纳米二氧化钛的制备及其光催化性能

分别采用水热法和溶胶-凝胶法制备了TiO2纳米粉体;利用X射线衍射仪和扫描电镜分析了两种方法制备的TiO2粉体的形貌和晶体结构,并测定了纳米TiO2粉体对罗丹明B的光催化降解活性.结果表明:采用水热法制备的TiO2纳米粉体含有锐钛矿相和金红石相,粒径较小,大约为50nm,而且分散均匀,光催化性能良好;采用溶胶-凝胶法制备的TiO2粉体经过550℃煅烧后仍然为锐钛矿相,而且粒径较大,大约为80nm.     

Preparation and photocatalytic activity of B,Ce Co-doped TiO2 hollow fibers photocatalyst

A series of B, Ce co-doped TiO₂ (B, Ce-TiO₂) photocatalytic materials with a hollow fiber structure were successfully prepared by template method using boric acid, ammonium ceric nitrate and tetrabutyltitanate as precursors and cotton fibers as template, followed by calcination at 500°C in an N₂ atmosphere for 2 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD), nitrogen adsorption-desorption measurements, and UV-visible spectroscopy (UV-Vis) were employed to characterize the morphology, crystal structure, surface structure, and optical absorption properties of the samples. The photocatalytic performance of the samples was studied by photodegradation phenol in water under UV light irradiation. The results showed that the TiO₂ fiber materials have hollow structures, and the fiber structure materials showed better photocatalytic properties for the degradation of phenol than pure TiO₂ under UV light. In the experiment condition, the photocatalytic activity of B, Ce co-doped TiO₂ fibers was optimal of all the prepared samples. In addition, the possibility of cyclic usage of B, Ce co-doped TiO₂ fiber photocatalyst was also confirmed, the photocatalytic activity of TiO₂ fibers remained above 90% of that of the fresh sample after being used four times. The material was easily removed by centrifugal separation from the medium. It can therefore be potentially applied for the treatment of water contaminated by organic pollutants.     

Carbon-containing nano-titania prepared by chemical vapor deposition and its visible-light-responsive photocatalytic activity

Ultraviolet and visible-light-responsive titania was synthesized and employed in the NO_x photomineralization. A thermal decomposition reaction of titanium isopropoxide was carried out with a metal-organic chemical vapor deposition (MOCVD), enabling continuous production of TiO₂ nanoparticles. Carbon-containing titanium dioxide with the anatase phase prepared at 500 °C under nitrogen atmosphere exhibited high photocatalytic activity for NO oxidation under visible-light illumination. Experimental results indicate that up to 48% removal of NO_x can be achieved in a continuous flow type of reaction system under visible-light illumination (green LED). The chamber temperature in this MOCVD process plays an important role in lattice structure formation, and also affected TiO₂ carbon content. The carbonaceous species on the TiO₂ surface, shown by X-ray diffractometry (XRD), and Raman, UV–vis, and X-ray photoelectron spectroscopies (XPS), is important to the visible-light absorption and visible-light-catalytic mineralization of NO_x.     

介孔二氧化钛的合成及其对甲基橙降解的光催化活性

以十六烷基三甲基溴化铵为模板剂,通过水解钛酸正丁酯合成了介孔二氧化钛分子筛,探讨了合成条件的影响。采用X射线粉末衍射(XRD)、红外光谱(FT-IR)、透射电子显微镜(TEM)和N2吸附-脱附等技术对介孔二氧化钛的晶相、结构、形貌、比表面积和孔径分布进行了表征。实验结果表明:得到的介孔二氧化钛分子筛的孔径为4-4.3nm,用抽提的方法去除模板剂得到的介孔二氧化钛的比表面积比焙烧的要高。以甲基橙为模型污染物,检验了所合成介孔二氧化钛的光催化性质。     

Long TiO2 hollow fibers with mesoporous walls: sol-gel combined electrospun fabrication and photocatalytic properties

