The Effects of Non-thermal Plasma on the Morphology of Ce-doped ZnO: Synthesis,Characterization and Photocatalytic Activity of Hierarchical Nanostructures

ZnO nanoparticles with and without 8 mol % Ce dopant were synthesized by precipitation method and the prepared samples were treated with various types of non-thermal plasma in order to study their effects on the morphology and photocatalytic activity of the samples. As-prepared Ce-doped ZnO has a hexagonal wurtzite structure and the crystal system was not changed by the plasma treatment. The morphology of Ce-doped ZnO was changed from spherical particle to flower and rod-like shapes by the plasma treatment. The particle size of the treated Ce-doped ZnO is smaller in comparison with that of untreated sample. The photodegradation of methylene blue by the plasma-treated Ce-doped ZnO in aqueous solution is higher than that of the untreated Ce-doped ZnO. The enhancement of the photocatalytic activity by the plasma-treated samples may come from the particle size reduction, enhancement in charge separation efficiency and increase of the surface area.     

Fe-Ni 共掺杂 ZnO 的制备及其光催化降解甲基橙活性

 采用溶液法制备了 Fe-Ni 共掺杂 ZnO 光催化剂, 并运用 X 射线衍射、扫描电镜和原子发射光谱等对催化剂进行了表征. 以甲基橙 (MO) 为模型污染物, 评价了样品的光催化活性, 考察了甲基橙初始浓度及其 pH 值, 以及催化剂用量等对光催化反应性能的影响. 结果表明, Fe-Ni 共掺杂降低了 ZnO 的结晶度, 并促进了晶粒的长大. 光催化降解反应表明, Fe-Ni 共掺杂显著提高了 ZnO 光催化降解甲基橙的活性, 当催化剂用量为 0.6 g/L, 经 120 min 紫外光照射时, 可使甲基橙溶液 (10 mg/L) 降解率达到 93.5%. 关键词：铁; 镍; 共掺杂; 氧化锌; 光催化; 甲基橙; 降解     

Multiple Steady States in the Photocatalytic Reactor for Colored Compounds Degradation

The paper reports the occurrence of multiple steady-state zones in most of the constructions of fixed-bed photocatalytic reactors. Such a phenomenon has not been ever observed in a field of photocatalytic reactors. The simulation has been provided for a common case in a photocatalysis—the degradation of colored compounds. The mathematical model of the photocatalytic reactor with immobilized bed has been stated by a simple ideal mixing model (analogous to the CSTR model). The solution has been continued by the two parameters—the Damköhler number and the absorption coefficient related to the inlet stream concentration. Some branches of steady states include the limit point. The performed two-parametric continuation of the limit point showed the cusp bifurcation point. Besides the numerical simulation, the physical explanation of the observed phenomenon has been provided; the multiple steady-states occurrence is controlled by light absorption–reaction rate junction. When the reaction rate is limited by the light absorption, we can say that a light barrier occurs. The dynamical simulations show that when the process is operated in a field of multiple steady states, the overall reactor efficiency is related to the reactor set-up mode.     

Comparison between the performance of an immobilized impinging jet stream reactor and a slurry impinging jet stream reactor for photocatalytic phenol degradation

A new immobilized photocatalytic impinging jet stream reactor was designed, and the influences of the effective parameters like jet flow rate, TiO₂ coating disc diameter, nozzle-to-disc distance, and initial concentration on phenol removal were investigated. The reactor was also used as a slurry reactor, and degradation efficiencies in both reactors were compared based on their catalyst loading. The results indicated that the slurry reactor has a higher degradation efficiency than the immobilized reactor at the same TiO₂ loading and other operational conditions. The slurry reactor needs to separate and recover the TiO₂ nanoparticles from the reaction medium which increases the overall process complexity and cost, while the immobilized reactor could be reused at least 4times without any significant decrease in removal efficiency. RTD result indicates that the tank in series model (N?=?5) could properly predict the reactors hydrodynamic behavior.     

