of methylene blue in TiO₂–ZnS/fluoropolymer fiber composites system was considerably higher than that of TiO₂ or TiO₂–ZnS nanoparticles system under visible-light irradiation, because the TiO₂–ZnS/fluoropolymer fiber composites possess good visible-light response ability, high specific surface areas, and adsorption–migration–photodegradation process. The photocatalytic activity of TiO₂–ZnS/fluoropolymer fiber composites changes indistinctively after 10 repeating photocatalysis tests.     

Removal of fluoride from aqueous solution by polypyrrole/Fe3O4 magnetic nanocomposite

Highly efficient visible light TiO₂ photocatalyst was prepared by the sol-gel method at lower temperature (≤300 °C), and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (UV-vis DRS), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and differential scanning calorimetry-thermogravimetric analysis (DSC-TGA). The effects of the heat treatment temperature and time of the as-prepared TiO₂ on its visible light photocatalytic activity were investigated by monitoring the degradation of methyl orange solution under visible light irradiation (wavelength ≥ 400 nm). Results show that the as-prepared TiO₂ nanoparticles possess an anatase phase and mesoporous structure with carbon self-doping and visible photosensitive organic groups. The visible light photocatalytic activity of the as-prepared TiO₂ is greatly higher than those of the commercial TiO₂ (P-25) and other visible photocatalysts reported in literature (such as PPy/TiO₂, P3HT/TiO₂, PANI/TiO₂, N-TiO₂ and Fe³⁺-TiO₂) and its photocatalytic stability is excellent. The reasons for improving the visible light photocatalytic activity of the as-prepared TiO₂ can be explained by carbon self-doping and a large amount of visible photosensitive groups existing in the as-prepared TiO₂. The apparent optical thickness (τ_app), local volumetric rate of photo absorption (LVRPA) and kinetic constant (k_T) of the photodegradation system were calculated.     

Fabrication and characterization of novel composite membranes composed of photonic crystals and TiO2 nanotube array films

Novel composite membranes composed of photonic crystals (PCs) and TiO₂ nanotube array (TNA) films have been fabricated by combining the room temperature floating self-assembly (RTFSA) method, recently developed by our research group, and the liquid-phase deposition technique. By applying this combined procedure, polystyrene (PS) opal PC/TNA and TiO₂ inverse opal PC/TNA composite membranes were prepared. Scanning electron microscopy and ultraviolet/visible spectroscopy analyses showed that the membrane samples possessed very high crystalline quality. Notably, the ordered packing of the PS microspheres from the top to the bottom of the opal PC film was not affected by the surface roughness of the porous TNA substrate. This is attributed to the self-assembly mechanism of the colloidal particles, which produces a three-dimensional ordered structure in the RTFSA method. Herein, the crystallization of the colloidal particles occurred at the surface of the colloidal suspension, and the crystal growth proceeded downward from the surface of the suspension to the substrate.     

Photoelectrochemical performance of Ag nanoparticles on TiO2 films prepared by aerosol pyrolysis

Titanium dioxide (TiO₂) layers were prepared by the pyrolysis of an ethanolic solution of di-iso-propoxy-titanium bis(acetylacetonate) in aerosol form, and then electrodeposited with Ag nanoparticles on their surface. The morphology and photoelectrochemical properties of the resulting Ag nanoparticles (NPs) on TiO₂ films were found to be significantly tuned by varying the electrodeposition time in an aqueous electrolyte containing AgNO₃ and KNO₃. Photocurrent density–voltage curves and electrochemical impedance spectra revealed that the Ag NPs remarkably improved the short-circuit current density and open circuit voltage, and considerably reduced the electrochemical impedance. Therefore, Ag NPs deposition enhanced the photo-absorption of the TiO₂ layer, excited photoelectrons by localised surface plasmon resonance, promoted photo-induced charge separation, and prevented electron–hole recombination.     

Photocatalytic properties of porous TiO2/Ag thin films

In this study, nanocrystalline TiO₂/Ag composite thin films were prepared by a sol-gel spin-coating technique. By introducing polystyrene (PS) spheres into the precursor solution, porous TiO₂/Ag thin films were prepared after calcination at a temperature of 500 °C for 4 h. Three different sizes (50, 200, and 400 nm) of PS spheres were used to prepare porous TiO₂ films. The as-prepared TiO₂ and TiO₂/Ag thin films were characterized by X-ray diffractometry (XRD) and by scanning electron microscopy to reveal structural and morphological differences. In addition, the photocatalytic properties of these films were investigated by degrading methylene blue under UV irradiation.When PS spheres of different sizes were introduced after calcination, the as-prepared TiO₂ films exhibited different porous structures. XRD results showed that all TiO₂/Ag films exhibited a major anatase phase. The photodegradation of porous TiO₂ thin films prepared with 200 nm PS spheres and doped with 1 mol% Ag exhibited the best photocatalytic efficiency where ∼ 100% methylene blue was decomposed within 8 h under UV exposure.     