Long TiO2 hollow fibers with mesoporous walls have been fabricated with the sol-gel combined two-capillary spinneret electrospinning technique using a triblock copolymer (Pluronic, P123, (H(C2H5O)20(C3H7O)70 (C2H5O)20OH) as a pore-directing agent. The as-prepared hollow fibers were as long as 30 cm with an outer diameter of 0.1-4 microm and wall thickness of 60-500 nm. The diameters and wall thicknesses of the hollow fibers could be tuned by adjusting the electrospinning parameters. The fiber walls were composed of mesopores 6.7 nm in diameter as calculated from the N2 adsorption/desorption isotherm. The high-resolution TEM (HR-TEM) images exhibited that the mesopores were hexagonally aligned with a low order because of the curving of the pores. When comparing with other nanostructured TiO2 materials such as commercial TiO2 nanoparticles (P25, Degussa) and mesoporous TiO2 powders, the hollow fibers exhibited higher photocatalytic activities toward degradation of methylene blue and gaseous formaldehyde.     

Effect of the composition and structure of titanosilicas on their photocatalytic activity in the decomposition of methylene blue

A comparison is made of the catalytic activity of the titanosilicas produced by pyrogenic synthesis and by the deposition of TiO₂ on pyrogenic SiO₂ in the photocatalytic decomposition of methylene blue (MB). The deposited titanosilicas exhibit high catalytic activity in the decomposition of MB as a result both of textural features and of the presence mainly of the anatase phase in the deposited TiO₂ compared with the pyrogenic titanosilicas. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 42, No. 1, pp. 23–28, January–February, 2006.     

Surface orientation effect of asymmetric polyimide hollow fibers on their gas transport properties

In this study, we focused on the shear stress effects within a spinneret during hollow fiber spinning on the formation of the hollow fibers and their gas transport properties. We fabricated asymmetric polyimide hollow fibers with a completely defect-free thin skin layer using a dry/wet phase inversion process. The apparent calculated skin layer thickness of the hollow fiber was 280 nm and the O₂ permeance was 2.9×10⁻⁵ cm³ (STP)/(cm² s cmHg). Interestingly, the skin layer thickness was reduced at the high shear rate. In addition, the gas permeances and selectivities of the hollow fibers increased with the increasing shear rate. We concluded that the oriented skin layer of the hollow fiber induced by shear stress had a significant influence on the formation of the skin layer and its gas transport properties. From the ATR-IR spectra results, it was clear that the surface skin layer of the hollow fiber was parallel oriented.     

Crystallization and photovoltaic properties of titania-coated polystyrene hybrid microspheres and their photocatalytic activity

The hybrid microspheres with polystyrene core coated by titania nanoparticles were prepared by miniemulsion polymerization, and the as-prepared samples were characterized by SEM, XRD, TG-DTA, XPS, and SPS techniques. TiO2 nanoparticles experienced two processes of phase transition, i.e., amorphous to anatase and anatase to rutile at the calcining temperature range from 400 to 1000 degrees C. The phase transformation temperature of TiO2 hybrid microspheres from anatase to rutile was increased by about 300 degrees C due to the blocking function of calcined polymer remainder. SPS results present that the band-gap of hybrid microspheres is 3.2-3.4 eV, which is larger than that of pure TiO2. The maximum intensity of the SPS signal is about 3 times larger for the hybrid material as compared to the pure TiO2. In addition, the photocatalytic degradation rate of TiO2 hybrid microspheres was 15% faster than that of pure TiO2 in the experiment of the photocatalytic degradation of methyl orange.     

Facile synthesis of SrTiO3 hollow microspheres built as assembly of nanocubes and their associated photocatalytic activity

SrTiO(3) hollow microspheres built by regular nanocubes were synthesized by a general and facile hydrothermal method. The resulting samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) measurements. Owing to the special hollow structure, the synthesized SrTiO(3) microspheres exhibit a superior photocatalytic activity in photoreduction of Cr(VI). As anatase and titanate contain common structural features, it makes this in situ phase transition from anatase to titanate relatively easy. Therefore, this method is rather convenient for controlling the morphology of the products by varying the presynthesized anatase TiO(2) precursor.     

