Sonodegradation and photodegradation of methyl orange by InVO4/TiO2 nanojunction composites under ultrasonic and visible light irradiation

The InVO₄/TiO₂ nanojunction composites with different weight ratio of 1:10, 1:25, 1:50 and 1:100 were successfully constructed using an ion impregnate method, followed by calcining temperature 400 °C for 2 h in Ar. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were evaluated through the degradation of methyl orange (MO) in aqueous solution under ultrasonic and visible light irradiation, respectively. The experimental results determined that the (1:50) InVO₄/TiO₂ nanojunction composite has exhibited the highest sonocatalytic activity. It can be ascribed to vectorial charge transfer at the co-excited InVO₄/TiO₂ interface under ultrasonic irradiation, results in the complete separation of electrons and holes. Interestingly, the (1:25) InVO₄/TiO₂ nanojunction composite displayed superior photocatalytic activity for MO degradation under visible light, indicating that InVO₄ as a narrow band gap sensitizer can expand photocatalytic activity of TiO₂ to visible region, and the charge transfer can be formed from high energy level of InVO₄ conduction band to the low energy level of TiO₂ conduction band in a present of excited InVO₄ alone under visible light irradiation. The sono- and photo-catalytic activities of the InVO₄/TiO₂ nanojunction composites were found to be dependent significantly on different InVO₄ contents, which can be explained by the influence of charge transfer on the basis of the work functions of different catalysis mechanism.     

TiO2 nanoparticles with high ability for selective adsorption and photodegradation of textile dyes under visible light by feasible preparation

Particular TiO₂ nanoparticles with high selective photocatalytic oxidation of anionic dyes are prepared by a feasible hydrothermal method. Moreover, its photocatalytic selectivity can be easily switched to cationic dyes by a simple post-treatment in ammonia solution, which makes the prepared TiO₂ have bi-directional selectivity in dye photodegradation. Based on the photocatalytic performances and the structure and surface characteristics of the catalyst, the bi-directional selectivity of the catalysts is found to be closely related to the adsorption selectivity. The adsorption selectivity originates from surface charge groups, which are introduced during the preparation and post-treatment progresses. This study provides a facile and economical approach towards selective degradation of dyes with high efficiency by the special TiO₂ nanoparticles synthesized through a simple hydrothermal method, which may be used practically in the future.     

Preparation of S-TiO2 photocatalyst and photodegradation of L-acid under visible light

S-doped TiO₂ (S-TiO₂) photocatalyst was synthesized by sol–gel method with tetrabutyl titanate and thiourea as precursor. S-TiO₂ was characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV–vis absorption spectroscopy, transmission electron microscopy (TEM) and the photocatalytic activity was evaluated by 1-naphthol-5-sulfonic acid (L-acid) under UV, visible light and solar light radiation. The results showed that doped S could improve photoabsorption property of TiO₂ in the visible region, leading the increase in the photocatalytical activity of TiO₂.

The average particle size of the S-TiO₂ photocatalyst is about 10 nm. The S-TiO₂-4 photocatalyst contains 100% anatase crystalline phase of TiO₂. In the S-TiO₂-4 photocatalyst, S does not exist independently, but is incorporated into the crystal lattice of TiO₂. In the inner crystal lattice of the S-TiO₂-4 photocatalyst, S as S²⁻ replaces O in TiO₂, while on the surface of crystal lattice, S exists as S⁴⁺ and S⁶⁺.

The photocatalytical activity of S-TiO₂-4 photocatalyst for the photodegradation of L-acid is better than that of pure TiO₂. Under the same conditions, the photodegradation efficiency of L-acid for the S-TiO₂-4 photocatalyst and the solar light irradiation is 85.1%, while it is only 26.4% for pure TiO₂. In addition, the final products of the photocatalysis of L-acid using the S-TiO₂-4 photocatalyst are not organic compounds with low molecular weight, but the inorganic compounds.     

