Preparation of TiO2 thin films on glass beads by a rotating plasma reactor

We experimentally coated the TiO₂ thin films on the glass beads by a rotating cylindrical plasma chemical vapor deposition (PCVD) process. The precursors for the thin films were generated by the plasma reactions, and they deposited on the glass beads to become the grains on the films. The TiO₂ thin films grow more quickly on the glass beads by increasing the reactor pressure, or the rotation speed of the reactor. As the applied power increases, the thickness of the thin films on the glass beads decreases. As the thickness of the TiO₂ thin films increases, the uniformity of the TiO₂ thin films decreases due to the deposition of larger grains or due to the increase of crack size. The rotating cylindrical PCVD process can be a good method to prepare the particles coated with metal or organic-doped thin films for highly functionalized materials.     

Simultaneous Removal of NOx and SOx from Flue Gas of a Glass Melting Furnace using a Combined Ozone Injection and Semi-dry Chemical Process

In this study, we propose a plasma-chemical hybrid NO_x removal process using nonthermal plasma for the treatment of flue gases emitted from glass melting furnaces; the process is demonstrated through a laboratory-scale model experiment conducted using a semi-dry desulfurization apparatus. The performance of the system for simultaneous removal of SO₂ and NO_x is investigated. As a result, NO is effectively oxidized to NO₂ by injecting ozone into the spray region and the removal efficiencies of 90% and 50% were obtained for NO and NO_x, respectively. In addition, the SO₂ removal efficiency of 84% was achieved.     

NH3 removal using the dielectric barrier discharge plasma-V-TiO2 photocatalytic hybrid system

This study investigates the photocatalytic performance of V-TiO₂ for removal of highly concentrated ammonia (1,000 ppm) in the dielectric barrier discharge (DBD), plasma-photocatalytic, hybrid system. The V (1.0, 5.0, 10.0 mol-%)-TiO₂ photocatalysts were prepared by using the conventional sol-gel method. Their surface areas were decreased with increasing vanadium component. The UV-visible absorption band slightly shifted to more visible wavelengths in V-TiO₂ compared to that in pure TiO₂. The NH₃-TPD result confirmed that the ability of NH₃ adsorption on the surface of V-TiO₂ increased with increasing vanadium content, and was maximized for 5.0-mol% V-TiO₂. The NH₃ decomposition was enhanced with the photocatalyst compared to the decomposition rate without catalysts, while the decomposition was further increased with the applied plasma voltage. The NH₃ decomposition reached 90% after 400 min at an applied plasma voltage of 10.0 kV, and various intermediates, such as-NH₂,-NH, and NO, were also identified by using the Fourier transform infrared (FT-IR) spectra. In addition, the NH₃ decomposition reached 100% in the plasma-5.0 mol% V-TiO₂, photocatalytic, hybrid system after 25 min, compared to 98% in the pure V-TiO₂ photocatalytic system after 150 min. In addition, the various undesirable byproducts were depressed when V-TiO₂ photocatalyst was used compared to that in the non-catalytic system.     

介质阻挡放电中气体成分对NOx脱除的影响

利用介质阻挡放电(DBD)产生低温等离子体进行烟气的脱硝实验,研究了在乙烯存在的条件下,温度和其他烟气成分对NO_x脱除率的影响。结果表明:随着温度的升高,NO脱除速率增快;模拟烟气中加入CO₂,在能量密度较低时,CO₂作为电负性分子会降低自由基的生成,导致NO的脱除率降低,随着能量密度的升高,CO₂对NO脱除的影响减小;模拟烟气中加入水后可以产生更多的OH、HO₂等自由基,促进NO的氧化;SO₂的加入会与自由基O反应,使初始反应中O与C₂H₄的反应速率减弱,从而影响了NO的氧化速率,但O₃、HO₂等强氧化自由基会优先与NO反应,因此SO₂的加入不会影响NO最终的脱除率。     

