Synthesis of Sc and V-doped TiO2 nanoparticles and photodegradation of rhodamine-B

Anatase TiO₂ nanoparticles doped with Sc and V were synthesized and their photocatalytic activities were evaluated through the photodegradation of rhodamine-B under UV irradiation. TiO₂ shows the highest photocatalytic activity and Sc doped TiO₂ and V doped TiO₂ show lower photocatalytic activity than TiO₂. In contrast, Sc and V codoped TiO₂ shows no any photocatalytic activity. The reasons for the decrease in photocatalytic activity is due to the presence of surficial Sc₂O₃ islands covering the reactive sites for Sc doped TiO₂ and the increased e?/h+ pair recombination resulted from the high level substitutional V(IV) ions for V doped TiO₂, respectively.     

Niobium‐Doped Titania Photocatalyst Film Prepared via a Nonaqueous Sol‐Gel Method

Niobium‐doped Titanium dioxide (Nb:TiO₂) transparent films were successfully deposited on glass substrates using a non‐aqueous sol‐gel spin coating technique. The effect of Nb concentration on the structural and photocatalytic properties of Nb:TiO₂ films was studied using X‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), and UV visible spectroscopy. The films with 12 at.% (atomic percent) Nb doped TiO₂ showed excellent photocatalytic activity through 97.3% degradation of methylene blue (MB) after 2 h of UV irradiation.     

Photoactive behavior of polyacrylonitrile fibers based on silver and zirconium co‐doped titania nanocomposites: Synthesis,characterization, and comparative study of solid‐phase photocatalytic self‐cleaning

Silver and zirconium co‐doped and mono‐doped titania nanocomposites were synthesized and deposited onto polyacrylonitrile fibers via sol–gel dip‐coating method. The resulted coated‐fibers were characterized by X‐ray diffraction (XRD), scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, diffuse reflectance spectroscopy, thermogravimetric analysis, and BET surface area measurement. Photocatalytic activity of the TiO₂‐coated and TiO₂‐doped coated fibers were determined by photomineralization of methylene blue and Eosin Y under UV–vis light. The progress of photodegradation of dyes was monitored by diffuse reflectance spectroscopy. The XRD results of samples indicate that the TiO₂, Ag‐TiO₂, Zr‐TiO₂, and Ag‐Zr‐TiO₂ consist of anatase phase. All samples demonstrated photo‐assisted self‐cleaning properties when exposed to UV–vis irradiation. Evaluated by decomposing dyes, photocatalytic activity of Ag–Zr co‐doped TiO₂ coated fiber was obviously higher than that of pure TiO₂ and mono‐doped TiO₂. Our results showed that the synergistic action between the silver and zirconium species in the Ag‐Zr TiO₂ nanocomposite is due to both the structural and electronic properties of the photoactive anatase phase. These results clearly indicate that modification of semiconductor photocatalyst by co‐doping process is an effective method for increasing the photocatalytic activity. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

TiO2 nanofibers doped with rare earth elements and their photocatalytic activity

In the present study rare earth doped (Ln³⁺–TiO₂, Ln = La, Ce and Nd) TiO₂ nanofibers were prepared by the sol–gel electrospinning method and characterized by XRD, SEM, EDX, TEM, and UV-DRS. The photocatalytic activity of the samples was evaluated by Rhodamine 6G (R6G) dye degradation under UV light irradiation. XRD analysis showed that all the synthesized pure and doped titania nanofibers contain pure anatase phase at 500 °C but at 700 °C it shows both anatase and rutile phase. XRD result also shows that Ln³⁺-doped titania probably inhibits the phase transformation. The diameter of nanofibers for all samples ranges from 200 to 700 nm. It was also observed that the presence of rare-earth oxides in the host TiO₂ could decrease the band gap and accelerate the separation of photogenerated electron–hole pairs, which eventually led to higher photocatalytic activity. To sum up, our study demonstrates that Ln³⁺-doped TiO₂ samples exhibit higher photocatalytic activity than pure TiO₂ whereas Nd³⁺-doped TiO₂ catalyst showed the highest photocatalytic activity among the rare earth doped samples.     