The preparation of vanadium-doped TiO2-montmorillonite nanocomposites and the photodegradation of sulforhodamine B under visible light irradiation

The photodegradation of sulforhodamine B on vanadium-doped TiO₂-montmorillonite (TiO₂-MMT) nanocomposites was investigated under visible light irradiation. V-TiO₂-MMT nanocomposites with different amounts of MMT were prepared by a sol-gel process. The microstructure and properties of V-TiO₂-MMT were characterized by XRD, TEM, XPS, DRS, nitrogen adsorption isotherms, and FTIR. These analytic results indicated that the different Ti/MMT ratios exerted a great influence on their microstructures and their photocatalytic activities. The average sizes of V-TiO₂-MMT were smaller than those of pure TiO₂ and V-TiO₂. And the layered structure of MMT was completely destroyed in the V-TiO₂-MMT with the relatively high ratio of Ti/MMT (240, 120, 80, 60 mmol/g), but it retained the partial MMT layered structure and had an enlargement of some basal space of MMT in V-TiO₂-MMT with the relatively low ratio of Ti/MMT (30, 24 mmol/g). V-TiO₂-MMT/120 (120 denotes the ratio of Ti/MMT is 120 mmol/g. The names of other catalysts followed the same convention.) and V-TiO₂-MMT/30 had relatively higher photocatalytic activity in comparison to the others. Besides, in the preparation process, we selected V-TiO₂-MMT/120 using different washing media to examine the effect of washing medium on the photocatalytic activity. The result indicated that it was critical to choose a proper washing medium to obtain an optimal photocatalytic activity.     

Photocatalytic photodegradation of xanthate over C, N, S-tridoped TiO2 nanotubes under visible light irradiation

C, N, S-tridoped TiO₂ nanotubes were synthesized via hydrothermal synthesis and post-treatment, and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS), the Brunauer-Emmett-Teller method (BET), and UV-vis diffuse reflectance spectroscopy (DRS). The UV-diffuse reflectance spectra of all the C, N, S-tridoped TiO₂ nanotubes greatly extended the absorption edge to the visible light region, and the absorbance in the visible region increased with increasing molar ratio of thiourea to Ti (R), which could be attributed to C, N, S-tridoping in the form of cation C-doping, interstitial N-doping, cation S-doping, and adsorbed ions’ states. The photocatalytic activity of C, N, S-tridoped TiO₂ nanotubes was evaluated by photocatalytic photodegradation of potassium ethyl xanthate (KEX) under visible light irradiation. It was found that the photocatalytic activity of the prepared samples increased with increasing molar ratio of thiourea to Ti (R). At R=6, the photocatalytic activity of the tridoped sample TNTS-6 reached a maximum value. With further increase in R, photocatalytic activity of the sample decreased, which could be attributed to the high visible light activity resulting from the balance between visible light absorption and recombination of electron/hole pairs.     

Sonochemical and visible light induced photochemical and sonophotochemical degradation of dyes catalyzed by recoverable vanadium-containing polyphosphomolybdate immobilized on TiO2 nanoparticles

Na₅PV₂Mo₁₀O₄₀ supported on nanoporous anatase TiO₂ particles, TiO₂–PVMo, was used as an efficient photocatalyst for photocatalytic degradation of different dyes by visible light using oxygen as oxidant. This catalyst showed a good catalytic activity in the sonocatalytic and sonophotocatalytic decomposition of different dyes in aqueous solutions. The TiO₂–PVMo composite showed higher photocatalytic and sonocatalytic activity than pure polyoxometalate or pure TiO₂.     

