TiO2/膨胀石墨复合材料的制备及其对亚甲基兰的光催化降解

采用快速升温法制备出以膨胀石墨为载体的TiO2/膨胀石墨光催化剂,用SEM及XRD对其表面形貌及结构进行表征,研究了该负载型光催化剂在紫外光照射下的催化能力,探讨了在催化剂中TiO2的负载量、亚甲基兰溶液的初始浓度及其pH值对光催化剂的降解能力的影响.结果发现,负载量为10%的光催化剂对40mg/L的亚甲基兰溶液5h的光降解率达到58.8%.     

Fabrication of TiO2/ZnO composite nanofibers by electrospinning and their photocatalytic property

TiO₂/ZnO composite nanofibers with diameters in the range of 85–200 nm were fabricated via the electrospinning technique using zinc acetate and titanium tetra-isopropoxide as precursors, cellulose acetate as the fiber template, and N,N-dimethylformamide/acetone 1:2 (v/v) mixtures as the co-solvent. After treated with 0.1 mol/L NaOH aqueous solution, TiO₂/zinc acetate/cellulose acetate composite nanofibers were transformed into TiO₂/Zn(OH)₂/cellulose composite nanofibers. TiO₂/ZnO composite nanofibers were obtained by calcinating the hydrolyzed composite fibers at 500 and 700 °C for 5 h. The structure and morphology of composite nanofibers were characterized by scanning electron microscopy, transmission electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. With the blending of ZnO into TiO₂, a new crystallite ZnTiO₃ was formed in addition to the ZnO and TiO₂ crystallites, and the ultraviolet light absorption efficiency was enhanced according to the UV–vis diffuse reflectance spectroscopy. The photocatalytic activity of TiO₂/ZnO composite nanofibers toward the decomposition of Rhodamine B and phenol was investigated. Almost 100% Rhodamine B and 85% phenol were decomposed in the presence of TiO₂/ZnO composite nanofibers under mild conditions. The results demonstrated that the blending of ZnO in the TiO₂/ZnO composite nanofibers increased the photocatalytic efficiency. The optimum ZnO content in the TiO₂/ZnO composite nanofibers was 15.76 wt% to reach the most efficient photocatalytic activity. A schematic diagram of photocatalytic mechanism of TiO₂/ZnO composite nanofibers was also presented.     

Effect of Fe-doped TiO2 nanoparticle derived from modified hydrothermal process on the photocatalytic degradation performance on methylene blue

Anatase Fe-doped TiO2 nanoparticles with 10-15 nm particles sizes were directly prepared with amorphous TiO2 nanoparticles and Fe(NO3)3.9H2O by hydrothermal method. The TiO2 crystallite grain sizes decreased with the increase of Fe contents. When Fe contents increased, the diffuse reflectance spectra of Fe-doped TiO2 nanoparticles displayed a red shift in the band gap transition. And the absorbing band edge moved to visible range when the Fe contents were more than 2 mol%. XPS analysis showed that Fe3+ was not on the surface of TiO2 nanoparticles, but inserting into the matrix interior. As a result, the photoactivity degradation of MB on Fe-doped TiO2 nanoparticles decreased.     

ZnO/CdO composite nanorods for photocatalytic degradation of methylene blue under visible light

Nanorods of ZnO and ZnO/CdO were synthesized by thermal decomposition of their respective acetate without any catalyst at 350 °C. It is a simple and low cost method to prepare ZnO and ZnO/CdO nanorods. The decomposition temperature of acetate and the formation of oxides were determined by thermogravimetric analysis before the synthesis process. The prepared samples were characterized by different techniques. The photocatalytic activity of ZnO/CdO was tested by the degradation of methylene blue (MB) in aqueous medium under visible light and the efficiency of the catalyst has been discussed in detail. The method is simple, fast and cost effective when compared to other methods.     

Effect of TiO2 nanoparticles aggregation in silicate thin coating films on photocatalytic behavior for antifouling materials

Two types of disperser namely, a high speed agitation bead mill and a colloidal mill, were used for the dispersion behavior control of TiO₂ nanoparticles (20 nm in average primary diameter) in an aqueous suspension. A composite thin film raging in thickness from 90 to 400 nm was prepared from the coating suspension following the addition of a commercial ethyl silicate oligomer binder into the prepared suspension by means of a spray coating method. The mean aggregate size of TiO₂ nanoparticles in the aqueous suspension was found to be 80 nm and 290 nm in diameter, respectively, when using the agitated bead and colloidal milling methods. Large aggregates on the order of several hundred nanometers were found to remain in the suspension after colloidal milling. Further, a fine dispersion of TiO₂ nanoparticles in the thin film produced using the agitation bead milling process promoted the photocatalytic activity and enhanced transparency of the film for visible light. The aggregate structure of TiO₂ nanoparticles in an aqueous suspension was well maintained in the film prepared by a spray coating process.     