Ti3C2@TiO2/g-C3N4 heterojunction photocatalyst with improved charge transfer for enhancing visible-light NO selective removal

Control of Nitrogen dioxide (NO₂) byproducts is of great importance for the photocatalytic NO removal and environmental remedy. However, individual semiconductor photocatalysts generally show limited capabilities for selective NO removal due to severe charge recombination and inadequate redox potentials. Herein, the cotton-like g-C₃N₄ was modified with Ti₃C₂@TiO₂ to construct a heterojunction photocatalyst Ti₃C₂@TiO₂/g-C₃N₄, which showed outperformed photocatalytic NO removal and MB degradation abilities compared to the individual photocatalysts under visible light irradiation. The UV–vis absorption spectra and photoluminescence (PL) spectra confirmed that Ti₃C₂@TiO₂/g-C₃N₄ photocatalyst was endowed with superior light utilization and separation/transfer ability of charge carriers due to the presence of n-n heterojunction and Schottky barrier. Furthermore, the g-C₃N₄, Ti₃C₂, and TiO₂ were closely contacted showing a high specific surface area, which promoted the charge transfer and the exposure of more active sites, further inducing the formation of more active species. Therefore, the designed photocatalyst delivered a high removal rate of NO and a suppressed discharge of NO₂. Notably, the photocatalyst Ti₃C₂@TiO₂/g-C₃N₄ also presented superior NO removal ability during the cycling experiment, indicating their outstanding stability and recyclability. Besides, the effects of active species were monitored using a trapping experiment to propose probable photocatalytic mechanism. This study could shed a new light to the design of photocatalyst for air purification in the future.     

Effect of the sonication and coating time on the photocatalytic degradation of TiO2, TiO2-Ag,and TiO2-ZnO thin film photocatalysts

Abstract

Today, the ultrasound utilizing for material synthesis has been extensively investigated. The unusual acoustic cavitation phenomenon caused by ultrasonic waves has created a new world for the production of high efficiency photocatalysts with new structures. In this study, TiO₂, TiO₂-Ag, and TiO₂-ZnO thin film photocatalysts were prepared using titanium isopropoxide Ti[OCH(CH₃)₂]₄, zinc acetate dehydrates (CH₃COO)₂Zn·2H₂O, and silver nitrate AgNO₃ by a sol–gel method under the ultrasonic irradiation. The prepared photocatalysts were characterized by UV–vis diffuse reflectance spectroscopy, X-ray diffraction, scanning electron microscopy (SEM), and energy dispersive spectroscopy. The SEM images showed that the Ag and ZnO particles were evenly dispersed in the photocatalysts due to the ultrasonic irradiation, and Ag particles were approximately 90?nm, which is relatively small compared to the photocatalysts which is not treated with ultrasonic irradiation. The catalytic activity of the photocatalysts was determined using Acid Red 27 dye. The most excellent catalytic degradation was obtained with TiO₂-ZnO thin film photocatalyst. In comparison to the conventional photocatalyst, the efficiency of photocatalytic activity of the photocatalyst produced under ultrasonication has been increased due to the reduced size of Ag and ZnO and its uniform dispersion.     

Aerosol-assisted flow synthesis of B-doped, Ni-doped and B–Ni-codoped TiO2 solid and hollow microspheres for photocatalytic removal of NO