Preparation and characterization of a novel activated carbon‐supported N‐doped visible light response photocatalyst (TiO2−xNy/AC)

A photocatalyst, TiO_2?xN_y/AC (activated carbon (AC) supported N‐doped TiO₂), highly active in both the Vis and UV range, was prepared by calcination of the TiO₂ precursor prepared by acid‐catalyzed hydrolysis in an ammonia atmosphere. The powders were characterized by diffuse reflectance spectroscopy, scanning electron microscopy, X‐ray diffraction, N₂ adsorption, Fourier transform infrared spectroscopy and phenol degradation. The doped N in the TiO₂ crystal lattice creates an electron‐occupied intra‐band gap allowing electron‐hole pair generation under Vis irradiation (500–560 nm). The TiO_2?xN_y/AC exhibited high levels of activity and the same activity trends for phenol degradation under both Vis and UV irradiation: TiO_2?xN_y/AC calcined at 500 °C for 4 h exhibited the highest activity. The band‐gap level newly formed by doped N can act as a center for the photo‐generated holes and is beneficial for the UV activity enhancement. The performance of the prepared TiO_2?xN_y/AC photocatalyst revealed its practical potential in the field of solar photocatalytic degradation of aqueous contaminants. Copyright © 2007 Society of Chemical Industry     

One-step fabrication of Ce–N-codoped TiO2 nano-particle and its enhanced visible light photocatalytic performance and mechanism

Ce, N codoped TiO₂ nano-particles were fabricated through sol–gel strategy in the absence of water. Results revealed that Ce was not implanted into the lattice of TiO₂ and existed as the forms of small cluster CeO₂ which uniformly diffused onto the surface or interstitial site of TiO₂, while N dopants were successfully incorporated into the structure of TiO₂ by substituting the lattice oxygen atoms and existed as the forms of N–Ti–O bonds, thereby resulting in the formation of impurity level above the valence band of TiO₂ and enhancement of visible photocatalytic (PC) performance. The enhanced visible PC mechanism was discussed.     

S–N Co-Doped TiO2 Photocatalysts with Visible-Light Activity Prepared by Sol–Gel Method

S–N co-doped anatase nanosized TiO₂ photocatalyst was successfully prepared by simple sol–gel method. The samples were characterized by XRD, XPS, UV–Vis. From the results of UV–Vis, a red shift of the absorption edge was brought out owing to the S and N codoping. XPS and UV–Vis studies revealed that N and S were in situ codoped in the lattice of TiO₂ and the absorbance in visible light region decreased with the calcination temperature increased. The photocatalytic activity was evaluated by the photocatalytic oxidation of penicillin solution under visible light irradiation. The results show that visible-light induced photocatalytic activities of the as-prepared TiO₂ powders were improved by S–N copoing. The high activity of S–N co-doped TiO₂ can be related to the results of the synergetic effects of strong absorption in the UV–Vis region, red shift in adsorption edge.     

How different dopants leads to difference in photocatalytic activity in doped TiO2?

This study explores the significance of dopant location in a doped TiO₂ nanostructure in ascertaining its photocatalytic properties. The un-doped TiO₂, boron-doped TiO₂ (B–TiO₂) and nitrogen-doped TiO₂ (N–TiO₂) photocatalysts were synthesized (with variable dopant concentrations) via sol-gel method. The photocatalysts were further characterized for structural, surface, and physico-chemical properties in reference to their influence on photocatalytic properties. The results of X-ray diffraction (XRD), micro Raman, Energy dispersive X-ray technique (EDX), X-ray photoelectron spectroscopy (XPS), and Fourier Transform infrared spectroscopy (FTIR) confirmed the existence of B and N atoms in the TiO₂ crystal lattice. The results also indicated that the B and N doping promoted the formation of rutile phase in doped TiO₂. Further, B doping leads to decrease in the surface area whereas N doping leads to increase in surface area of TiO₂. The UV–Vis DRS analysis revealed that a red shift in absorption band edge occurs upon B and N doping. The band gap values also decreased to 2.96 and 2.27 eV in B–TiO₂ and N–TiO₂, respectively in comparison to 2.98 for un-doped TiO₂. The photocatalytic degradation studies of diclofenac sodium (DCLF) were conducted to examine the effect of dopant role on the efficiency of doped photocatalyst. B–TiO₂ exhibited maximum photocatalytic activity by degrading 98% of DCLF in comparison to N–TiO₂, which showed 95% degradation.     

