Preparation and Characterization of Three-dimensional Photocatalyst-TiO2 Particulate Film Immobilized on Activated Carbon Fibers

A novel three-dimensional photocatalyst, TiO2 particulate film immobilized on activated carbon fibers (TiO2/ACFs), was prepared by liquid phase deposition. The photocatalyst was characterized by SEM, XRD, BET surface area and photodegradation of methylene blue solution. TiO2 particulate film, with a thickness of nearly 200 nm and grain sizes of 30~50 nm, was deposited on almost each carbon fiber. The inner space between adjacent fibers remained as unmodified ACFs, therefore, both UV illumination and polluted solutions were allowed to pass through the felt-form photocatalyst to form a three-dimensional environment for photocatalytic reactions. With BET surface areas of 400~600 m2/g, the TiO2/ACFs exhibited an enhanced adsorption of pollutants for photocatalysis. Comparative degradations indicated that photocatalytic activity of the TiO2/ACFs was slightly higher than that of Degussa P-25 TiO2. Two special properties, the three-dimensional structure and combined effects of ACFs' adsorption and titania's photodegradation, made contribution to high photocatalytic activity. Additionally, the TiO2/ACFs exhibited high stability and potentially application for practical usage.     

TiO2/SiO2气凝胶的非超临界干燥法制备及其对吡啶降解的光催化活性

TiO2/SiO2 aerogels with different molar ratio of SiO2/TiO2 were prepared via non-supercritical method using tetrabutyl titanate and silica sols as raw materials. The samples were characterized by TEM, SEM, BET, IR, XRD and so on. The results indicate that the BET surface area of TiO2/SiO2 aerogels calcined at 550℃ which consisted of anatase structure of TiO2 with narrow distribution pores of 5-25 nm is as high as 357.89 m^2·g^-1. For the photocatalytic degradation of pyridine, the catalytic activities of TiO2/SiO2 aerogels are much higher than that of TiO2 powder. The photocatalytic activity of TiO2/SiO2 aerogels calcined at 800℃ is the optimum. The higher the content of SiO2, the higher the photocatalytic activity of TiO2/SiO2 aerogels. The cost for preparation of the aerogels is greatly reduced by using non-supercritical drying method, and the aerogels are hopefully applied in the treatment of industrial waste water such as coking effluent treatment.     

纳米N掺杂TiO2的制备及可见光催化活性研究

N-doped TiO2 nanoparticle photocatalysts were prepared through a sol-gel procedure using NH4C1 as the nitrogen source and followed by calcination at certain temperature. Systematic studies for the preparation parameters and their impact on the structure and photocatalytic activity under ultraviolet （UV） and visible light irra-diation were carried out. Multiple techniques （XRD, TEM, DRIF, DSC, and XPS） were commanded to characterize the crystal structures and chemical binding of N-doped TiO2. Its photocatalytic activity was examined by the deg- radation of organic compounds. The catalytic activity of the prepared N-doped TiO2 nanoparticles under visible light （λ〉400nm） irradiation is evidenced by the decomposition of 4-chlorophenol, showing that nitrogen atoms in the N-doped TiO2 nanoparticle catalyst are responsible for the visible light catalytic activity. The N-doped TiO2 nanoparticle catalyst prepared with this modified route exhibits higher catalytic activity under UV irradiation in contrast to TiO2 without N-doping. It is suggested that the doped nitrogen here is located at the interstitial site of TiO2 lattice.     

