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.     

Structural and Photocatalytic Activity of Mesoporous N-Doped TiO2 with Band-to-Band Visible Light Absorption Ability

White colored N-doped TiO₂ and a neat TiO₂ powder were synthesized via sol–gel method. Prepared samples were characterized by means of x-ray diffractions, Brunauer–Emmet–Teller and Barrett–Joyner–Halenda methods, x-ray photoelectron spectroscopy, ultraviolet-visible analysis, scanning electron microscopy, and energy dispersive x-ray spectroscopy. Both of the N-doped TiO₂ and neat TiO₂ consisted of anatase phase of titania with mesoporous nature and according to XPS analysis prepared N-doped TiO₂ is a substitutional nitrogen containing sample. The band gap of N-doped TiO₂ and neat TiO₂ were estimated from ultraviolet-visible spectroscopy data to be 2.7 and 3.2 eV, respectively. Prepared substitutional N-doped TiO₂ featured steep light absorption edge with an approximately parallel characteristic of its absorption edge to that neat TiO₂. This is due to its band-to-band visible light absorption ability. Synthesized N-doped TiO₂ had a large surface area value of 193 m²/g and high photon absorption ability causing superior photocatalytic properties towards Congo red azo dye compared to neat TiO₂ either under ultraviolet or visible light illumination.     

Visible light photoelectrocatalysis with salicylic acid-modified TiO2 nanotube array electrode for p-nitrophenol degradation

This research focused on immersion method synthesis of visible light active salicylic acid (SA)-modified TiO₂ nanotube array electrode and its photoelectrocatalytic (PEC) activity. The SA-modified TiO₂ nanotube array electrode was synthesized by immersing in SA solution with an anodized TiO₂ nanotube array electrode. Scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR), UV–vis diffuse reflectance spectrum (DRS), and Surface photovoltage (SPV) were used to characterize this electrode. It was found that SA-modified TiO₂ nanotube array electrode absorbed well into visible region and exhibited enhanced visible light PEC activity on the degradation of p-nitrophenol (PNP). The degradation efficiencies increased from 63 to 100% under UV light, and 79–100% under visible light (λ > 400 nm), compared with TiO₂ nanotube array electrode. The enhanced PEC activity of SA-modified TiO₂ nanotube array electrode was attributed to the amount of surface hydroxyl groups introduced by SA-modification and the extension of absorption wavelength range.     

NO treated TiO2 as an efficient visible light photocatalyst for NO removal

In this study, we report that nitrogen doped TiO₂ could be achieved via thermal treatment of Degussa P25 TiO₂ in NO atmosphere directly (P25-NO). The samples were characterized with XRD, XPS, and FT-IR. The characterization results suggested that nitrogen species were interstitially doped in P25-NO during the NO thermal treatment process. In comparison with P25, the P25-NO exhibited significantly enhanced photocatalytic activities under visible light irradiation (λ > 420 nm) for gaseous NO removal. On the basis of electronic band structure theory, we proposed a possible mechanism for the enhanced visible light driven photocatalytic oxidation process over the interstitial N doping P25-NO samples. This work could not only deepen understanding of the enhanced photoactivity originated from interstitial N doping in TiO₂, but also provide a facile route to prepare nitrogen doped TiO₂ for environmental and energy applications.     

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.     

A new method to prepare high-surface-area N-TiO2/activated carbon

A new method, combining impregnation and vapor-hydrolysis, was developed to prepare hybrid photocatalyst: nitrogen doped TiO₂ coated activated carbon (N-TiO₂/AC). The activated carbon (AC) was impregnated into titanium tetraethoxide/urea/methanol solution, and then the impregnated AC powder was kept in water vapor at 90 °C for 3 h for hydrolysis. Then it was calcinated to fabricate N-TiO₂/AC. Transmission electron microscopy (TEM) results showed that the nitrogen doped TiO₂ (N-TiO₂) in the as-synthesized hybrid was anatase TiO₂ powder with 10-20 nm in grain size, and the bandgap was about 3.08 eV. Moreover, the hybrid photocatalyst (8 wt.% N-TiO₂) had high specific surface area that was up to 1321 m²/g. The hybrid photocatalyst is expected to have high photocatalytic performance with visible irradiation.     