UV–Visible Light Driven Photocatalytic Degradation of Ciprofloxacin by N,S Co-doped TiO2: The Effect of Operational Parameters

Photocatalytic degradation using TiO₂ is one of the most effective techniques for treating residual emerging compounds present in water. However, practical applications are limited since it only absorbs ultraviolet irradiation. Nitrogen and sulfur (N, S) co-doped TiO₂ nanomaterials (N,S-TiO₂) were prepared by a controlled sol–gel method; the characterization and photocatalytic activity have been studied for the removal of ciprofloxacin antibiotic under UV–Visible light. The interstitial doping of nitrogen and sulfur substitute oxygen and titanium into the TiO₂ lattice, which increases the valence band and decreases the conduction band, respectively. The lowest value band-gap of 2.5 eV and the crystallite size of 5.13 nm compared to other available synthesis methods was observed on N,S-TiO₂ which allowed to broaden the light absorption to the visible region. The low level electron and hole recombination was related by the N, S doping. The optimal ciprofloxacin removal was obtained at pH 5.5, a dosage of 0.05 g, initial concentration of 30 mg L^?1 with a removal efficiency of 78.7%. A comparison of the effectiveness of antibiotic treatment of N,S-TiO₂ with synthetic TiO₂ and commercial TiO₂ was also made, taking the potential for regeneration into account. The photocatalytic degradation of ciprofloxacin catalyzed by N,S-TiO₂ was described by pseudo-first-order kinetics.

     

Highly visible light responsive metal loaded N/TiO2 nanoparticles for photocatalytic conversion of CO2 into methane

Photocatalytic reduction of carbon dioxide (CO₂) into valuable hydrocarbon such as methane (CH₄) using water as reducing agent is a good strategy for environment and energy applications. In this study, a facile and simple sol-gel method was employed for the synthesis of metal (Cu and Ag) loaded nanosized N/TiO₂ photocatalyst. The prepared photocatalysts were characterized by X-ray diffraction, transmission electron microscopy, BET Surface area analyzer, X-ray photoelectron spectroscopy and UV–vis diffuses reflectance spectroscopy. The photocatalytic conversion of CO₂ into methane was carried out under visible light irradiation (λ≥420 nm) by prepared photocatalysts in order to evaluate the photocatalytic efficiency. The results demonstrate that Ag loaded N/TiO₂ showed enhanced photocatalytic performance for methane production from CO₂ compared to other Cu–N/TiO₂, N/TiO₂ and TiO₂ photocatalysts. The improvement in the photocatalytic activity could be attributed to high specific surface area, extended visible light absorption and suppressed recombination of electron – hole pair due to synergistic effects of silver and nitrogen in the Ag–N/TiO₂ photocatalyst. This study demonstrates that Ag–N/TiO₂ is a promising photocatalytic material for photocatalytic reduction of CO₂ into hydrocarbons under visible light irradiation.     

Preparation and characterisation of silver‐ or copper‐doped TiO2 catalysts and their catalytic activity in dye degradation

In this study, silver‐ or copper‐doped TiO₂–Ce‐, TiO₂–La‐, and commercial TiO₂ (P25)‐supported catalysts were prepared. The catalysts and supports were characterised by powder X‐ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption studies. UV‐light‐assisted heterogeneous Fenton‐like oxidation of two different‐structure dyes (anionic azo dye Orange II, CI Acid Orange 7 and cationic triphenylmethane dye Crystal Violet, CI Basic Violet 3) was investigated over the catalysts. Higher catalytic activity was observed in the oxidation of Orange II than in the oxidation of Crystal Violet. For both dyes, the TiO₂–Ce and TiO₂–La‐supported catalysts, which were in the form of anatase only, gave higher photocatalytic activity than the P25‐supported catalysts, which were in the form of anatase and rutile. Complete colour removal was observed during oxidation of Orange II over Cu/TiO₂–Ce and Cu/TiO₂–La catalysts, whereas the highest degree of decolorisation, 89.3%, was achieved by oxidation of Crystal Violet over Ag/TiO₂–Ce. The pH of the solution affected the surface state of the TiO₂, thus affecting the photocatalytic degradation of the dyes. The surface area of the catalysts is also a key parameter that influences their photocatalytic activity. It was observed that catalysts having higher surface areas brought about greater dye degradation.     