In this study, highly effective B-doped, Ni-doped and B–Ni-codoped TiO₂ microspheres photocatalysts were directly synthesized via an aerosol-assisted flow synthesis method. The resulting samples were characterized by XRD, SEM, TEM, UV–vis diffuse reflectance spectroscopy, nitrogen adsorption and XPS. The characterizations revealed hollow microspherical structure of the B-doped and B–Ni-codoped TiO₂ photocatalysts, while the Ni-doped and undoped TiO₂ products consisted of solid microspheres. It was found that the boron dopant was partially embedded into the interstitial TiO₂ structure, existing in the form of Ti–O–B structure. The band gap was enlarged after the boron doping. However, both Ni-doped and B–Ni-codoped TiO₂ samples showed obvious red shift in their absorption edges because of the Ni doping. The photocatalytic activities of these samples were evaluated on the photocatalytic removal of NO under simulated solar light irradiation. All the aerosol-assisted flow synthesized samples had much higher photocatalytic activities than P25 and the doped TiO₂ microspheres exhibited enhanced photocatalytic activity than the undoped counterparts. More interestingly, the B–Ni-codoped TiO₂ photocatalyst possessed superior photocatalytic activity to the as-prepared single doped TiO₂ products. The enhanced photocatalytic activity was explained and the formation mechanisms of hollow and solid microspheres were also proposed on the basis of characterizations. We think this general method may be easily scaled up for industrial production of highly active microspherical photocatalysts for efficient NO removal under simulated solar light irradiation.     

Photocatalytic decomposition of NO on titanium oxide thin film photocatalysts prepared by an ionized cluster beam technique

Transparent TiO₂ thin film photocatalysts were prepared on transparent porous Vycor glass (PVG) by an ionized cluster beam (ICB) method. The UV‐VIS absorption spectra of these films show specific interference fringes, indicating that uniform and transparent TiO₂ thin films are formed. The results of XRD measurements indicate that these TiO₂ thin films consist of both anatase and rutile structures. UV light (λ > 270 nm) irradiation of these TiO₂ thin films in the presence of NO led to the photocatalytic decomposition of NO into N₂, O₂ and N₂O. The reactivity of these TiO₂ thin films for the photocatalytic decomposition of NO is strongly dependent on the film thickness, i.e., the thinner the TiO₂ thin films, the higher the reactivity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Investigation on elemental mercury oxidation mechanism by non-thermal plasma treatment

Converting elemental mercury into divalent compound is one of the most important steps for mercury abatement from coal fired flue gas. The oxidation of elemental mercury was investigated in this paper using dielectric barrier discharge (DBD) non-thermal plasma (NTP) technology at room temperature. Effects of different flue gas components like oxygen, moisture, HCl, NO and SO₂ were investigated. Results indicate that active radicals including O, O₃ and OH all contribute to the oxidation of elemental mercury. Under the conditions of 5% O₂ in the simulated flue gas, about 90.2% of Hg⁰ was observed to be oxidized at 3.68 kV discharge voltage. The increase of discharge voltage, O₂ level and H₂O content can all improve the oxidation rate, individually. With O₂ and H₂O both existed, there is an optimal moisture level for the mercury oxidation during the NTP treatment. In this test, the observed optimal moisture level was around 0.74% by volume. Hydrogen chloride can promote the oxidation of mercury due to chlorine atoms produced in the plasma process. Both NO and SO₂ have inhibitory effects on mercury oxidation, which can be attributed to their competitive consumption of O₃ and O.     

TiO2 photocatalyst for water treatment applications

Recently, many water treatment technologies, such as biological treatment, coagulation/precipitation techniques, Fenton oxidation treatments, and advanced oxidation techniques, have been assessed to address the worsening clean water shortage. This review summarizes these technologies and provides the background and principle of photocatalysis for advanced oxidation technology. In particular, this paper focuses on semiconductor TiO₂ photocatalysts as well as the latest modifications of TiO₂ photocatalyst, such as the introduction of metals or heteroatoms onto TiO₂, physical modification of TiO₂ for a variety of morphologies, and hybrid TiO₂/nanocarbon composites, to improve the photocataytic activities for an advanced oxidation process. This review provides useful information to scientists and engineers in this field.     