硫掺杂TiO2的制备及其光催化降解次甲基蓝研究

以TiCl4、(NH4)2SO4为原料,采用溶胶-凝胶法制备了硫掺杂纳米TiO2,利用XRD、TEM、FTIR等对样品进行了表征,并将其用于光催化降解次甲基蓝溶液.结果表明:制备的纳米TiO2为锐钛矿晶型,具有超强酸特征,平均粒径分布为10～30nm,S掺杂对TiO2的晶粒长大有抑制作用,经过硫掺杂的纳米TiO2光催化活性明显优于纯TiO2.     

Ag-CNT/TiO_2复合电极对亚甲基蓝的光电催化降解作用(英文)

采用金属银修饰的碳纳米管制备了Ag-CNT/TiO2复合电极。利用X-射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),和能量分散性X射线分析(EDX)对所制的Ag-CNT/TiO2复合材料进行了表征。结果表明:二氧化钛颗粒和金属银颗粒在碳纳米管上均匀分布,所制电极具有较高的光电催化性能。其对亚甲基蓝的光电催化降解归因于一种协同效应,即二氧化钛的光降解、碳纳米管网络的电子辅助、金属银的增强和外加电势的作用。尤其是,经银修饰的复合电极增强了其对亚甲基蓝的光电降解,且随银含量的增加其光电催化效果增加。     

TiO_2-海藻酸钙复合膜的表征、对染料的光催化降解及TiO_2回收

为了解决TiO2纳米粒子难分离,负载的催化剂难回收等问题,首先,将TiO2与海藻酸钠充分混合制成铸膜液,在玻璃板上刮膜,经钙离子交联制备了TiO2-海藻酸钙(T-CA)复合膜。然后,对T-CA复合膜进行了SEM和XRD表征,并研究了T-CA复合膜对染料的光催化降解性能。最后,将T-CA复合膜从染料降解液中取出,浸泡在柠檬酸钠水溶液中,柠檬酸根对钙离子的结合力较强,可使海藻酸盐水凝胶溶解,离心分离TiO2纳米粒子并清洗干燥后,得到了回收TiO2;利用SEM、TEM、FTIR和XRD对回收TiO2进行了表征。结果表明:T-CA复合膜对甲基橙的光催化降解率可达82.37%。回收TiO2与初始的TiO2几乎完全一样,可重新使用且催化能力不变。该方法是一种绿色环保、方便快速的从载体中回收TiO2纳米粒子的方法。     

Preparation of MoO3/MoS2/TiO2 composites for catalytic degradation of methylene blue

Metastable hexagonal MoO3 microrods were grown from bulk MoS2 and used as support materials for MoS2 and TiO2 nanoparticles. The hybrid composites that consisted of MoO3, MoS2, and TiO2 were prepared at a low temperature using the one-step synthesis method. The crystallinity and morphology of the MoO3/MoS2/TiO2 composites that were prepared using HNO3 and titanium tetraisopropoxide were compared with those of the MoO3/MoS2 composites that were prepared without titanium tetraisopropoxide. Titanium isopropoxide facilitated the formation of the MoO3 microrods from the oxidation of the bulk MoS2. The desired MoO3/MoS2/TiO2 composites were obtained using 0.5 g of bulk MoS2, 3-4 ml of HNO3, and 0.367 ml of titanium tetraisopropoxide. The MoO3/MoS2/TiO2 composites that were treated with ultrasonic waves showed rapid degradation of the methylene blue solution (2 x 10(-4) M) in the dark and good photocatalytic ability under ultraviolet light irradiation. The decomposition of methylene blue depended on the composition of the composite.     

炭包覆TiO2复合物对低浓度苯的光催化降解

通过将TiO2粉末和聚乙二醇混合,随后在氮气气氛下热处理合成了炭包覆TiO2.利用粉末X射线衍射、紫外-可见漫反射光谱、透射电子显微镜和氮吸附对炭包覆TiO2复合物样品进行了表征,并研究了其对浓度为～1.2×10-5苯的光催化活性.结果表明:炭包覆量受热处理温度和聚乙二醇用量的影响,随着温度的升高和聚乙二醇量的减少而减少;TiO2的结晶度随着温度的升高而提高,但是炭包覆对TiO2晶体的生长有抑制作用.炭包覆锐钛矿样品比纯TiO2表现出对苯更高的光催化活性,这是由于炭吸附作用导致锐钛矿颗粒周围的苯浓度增加以及包覆炭可导致电荷的有效分离;另一个原因是锐钛矿相结晶度的提高.因此,要获得对苯具有高光催化活性的炭包覆TiO2需要综合考虑碳含量和锐钛矿晶体结构.