Preparation, characterization of the Ta-doped ZnO nanoparticles and their photocatalytic activity under visible-light illumination

This paper describes a novel catalyst of the Ta-doped ZnO nanocrystals prepared by a modified polymerizable complex method using the water-soluble tantalum precursor as the sources of Ta. The catalysts were characterized by means of various analytical techniques as a function of Ta content (x=0–4 mol%) systematically. A remarkable advantage of the results was confirmed that dopant Ta enhanced the visible-light absorption of ZnO and the low-solubility tantalum doping could restrain the growth of crystal and minish the particle size. The relationship between the physicochemical property and the photocatalytic performance was discussed, and it was found that the photocatalytic activity in the photochemical degradation of methylene blue under visible-light irradiation (λ420 nm) was dependent on the contents of the dopant, which could affect the particle size, concentration of surface hydroxyl groups and active hydrogen-related defect sites, and the visible-light absorption. The highest photocatalytic activity was obtained for the 1.0 mol% Ta-doped ZnO sample.     

A Highly Efficient and Stable Photocatalyst; N-Doped ZnO/CNT Composite Thin Film Synthesized via Simple Sol-Gel Drop Coating Method

The thin film of N-doped ZnO/CNT nanocomposite was successfully fabricated on soda lime glass substrate by a simple sol-gel drop-coating method. The structural, morphological, chemical, and optical properties of as prepared samples were characterized by a variety of tools such as X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Fourier Transform Infrared spectroscopy (FT-IR), and UV-visible spectroscopy. The hexagonal crystalline structure was confirmed from XRD measurement without any other impurity phase detection in samples. The N-doped ZnO/CNT composite showed excellent photo-catalytic activity towards cationic methylene blue (MB) dye degradation with 100% removal rate under UV light irradiation as compared to N-doped ZnO (65%) and pure ZnO (47.36%). The convincing performance has also been observed for the case of visible light irradiation. The enhancement of that photocatalytic activity might be due to narrowing the band gap as well as the reduction of electron–hole pair recombination in ZnO matrix with the incorporation of dopant nitrogen and CNT. It is assumed from the obtained results that N-doped ZnO/CNT nanocomposite thin film can be employed as an economically achievable and ecofriendly method to degrade dye with UV and visible light irradiation. Additionally, density functional theory (DFT) calculations were applied to explore the effect of N-doping on electronic structure of ZnO. The computational study has supported the experimental results of significant band gap contraction, which leads to the maximum absorption towards higher wavelength and no appreciable change of lattice parameters after doping. A conceivable photocatalytic mechanism of N-doped ZnO/CNT nanocomposite has been proposed as well.     

Supported nanometric titanium oxide sols as a new efficient photocatalyst

We report on the first study of the photocatalytic performance of immobilized smallest titanium oxide oxoparticles of the size 2R = 5.0 nm on a glass support. The nanometric particles are prepared in the sol-gel reactor with rapid reagent mixing and temperature, atmosphere, and particle size control. The surface coverage is achieved by inserting the support into the reactor solution during the induction period, where chemically active nanoparticles are relatively stable. We show that this immobilized amorphous oxo phase of titanium oxide exhibits considerable activity toward photocatalytic degradation of trichloroethylene in the gas phase. Moreover, one of the important factors appears to be the catalyst surface preparation, which has to be free of the adsorbed alcohol molecules. UV-assisted exchange between propoxy and hydroxy groups is suggested as the surface activation mechanism. The film thickness is expected to strongly affect the material photocatalytic efficiency because of the internal traps population.     

Fe3+改性纳米ZnO光催化降解壬基酚聚氧乙烯醚

采用氨浸法制备了不同Fe3 含量的Fe3 /ZnO光催化剂,并用X射线衍射、N2吸附、X射线光电子能谱和紫外-可见漫反射光谱对纳米Fe3 /ZnO进行了表征.以壬基酚聚氧乙烯醚(NPE-10)为模型污染物,分别在紫外光和可见光下考察了纳米Fe3 /ZnO的光催化活性.结果表明,该方法能成功地将Fe掺杂到ZnO晶体上,且随着Fe3 添加量的增加,ZnO的晶粒尺寸逐渐减小,比表面积逐渐增大.与纳米ZnO样品相比,Fe3 /ZnO中Fe2p结合能减小,而Zn2p和O1s结合能增大,ZnO表面的羟基氧和吸附氧含量增加,光催化活性提高.当Fe3 的添加量大于0.5%时,Fe3 /ZnO样品的吸收光谱发生红移,在可见光区出现吸收.光催化降解结果显示,0.5?3 /ZnO样品的光催化活性最高,在紫外光和可见光照射3h后对NPE-10的降解率分别比纯ZnO提高18%和69%.     