Preparation of TiO2‐Coated Mo Powders for High Photocatalytic Property

An approach is introduced for fabricating the TiO₂‐coated molybdenum (Mo) powders via hydrothermal method, in which the Mo nanopowders were prepared by the electric explosion of wire method. The microstructure and photocatalytic properties of the samples were characterized by X‐ray diffraction, scanning electron microscopy, high‐resolution transmission electron microscopy, Raman spectroscopy (Raman), low temperature sorption of nitrogen (BET), and diffuse reflectance accessory of UV–Vis spectrophotometer. It was revealed that compared with pure TiO₂, the TiO₂‐coated Mo powders exhibited an improved photocatalytic activity, and the highest photocatalytic activity was achieved at the 1 wt% optimal mass percentage of the Mo nanopowders. The preparation of TiO₂‐coated Mo powders involved a relatively simple, economical, scalable, and also environment‐friendly approach.     

Efficient visible-light photocatalysts from Gd–La codoped TiO2 nanotubes

Robust visible-light Gd–La codoped TiO₂ nanotubes were successfully synthesized via an ultrasonic hydrothermal method and the photocatalytic activities were evaluated by photodegrading Rhodamine B (RB). The calcined Gd–La codoped TiO₂ nanotubes have significantly enhanced photocatalytic activities than the uncalcined ones. The La³⁺ and Gd³⁺ in the lattices of rare earth oxides may be substituted by Ti⁴⁺, creating abundant oxygen vacancies and surface defects for electron trapping and dye adsorption, accelerating the separation of photogenerated electron–hole pairs and RB photodegradation. The formation of an excitation energy level below the conduction band of TiO₂ from the binding of electrons and oxygen vacancies decreases the excitation energy of Gd–La codoped TiO₂ nanotubes, resulting in robust photocatalysts. The results suggest that Gd–La codoped TiO₂ nanotubes calcined at 500 °C are very promising for enhancing the photocatalytic activity of photocatalysts in visible-light region.     

Microwave photocatalysis III. Transition metal ion‐doped TiO2 thin films on mercury electrodeless discharge lamps: preparation,characterization and their effect on the photocatalytic degradation of mono‐chloroacetic acid and Rhodamine B

BACKGROUND: Mercury electrodeless discharge lamps (Hg‐EDLs) were used to generate UV radiation when exposed to a microwave field. EDLs were coated with doped TiO₂ in the form of thin films containing transition metal ions Mⁿ⁺ (M = Fe, Co, Ni, V, Cr, Mn, Zr, Ag). Photocatalytic degradation of mono‐chloroacetic acid (MCAA) to HCl, CO₂, and H₂O, and decomposition of Rhodamine B on the thin films were investigated in detail. RESULTS: Polycrystalline thin doped TiO₂ films were prepared by dip‐coating of EDL via a sol–gel method using titanium n‐butoxide, acetylacetone, and a transition metal acetylacetonate. The films were characterized by Raman spectroscopy, UV/Vis absorption spectroscopy, X‐ray photoelectron spectroscopy (XPS), electron microprobe analysis and by atomic force microscopy (AFM). The photocatalytic activity of doped TiO₂ films was monitored in the decomposition of Rhodamine B in water. Compared with the pure TiO₂ film, the UV/Vis spectra of V, Zr and Ag‐doped TiO₂ showed significant absorption in the visible region, and hence the photocatalytic degradation of MCAA had increased. The best apparent degradation rate constant (0.0125 min^?1), which was higher than that on the pure TiO₂ film by a factor of 1.7, was obtained with the Ag(3%)/TiO₂ photocatalyst. The effect of doping level of vanadium acetylacetonate on the photocatalytic efficiency of the V‐doped TiO₂ was determined. CONCLUSIONS: Transition metal ion‐doped TiO₂ thin films showed significant absorption in the visible region. The metal doped TiO₂ photocatalyst (with an appropriate amount of V, Zr and Ag) on the Hg‐EDLs increased the degradation efficiency of MCAA in a microwave field. Copyright © 2009 Society of Chemical Industry     