Self-assembled mesoporous hierarchical-like In2S3 hollow microspheres composed of nanofibers and nanosheets and their photocatalytic activity

Novel template-free hierarchical-like In(2)S(3) hollow microspheres were synthesized using thiosemicarbazide (NH(2)NHCSNH(2)) as both a sulfur source and a capping ligand in a ethanol/water system. In this study, we demonstrate that several process parameters, such as the reaction time and precursor ratio, strongly influence the morphology of the final product. The In(NO(3))(3)/thiosemicarbazide ratios were found to effectively play crucial roles in the morphologies of the hierarchical-like In(2)S(3) hollow microsphere nanostructure. With the ratios increasing from two to four, the In(2)S(3) crystals exhibited almost spherical morphologies. The synthesized products have been characterized by a variety of methods, including X-ray powder diffraction (XRD), Raman spectroscopy, field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), energy-dispersive X-ray (EDX) analysis, X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible diffused reflectance spectroscopy (UV-vis DRS). XRD analysis confirmed the tetragonal structure of the In(2)S(3) hollow microspheres. The products show complex hierarchical structures assembled from nanoscale building blocks. The morphology evolution can be realized on both outside (surface) and inside (hollow cavity) the microsphere. The surface area analysis showed that the porous In(2)S(3) possesses a specific surface area of 108 m(2)/g and uniform distribution of pore sizes corresponding to the size of pores resulting from the self-assembled structures with flakes. The optical properties of In(2)S(3) were also investigated by UV-vis DRS, which indicated that our In(2)S(3) microsphere samples possess a band gap of ～1.96 eV. Furthermore, the photocatalytic activity studies revealed that the synthesized In(2)S(3) hollow microspheres exhibit an excellent photocatalytic performance in rapidly degrading aqueous methylene blue dye solution under visible light irradiation. These results suggest that In(2)S(3) hollow microspheres will be an interesting candidate for photocatalytic detoxification studies under visible light radiation.     

Structural characterization and photocatalytic activity of hollow binary ZrO2/TiO2 oxide fibers

The formation of hollow binary ZrO₂/TiO₂ oxide fibers using mixed precursor solutions was achieved by activated carbon fibers templating technique combined with solvothermal process. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N₂ adsorption, X-ray photoelectron spectroscopy (XPS), UV-vis, and infrared (IR) spectroscopy. The binary oxide system shows the anatase-type TiO₂ and tetragonal phase of ZrO₂, and the introduction of ZrO₂ notably inhibits the growth of TiO₂ nanocrystallites. Although calcined at 575 °C, all hollow ZrO₂/TiO₂ fibers exhibit higher surface areas (>113 m²/g) than pure TiO₂ hollow fibers. The Pyridine adsorption on ZrO₂/TiO₂ sample indicates the presence of stronger surface acid sites. Such properties bring about that the binary oxide system possesses higher efficiency and durable activity stability for photodegradation of gaseous ethylene and trichloromethane than P25 TiO₂. In addition, the macroscopic felt form for the resulting materials is more beneficial for practical applications than traditional catalysts forms.     

Fabrication and photocatalytic properties of SnO2 double-shelled and triple-shelled hollow spheres

SnO₂ double-shelled and triple-shelled hollow spheres were tailored by adjusting concentration of tin (IV) chloride solution during the process of the tin (IV) ions infused carbonaceous spheres. The structures of these SnO₂ multi-shelled hollow spheres were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and their possible formation mechanism were also discussed. In virtue of triple-shelled hollow porous structure and higher specific surface area, SnO₂ triple-shelled hollow spheres exhibited enhanced photocatalytic properties compared to SnO₂ double-shelled hollow spheres.     

Au-ZnO hybrid nanopyramids and their photocatalytic properties

We successfully synthesized Au-ZnO hybrid nanoparticles with a novel hexagonal pyramid-like structure. The growth process of the as-prepared hybrid nanopyramids is clearly discussed. Because of their homogeneous composition and controlled morphology, the Au-ZnO hybrid nanopyramids demonstrate better photocatalytic efficiency than pure ZnO nanocrystals.     