贵金属负载的棒状ZnO复合光催化剂的制备及其提升的光催化性能

以水热制备的ZnO纳米棒为基底,通过乙二醇液相还原法负载不同贵金属颗粒(Pt、Pd、Ru)构筑贵金属负载的ZnO纳米棒复合光催化剂。实验结果表明在制备条件相同时,Pt/ZnO样品中Pt颗粒尺寸较小,分布均匀;Pd/ZnO样品中Pd颗粒尺寸较大且团聚严重;Ru/ZnO样品则几乎没有Ru颗粒负载。在紫外光照射下降解亚甲基蓝的反应中,Pt/ZnO表现出最高的光催化性能,Pd/ZnO样品次之,而Ru/ZnO则表现出与ZnO纳米棒相似的光催化活性;表明小尺寸和大小均匀的贵金属颗粒对ZnO纳米棒的催化性能有着显著的提升作用。对Pt/ZnO来说,当Pt载量为3.2%时Pt/ZnO催化剂的光催化活性最高。     

Antibacterial inactivation of spiramycin after titanium dioxide photocatalytic treatment

The photocatalytic degradation of an antibiotic (spiramycin) has been studied using immobilized titanium dioxide (TiO₂) as a photocatalyst in a laboratory reactor under ultraviolet illumination (365 nm). The degradation of the antibiotic was monitored by ultraviolet spectrophotometry and high-pressure liquid chromatography and confirmed by an antibacterial activity evaluation. Two types of TiO₂ (P25 and PC500) immobilized on glass plates were compared. For TiO₂ PC500 immobilization on glass and paper was also studied. A slightly better degradation was obtained with TiO₂ P25 for which the degradation kinetics were investigated. The Langmuir–Hinshelwood kinetic model is satisfactorily obeyed at initial time and in the course of the reaction. Adsorption and apparent rate constants were determined. These results show a complete degradation of spiramycin, which was confirmed by the inhibition of the antibacterial activity of Staphylococcus xylosus, when exposed to spiramycin solutions treated with photocatalyst for a short time. In addition, the codegradation of spiramycin and tylosin was investigated and showed that tylosin had a higher affinity to the catalyst TiO₂ P25 than spiramycin. The complete degradation of spiramycin confirms the feasibility of such a photocatalytic treatment process for spiramycin elimination from contaminated water.     

Superior Photostability and Photocatalytic Activity of ZnO Nanoparticles Coated with Ultrathin TiO2 Layers through Atomic‐Layer Deposition

Atomic‐layer deposition (ALD) is a thin‐film growth technology that allows for conformal growth of thin films with atomic‐level control over their thickness. Although ALD is successful in the semiconductor manufacturing industry, its feasibility for nanoparticle coating has been less explored. Herein, the ALD coating of TiO₂ layers on ZnO nanoparticles by employing a specialized rotary reactor is demonstrated. The photocatalytic activity and photostability of ZnO nanoparticles coated with TiO₂ layers by ALD and chemical methods were examined by the photodegradation of Rhodamine B dye under UV irradiation. Even though the photocatalytic activity of the presynthesized ZnO nanoparticles is higher than that of commercial P25 TiO₂ nanoparticles, their activity tends to decline due to severe photocorrosion. The chemically synthesized TiO₂ coating layer on ZnO resulted in severely declined photoactivity despite the improved photostability. However, ultrathin and conformal ALD TiO₂ coatings (≈0.75–1.5 nm) on ZnO improved its photostability without degradation of photocatalytic activity. Surprisingly, the photostability is comparable to that of pure TiO₂, and the photocatalytic activity to that of pure ZnO.     