Nanostructured Solids from Freeze‐Dried Precursors: Multigram Scale Synthesis of TiO2‐Based Powders

Nanocrystalline TiO₂ and Ti_1?xV_xO₂ (x = 0.01) powders have been prepared by thermal decomposition, in air, of amorphous precursors resulting from the freeze‐drying of appropriate solutions. In addition, TiO_2?xN_y (anatase and rutile) and TiO_xN_y (rock‐salt) have been prepared by thermal treatment in ammonia of a crystalline precursor (TiO₂ obtained at 673 K). TEM and SEM images, as well as the analysis of the X‐ray diffraction (XRD) patterns, show the nanoparticulated character of those solids obtained at low temperatures, with typical particle sizes in the 10–20 nm range when prepared at 673 K. The UV–Vis results indicate both the insertion of V in the anatase lattice and the feasibility of nitridation at low temperatures. The photocatalytic properties of these materials (as prepared and after their incorporation to mortar samples) in the degradation of nitrogen oxides have been preliminary evaluated. Although N‐doping enhances the photocatalytic activity of the TiO₂ matrix, V‐doping worsens it.     

A biotemplate synthesized hierarchical Sn-doped TiO2 with superior photocatalytic capacity under simulated solar light

Despite a number of studies have been carried out on TiO₂ based materials as photocatalysts for water pollutant treatment, it still needs sustained effort to extend the optical range of the photocatalysts and inhibit the recombination of photo-induced carriers to improve their catalytic activities under solar light. In this work, a series of Sn-doped TiO₂ with different amounts of Sn doping (1, 5, 10 and 20 mol%) were biomimetically synthesized by a facile sol–gel method using cellulosic cotton as biotemplate. The Sn-doped TiO₂ materials possess a typical three-dimensional hierarchical structure of microtubes consisting of interwoven nanofibers. The photocatalytic performance was evaluated via the degradation of methylene blue (MB) (10.0 mg L^?1) under Xenon lamp simulated solar irradiation. The results show that Sn(5)-TiO₂ (5 mol% Sn doping) sample exhibits an outstanding photocatalytic capacity with a superior degradation rate of higher than 98% within 30 min and a good reusability without significant decrease of activity after reused for four cycles. The most significantly improved photocatalytic capacity of TiO₂ is ascribed to more extra surface hydroxyl groups and accessible active sites provided by the relatively high surface area, and a higher light capturing and utilization efficiency with less recombination of the photogenerated electron-hole pairs endowed by the good synergistic effect of the special hierarchically porous microstructure and the appropriate amount of Sn doping. Whereas, the excessive Sn doping reduces the photocatalytic activity obviously, resulting from the phase transformation of TiO₂ generating more rutile phase with less reactivity, the phase separation with clear grain boundary blocking the active sites, and the extra Sn⁴⁺ acting as the recombination center. This research presents a facile biomimetic synthesis strategy combined with the traditional sol–gel method to develop various ion doped metal oxides as photocatalysts with enhanced activity.     