Improved phenol decomposition and simultaneous regeneration of granular activated carbon by the addition of a titanium dioxide catalyst under a dielectric barrier discharge plasma

A catalytic method using titanium dioxide (TiO₂) under a dielectric barrier discharge (DBD) plasma was studied to improve the decomposition of phenol adsorbed on granular activated carbon (GAC) and the simultaneous regeneration of the saturated GAC. The TiO₂–GAC hybrid was fabricated by an impregnation-desiccation method and characterised by X-ray diffraction, scanning electron microscopy, Fourier transform infrared spectroscopy, nitrogen adsorption isotherms and Boehm titration to investigate its adsorption and catalytic characteristics before and after the adsorption and DBD processes. The adsorption experiments showed that the GAC and TiO₂–GAC both followed pseudo-second-order kinetic models with adsorption isotherms that were well represented by the Langmuir model. TiO₂–GAC exhibited remarkable catalytic activity, increasing the phenol degradation by 19% and TOC removal by 8.7% relative to GAC in DBD treatment. TiO₂–GAC also exhibited better regeneration efficiency than GAC, and the reusability of the hybrid material was examined over four consecutive adsorption-regeneration cycles. The above results may be due to the enhanced generation of active species, such as hydroxyl radicals and hydrogen peroxide, on TiO₂–GAC relative to GAC during the discharge process, and the main intermediate products were analysed to explore the mechanisms involved in DBD plasma.     

Synthesis and characterisation of novel titania impregnated kaolinite nano-photocatalyst

Nano-sized titanium dioxide (TiO₂) has received a great attention in the field of research and development as a promising photocatalyst to promote the degradation of organic contaminants in water. One of the key technical challenges involved in separation and recovery of the photocatalyst particles from the water treatment system makes this technology unviable as an industrial process. A novel titania impregnated kaolinite (TiO₂/K) photocatalyst was synthesized by a modified two step sol–gel method: hydrolysis of titanium(IV) butoxide and heterocoagulation with pre-treated kaolinite (K) clay. The TiO₂/K photocatalysts were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and BET specific surface area measurements (BET). The photocatalytic activity was evaluated by the degradation of Congo red in aqueous solution. The TiO₂/K photocatalyst had a rigid porous layer structure and promising nano-size properties, and demonstrated an enhanced adsorption and photocatalytic ability for the removal of Congo red. The TiO₂/K photocatalyst can be easily separated and recovered from the water treatment system. The TiO₂/K photocatalyst is expected to deliver a true engineering solution for an industrial water/wastewater treatment process.     

Physicochemical stability of calcium alginate beads immobilizing TiO2 nanoparticles for removal of cationic dye under UV irradiation

Recently, there have been considerable interests to immobilize photocatalyst in alginate beads for removing pollutants from water sources. However, the feasibility of using alginate beads in industry largely depends on its long‐term stability during operation. This study investigated the physicochemical stability of alginate/titanium dioxide beads (Alg/TiO₂) when exposed to UV irradiation in aqueous environment. The degradation of Alg/TiO₂ beads was evident because the diameter and mass of the beads was reduced by 12% and 40%, respectively, after 120 h of irradiation. A substantial amount of TiO₂ was leached into the external medium. Consequently, the removal efficiency of model cationic dye was found to reduce after every process cycle. Morphological analysis showed the formation of cavities on the surface of the Alg/TiO₂ beads. Interestingly, the blank alginate beads degraded more rapidly than the Alg/TiO₂ beads, confirming the UV‐shielding effect of TiO₂. Nevertheless, this study reveals the need to improve the UV stability of alginate‐based beads before they can be considered for practical application. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45002.     

Synthesis of TiO2-entrapped EFAL-removed Y-zeolites: Novel photocatalyst for decomposition of 2-methylisoborneol

As a new photocatalyst, TiO₂-entrapped EFAL (extra-framework-aluminium)-removed Y-zeolites (TiO₂–EFAL-removed Y-zeolites) were synthesized, and they were applied to photocatalytic decomposition of 2-methylisoborneol (2-MIB) dissolved in water. UV-absorption spectroscopic and GC-mass spectrometric studies released that the photocatalytic decomposition of 2-MIB is achieved through formation of a cyclopentene-type intermediate. It was found by kinetic studies that TiO₂–EFAL-removed Y-zeolites are highly adsorptive and their photocatalytic quantum efficiency was about 0.04, much larger than that of Degussa P-25 TiO₂. These results suggest that TiO₂–EFAL-removed Y-zeolites would be promising photocatalysts for efficient and rapid removal of taint compounds in natural water resources.     