Photocatalytic degradation of dyes using dioxygen activated by supported metallophthalocyanine under visible light irradiation

Zinc tetraaminophthalocyanine (Zn-TAPc) modified by cyanuric chloride was immobilized on silk fibers by covalent bond to obtain a supported photocatalyst (Zn-TDTAPc-SF). The photocatalytic degradation of acid orange II based on Zn-TDTAPc-SF/O₂ system was investigated under visible light irradiation (λ ≥ 400 nm). The results indicated that Zn-TDTAPc-SF exhibited excellent photocatalytic performance in the presence of O₂ under visible light irradiation. In 6 h, more than 93% of acid orange II (AO2) in Zn-TDTAPc-SF/O₂ system was eliminated at initial pH 5 under visible light irradiation, and Zn-TDTAPc-SF still remained effective in repetitive fives cycles. Furthermore, NaCl played a positive role in the catalytic reaction, different from the negative one observed in homogeneous catalysis, and the reaction can proceed in a more wide pH range from acidic to alkaline. Based on the analysis of FT-IR and Gas Chromatography/Mass Spectrometry (GC–MS), AO2 was mainly converted into some small molecular biodegradable aliphatic carboxylic compounds such as maleic acid, fumaric acid, succinic acid, etc. The photodegradation mechanism for the evolution of AO2 was proposed by Electron Paramagnetic Resonance (EPR) spectra.     

Integrated TiO2 resonators for visible photonics

We demonstrate waveguide-coupled titanium dioxide (TiO(2) racetrack resonators with loaded quality factors of 2.2×10(4) for the visible wavelengths. The structures were fabricated in sputtered TiO(2) thin films on oxidized silicon substrates using standard top-down nanofabrication techniques, and passively probed in transmission measurements using a tunable red laser.     

Products of photodegradation for coumarin laser dyes

The products of conventional photolysis of the coumarin laser dyes, C1, C35, C153, and C152 have been investigated. The previously reported dealkylation of C1 is documented for the fluorinated dyes, C35, and C152 in deaerated solvents. In addition, a reduction product is identified for C1, consistent with a radical mechanism for decomposition. Evidence is provided that the concentration quenching (self quenching) of singlet dye is important to the degradation mechanism. For the rigid dye, C153, a photooxidation product involving the amine functionality results from decomposition in aerated media. For several dyes, very low triplet yields have been measured.     

Cathodic shift of onset potential on TiO2 nanorod arrays with significantly enhanced visible light photoactivity via nitrogen/cobalt co-implantation

Despite anionic doping has been widely implemented to increase the visible light activity of TiO$_{2}$, it often gives rise to a dramatical anodic shift in current onset potential. Herein, we show an effective method to achieve the huge cathodic shift of TiO$_{2}$ photoanode with significantly enhanced visible light photo-electrochemical activity by nitrogen/cobalt co-implantation. The nitrogen/cobalt co-doped TiO$_{2}$ nanorod arrays (N/Co-TiO$_{2}$) exhibit a cathodic shift of 350 mV in onset potential relative to only nitrogen-doped TiO$_{2}$ (N-TiO$_{2}$). Moreover, the visible-light ($\lambda >420 $ nm) photocurrent density of N/Co-TiO$_{2}$ reaches 0.46 mA/cm$^{2}$, far exceeding 0.07 mA/cm$^{2}$ in N-TiO$_{2}$ at 1.23 V $versus$ reversible hydrogen electrode (RHE). Systematic characterization studies demonstrate that the enhanced photo-electrochemical performance can be attributed to the surface synergic sputtering of high-energy nitrogen/cobalt ions.     

Fabrication of Fe-doped TiO2 nanoparticles and investigation of photocatalytic decolorization of reactive red 198 under visible light irradiation

In this research, Fe-doped TiO₂ nanoparticles with various Fe concentrations (0. 0.1, 1, 5 and 10 wt%) were prepared by a sol–gel method. Then, nanoparticles were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray analysis (EDX), BET surface area, photoluminescence (PL) spectroscopy and UV–vis diffuse reflectance spectroscopy (DRS). The photocatalytic activity of the nano-particles was evaluated through degradation of reactive red 198 (RR 198) under UV and visible light irradiations. XRD results revealed that all samples contained only anatase phase. DRS showed that the Fe doping in the titania induced a significant red shift of the absorption edge and then the band gap energy decreased from 3 to 2.1 eV. Photocatalytic results indicated that TiO₂ had a highest photocatalytic decolorization of the RR 198 under UV irradiation whereas photocatalytic decolorization of the RR 198 under visible irradiation increased in the presence of Fe-doped TiO₂ nanoparticles. Among the samples, Fe-1 wt% doped TiO₂ nanoparticles showed the highest photocatalytic decolorization of RR198 under visible light irradiation.     