Solar photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) using TiO2/SiO2 aerogel composite photocatalysts

Silica aerogels and TiO₂/silica aerogel composite photocatalysts were synthesized by sol–gel technique at ambient pressure using orthosilioate and tetra-n-butyl titanate as precursors, respectively. The prepared composite photocatalysts were characterized by XRD, TEM, BET surface area, FT-IR and UV–vis absorption spectra. The results showed that the TiO₂/silica aerogel composite photocatalysts possess high surface area. The addition of silica aerogels inhibited the grain growth and phase transformation of anatase to rutile during calcination. The TiO₂/silica aerogel composite sample calcined at 500 °C with an optimal silica aerogel content of 7 wt.% afforded the highest photocatalytic activity. The photocatalytic degradation of 2-sec-butyl-4,6-dinitrophenol (DNBP) was investigated by using this novel TiO₂/silica aerogel composite photocatalyst under solar light irradiation. The effects of irradiation time, pH, catalyst concentration, temperature and initial DNBP concentration were examined as operational parameters. The optimal operational parameters were found as follows: pH as solution pH 4.82, 8 g L⁻¹ catalyst concentration, 20 °C, and 240 min irradiation time. The kinetics of DNBP degradation by TiO₂/silica aerogel composite fit well a pseudo-first-order kinetic model. The repeatability of photocatalytic activity was also tested. This study showed the feasible and potential use of TiO₂/silica aerogel composite photocatalysts in degradation of toxic organic contaminants.     

Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions

The photo-catalytic degradation of an azo dye − Amaranth (AM) - has been investigated in TiO₂/UV aqueous suspensions. The results obtained from the experiments during H₂O₂/TiO₂ addition show that the highest decolorization rate is provided by the combination of (UV + TiO₂ + H₂O₂). The decolorization efficiencies were 17%, 26%, 38% and 64% in the runs UV, UV + H₂O₂, UV + TiO₂ and (UV + TiO₂ + H₂O₂) after approximately 100 min illumination periods, respectively. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. Different experimental conditions, such as temperature, pH and presence of electron acceptor were investigated. The temperature effect was investigated at the range of 293-313 K and it was observed that decolorization rate increased by the increase in temperature. Chemical oxygen demand and dye absorbance of the photodegraded dye solution substantially decreased. Effect of pH was also investigated and it was observed that the lower the pH the higher the degradation. In addition, an enhancement in the photodegradation rate was observed by the addition of hydrogen peroxide as an electron acceptor. The adsorption trends of Amaranth at various initial concentrations followed the Langmuir isotherm trend. This work adds to the global discussion on the role of the advanced oxidation processes in water treatment.     

Mesoporous Au/TiO2 composites preparation,characterization, and photocatalytic properties

In this work, mesoporous Au/TiO₂ composites have been synthesized and tested on photodegradation of methylene blue dye solution. Mesoporous TiO₂ prepared at 450 °C using triblock polymer F127 as structure-directing agent was applied as substrate, while various HAuCl₄ concentrations were used for Au loading through deposition-precipitation method using urea as precipitator and hydrogen reducing process. The influences of Au loading on the microstructures of mesoporous TiO₂ including degree of dispersion, particle size, surface area, light absorption, and band gap were studied with transmission electron microscopy (TEM), X-ray diffraction (XRD), diffuse reflection infrared Fourier transformed spectroscopy (DRIFT), N₂ adsorption–desorption isotherm analysis (BET), and UV–Vis diffuse reflectance spectra. With Au loading, the size of TiO₂ nanoparticles in Au/TiO₂ composites is similar as that of TiO₂ substrate. However, the degree of dispersion was greatly improved. Furthermore, an obvious surface plasmon resonance centered at 570 nm was found in UV–Vis diffuse reflectance spectra for Au/TiO₂ composites. Au loading also induced an obvious red shift of light absorption from UV region to visible region and strengthened both UV and visible light absorption in contrast to substrate. Photodegradation results verified that photocatalytic activity of mesoporous TiO₂ was improved by Au loading. 0.25%Au/TiO₂ composite showed the highest activity, which may be ascribed to its high surface hydroxyl content and the formed Schottky junction after Au loading. These results suggested that noble metal modification is a promising way to synthesize photocatalysts with both high activity and visible light sensitivity.     