Wavelength-sensitive photocatalytic degradation of methyl orange in aqueous suspension over iron(III)-doped TiO2 nanopowders under UV and visible light irradiation

Well-crystallized iron(III)-doped TiO2 nanopowders with controlled Fe3+ doping concentration and uniform dopant distribution, have been synthesized with plasma oxidative pyrolysis. The photocatalytic reactivity of the synthesized TiO2 nanopowders with a mean particle size of 50-70 nm was quantified in terms of the degradation rates of methyl orange (MO) in aqueous TiO2 suspension under UV (mainly 365 and 316 nm) and visible light irradiation (mainly 405 and 436 nm). The photodecomposition of MO over TiO2 nanopowders followed a distinct two-stage pseudo first order kinetics. Interestingly, the photocatalytic reactivity depends not only on the iron doping concentration but also on the wavelength of the irradiating light. Under UV irradiation, nominally undoped TiO2 had much higher reactivity than Fe3+ -doped TiO2, suggesting that Fe3+ doping (> 0.05 at. %) in TiO2 with a mean particle size of approximately 60 nm was detrimental to the photocatalytic decomposition of methyl orange. Whereas, under visible light irradiation, the Fe3+ -doped TiO2 with an intermediate iron doping concentration of approximately 1 at. % had the highest photocatalytic reactivity due to the narrowing of band gap so that it could effectively absorb the light with longer wavelength. A strategy for improving the photocatalytic reactivity of Fe3+ -doped TiO2 used in the visible light region is also proposed.     

Synthesis and Photocatalytic Properties of Coupled Nanocrystalline ZnO/ZnS in Nafion Membrane

The coupled nanocrystalline ZnO/ZnS was fabricated and immobilized in Nafion membrane by using sodium sulfide (Na2S) as the single anion precursor. The molar ratio of ZnO to ZnS can be controlled by simply adjusting the reaction time. The as-prepared ZnO/ZnS-Nafion samples were characterized by various methods, including optical absorption, X-ray diffraction and high-resolution transmission electron microscopy. These coupled ZnO/ZnS nanocrystals embedded in Nafion membrane displayed excellent photocatalytic activities for their efficient charge separation properties. A mechanism of ZnO/ZnS nanoparticle fabrication in Nafion was deduced from the solubility difference, and the photocatalytic mechanism of coupled ZnO/ZnS was discussed as well.     

Photocatalytic degradation of anionic surfactant using zinc oxide nanoparticles

In this paper the photocatalytic degradation of anionic surfactant LABS was studied by a batch process using ZnO nanoparticles with diameter size of 20 nm catalyst on irradiation with UV light and their behavior comparatively examined with respect to ZnO commercial powder. The effect of parameters such as initial surfactant concentration, initial solution pH has been studied. Also degradation at LABS in the presence of an electron acceptor like potassium peroxydisulfate and effect of anion presence on surfactant degradation has been systematically investigated. The obtained result demonstrated a high photocatalytic activity of nanosize semiconducting particles.     

Microwave-assisted solution synthesis and photocatalytic activity of Ag nanoparticles supported on ZnO nanostructure flowers

Ag nanoparticles supported on the surface of three-dimensional (3D) flower-like ZnO nanostructure were synthesized by a microwave-assisted solution method. The obtained products were characterized by X-ray diffraction analysis, field-emission scanning electron microscopy, Fourier-transform infrared spectroscopy, Raman spectrophotometry, X-ray photoelectron spectroscopy, and photoluminescence spectroscopy. The analytical results confirmed homogeneously distributed Ag nanoparticles supported on the surface of flower-like ZnO nanostructure. The photocatalytic effect of the heterostructure Ag/ZnO nanocomposites was investigated using photodegradation under ultraviolet (UV) light of methylene blue as model dye. The heterostructure Ag/ZnO nanocomposites exhibited much higher photocatalytic activity than pure ZnO flowers. The improved photocatalytic properties are attributed to formation of a Schottky barrier at the metal–semiconductor interface of the Ag/ZnO nanocomposites.     

Fe3+/V5+/TiO2复合纳米微粒光催化性能的研究

采用溶胶凝胶法制备了Fe^3 /V^5 /TiO2复合纳米微粒作为光催化剂。光降解反应结果表明，其掺杂催化剂Fe^3 /V^5 /TiO2的光催化活性明显提高。光电化学研究显示，铁离子可以成为电荷陷阱，促进空穴的界面传递反应。适量钒离子掺杂使TiO2电极的光电流升高，导带中电子浓度的增大，加快了界面的电子传递反应。共掺杂催化剂中，Fe^3 、V^5 分别提供了空穴与电子的陷阱，同时加快了电子与空穴的界面传递反应，从 更有效地提高光催化活性。双组份共掺杂为提高TiO2光催化活性提供新的途径。     