Synthesis and visible‐light‐derived photocatalysis of titania nanosphere stacking layers prepared by chemical vapor deposition

BACKGROUND: In this study, visible‐light‐derived photocatalytic activity of metal‐doped titanium dioxide nanosphere (TS) stacking layers, prepared by chemical vapor deposition (CVD), was investigated. The as‐grown TS spheres, having an average diameter of 100–300 nm, formed a layer‐by‐layer stacking layer on a glass substrate. The crystalline structures of the TS samples were of anatase‐type. RESULTS: Ultraviolet (UV) absorption confirmed that metallic doping (i.e. Co and Ni) shifted the light absorption of the spheres to the visible‐light region. With increasing dopant density, the optical band gap of the nanospheres became narrower, e.g. the smallest band gap of Co‐doped TS was 2.61 eV. Both Ni‐ and Co‐doped TS catalysts showed a photocatalytic capability in decomposing organic dyes under visible irradiation. In comparison, Co‐doped TiO₂ catalyst not only displays the adsorption capacity, but also the photocatalytic activity higher than the N‐doped TiO₂ catalyst. CONCLUSION: This result can be attributed to the fact that the narrower band gap easily generates electron–hole pairs over the TS catalysts under visible irradiation, thus, leading to the higher photocatalytic activity. Accordingly, this study shed some light on the one‐step efficient CVD approach to synthesize metal‐doped TS catalysts for decomposing dye compounds in aqueous solution. Copyright © 2010 Society of Chemical Industry     

Photocatalytic degradation of dyestuff wastewater under visible light irradiation using micron‐sized mixed crystal TiO2 powders

A phase transformation of micron‐sized TiO₂ powder from anatase to rutile was attempted by heat‐treatment in order to generate a new mixed crystal TiO₂ with high associated photocatalytic activity. Heat‐treated micron‐sized TiO₂ powders at different transition stages were characterized by X‐ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT‐IR) and transmission electron microscopy (TEM) methods. The tests of photocatalytic activity of the heat‐treated micron‐sized TiO₂ powders were conducted by the photocatalytic degradation of Rhodamine B and Acid Red B under visible light irradiation. The results indicate that mixed crystal TiO₂ photocatalyst heat‐treated at 400 °C for 60 min shows the highest photocatalytic activity. It can effectively decompose the Rhodamine B and Acid Red B in aqueous solution after 6 h visible light irradiation. A remarkable improvement in photocatalytic activity of TiO₂ is caused by the formation of combined rutile–anatase phases and separation of photogenerated electron–hole pairs. Copyright © 2007 Society of Chemical Industry     

Photocatalytic Activity and Electronic Structure Analysis of N‐doped Anatase TiO2: A Combined Experimental and Theoretical Study

N‐Doped TiO₂ photocatalysts were prepared by a hydrothermal method with tetra‐n‐butyl titanate (TTNB) and triethanolamine as precursors. The obtained samples were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), and UV‐visible diffuse reflectance spectra (DRS), respectively. Photocatalytic activities of the anatase products were investigated on the degradation of methyl orange (MO). The incorporation of nitrogen impurity in anatase TiO₂ was studied by the first‐principles calculations based on the density functional theory (DFT). The calculated electronic band structures for substitutional and interstitial N‐doped TiO₂ indicated the formation of localized states in the band gap, which lied above the valence band. Excitation from the impurity states of N 2p to the conduction band could account for the optical absorption edge shift toward the lower energies. It was consistent with the experimentally observed absorption of N‐doped samples in the visible region.     

The comparative study of photocatalytic self‐cleaning properties of synthesized nanoscale titania and zirconia onto polyacrylonitrile fibers

The photocatalytic activity of TiO₂ and ZrO₂‐coated polyacrylonitrile (PAN) fibers was compared through the self‐cleaning of methylene blue and eosin yellowish. TiO₂ and ZrO₂ nanocrystals were successfully synthesized and deposited onto PAN fibers with photocatalytic self‐cleaning activity using the sol‐gel process at low temperature. The pristine and treated samples have been characterized by several techniques, such as scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, diffuse reflectance spectroscopy, X‐ray diffraction, and thermogravimetric analysis. The TiO₂ nanoparticles with 10–20 nm in size, and ZrO₂ with 20–40 nm have been synthesized to form dispersed particles on the fiber surface, which shows photocatalytic properties when exposed to UV–Vis light. The photocatalytic activity, tested by measuring the degradation of adsorbed methylene blue and Eosin Y. Photocatalytic activity of TiO₂‐coated fibers toward dyes degradation was higher than that of ZrO₂‐coated fibers. This preparation technique can be also applied to new fabrics to create self‐cleaning and UV irradiation protection properties in them. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010