Enhancement of titania by doping rare earth for photodegradation of organic dye (Direct Blue)

Lanthanide ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and Yb³⁺)/doped TiO₂ nanoparticles were successfully synthesized by sol–gel method. Their photocatalytic activities were evaluated using Direct Blue dye (DB53) as a decomposition objective. The structural features of TiO₂ and lanthanide ions/TiO₂ were investigated by XRD, SEM, UV-diffuse reflectance, and nitrogen adsorption measurements. Our findings indicated that XRD data characteristic anatase phase reflections and also XRD analysis showed that lanthanides phase was not observed on Lanthanide ions/TiO₂. The results indicated that Gd³⁺/TiO₂ has the lowest bandgap and particle size and also the highest surface area and pore volume (V_p) as well. Lanthanide ions can enhance the photocatalytic activity of TiO₂ to some extent as compared with pure TiO₂ and it was found that Gd³⁺/TiO₂ is the most effective photocatalyst. The photocatalytic tests indicate that at the optimum conditions; illumination time 40 min, pH ∼4, 0.3 g/L photocatalyst loading and 100 ppm DB53; the dye removal efficiency was 100%. Details of the synthesis procedure and results of the characterization studies of the produced lanthanide ions/TiO₂ are presented in this paper.     

Determination of photo-catalytic activity of un-doped and Mn-doped TiO2 anatase powders on acetaldehyde under UV and visible light

Titanium dioxide (TiO₂) photocatalytic powder materials doped with various levels of manganese (Mn) were synthesized to be used as additives to wall painting in combating indoor and outdoor air pollution. The heterogeneous photocatalytic degradation of gaseous acetaldehyde (CH₃CHO) on Mn-TiO₂ surfaces under ultraviolet and visible (UV/Vis) irradiation was investigated, by employing the Photochemical Static Reactor coupled with Fourier-Transformed Infrared spectroscopy (PSR/FTIR) technique. Experiments were performed by exposing acetaldehyde (~ 400 Pa) and synthetic air mixtures (~ 1.01 × 10⁵ Pa total pressure) on un-doped TiO₂ and doped with various levels of Mn (0.1-33% mole percentage) under UV and visible irradiation at room temperature. Photoactivation was initiated using either UV or visible light sources with known emission spectra. Initially, the photo-activity of CH₃CHO under the above light sources, and the physical adsorption of CH₃CHO on Mn-TiO₂ samples in the absence of light were determined prior to the photocatalytic experiments. The photocatalytic loss of CH₃CHO on un-doped TiO₂ and Mn-TiO₂ samples in the absence and presence of UV or visible irradiation was measured over a long time period (≈ 60 min), to evaluate their relative photocatalytic activity. The gaseous photocatalytic end products were also determined using absorption FTIR spectroscopy. Carbon dioxide (CO₂) was identified as the main photocatalysis product. It was found that 0.1% Mn-TiO₂ samples resulted in the highest photocatalytic loss of CH₃CHO under visible irradiation. This efficiency was drastically diminished at higher levels of Mn doping (1-33%). The CO₂ yields were the highest for 0.1% Mn-TiO₂ samples under UV irradiation, in agreement with the observed highest CH₃CHO decomposition rates. It was demonstrated that low-level (0.1%) doping of TiO₂ with Mn results in a significant increase of their photocatalytic activity in the visible range, compared to un-doped TiO₂. This elevated activity is lost at high doping levels (1-33%). Finally, the photocatalytic degradation mechanism of CH₃CHO on 0.1% Mn-TiO₂ surfaces under visible irradiation leading to low CO₂ yields is different than that under UV irradiation resulting to high CO₂ yields.     

Iron promotion of the TiO2 photosensitization process towards the photocatalytic oxidation of azo dyes under solar-simulated light irradiation

The photocatalytic oxidation of the azo dye Orange-II (Or-II) using Fe loaded TiO₂ (Fe–TiO₂) was studied under ultraviolet (UV), visible (vis) and simultaneous UV–vis irradiations using a solar light simulator. Photocatalysts were characterized by means of XRD, SEM-EDX, FTIR and DRS. Fe³⁺ species, identified in XPS analyses, were responsible of the increased absorption of visible light. Moreover, DRS analyses showed a decrease in the bandgap due to Fe³⁺ loading. Photocatalystic tests proved that Fe modification enhanced the TiO₂ photocatalytic activity towards Or-II photodegradation under simultaneous UV–vis irradiation. Even so, the performance of the Fe–TiO₂ samples towards the photodegradation of phenol, under UV irradiation, was lower than TiO₂ suggesting the recombination of the UV photogenerated electron–hole pair. Therefore, results evidence a Fe³⁺ promotion of the electron caption in the photosensitization process of TiO₂ by Or-II acting as a sensitizer. Such process leads to the Or-II photooxidation under UV–vis irradiation by losing energy in electron transferring processes to sensitize TiO₂, and, the formation of reactive oxygen species promoted by the injected electron to the TiO₂ conduction band.     