Abstract：

Carbon-coated TiO2 was synthesized by mixing TiO2 powders and polyethylene glycol,followed by heat treatment in nitrogen atmosphere. All samples were characterized by powder X-ray diffraction,UV diffuse reflectance spectroscopy,high-resolution transmission electron microscopy,and nitrogen adsorption. The photocatalytic activity of carbon-coated TiO2 for benzene degradation was investigated with a benzene concentration of ～ 1.2 × 10-5. Results showed that the residual carbon content was influenced greatly by heat treatment temperature (HTT)and the amount of PEG,which decreased and increased with increasing the temperature and the amount of PEG,respectively. The crystallinity of TiO2 was improved when the HTT increased. However,the carbon residue had an inhibition effect on the crystal growth of TiO2. The carbon-coated anatase samples were shown to exhibit higher photocatalytic activities than the pristine TiO2 because of the adsorption enrichment of benzene by carbon around the anatase particles and of the effective charge separation due to the electronic conduction of carbon. Another important factor affecting photocatalytic activity was the crystallinity of the anatase phase. High photocatalytic activity for benzene requires a balance between the carbon content and the anatase crystalline structure.     

A facile synthesis of CNTs/Cu2O-CuO heterostructure composites by spray pyrolysis and its visible light responding photocatalytic properties

Carbon nanotubes (CNTs)/Cu₂O-CuO composite powder was fabricated by a spray pyrolysis (SP) method. The copper acetate monohydrate (Cu(CH₃COO)₂·H₂O) solution within CNTs dispersion was used as a precursor. The influences of decomposition temperatures, concentration of Cu(CH₃COO)₂ solutions and CNTs mass fractions on the constituent phases and microstructures of the composite powder were investigated by XRD, FESEM, TEM, UV–Vis analysis methods. The results show that the composite powder prepared at 500?°C, with the concentration of 1.0?g/l Cu(CH₃COO)₂·H₂O and 30.0?wt.% CNTs mass fraction, has the best photocatalytic performance due to the numerous particles precipitated on the CNTs surface and lower recombination rate of the photogenerated electron-hole pairs. Furthermore, tentative mechanisms of the nucleation-growth and photodegradation properties were explored based on the microstructure and photocatalytic analysis.     

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).     

Plasma emission control of reactive sputtering process in mid-frequency mode with dual cathodes to deposit photocatalytic TiO2 films

Titanium dioxide (TiO₂) films were deposited on unheated non-alkali glass substrates by reactive mid-frequency (mf) magnetron sputtering using dual cathodes with two Ti metal targets. In order to achieve a very high deposition rate, the depositions were carried out in the ‘transition region’ between the metallic and the reactive (oxide) sputter mode where the target surface was metallic and oxidized, respectively. Stable deposition was successfully carried out in the whole transition region at both total pressures of 1 Pa and 3 Pa, using the plasma control unit (PCU). The highest deposition rate in this study for the photocatalytic TiO₂ films deposited in the transition region was over 30 nm/min, which was larger than that for the conventional sputter deposition by one order of magnitude. These films could be crystallized by post-annealing in air at 200 °C. Photoinduced decomposition of acetaldehyde and photoinduced hydrophilicity was successfully demonstrated.     

CdS/CNT-TiO2光催化剂的合成及其对亚甲基蓝的光催化降解（英文）

采用多壁碳纳米管(MWCNTs)为载体,分别以醋酸镉((CH3COO)2Cd.2H2O)和硫化钠(Na2S.5H2O)为镉源和硫源,经简单逐滴滴入途径制备了CdS/CNT复合材料。再以四丁氧基钛(TNB)为钛源,苯为溶剂,成功地将二氧化钛(TiO2)纳米粒子沉积在CdS修饰的MWCNTs表面而得到CdS/CNT-TiO2光催化剂。利用N2吸附等温线、扫描电子显微镜、X射线衍射、能量分散性X射线分析以及透射电子显微镜对所制CdS/CNT-TiO2光催化剂进行表征。CdS/CNT-TiO2复合材料呈多孔结构,MWCNTs均匀分散在材料中,且未出现明显的TiO2和CdS纳米颗粒团聚体。该材料在紫外和可见光照射下对亚甲基蓝具有优异的降解活性。这不仅归因于TiO2对自由基的反应和MWCNTs吸附能力,且归因于引入窄带隙半导体CdS,使粒子在MWCNTs表面的电子转移速率得到提高。     