磁性Fe3O4纳米粒子用作靶向药物载体的制备及分析

Fe3O4 magnetic nanoparticles were prepared by the aqueous co-precipitation of FeCl3-6H2O and FeCl2-4H2O with addition of ammonium hydroxide. The conditions for the preparation of Fe3O4 magnetic nanoparticles were optimized, and Fe3O4 magnetic nanoparticles obtained were characterized systematically by means of transmission electron microscope （TEM）, dynamic laser scattering analyzer （DLS） and X-ray diffraction （XRD）. The results revealed that the magnetic nanoparticles were cubic shaped and dispersive, with narrow size distribution and average diameter of 11.4 nm. It was found that the homogeneous variation of pH value in the solution via the control on the dropping rate of aqueous ammonia played a critical role in size distribution. The magnetic response of the product in the magnetic field was also analyzed and evaluated carefully. A 32.6 mT magnetic field which is produced by four ferromagnets was found to be sufficient to excite the dipole moments of 0.05 g Fe3O4 powder 2 cm far away from the ferromagnets. In conclusion, the Fe3O4 magnetic nanoparticles with excellent properties were competent for the magnetic carders of targeted-drug in future application.     

Enhanced performance of g-C3N4/TiO2 photocatalysts for degradation of organic pollutants under visible light☆

Photocatalytic degradation is one of the most promising remediation technologies in terms of advanced oxida-tion processes (AOPs) for water treatment. In this study, novel graphitic carbon nitride/titanium dioxide (g-C3N4/TiO2) composites were synthesized by a facile sonication method. The physicochemical properties of the photocatalyst with different mass ratios of g-C3N4 to TiO2 were investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), N2 sorption, Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and UV–vis DRS. The photocatalytic performances were evaluated by degradation of methylene blue. It was found that g-C3N4/TiO2 with a mass ratio of 1.5:1 exhib-ited the best degradation performance. Under UV, the degradation rate of g-C3N4/TiO2 was 6.92 and 2.65 times higher than g-C3N4 and TiO2, respectively. While under visible light, the enhancement factors became 9.27 (to g-C3N4) and 7.03 (to TiO2). The improved photocatalytic activity was ascribed to the interfacial charge transfer between g-C3N4 and TiO2. This work suggests that hybridization can produce promising solar materials for envi-ronmental remediation.     

DESIGN AND APPLICATION OF FLUIDIZED BED PHOTOCATALYTIC REACTOR

Photocatalytic degradation of organic pollutant is a new and potential method to transform it to harmless inorganic material, such as CO2 and H2O. So far, most of photocatalytic reactors were cylinder or tabulate photoreactor. The relevant photocatalyst was TiO2 nanometer powder. Although a few investigators had aimed their research field to fluidized bed reactor, their reaction systems were of biphase, such as solid-liquid or solid-gas. Few people focused their research on the triphasic fluidized bed photocatalytic reactor［1］. Compared with traditional photoreactors, a triphasic fluidized bed photoreactor has more advantages［2］: (1) The solid photocatalyst can be separated easily. (2) Its configuration meets the requirement of higher surface area-to-volume ratio of photocatalytic, which is much lower in a fixed bed or a plate photoreactor. (3) The UV light can be used more efficiently. (4) The mass transfer conditions can be controlled and improved easily. (5) It suited to pilot-scale or large-scale operations. For the UV light penetration and photon efficiency should be considered, the photocatalytic reactor differed greatly from a typical fluidized bed reactor.     

Porous TiO2-coated Magnetic Core-Shell Nanocomposites: Preparation and Enhanced Photocatalytic Activity

The core-shell structured TiO₂/SiO₂@Fe₃O₄ photocatalysts were prepared using Fe₃O₄ as magnetic core, tetraethoxysilane (TEOS) as silica source and tetrabutyl titanate (TBOT) as titanium sources. The as-obtained structure was composed of a SiO₂@Fe₃O₄ core and a porous TiO₂ shell. The diameter of SiO₂@Fe₃O₄ core was about 205 nm with thickness of porous TiO₂ of about 5-6 nm. The 9%TiO₂/6% SiO₂@Fe₃O₄ microspheres possess the highest BET surface area and the BJH pore volume, which are 373.5 m²穏^-1 and 0.28 cm³穏^-1, respectively. The 9%TiO₂/6%SiO₂@Fe₃O₄ photocatalyst exhibited an excellent performance for the degradation of methyl orange and methylene blue dyes. Two different dyes were completely decolorized in 60 min under UV irradiation. The photocatalytic activity and the amount of catalyst were almost not decrease after recycling for 6 times by using external magnetic field.     