Synthesis and photocatalytic activity of single-crystalline hollow rh-In2O3 nanocrystals

We report here for the first time the hollow, metastable, single-crystal, rhombohedral In(2)O(3) (rh-In(2)O(3)) nanocrystals synthesized by annealing solvothermally prepared InOOH solid nanocrystals under ambient pressure at 400 °C, through a mechanism of the Kirkendall effect, in which pore formation is attributed to the difference in diffusion rates of anions (OH(-) and O(2-)) in a diffusion couple. The InOOH solid nanocrystals were prepared via a controlled hydrolysis solvothermal route by using In(NO(3))(3)·4.5H(2)O as a starting material and glycerol-ethanol as a mixed solvent. The glycerol-ethanol mixed solvent plays a key role on the formation of the intermediate InOOH, thus the final product of rh-In(2)O(3). The as-synthesized In(2)O(3) nanocrystals present excellent photocatalytic degradation of rhodamine B (RhB) and methylene blue (MB) dyes, which present ～92% degradation of RhB or MB after 4 or 3 h reaction in the presence of the as-synthesized In(2)O(3) nanocrystals, respectively.     

A facile method to fabricate ZnO hollow spheres and their photocatalytic property

This paper presents a novel and facile method for the fabrication of ZnO hollow spheres. In this approach, zinc ions were first adsorbed onto the surfaces of sulfonated polystyrene core-shell template spheres, and then reacted with NaOH to form a ZnO crystal nucleus, which was followed by a growth step to form ZnO nanoshells. During the formation of ZnO nanoshells or later on, the template spheres were "dissolved" in the same media to obtain ZnO hollow spheres directly. Neither additional dissolution nor calcination process was needed in this method to remove the templates, and the reaction conditions were very mild: neither high temperature nor long time was needed. Transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and Brunauer-Emmett-Teller analysis were used to investigate the morphology, surface composition, crystalline structure, specific surface area, and porosity of the ZnO hollow spheres, respectively. UV-visible spectra show that these ZnO hollow spheres had very good photocatalytic activity.     

Basic properties of alkaline earth metal oxides and their catalytic activity in the decomposition of diacetone alcohol

The effect of CO₂ adsorption on the catalytic activity of alkaline earth metal oxides in the title reaction reveals that the number of active (basic) sites follows the order MgO>CaO>SrO>BaO, and the order of base strength is MgO

CO₂ , () : MgO>CaO>SrO>BaO, : MgO     

La掺杂 BiFeO3对苯酚光催化降解性能的影响

苯酚是一种稳定、毒性大且难降解的有机物,对人类和生态环境产生很大威胁,因此急需研发出能有效移除工业废水中苯酚污染物的方法.其中,绿色、高效的光催化氧化技术得到研究人员青睐.在半导体光催化剂中, BiFeO3具有带隙窄(2.2–2.5 eV)、化学稳定性好及成本低等优点,被看作是最有潜力的光催化剂.但是, BiFeO3存在光生电子空穴对复合率高,制备过程中易形成杂质相的缺点,使得其光催化活性很差,限制了 BiFeO3在光催化领域的应用.异种离子的引入能产生杂质能级或裁剪半导体带隙,同时促进光生载流子分离,故可考虑采用离子掺杂改性 BiFeO3的手段来抑制杂质相生成,提高载流子分离,从而提高 BiFeO3的光催化性能.本文以柠檬酸为络合剂,通过一步溶胶凝胶法合成了系列样品 Bi1-xLaxFeO3(摩尔分数x =0,0.10,0.15,0.20).通过 X射线衍射(XRD)、扫描电镜(SEM)、能谱(EDS)、透射电镜(TEM)、X射线光电子能谱(XPS)、紫外可见漫反射(UV-Vis DRS)及荧光光谱(PL)等手段对不同样品的物相、形貌、表面价态和光学性能进行了表征.并通过活性物种捕获实验和羟基自由基(?OH)产生实验分析了 Bi0.85La0.15FeO3样品在苯酚降解过程中的主要活性物种和降解机理.相对于单相 BiFeO3, La改性 BiFeO3催化剂的光降解苯酚性能均有提高,其中 La最佳掺杂量为0.15.在模拟太阳光下照射180 min后, Bi0.85La0.15FeO3的光催化活性达到96%,同时 COD去除率达到81.53%,并表现出好的循环使用活性和稳定性.研究发现,该光催化过程中主要的活性物种为?OH. XRD, SEM, TEM和 EDS结果表明, La元素掺杂进 BiFeO3结构中,且各元素分布均匀,同时,适量 La元素掺杂能有效抑制杂质相 Bi25FeO40的形成,而且 La掺杂 BiFeO3样品的颗粒尺寸略有减小,有利于电子空穴转移. XPS显示, La改性 BiFeO3样品的表面有氧空位形成,将有利于有机物的吸附和降解;另外,羟基氧和吸附氧含量增大,有利于活性氧物种形成. UV-Vis DRS和 PL测试证明, La改性后的样品对可见光的响应增强,样品带隙变窄,产生杂质能级,抑制了光生载流子复合,有利于产生更多载流子来促进活性物种形成,从而提高光催化活性.氧物种捕获实验说明,在 Bi0.85La0.15FeO3参与的苯酚降解过程中的主要活性物种是?OH,同时?OH的产生实验也证明了在光照下?OH在 Bi0.85La0.15FeO3光催化剂表面持续产生,并提出了光催化降解机理.     