Enhanced photocatalytic performance of CuFeO2-ZnO heterostructures for methylene blue degradation under sunlight

One of the strategies to overcome the drawbacks of fast charge recombination of a photocatalyst is to develop semiconductor heterostructures. Herein, we report a two-step precipitation-hydrothermal process to create CuFeO₂-ZnO heterostructures with different weight percentages of CuFeO₂ (0.5, 1, 5, and 10%). Though X-ray diffraction detected the presence of CuFeO₂ on ZnO above 5%, Raman spectroscopy could reveal the presence of CuFeO₂ phase as low as 0.5 wt%. For all of the compositions, the bandgap of ZnO did not vary (3.15 eV) on forming heterostructures with CuFeO₂. The oxidation of methylene blue under sunlight was used to determine the photocatalytic performance of the heterostructures. In comparison to pure ZnO and CuFeO₂, CuFeO₂-ZnO heterostructures exhibited a better photocatalytic efficiency. Overall, 5 wt% CuFeO₂ on ZnO showed 100% degradation with a rate constant of 0.272?±?0.002 min^?1, which is 16 times faster than ZnO. Time-resolved photoluminescence analysis indicated a higher lifespan of charge carriers in the 5wt% CuFeO₂-ZnO heterostructure (32.3 ns) than that of CuFeO₂ (0.85 ns) and ZnO (27.6 ns). The Mott–Schottky flat band potentials of ZnO and CuFeO₂ was determined to be -0.82 and 1.17 eV, respectively, revealing the presence of Type I heterostructures. The heterostructures also showed outstanding recyclability, with a degradation rate of 97% even after four cycles. The current study shows the significance of forming p-type CuFeO₂ and n-type ZnO heterostructures for enhanced photocatalysis.

     

Application of carbon-coated TiO2 for decomposition of methylene blue in a photocatalytic membrane reactor

An application of carbon-coated TiO(2) for decomposition of methylene blue (MB) in a photocatalytic membrane reactor (PMR), coupling photocatalysis and direct contact membrane distillation (DCMD) was investigated. Moreover, photodegradation of a model pollutant in a batch reactor without membrane distillation (MD) was also examined. Carbon-modified TiO(2) catalysts containing different amount of carbon and commercially available TiO(2) (ST-01) were used in this study. The carbon-coated catalyst prepared from a mixture of ST-01 and polyvinyl alcohol in the mass ratio of 70/30 was the most effective in degradation of MB from all of the photocatalysts applied. Photodecomposition of MB on the recovered photocatalysts was lower than on the fresh ones. The photodegradation of MB in the PMR was slower than in the batch reactor, what probably resulted from shorter time of exposure of the catalyst particles to UV irradiation. The MD process could be successfully applied for separation of photocatalyst and by-products from the feed solution.     

Effect of metal ion dopants on photochemical properties of anatase TiO2 films synthesized by a modified sol-gel method

Anatase TiO₂ films were successfully synthesized by a modified sol-gel method wherein peroxo titanic acid solution was derived from TiCl₄/ethanol/water solution at room temperature. The as-prepared films were further surface-doped by photodeposited Fe₂O₃ and Cr₂O₃ to improve its physicochemical properties. The phase and structure of the films were investigated by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. The physicochemical properties of the films were also measured. The results show that both hydrophilicity and photocatalytic activity of the films were remarkably improved by doping transition metal ion Fe³⁺. In case of Cr³⁺ doped films, hydrophilicity was also significantly enhanced but photocatalytic activity for methyl orange under UV irradiation was still comparable with the undoped films.     

Fabrication and efficient photocatalytic degradation of methylene blue over CuO/BiVO4 composite under visible-light irradiation

CuO/BiVO₄ composite photocatalysts were prepared by solution combustion synthesis method and impregnation technique. X-ray diffraction, X-ray photoelectron spectroscopy, field-emission scan electron microscopy and UV-vis diffusion reflectance spectra were used to identify the physical properties and photophysical properties of CuO/BiVO₄ composite photocatalysts. The photocatalysts exhibit the enhanced photocatalytic properties for degradation of methylene blue under visible-light (λ > 420 nm). The mechanism of improved photocatalytic activity is also discussed.