负载金属改性活性炭纤维的脱硫性能

Metal-loaded activated carbon fibers （ACFs） were prepared by impregnation and characterized by N2 adsorption at 77K, XRD, XPS and SEM. Their properties on SO2 removal were examined in a tubular fixed bed reactor with a model flue gas. Cobalt-loaded ACF showed the best activity among the prepared metal-loaded ACFs and a constant removal ratio of SO2 above 87% during continuous exposure to the flow of SO2/O2/H2O/N2 at 45℃ for more than 216h. The characteristic of the prepared loaded-ACFs showed that the exceptional activity of Co-ACF was attributed to the high amount of active sites due to modification by loading cobalt.     

载体对镍催化剂催化间二硝基苯加氢制间苯二胺反应性能的影响

The hydrogenation of m-dinitrobenzene to m-phenylenediamine in liquid phase was studied with the nickel catalysts supported on SiO2, TiO2, γ-Al2O3, MgO and diatomite carders. Based on the experiments of X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, temperature-programmed reduction （TPR）, temperature-programmed desorption of hydrogen （H2-TPD） and activity evaluation, the physico-chemical and catalytic properties of the catalysts were investigated. Among the catalysts tested, the SiO2 supported nickel catalyst showed the highest activity and selectivity towards m-phenylenediamine, over which 97.3% m-dinitrobenzene conversion and 95.1% m-phenylenediamine yield were obtained at 373K under hydrogen pressure of 2.6MPa after reaction for 6 h when using ethanol as solvent. Although TiO2 and diatomite supported nickel catalysts also presented high activity, they had lower selectivity towards m-phenylenediamine. As for γ-Al2O3 and MgO supported catalysts were almost inactive for the object reaction. It was shown that both the activity and selectivity of the catalysts were strongly depended on the interaction between nickel and the support. The higher activities of Ni/SiO2, Ni/TiO2 and Ni/diatomite could be attributed to the weaker metal-support interaction, on which Ni species presented as crystallized Ni metal particles. On the other hand, there existed strong metal-support interaction in Ni/MgO and Ni γ-Al2O3, which causes these catalysts more difficult to be reduced and the availability of Ni active sites decreased, resulting in their low catalytic activity.     

相对湿度对不同载体的负载Cu催化剂催化燃烧甲苯的影响

The copper based catalysts, CuO/γ-Al2O3, CuO/γ-Al2O3-cordierite (Cord) and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor, and the catalysts were characterized. Temperature program desorption (TPD) experiments of toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts. The higher the concentration of the water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water mole-cules and three catalysts followed the order: CuO/γ-Al2O3>CuO/γ-Al2O3-Cord>CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order: CuO/γ-Al2O3>CuO/γ-Al2O3-Cord>CuO/Cord. However, the negative effect of the water vapor was reversible.     

磁载纳米二氧化钛光催化剂的制备及光催化性能

以共沉淀法制备纳米级Fe3O4磁载体,以SiO2为过渡层,通过溶胶-凝胶法制得包覆型光催化剂TiO2/SiO2/Fe3O4复合粒子。通过TEM、XRD、IR等测试手段对样品进行表征。以甲基橙为目标降解物,考察磁载光催化剂TiO2/SiO2/Fe3O4在紫外光下的光催化活性。结果表明,在TiO2和Fe3O4之间包覆一层无定型SiO2的TiO2/SiO2/Fe3O4的光催化活性明显优于纯TiO2和TiO2/Fe3O4的光催化活性,且具有较好的磁性,在有外加磁场时可将催化剂从溶液中分离出来,回收处理后循环使用。     