Nanoflower-like CdS and SnS2 loaded TiO2 nanotube arrays for photocatalytic wastewater treatment and hydrogen production

In this work, nanoflower-like CdS/SnS₂/TiO₂ NTs ternary heterojunction photocatalysts were synthesized by a hydrothermal method, the relationship between the morphology, microscopic morphology, crystallinity, elemental presence state and hydrogen production performance of the ternary photocatalysts were investigated by SEM, TEM, XRD and XPS, respectively. The photocatalytic performance, electrochemical property and hydrogen production capacity of CdS/SnS₂/TiO₂ NTs were compared with pure TiO₂ NTs, CdS/TiO₂ NTs and SnS₂/TiO₂ NTs. After 2 h of photocatalytic reaction, the removal efficiency of MB wastewater reached 100%, and the photocatalytic efficiencies toward RhB and Cr(VI) removal reached 86.08% and 80.93% after 3 h, respectively. The electron spin resonance (ESR) technique certified the active radical groups that played a role in the catalytic process and further investigated the possible photocatalytic mechanism. Hydrogen production per unit time achieved 97.14 μmol h^?1 cm^?2, this work provides the new technique to achieve solar energy conversion for hydrogen generation.     

Novel CdIn2S4 nano-octahedra/TiO2 hollow hybrid heterostructure: In-situ synthesis,synergistic effect and enhanced dual-functional photocatalytic activities

The development of highly efficient and multifunctional composite photocatalysts for both energy conversion and environmental governance has obtained great concerns. Here, a novel CdIn₂S₄/TiO₂ (CIS/THS) hollow composite photocatalyst was firstly designed and synthesized via a facile in-situ growth process, where the CdIn₂S₄ nano-octahedra densely attached on the surface of TiO₂ hollow spheres to form the unique hybrid heterostructure. The as-synthesized CIS/THS heterojunctions exhibit much superior photocatalytic activities for hydrogen evolution and Methyl Orange (MO) decomposition in comparison to pure CdIn₂S₄ and TiO₂ hollow spheres. The experimental results display that the CIS/THS-3 sample with the 30 wt% of TiO₂ presents the optimal photocatalytic H₂ production efficiency and its generation rate is 3.38 and 2.56 times as high as those of pure TiO₂ and CdIn₂S₄. Besides, the as-synthesized CIS/THS-3 hybrid also possesses the best MO photodegradation performance and its rate constant is 11.43 and 8.34 times higher than those of pure TiO₂ and CdIn₂S₄. The enhanced photocatalytic activities can be assigned to the synergistic effect, optimized light-harvesting capacity and the formation of hybrid heterostructure for boosting interfacial charge transfer and separation. Furthermore, based on the trapping experiments and ESR analysis, the possible type-Ⅱ interface charge transport mechanism was also proposed. Our study may provide the direct guidance for constructing other hollow TiO₂-based composite photocatalysts with superior photocatalytic water splitting and degradation performances.     

Increasing of Photocatalytic Performance of TiO2 Nanotubes by Doping AgS and CdS

Highly ordered titanium nanotubes (TiO₂ NTs) photocatalyst was prepared by the anodic oxidation method, and AgS, CdS, and AgS/CdS nanoparticles were doped on the surface of TiO₂ NTs by the successive ion adsorption and reaction (SILAR) method. The photocatalysts were characterized by SEM, EDS, XRD, and potentiostat system. The SEM and EDS analyses respectively show that the average outer diameter of prepared photocatalysts is in the range of 50–120?nm, and the presence of Ti, O, Ag, and Cd is successfully proved. The photocatalytic properties of TiO₂ NTs and doped TiO₂ NTs were studied by measuring the degradation of Methylene Blue (MB) solution. The experimental results show that AgS/CdS/TiO₂ photocatalyst exhibited most efficient photocatalytic activity with 340?µA/cm² photocurrent value. AgS/CdS/TiO₂ NTs photocatalyst shows up to 22.20% higher than TiO₂ NTs, 16.42% higher than CdS/TiO₂ NTs, and 4.3% higher than AgS/TiO₂ NTs.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript>-coated coal fly ash for photocatalyst

