Controllable synthesis of SnO2 photocatalyst with superior photocatalytic activity for the degradation of methylene blue dye solution

SnO₂ photocatalyst was successfully synthesised by novel chemical route in hydrothermal environment and annealed at two different temperatures viz 550 and 600 °C, respectively. The crystal structure, optical properties, surface and bulk morphology have been characterised using various tools like X-ray diffraction (XRD), UV visible spectroscopy, Fourier transform infrared spectroscopy, transmission electron microscope (TEM) and scanning electron microscope (SEM). Cubic, spheres and porous like morphology of SnO₂ photocatalyst was successfully confirmed using SEM micrographs and TEM. In addition to this the photocatalytic activity was evaluated towards the degradation of methylene blue dye solution. SnO₂ photocatalyst annealed at 600 °C exhibits excellent photocatalytic efficiency which may be attributed to the unique morphology, high crystalline nature and charge separation. The photocatalyst efficiency was further tested towards the concentration of dye, catalyst dosage and pH of the dye. The involvement of ?OH in the photocatalytic reaction was evidenced using trapping experiment by employing different scavengers. The photocatalyst was moderately active, stable upto its fifth usage and stability of the photocatalyst before and after the photocatalytic reaction was also been studied using XRD and SEM.     

Solar photocatalytic degradation of isoproturon over TiO2/H-MOR composite systems

The photocatalytic degradation and mineralization of isoproturon herbicide was investigated in aqueous solution containing TiO₂ over H-mordenite (H-MOR) photocatalysts under solar light. The catalysts are characterized by X-ray diffraction (XRD), UV–Vis diffused reflectance spectra (UV–Vis DRS), Fourier transform-infra red spectra (FT-IR) and scanning electron microscopy (SEM) techniques. The effect of TiO₂, H-MOR support and different wt% of TiO₂ over the support on the photocatalytic degradation and influence of parameters such as TiO₂ loading, catalyst amount, pH and initial concentration of isoproturon on degradation are evaluated. 15 wt% TiO₂/H-MOR composite is found to be optimum. The degradation reaction follows pseudo-first order kinetics and is discussed in terms of Langmuir–Hinshelwood (L–H) kinetic model. The extent of isoproturon mineralization studied with chemical oxygen demand (COD) and total organic carbon (TOC) measurements and 80% mineralization occurred in 5 h. A plausible mechanism is proposed based on the intermediates identified by liquid chromatography–mass spectroscopy (LC–MS).     

Growth of carbon nanotubes over Fe-Co and Ni-Co catalysts supported on different phases of TiO2 substrate by thermal CVD

The aim of this work is to examine the properties of CNTs formed on Fe-Co and Ni-Co bimetallic catalysts supported on different phases of TiO₂ (anatase and rutile) by wet impregnation method. The CNTs are grown from decomposition of acetylene via Thermal CVD at 700°C using the prepared catalysts. The nanomaterials were characterized by XRD, Xmap, BET, FESEM, TEM, and Raman spectroscopy. It was found that the catalyst samples supported on rutile TiO₂ have higher specific surface area, smaller catalytic nanoparticles with denser distribution and very more activity compared to anatase ones. Consequently, the CNTs nucleated from nanoparticles supported on rutile TiO₂ possess higher density, smaller average diameters and narrower diameter distribution compared to grown CNTs on anatase samples. Moreover, it was observed that the Fe-Co bimetallic catalysts regardless of TiO₂ support phase, possesses more catalytic activity and higher average growth rate of CNTs in compare with Ni-Co catalysts.     

Coating of multi-walled carbon nanotubes with SnO2 films of controlled thickness

Multiwalled carbon nanotubes coated with SnO₂ layers of different thickness were prepared by a simple wet-chemical method. The samples have been characterized by X-ray diffraction and transmission electron microscopy. The thickness of the coatings can be easily controlled by changing the synthesis conditions, such as pH value of the solution and hydrolysis time. The smoothness and uniformity of the SnO₂ layers were greatly influenced by the addition of thioglycolic acid, which was used as connecter. The samples prepared by using thioglycolic acid showed very smooth and uniform coating layers, without cracks and broken segments. The growth behavior of the coating layer is also discussed.     