Mn-doped TiO2 nanopowders with remarkable visible light photocatalytic activity

TiO₂ nanocrystalline powders with various Mn-doping levels were synthesized by the sol-gel process using tetrabutyl titanate and manganese nitrate as precursors. The crystal structure, morphology, doping concentration, optical absorption property, and elemental state of the obtained samples were analyzed. TEM results showed that the synthesized TiO₂ powders were anatase nanoparticles about 7 nm in size. EDX and XPS analyses proved the incorporation of Mn ions into the TiO₂ lattice. A remarkable red shift of the absorption edge was achievable by increased Mn content, leading to gigantically narrowed energy gap to permit absorption well into the infrared spectral region. The dramatic optical absorbance of the doped TiO₂ nanopowders in the visible spectral region led to strong photocatalytic activity under visible light illumination, which was observed by measuring the degradation of methylene blue. In contrast, little degradation was observed for the pure TiO₂ powder. The optimum Mn/Ti ratio was observed to be 0.2 at.% for photocatalytic applications.     

Characterization of N-doped TiO2 films prepared by reactive sputtering using air/Ar mixtures

Nitrogen-doped titanium dioxide (TiO_2 − xN_x) thin films desirable for visible light photocatalysts were prepared by reactive sputtering using air/Ar mixtures. Using air as the reactive gas allows the process to conduct at high base pressures (low vacuum), which reduces substantially the processing time. The obtained films transformed from mixed phases to anatase phase as the air/Ar flow ratio increased. Substitutional doping of nitrogen verified by X-ray photoelectron spectroscopy accounts for the red-shift of absorption edge in the absorption spectra. Anatase TiO_2 − xN_x films could incorporate up to about 7.5 at.% substitutional nitrogen and a maximum of 23 at.% nitrogen was determined in the films with mixed phases. The optical band gaps of the TiO_2 − xN_x films calculated from Tauc plots varied from 3.05 to 3.11 eV and those of the mixed phase ranged from 2.77 to 3.00 eV, which are all lower than that for pure anatase TiO₂ and fall into the visible light regime.     

Structures and properties of titania thin films annealed under different atmosphere

The effects of crystallinity, phase and oxygen vacancies on optical and photocatalytic properties of titania (TiO₂) thin films were systematically studied. The as-deposited amorphous titania films were prepared by reactive sputtering titanium metal targets in argon–oxygen plasma at 100 °C and subsequently annealed at various temperatures of 400–800 °C in air, vacuum and H₂ atmosphere. The results indicate that in general the crystallinity of the annealed films is enhanced with the increasing annealing temperature. At the same temperature, the H₂ annealed films achieve better crystallinity but containing more oxygen vacancies than the films annealed in air and in vacuum. In H₂ or in vacuum, the concentration of oxygen vacancies in the annealed films increases with increasing temperature, while in air it remains constant. Oxygen vacancies in titania film not only facilitate phase transformation but also lower the band gap of titania, and make the film visible-light responsive. Photocatalytic properties of the TiO₂ films were characterized in UV and visible light irradiation by following the Ag reduction and degradation of methylene blue. The films annealed at 600–700 °C in H₂ possess the best film crystallinity and the proper concentration of oxygen vacancies and exhibit the best photocatalytic performance under both UV and visible light.     