Synthesis and photochemical properties of HTaWO6/ (Pt,TiO2) nanocomposite under visible light irradiation

A new layered nanocomposite, HTaWO₆/(Pt, TiO₂) was synthesized using n-type semi-conductor HTaWO₆ as a host material. HTaWO₆ and HTaWO₆/TiO₂were white, while both HTaWO₆/Pt and HTaWO₆/(Pt, TiO₂) were yellow. The yellow color might be attributed to H_1-xTaWO_6-x/2 formed by the photo-induced phase transformation promoted by Pt. Although HTaWO₆/Pt showed absorption in visible light region (λ > 400 nm), the hydrogen evolution activity was negligibly small. On the other hand HTaWO₆/(Pt, TiO₂) showed excellent photocatalytic activities even under visible light irradiation. The sample containing rutile type titania such as TiO₂(P-25) also showed hydrogen evolution activity, but the activity was smaller than that of HTaWO₆/(Pt, TiO₂). These results suggested that rutile type titania, which can be excited by visible light of wavelength less than 413 nm, played an important role in the visible light-induced photocatalytic activity. The improvement of the hydrogen evolution activity of rutile type titania by intercalating into HTaWO₆/Pt may be due to the depression of the recombination of photoinduced electrons and holes by the heterogeneous electron transfer from rutile type TiO₂ to HTaWO₆/Pt.     

Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination

Through an ultrasound assisted method, TiO₂/WO₃ nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO₂/WO₃ nanoparticles matches well with that of pure monoclinic WO₃ and rutile TiO₂ nanoparticles. TEM images show that the prepared TiO₂/WO₃ nanoparticles consist of mixed square and hexagonal shape particles about 8–12 nm in diameter. The photocatalytic activity of TiO₂/WO₃ nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO₂/WO₃ nanoparticles exhibits a higher degradation rate constant (6.72 × 10⁻⁴ s⁻¹) than bare TiO₂ nanoparticles (1.72 × 10⁻⁴ s⁻¹) under similar experimental conditions.     

Hydrothermal synthesis of well-dispersed ultrafine N-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light

Ultrafine nitrogen-doped TiO₂ nanoparticles with narrow particle size distribution, good dispersion, and high surface area were synthesized in the presence of urea and PEG-4000 via a hydrothermal procedure. TEM observation, N₂ adsorption, XRD, UV-vis spectroscopy, the Raman spectroscopy and XPS analysis were conducted to characterize the synthesized TiO₂ particles. The synthesized TiO₂ particles were a mixture of 49.5% anatase and 50.5% rutile with a size of around 5 nm. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive Brilliant Blue KN-R under both UV and visible light. The synthesized TiO₂ particles showed much higher photocatalytic activity than a commercial P25 TiO₂ powder under both UV and visible light irradiations. The high performance is associated to N doping, the reduced particle size, good dispersion, high surface area, and a quantum size effect.     

Fabrication of CaGa2O4 nanofibers by electrospinning and CaGa2O4-assisted photodegradation of crystal violet in aqueous dispersions under visible light illumination

CaGa₂O₄ nanofibers were prepared by electrospinning technology. The morphology and structure of as-prepared CaGa₂O₄ nanofibers were characterized by scanning electron microscopy and X-ray diffraction, respectively. Based on the three-flux approximation, the direct band gap of CaGa₂O₄ nanofibers was estimated from the UV–vis diffuse reflectance spectroscopy. From the results obtained in the photodegradation experiments, it is observed that the photodegradation of crystal violet can take place under exposure to visible light in aqueous CaGa₂O₄ dispersions. Mechanistically, crystal violet absorbs visible light radiation and self-sensitizes its own oxidative transformation. At low concentrations of crystal violet, the suitability of Langmuir model to describe the photoadsorption phenomenon has been checked.     