Immobilization of TiO2 nanoparticles on Fe-filled carbon nanocapsules for photocatalytic applications

Using a simple sol-gel method, a novel magnetic photocatalyst was produced by immobilization of TiO₂ nano-crystal on Fe-filled carbon nanocapsules (Fe-CNC). High resolution TEM images indicated that the immobilization of TiO₂ on Fe-CNC was driven primarily by heterogeneous coagulation, whereas surface nucleation and growth was the dominant mechanism for immobilizing TiO₂ on acid-functionalized hollow CNC. The TiO₂ immobilized on Fe-CNC exhibited the anatase phase as revealed by the X-ray diffraction (XRD) patterns. In comparison with free TiO₂ and TiO₂-coated CNC, TiO₂-coated Fe-CNC displayed good performance in the removal of NO gas under UV exposure. Due to the advantages of easy recycling and good photocatalytic efficiency, the novel magnetic photocatalyst developed here has potential use in photocatalytic applications for pollution prevention.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms

Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.     

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

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

Photodegradation of an azo dye using immobilized nanoparticles of TiO2 supported by natural porous mineral

Natural mordenite, replacing the synthetic zeolites, has been employed as the support of TiO2, and its photocatalytic activity has been examined in methyl orange (MO) aqueous under UV light. AFM, TEM, XRD, FTIR and fluorescence spectra have been used to reveal the loading effects of TiO2 on mordenite. The results show that the photocatalytic degradation (PCD) reaction rates are sharply increased by natural zeolite supports. Since mordenite is photo-inert, the PCD-enhancement is mostly caused by the bonding effects of Ti-O-Si and Ti-O-Al. Moreover, another two distinct natural zeolites have been employed as the supports of TiO2, in order to check the universality of PCD-enhancement effect of natural zeolites on TiO2. And the factors of PCD reaction on TiO2-zeolite, such as pH and catalyst dose, have been investigated.     

Catalytic combustion of toluene over platinum supported on Ce–Zr–O solid solution modified by Y and Mn

A series of CeO₂–ZrO₂ mixed oxides were prepared using coprecipitation method and characterized by BET, oxygen storage capacity (OSC), X-ray diffraction (XRD) and H₂-temperature-programmed reduction (H₂-TPR). The catalytic activities toward toluene combustion were investigated in a micro-reactor. The results demonstrate that the catalytic activity of Pt/γ-Al₂O₃/Ce_0.50Zr_0.50O₂ monolithic catalyst can be greatly improved by doping metal into Ce_0.50Zr_0.50O₂. When doping Y and Mn into Ce_0.50Zr_0.50O₂ simultaneously, the catalyst Pt/γ-Al₂O₃/Ce_0.40Zr_0.40Y_0.10Mn_0.10O_X shows the highest activity. The T₁₀ (the temperature of 10% toluene conversion) and the complete conversion temperature (the temperature of 90% toluene conversion) of toluene are 443 and 489 K, respectively. Gas hourly space velocity (GHSV) results show that the prepared catalyst can be applied in a wide range of GHSV (from 12,000 to 20,000 h⁻¹). The catalyst prepared shows great potential for practical application.     

Dye-sensitized TiO2 film with bifunctionalized zones for photocatalytic degradation of 4-cholophenol

A new strategy to photocatalytic degradation of 4-cholophenol (4-CP) under visible light irradiation was described. The TiO₂ film deposited on an ordinary glass sheet was distributed into two zones. One zone was sensitized by N719 dye and fabricated to be a sandwich type cell with a similar structure of dye-sensitized solar cells. The other zone was inserted into pollutants solution for degradation. A highly oxidized overvoltage anode was achieved from the dye-sensitized zone. The bifunctionalized TiO₂ film and the anode could degrade 4-chlorophenol in two separate reactors with 97% and 96% removal of 4-CP after 5 h, respectively. The degradation efficiency could be improved by addition of FeSO₄. The as-prepared bifunctionalized TiO₂ film was comparably stable in the process of degradation.     