磁性纳米TiO2/SiO2/Fe3O4光催化剂的制备及光催化性能研究

以化学共沉淀法制备的纳米铁氧体Fe₃O₄ 为磁载体,采用溶胶-凝胶法制备易于固液分离回收的新型磁性纳米TiO₂/SiO₂/Fe₃O₄ 光催化剂。采用X射线衍射、透射电镜、扫描电镜、傅立叶红外变换光谱和紫外可见漫反射光谱等对催化剂进行表征。以酸性大红3R为目标降解物,对催化剂的光催化性能进行了研究。结果表明,磁性纳米TiO₂/SiO₂/Fe₃O₄ 光催化剂样品混晶中,锐钛矿相TiO₂ 占90%以上,制备的催化剂样品为层状结构,平均颗粒粒径约为(50~80) nm,呈现顺磁性,在外加磁场的作用下,催化剂可与液相迅速分离。同时,磁性纳米TiO₂/SiO₂/Fe₃O₄ 光催化剂具有较强的光催化活性,在光催化剂用量0.5 g·L^-1 、溶液初始浓度100 mg·L^-1 和光催化反应120 min条件下,酸性大红3R降解率达95%。     

Preparations and photocatalytic properties of magnetically separable nitrogen-doped TiO2 supported on nickel ferrite

A magnetically separable nitrogen-doped photocatalyst TiO_2−xN_x/SiO₂/NiFe₂O₄ (TSN) with a typical ferromagnetic hysteresis was prepared by a simple process: the magnetic SiO₂/NiFe₂O₄ (SN) dispersion prepared by a liquid catalytic phase transformation method and the visible-light-active photocatalyst TiO_2−xN_x were mixed, sonificated, dried, and calcined at 400 °C. The prepared photocatalyst is photoactive under visible light irradiation and easy to be separated from a slurry-type photoreactor under the application of an external magnetic field, being one of promising photocatalysts for wastewater treatment. Transmission electron microscope (TEM) and X-ray diffractometer (XRD) were used to characterize the structure of the TSN photocatalyst. The results indicate that the magnetic SiO₂/NiFe₂O₄ (SN) nanoparticles adhere to the surface of TiO_2−xN_x congeries. The magnetic photocatalyst TSN shows high catalytic activity for the degradation of methyl orange in water under UV and visible light irradiation (λ > 400 nm). SiO₂ coating round the surface of NiFe₂O₄ nanoparticles prevents effectively the injection of charges from TiO₂ particles to NiFe₂O₄, which gives rise to the increase in photocatalytic activity. Moreover, the recycled TSN exhibits a good repeatability of the photocatalytic activity.     

微乳液法制备纳米SiO2/TiO2及其光催化性能

以无机物聚合硅酸为硅源、硫酸钛为钛源,采用微乳液法制备了SiO2/TiO2复合光催化剂,考察了制备条件对SiO2/TiO2光催化活性的影响,并利用SEM、FTIR、XRD和BET等技术手段对光催化剂进行了表征。结果证明,SiO2和TiO2颗粒之间存在着强的相互作用,形成了Ti-O-Si键,从而抑制了TiO2粒径的增大,延缓了TiO2由锐钛矿相向金红石相的转变。对甲基橙等染料的光催化降解实验结果表明,SiO2/TiO2的光催化活性并非随着TiO2的含量增加而提高,当硅与钛物质的量比为1∶1并在160℃的温度下水热合成2.5 h时,SiO2/TiO2光催化剂在紫外光照15 min后对甲基橙的脱色率为85.5%,与同等条件下制备的TiO2相比具有更好的光催化活性和更大的比表面积。     

TiO2/SiO2/Fe3O4的光催化性能及动力学

采用溶胶－凝胶法在表面包覆了SiO2的磁基体Fe3O4上负载TiO2,制备了复合光催化剂TiO2/SiO2/Fe3O4。用AFM和XRD等对其进行了表征,并对其光催化降解溴氨酸的pH值、催化剂加入量、初始溶液浓度等条件进行了探讨。结果表明,当pH＝4.0、催化剂用量为2.0 g/L、初始溶液浓度为30 mg/L、光照时间为30 min时,溴氨酸脱色率可达96.2％,COD去除率为85.1％;动力学研究表明：在实验浓度范围内,溴氨酸的光催化降解反应符合一级动力学规律,反应速率常数（k）与初始溶液浓度（c0）的关系为lnk =－0.171lnc0－2.360;经过4次循环使用后,复合光催化剂仍能保持较高的光催化活性和较高的回收率。     