Preparation and characterization of Co-doped TiO2 materials for solar light induced current and photocatalytic applications

Different amounts of Co-doped TiO₂ powders and thin films were prepared by following a conventional co-precipitation and sol–gel dip coating technique, respectively. The synthesized powders and thin films were subjected to thermal treatments from 400 to 800 °C and were thoroughly investigated by means of X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive analysis with X-rays, FT-infrared, FT-Raman, diffuse reflectance spectroscopy, ultraviolet–visible spectroscopy, BET surface area, zeta potential, flat band potential measurements, band-gap energy, etc. The photocatalytic ability of the powders was evaluated by methylene blue (MB) degradation studies. The thin films were characterized by photocurrent and ultraviolet–visible (UV–Vis) spectroscopy techniques. The characterization results suggest that the Co-doped TiO₂ powders synthesized in this study consist mainly anatase phase, and possess reasonably high specific surface area, low band gap energy and flat band potentials amenable to water oxidation in photoelectrochemical (PEC) cells. The photocatalytic degradation of MB over Co-doped TiO₂ powders followed the Langmuir–Hinshelwood first order reaction rate relationship. The 0.1 wt.% Co-doped TiO₂ composition provided the higher photocurrent, n-type semi-conducting behavior and higher photocatalytic activity among various Co-doped TiO₂ compositions and pure TiO₂ investigated.     

Ag surfactant effects of TiO2 films prepared by sputter deposition

The surfactant effect of Ag on the thin film structure of TiO₂ by radio frequency magnetron sputtering has been investigated. Comparisons between the atomic force microscopy images revealed that the surface roughness of TiO₂ film mediated by Ag was smaller than that of the TiO₂ film without Ag. The surface segregation effect of Ag was confirmed using X-ray photoelectron spectroscopy. The results of X-ray diffraction revealed that the initial deposition of a 0.4 nm thick Ag surfactant layer onto a Fe buffer layer prior to the deposition of the TiO₂ film reduced the rutile (110) growth and enhanced the anatase (100) growth. It was concluded that Ag was an effective surfactant for changing the thin film structure of TiO₂ on the Fe buffer layer. The photocatalytic effect of the fabricated TiO₂ film was also investigated using the remote oxidation process. TiO₂ films with the Ag surfactant exhibited higher photocatalytic activity than conventionally deposited TiO₂ films.     

Synthesis of TiO2/Pt/TiO2 multilayer films via radio frequency magnetron sputtering and their enhanced photocatalytic activity

TiO₂/Pt/TiO₂ (TPT) multilayered films with different thicknesses of Pt layers from about 0.75 to 12 nm were prepared by radio frequency magnetron sputtering method. The as-prepared films were characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy, UV-visible diffuse reflectance spectroscopy, and photoluminescence spectroscopy. The photocatalytic activity of the samples was evaluated by the photocatalytic decolorization of methyl blue aqueous solution under ultraviolet light irradiation. The photocatalytic activities of all TPT multilayer films were higher than that of the pure TiO₂ films. When Pt thickness was increased to 3 nm, the measured photocatalytic activity of the TPT film was highest, and exceeded that of the pure TiO₂ films by a factor of more than three times. Such enhancement was ascribed to the presence of Pt layer, which inhibits the recombination of the photogenerated charge and carriers, as well as modifies the crystallinity of the TiO₂ top layer.     

Ag surfactant effects of TiO2 films prepared by sputter deposition

The surfactant effect of Ag on the thin film structure of TiO₂ by radio frequency magnetron sputtering has been investigated. Comparisons between the atomic force microscopy images revealed that the surface roughness of TiO₂ film mediated by Ag was smaller than that of the TiO₂ film without Ag. The surface segregation effect of Ag was confirmed using X-ray photoelectron spectroscopy. The results of X-ray diffraction revealed that the initial deposition of a 0.4 nm thick Ag surfactant layer onto a Fe buffer layer prior to the deposition of the TiO₂ film reduced the rutile (110) growth and enhanced the anatase (100) growth. It was concluded that Ag was an effective surfactant for changing the thin film structure of TiO₂ on the Fe buffer layer. The photocatalytic effect of the fabricated TiO₂ film was also investigated using the remote oxidation process. TiO₂ films with the Ag surfactant exhibited higher photocatalytic activity than conventionally deposited TiO₂ films.     

Pd nanoparticle loaded TiO<Subscript>2</Subscript> semiconductor for photocatalytic degradation of Paraoxon pesticide under visible-light irradiation

Overuse of the organophosphorus pesticides such as Paraoxon in agriculture industry has raised significant threats to the environment by contamination of soils and groundwaters. Therefore, extensive studies have been carried out to develop an effective method for removing of these poisonous pollutants from contaminated resources. In the current study, Pd nanoparticle loaded TiO₂ nanocomposites with different weight percentages of Pd were prepared via a facile photoreduction method and for the first time, were used for photocatalytic degradation of Paraoxon under visible-light irradiation. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy, diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy techniques. In these nanocomposites, the presence of Pd nanoparticles enhances the photocatalytic activity of TiO₂ by their surface plasmon resonance effect and also by narrowing the band gap energy of TiO₂. The results of photocatalytic activity measurements indicate that the nanocomposite with 0.8 wt% content of Pd (PT0.8) has the best photocatalytic activity. The result of total organic carbon test shows that Paraoxon was completely mineralized by PT0.8 photocatalyst after 120 min, under visible-light irradiation.