Rapid synthesis of homogeneous MnO2/multi-wall carbon nanotubes nanostructure and its electrochemical capacitive behavior

A homogeneous composite of MnO₂/multi-wall carbon nanotubes (MnO₂/MWCNTs) was rapidly and efficiently synthesized by a redox reaction of MnO₄⁻ and Mn²⁺ on the MWCNTs under ultrasonic irradiation. The structure and morphology of the obtained MnO₂ and MnO₂/MWCNTs composite were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy. Electrochemical investigation indicated that the maximum specific capacitance of the MnO₂/MWCNTs composite, measured by galvanostatic charge-discharge test, was 315 F g^− 1, compared to the pristine MnO₂ (192 F g^− 1) and MWCNTs electrode (25 F g^− 1), showing the synergistic effect of MWCNTs and MnO₂. The homogeneous hybrid nanostructure and the good conductivity of MWCNTs were considered to be responsible for its preferable electrochemical performances.     

碳纤维负载钐掺杂纳米TiO2复合材料的制备与表征

采用静电纺丝法和热处理工艺制备了纳米碳纤维负载掺杂1.5%(摩尔分数)Sm的纳米Ti O2复合材料(Sm-Ti O2/CNFs),利用SEM、EDX、TEM、FTIR和XRD对其组成和结构进行了表征,并以甲基橙为降解对象,考察了Sm-Ti O2/CNFs复合材料在紫外光照射下对甲基橙的光催化降解效果。结果表明,掺杂Sm3+的Ti O2以锐钛矿晶型均匀分散在碳纳米纤维的表面和内部,质量分数为20%左右;相对于未掺杂的Ti O2/CNFs样品,Sm-Ti O2/CNFs的光催化活性提高约37%。     

Prediction ofT c for YBa2Cu3Oz doped with Ca using neural network

In order to predict the superconducting transition temperatureT _c of YBa₂Cu₃O_z doped with Ca, we have constructed a neural network NN which is composed of three layers; we considered 28 constituent elements and their concentration in the input layer to provideT _c in the output layer. The NN was trained by the error-back-propagation method using data from the database “SUPERCON” for high-T_c superconducting materials. The effect of Ca doping onT _c of (Y_1-x-Ca_x)Ba₂Cu₃O_z and Y(Ba_2-xCa_x)Cu₃O_z was investigated using this method. It turned out that a higherT _c is expected for the sample withx = 0.3 andz = 6.5 in the former system and that the oxygen concentrationz can be varied for different Ca contents in the latter system.     

基于BP神经网络的Cu-Ce掺杂TiO2光催化剂性能预测组合模型研究

采用环境测试舱模拟可见光下的室内环境,以甲醛气体的光催化降解为探针反应,评价了Cu-Ce/TiO2光催化剂的光催化活性及对甲醛气体的去除效果。利用指数平滑-神经网络ES-BP组合模型对Cu-Ce/TiO2光催化剂的性能做预测分析。结果表明:经过Cu-Ce/TiO2光催化剂处理后细木工板中甲醛释放浓度明显降低,平均光催化降解甲醛气体效率为42.8%;ES-BP组合预测模型在Cu-Ce/TiO2光催化剂的性能预测中取得了较好的效果,平均绝对误差为-0.00011mg/m3,平均相对误差为-0.317%;ES-BP组合预测模型实现了BP神经网络模型和指数平滑模型的优势互补,提高了对数据长期预测的准确性。     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

Abstract

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Photocatalytic degradation of phenol in aqueous solutions by Pr-doped TiO2 nanoparticles

Photocatalytic degradation of phenol in water was examined using Pr-doped TiO₂ nanoparticles. These photocatalysts were synthesized by an acid-peptized sol–gel method from titanium tetra-isopropoxide with different concentrations of Pr(III) dopant and calcination temperatures. Several tools such as XRD, BET surface area, SEM, and EDX, were used to evaluate particle structure, size distribution, and composition. The optical absorption properties of the prepared particles were also measured. Photocatalytic activity of the particles was studied in a batch reactor containing phenol solution with 400 W UV irradiation. Parameters affecting photocatalytic process such as the catalyst crystallinity, light absorption efficiency, the dosage of catalyst, dopant and phenol concentrations were investigated. The Pr-doped TiO₂ showed high activity for photocatalytic degradation of phenol. The presence of Pr ions in the TiO₂ particles would cause a significant absorption shift towards the visible region. The degradation process was optimized using 1 g/L Pr-doped TiO₂ with a Pr(III) concentration of 0.072 mol% after 2 h irradiation. It was shown that photodegradation followed a pseudo-first-order kinetics and the rate constant changed with phenol concentration.     