纳米磁载催化剂WO3/TiO2/SiO2/Fe3O4的制备及其光催化性能

以硫酸铁铵为原料,通过水解-还原法制备了磁基体Fe3O4,采用溶胶-凝胶法得到易于磁分离回收的纳米磁载光催化剂WO3/TiO2/SiO2/Fe3O4,利用TEM进行了表征.研究了焙烧温度、WO3掺杂量等因素对光催化剂催化活性的影响.在紫外灯照射下该催化剂对亚甲基蓝1 h的脱色率可达93%以上.     

以稻壳-TiO_2为原料化学活化制备TiO_2/SiO_2/AC光催化剂

以钛酸四丁酯[Ti(OBu)4]为钛源,采用溶胶-凝胶法将TiO2前驱体负载于稻壳表面,进一步以该复合物为原料,经炭化和KOH化学活化制得具有可见光激发活性的活性炭负载TiO2/SiO2光催化剂。以对亚甲基蓝的脱色率为依据探讨了钛酸四丁酯的用量及煅烧温度对催化剂光催化性能的影响。利用傅立叶变换红外光谱、扫描电镜及X射线衍射等测试手段对光催化剂的结构、表面形态及晶相结构进行了表征。结果表明,TiO2晶型为锐钛矿相结构,并且与SiO2作用形成了Ti—O—Si键。     

Fabrication of Bifunctional Titania/Silica-Coated Magnetic Spheres and their Photocatalytic Activities

A magnetic photocatalyst is prepared by coating a magnetic core with a dual layer of inert silica (SiO₂) and photoactive titania (TiO₂). The complete photoactive TiO₂ shell is directly formed on the SiO₂-coated magnetic spheres. Subsequent hydrothermal treatment improves the degree of crystallinity of TiO₂. TiO₂/SiO₂-coated magnetic spheres show good photocatalytic activities in the degradation of methylene blue in the aqueous solution. The photocatalytic TiO₂ surface shell is electrically insulated by the intermediate SiO₂ layer from the magnetic core to maintain good photocatalytic activity of the TiO₂ shell. The magnetic photocatalyst can be easily recovered by applying external magnetic field.     

光催化自洁涂料的制备及其光活性研究

以钛酸四丁酯、正硅酸乙酯作为前驱体,通过溶胶—凝胶二步水解法制备了TiO2/SiO2复合物,并以此为光催化剂,创新性地将其应用于丙烯酸清漆,制成光催化自洁涂料。以亚甲基蓝为降解对象,考察了自洁涂料的光催化性能。光催化研究表明：与单一的锐钛型TiO2相比,添加TiO2/SiO2复合物的涂料具有更强的光催化性能,添加量为3%（质量分数,下同）时对亚甲基蓝的降解性能最好。     

可见光响应的铁掺杂二氧化钛的制备及其光催化性能研究

以硝酸铁、硫酸氧钛为出发原料,通过直接化学法合成了锐钛矿型的Fe掺杂的Ti O2纳米光催化剂;通过X射线衍射仪、傅里叶红外光谱仪、紫外-可见-近红外分光光度计、热差热重分析仪对样品的结构以及性能进行了表征。结果表明:Fe掺杂的纳米Ti O2光催化剂的紫外吸收光谱和纯Ti O2相比,吸收带边发生红移,光响应范围拓展到在可见光区域;Fe的掺杂可以提高Ti O2的光催化性能,其中1%的Fe-Ti O2对亚甲基蓝的光催化活性最高。在模拟可见光条件下,Fe-Ti O2表现出了较优的光催化性能,光照10 min后,降解率高达83.9%。