The influence of cobalt doping on photocatalytic nano-titania: Crystal chemistry and amorphicity

Photocatalysts of nominal composition (Ti_1−xCo_x)O_2−δ with 0.001?x?0.05 were prepared via a sol-gel technique followed by air firing (200-1000 °C). The incorporation of cobalt inhibited crystal growth and slightly raised the anatase to rutile transformation temperature (∼700 °C). An amorphous component was invariably significant with the maximum content (41-53 wt%) appearing simultaneously with the removal of anatase, suggesting that rutile crystallizes via an aperiodic structure. While the introduction of cobalt shifted the apparent band gap to visible light energies this did not enhance performance as there was limited miscibility of cobalt in titania, non-catalytic secondary phases were present, and active Ti³⁺ sites were displaced by cobalt.     

Physical and mechanical properties of ultra-oriented high-density polyethylene fibers

Ultra-oriented high-density polyethylene fibers (HDPE) have been prepared by solid-state extrusion over 60–140°C range using capillary draw ratios up to 52 and extrusion pressures of 0.12 to 0.49 GPa. The properties of the fibers have been assessed by birefringence, thermal expansivity, differential scanning calorimetry, x-ray analysis, and mechanical testing. A maximum birefringence of 0.0637 ± 0.0015 was obtained, greater than the calculated value of 0.059 for the intrinsic birefringence of the orthorhombic crystal phase. The maximum modulus obtained was 70 GPa. The melting point, density, crystallinity, and negative thermal expansion coefficient parallel to the fiber axis all increase rapidly with draw ratio and at draw ratios of 20–30 attain limiting values comparable with those of a polyethylene single crystal. The properties of the fibers have been analyzed using the simple rule of mixtures, assuming a two-phase model of crystalline and noncrystalline microstructure. The orientation of the noncrystalline phase with draw ratio was determined by birefringence and x-ray measurements. Solid-state extrusion of HDPE near the ambient melting point produced a c-axis orientation of 0.996 and a noncrystalline orientation function of 0.36. Extrusion 50°C below the ambient melting point produced a decrease in crystallinity, c-axis orientation, melting point, and birefringence, but the noncrystalline orientation increased at low draw ratios and was responsible for the increased thermal shrinkage of the fibers.     

Surface properties and photocatalytic activity of nanocrystalline titania films

In this work the efficiency and physicochemical details of a thin film produced by help of a microwave assisted sol gel technique is compared to different commercial powders (Degussa P25 and Hombikat UV100) deposited on glass substrates. Furthermore, a supercritical produced TiO₂ powder (SC 134) was included in the comparison.The prepared TiO₂ films were characterized using XRD, XPS, AFM, DSC and DLS. The photocatalytic activity was determined using stearic acid as a model compound. Investigation of the prepared films showed that the Degussa P25 film and the sol–gel film were the most photocatalytic active films. The activity of the films was found to be related to the crystallinity of the TiO₂ film and the amount of surface area and surface hydroxyl groups. Based on the XPS investigation of the films before and after UV irradiation it was suggested that the photocatalytic destruction of organic matter on TiO₂ films proceeds partly through formation of hydroxyl radicals which are formed from surface hydroxyl groups created by interactions between adsorbed water and vacancies on the TiO₂ surface. Furthermore a correlation between the amount of OH groups on the surface of the different TiO₂ films and the photocatalytic activity was found.