Promotional effects of carbon nanotubes on V2O5/TiO2 for NOX removal

A series of V₂O₅/TiO₂-carbon nanotube (CNT) catalysts were synthesized by sol-gel method, and their activities for NO_X removal were compared. A catalytic promotional effect was observed by adding CNTs to V₂O₅/TiO₂. The catalyst V₂O₅/TiO₂-CNTs (10 wt.%) showed an NO_X removal efficiency of 89% at 300 °C under a GHSV of 22,500 h⁻¹. Based on X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, NH₃-temperature-programmed desorption, temperature-programmed reduction, Brunauer-Emmett-Teller surface area measurements, differential scanning calorimetry, and thermogravimetric analysis, the increased acidity and reducibility, which could promote NH₃ adsorption and oxidation of NO to NO₂, respectively, contributed to this promotion.     

Effects of SO2 on selective catalytic reduction of NO with NH3 over a TiO2 photocatalyst

The effect of SO₂ gas was investigated on the activity of the photo-assisted selective catalytic reduction of nitrogen monoxide (NO) with ammonia (NH₃) over a TiO₂ photocatalyst in the presence of excess oxygen (photo-SCR). The introduction of SO₂ (300 ppm) greatly decreased the activity of the photo-SCR at 373 K. The increment of the reaction temperature enhanced the resistance to SO₂ gas, and at 553 K the conversion of NO was stable for at least 300 min of the reaction. X-ray diffraction, FTIR spectroscopy, thermogravimetry and differential thermal analysis, x-ray photoelectron spectroscopy (XPS), elemental analysis and N₂ adsorption measurement revealed that the ammonium sulfate species were generated after the reaction. There was a strong negative correlation between the deposition amount of the ammonium sulfate species and the specific surface area. Based on the above relationship, we concluded that the deposition of the ammonium sulfate species decreased the specific surface area by plugging the pore structure of the catalyst, and the decrease of the specific surface area resulted in the deactivation of the catalyst.     

Influence of operational parameters on the TiO2 photocatalytic degradation of Methylene blue

Thin films of titanium oxide were obtained by dip-coating, using the sol–gel method. TiO₂ powder (Degussa, P25) and polyethylene glycol (PEG) were added to enhance the photocatalytic properties of resulting films. Effects of experimental variables on the photocatalytic properties of the coatings were evaluated based on the degradation efficiency of the reference dye (Methylene blue). The photocatalytic activity of resulting TiO₂ coatings was improved with the loading of TiO₂ powder (Degussa, P25) and PEG in the sols. The electron-hole pair photogeneration increases with the energy of irradiation and improves photocatalytic efficiency. Increasing coating thickness leads to a rough surface with more reaction sites. Photodegradation conversion of Methylene blue (Mb) decreases with an increase in the initial concentration of Mb.     

基于BP神经网络模型的Ni-SiC纳米镀层耐磨性能预测研究

采用神经网络技术,构建结构为3×8×1型的BP神经网络模型,并利用该模型对超声电沉积Ni-SiC纳米镀层的耐磨性能进行预测。通过磨损试验测试并研究Ni-SiC纳米镀层的耐磨性能,利用扫描电镜(SEM)、原子力显微镜(AFM)和X射线衍射(XRD)观察不同参数下Ni-SiC纳米镀层的组织结构及成分。结果表明,在BP神经网络模型的隐含层数和神经元数分别为1和8时,该BP神经网络模型的均方根误差最小,其最小值为1.24%。该BP神经网络模型的预测值与实验值相差不大,其最大误差为1.51%。当采用SiC粒子浓度8 g/L、电流密度2 A/dm^2、温度40℃时,SiC粒子均匀分布于Ni-SiC纳米镀层中,且镀层镍晶粒显著细化,其镍晶粒的衍射峰变宽、变矮。