Effects of doping La and Cu on photoinduced charge properties of TiO_2 and its relationships with photocatalytic activity

In recent years, nanosized TiO2 materials have been widely studied in photocatalytic and photoelectric conversion fields because of their intrinsic characteris- tics, such as stable chemical property, strong oxidizing capability and nontoxicity[1,2]. And the preparation, characterization and modification of nanosized TiO2 are always crucial contents in semiconductor photo- electric chemistry and photocatalytic researches[3,4]. To further improve TiO2 performance, doping metal ion is consider…     

Heterometal alkoxides as precursors for the preparation of porous Fe- and Mn-TiO2 photocatalysts with high efficiencies

Transition-metal-doped titanium glycolates (M-TG, with M=Fe, Mn), which are the first non-stoichiometric heterometal alkoxides, have been synthesised through a solvothermal doping approach. X-ray diffraction, UV/Vis diffuse reflectance and ESR spectroscopy revealed that the dopant ion (Fe(3+) or Mn(2+)) is substituted for Ti(4+) in the TG lattice. Fe(3+) prolongs the crystallisation time of Fe-TG, whereas Mn(2+) has a smaller effect on the crystallisation time in comparison with Fe(3+). The as-synthesised M-TG materials were used directly as single-source precursors for the preparation of metal-doped titania (M-TiO(2)) through a simple thermal treatment process. The as-prepared M-TiO(2) materials maintain the rod-like morphology of the precursors and possess a mesoporous structure with high crystallinity. It has been proved that the dopant ions are incorporated into the TiO(2) lattice at the Ti(4+) positions. The photocatalytic activities of the M-TiO(2) materials obtained were evaluated by testing the degradation of phenol under UV irradiation. From the photocatalytic results, it was concluded that high crystallinity, a large surface area and appropriate transition-metal-doping are all beneficial to the enhancement of the photocatalytic performance of the doped TiO(2) material. In addition, it was noted that in comparison with Mn-TiO(2), Fe-TiO(2) shows higher photocatalytic activity due to the better inhibition effect of Fe(3+) on recombination of photogenerated electron-hole pairs. In contrast to the conventional nanosized TiO(2) photocatalyst, the micrometre-sized M-TiO(2) particles we obtained can be easily separated and recovered after the photocatalytic reactions.     

纳米TiO_2光催化芳香醛的缩醛反应研究

本文以纳米TiO2为催化剂,UV-LED（=365 nm）为紫外光源,在自制的恒温石英玻璃光催化反应器中成功实现了芳香醛的非均相光催化缩醛反应.以乙醇等作为溶剂和反应物,快速高效和高选择性地合成了苯甲醛二乙基缩醛（BDA）.在光强为0.6 mw/cm2,苯甲醛初始浓度为0.05 mol/L,催化剂TiO2（P25）用量为5.0 g/L,反应时间为15 min的条件下,苯甲醛二乙缩醛的产率可达99.86%.研究表明,氧气的存在是顺利发生光催化缩醛反应的重要条件.反应液pH值、醇溶剂种类及苯环对位取代基等因素都会对光催化缩醛反应速率和产率产生影响.pH值及醇溶剂的pKa越小,缩醛反应速率越快.苯环上对位取代基会抑制缩醛反应的进行,其中供电子取代基相对吸电子取代基更有利于缩醛反应进行.结合实验,提出了光催化缩醛反应的机理.     

Effect of 3D ZnO:Fe morphology on the photocatalytic activity under solar irradiation

Nanoparticles, microsphere, hedgehog sphere-like and flower-like ZnO:Fe photocatalysts were prepared by the hydrothermal method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet/visible absorption spectra (UV?CVis). The results show that the ZnO:Fe photocatalysts with different 3D morphologies are a hexagonal wurtzite structure with space group of p63mc. The pH value of the precursor has a great influence on various morphologies of ZnO:Fe photocatalysts. The flower-like and hedgehog sphere-like ZnO:Fe photocatalysts exhibit the high solar photocatalytic behavior on methylene blue (MB). The ZnO:Fe order of photocatalytic activity is as follows: flower?>?hedgehog sphere?>?microsphere?>?nanoparticle. The flower-like ZnO:Fe is optimal, which exhibits the highest degradation rate of 98% for light time of 5?h.