Influence of metal plasma ion implantation on photo-sensitivity of anatase TiO2 thin films

Nano-scale TiO₂ thin films were synthesized by using sol-gel and spin-coating techniques on glass substrates for photo-catalytic applications. The Ti(IV) butoxide-based TiO₂ thin films were optimized for transforming into the high-purity crystalline anatase phase when calcined at 500 °C. To further enhance the photo-catalysis sensitivity of TiO₂ thin films for use in visible light environments, a metal plasma ion implantation process was implemented to modify the band gap electron configuration of Ti. Various transition metal atoms such as Ni, Cu, V, and Fe were ionized and accelerated at 20 keV to impinge on the surface of TiO₂ substrates at a dosage of 5 × 10¹⁵ ions/cm². ESCA analysis confirmed the binding energy shift of Ti by 0.8-1.2 eV, which accounted for the increased effective positive charge of Ti, resulting in more effective electron trapping capability and, thus, the electron-hole pair separation. In addition, the absorption spectroscopy demonstrated that optical absorption in the visible light regime occurred in specimens implanted with transition metal ions, likely due to the formation of extra impurity energy levels within the original TiO₂ band gap energy structure. Among all tested implant materials, the band gap energy of TiO₂ was effectively reduced by Cu and Fe ion implantation by 0.9-1.0 eV, which was sufficient enough to excite valence electrons over the band gap in visible light environments. The feasibility of the metal-doped TiO₂ thin films for effective applications under visible light irradiation was further confirmed by using super-hydrophilicity contact-angle measurement.     

Preparation of metal ion (Fe and Ni) doped TiO2 nanoparticles supported on ZSM-5 zeolite and investigation of its photocatalytic activity

Metal ion doped TiO₂ nanoparticles supported on ZSM-5 zeolite (M-TiO₂/ZSM-5 composites, M = Fe or Ni) were synthesized by hydrothermal method. The prepared composites were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and UV–vis diffuse reflectance spectra (DRS). The photocatalytic activities of composites were evaluated by degradation of yellow GX aqueous solution under ambient condition. Fe-TiO₂/ZSM-5 composite showed to be more efficient catalyst for degradation of dye molecules as compared with Ni-TiO₂/ZSM-5 and TiO₂/ZSM-5. Its higher photocatalytic activity is attributed to the effective separation of charge carriers that will be discussed in this paper in detail.     

Photocatalytic degradation of three azo dyes using immobilized TiO2 nanoparticles on glass plates activated by UV light irradiation: Influence of dye molecular structure

In order to discuss the effect of chemical structure on photocatalysis efficiency, the photocatalytic degradation of three commercial textile dyes (C.I. Acid Orange 10 (AO10), C.I. Acid Orange 12 (AO12) and C.I. Acid Orange 8 (AO8)) with different structure and different substitute groups has been investigated using supported TiO₂ photocatalyst under UV light irradiation. All the experiments were performed in a circulation photochemical reactor equipped with a 15-W UV lamp emitted around 365 nm. The investigated photocatalyst was industrial Millennium PC-500 (crystallites mean size 5–10 nm) immobilized on glass plates by a heat attachment method. SEM images of the immobilized TiO₂ nanoparticles showed the good coating on the plates, after repeating the deposition procedure three times. Our results indicated that the photocatalytic decolorization kinetics of the dyes were in the order of AO10 > AO12 > AO8. Photocatalytic mineralization of the dyes was monitored by total organic carbon (TOC) decrease, changes in UV–vis spectra and ammonium ion formation. The dye solutions could be completely decolorized and effectively mineralized, with an average overall TOC removal larger than 94% for a photocatalytic reaction time of 6 h. The nitrogen-to-nitrogen double bond of the azo dyes was transformed predominantly into NH₄⁺ ion. The kinetic of photocatalytic decolorization of the dyes was found to follow a first-order rate law. The photocatalysis efficiency was evaluated by figure-of-merit electrical energy per order (E_EO).     

Photocatalytic activity of pulsed laser deposited TiO2 thin films in N2, O2 and CH4

We report on pulsed laser deposition of TiO₂ films on glass substrates in oxygen, methane, nitrogen and mixture of oxygen and nitrogen atmosphere. The nitrogen incorporation into TiO₂ lattice was successfully achieved, as demonstrated by optical absorption and XPS measurements. The absorption edge of the N-doped TiO₂ films was red-shifted up to ∼ 480 nm from 360 nm in case of undoped ones.The photocatalytic activity of TiO₂ films was investigated during toxic Cr(VI) ions photoreduction to Cr(III) state in aqueous media under irradiation with visible and UV light. Under visible light irradiation, TiO₂ films deposited in nitrogen atmosphere showed the highest photocatalytic activity, whereas by UV light exposure the best results were obtained for the TiO₂ structures deposited in pure methane and oxygen atmosphere.