Properties of carbon and iron modified TiO2 photocatalyst synthesized at low temperature and photodegradation of acid orange 7 under visible light

The nanoparticles of TiO₂ modified with carbon and iron were synthesized by sol-gel followed solvothermal method at low temperature. Its chemical composition and optical absorption were investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), photoluminescence emission spectroscopy (PL), UV-vis absorption spectroscopy, and electron paramagnetic resonance (EPR). It was found that carbon and iron modification causes the absorption edge of TiO₂ to shift the visible light region. Fe(III) cation could be doped into the matrix of TiO₂, by which could hinder the recombination rate of excited electrons/holes. Superior photocatalytic activity of TiO₂ modified with carbon and iron was observed for the decomposition of acid orange 7 (AO7) under visible light irradiation. The synergistic effects of carbon and iron in modified TiO₂ nanoparticles were responsible for improving visible light photocatalytic activity.     

Synergetic effects of hydrophilic surface modification and N-doping for visible light response on photocatalytic activity of TiO2

We made attempts to improve photocatalytic activity of TiO₂ nanoparticles under visible light exposure by combining additional treatments. N-doping of TiO₂ by ammonia gas treatment increased absorbance of visible light. By coating thin film of polydimethylsiloxane, and subsequently vacuum-annealing, TiO₂ surface became more hydrophilic, thereby enhancing photocatalytic activity of TiO₂. These two treatments were combined for the first time in this work and photocatalytic activity under visible light irradiation exceeded sum of individual effects of N-doping and hydrophilic modification.     

Synthesis and characterization of nitrogen-doped TiO2 coatings on reduced graphene oxide for enhancing the visible light photocatalytic activity

Nitrogen-doped TiO₂ coatings on reduced graphene oxide were prepared via a sonochemical synthesis and hydrothermal process. The nanocomposites showed improved photocatalytic activity due to their large specific surface areas (185–447 m²/g), the presence of TiO₂ in the anatase phase, and a quenched photoluminescence peak. In particular, GN3-TiO₂ (nitrogen-doped TiO₂ coatings on rGO with 3 ml of titanium (IV) isopropoxide) exhibited the best photocatalytic efficiency and degradation rate among the materials prepared. With nitrogen-doped on the reduced graphene oxide surface, the photocatalytic activity is enhanced approximately 17.8 times compared to that of the pristine TiO₂. The dramatic enhancement of activity is attributed to the nitrogen contents and rGO effectively promoting charge-separation efficiency and providing abundant catalytically active sites to enhance the reactivity. The composites also showed improved pollutant adsorption capacity, electron–hole pair lifetime, light absorption capability, and absorbance of visible light.     

Low-frequency ultrasound induces oxygen vacancies formation and visible light absorption in TiO2 P-25 nanoparticles

Low-frequency ultrasound (LFUS) irradiation induces morphological, optical and surface changes in the commercial nano-TiO₂-based photocatalyst, Evonik-Degussa P-25. Low-temperature electron spin resonance (ESR) measurements performed on this material provided the first experimental evidence for the formation of oxygen vacancies (V_o), which were also found responsible for the visible-light absorption. The V_o surface defects might result from high-speed inter-particle collisions and shock waves generated by LFUS sonication impacting the TiO₂ particles. This is in contrast to a number of well-established technologies, where the formation of oxygen vacancies on the TiO₂ surface often requires harsh technological conditions and complicated procedures, such as annealing at high temperatures, radio-frequency-induced plasma or ion sputtering.Thus, this study reports for the first time the preparation of visible-light responsive TiO₂-based photocatalysts by using a simple LFUS-based approach to induce oxygen vacancies at the nano-TiO₂ surface. These findings might open new avenues for synthesis of novel nano-TiO₂-based photocatalysts capable of destroying water or airborne pollutants and microorganisms under visible light illumination.