In order to more easily separate TiO₂ photocatalyst from treated wastewater, TiO₂ photocatalyst is immobilized on coal fly ash by precipitation method. The titanium hydroxide precipitated on coal fly ash by neutralization of titanium chloride is transformed into titanium dioxide by heat treatment in the temperature range of 300–700 ‡C. The crystalline structure of the titanium dioxide shows anatase type in all ranges of heat treatment temperature. The crystal size of anatase increases with increasing heat treatment temperature, with the drawback being the lower removal ability of NO gas. When the coal fly ash coated with 10 wt% of TiO₂ was calcined at 300 and 400 ‡C for 2 hrs, the average crystal size of anatase appeared about 9 nm, and the removal rates of NO gas were 63 and 67.5%, respectively. The major iron oxide, existing in coal fly ash as impurity, is magnetite (Fe₃O₄). Phase transformation of magnetite into hematite (Fe₂O₃) by heat treatment improves the removal rate of NO gas for TiO₂-coated coal fly ash.     

TiO2 photocatalyst loaded on hydrophobic Si3N4 support for efficient degradation of organics diluted in water

TiO₂ photocatalyst loaded on Si₃N₄ (TiO₂/Si₃N₄) was prepared by a conventional impregnation method and its photocatalytic performance for the degradation of organics (2-propanol) diluted in water was compared with that of TiO₂ photocatalysts (TiO₂/SiO₂, TiO₂/Al₂O₃, and TiO₂/SiC) loaded on various types of supports (SiO₂, Al₂O₃, and SiC). The formation of the well-crystallized anatase phase of TiO₂ was observed on the calcined TiO₂/Si₃N₄ photocatalyst, while a small anatase phase of TiO₂ was observed on the TiO₂/SiC photocatalyst and amorphous TiO₂ species was the main component on the TiO₂/SiO₂ and TiO₂/Al₂O₃ photocatalysts. The measurements of the water adsorption ability of photocatalysts indicated that the TiO₂/Si₃N₄ photocatalyst exhibited more hydrophobic surface properties in comparison to other support photocatalysts. Under UV-light irradiation, the TiO₂/Si₃N₄ photocatalyst decomposed 2-propanol diluted in water into acetone, CO₂, and H₂O, and finally, acetone was also decomposed into CO₂ and H₂O. The TiO₂/Si₃N₄ photocatalyst showed higher photocatalytic activity than TiO₂ photocatalyst loaded on other supports. The well-crystallized TiO₂ phase deposited on Si₃N₄ and the hydrophobic surface of Si₃N₄ support are important factors for the enhancement of photocatalytic activity for the degradation of organic compounds in liquid-phase reactions.     

Removal of NO from flue gas by wet scrubbing with NaClO2/(NH2)2CO solutions

The experiments were performed in a countercurrent packed column in a continuous mode to study the absorption of nitric oxide in sodium chlorite/urea solutions. Sodium chlorite mainly works as an agent to oxidize NO to NO₂. A combined SO₂/NO removal system was also tested. On the basis of high SO₂ removal efficiency, the NO removal efficiencies under various experimental conditions were emphatically measured. Among the operating variables such as initial NaClO₂ concentration, urea concentration, temperature and initial pH value, the pH value of the absorbing liquid was found to have a great impact on both NO removal efficiency and NO₂ concentration. NO removal efficiency was increased with increasing NaClO₂ concentration and temperature. Urea almost has no negative effect on NO removal efficiency, however it aids the abatement of NO₂ greatly. The anions in the spent scrubbing liquor were analyzed by ion chromatography.