MCM-41分子筛担载纳米TiO2复合材料光催化降解罗丹明B

采用溶胶-凝胶法将TiO2担载在介孔MCM-41分子筛上, 制备了不同TiO2含量的系列TiO2/MCM-41复合材料, 利用X射线衍射、N2吸附、紫外-可见光谱和透射电镜等方法对其进行表征. TiO2的晶型为锐钛矿相, 复合材料的比表面积和孔体积随其中TiO2担载量(复合材料中TiO2与MCM-41的质量比)的增加而减小, TiO2的平均粒径随其担载量的增加而增大. 以罗丹明B的光催化降解为探针反应, 评价了TiO2/MCM-41复合材料的光催化降解活性. 结果表明, 在紫外光照射下, 罗丹明B在该复合材料上的光催化降解反应遵循一级反应动力学, 复合材料对罗丹明B的光催化降解活性明显高于商用TiO2 (P-25), 复合材料的光催化降解活性由复合材料的吸附能力和所含TiO2的光催化活性共同决定.     

Titania supported gold nanoparticles as photocatalyst

This Perspective is focused on the photocatalytic activity of gold nanoparticles supported on titania (Au/TiO(2)). Titania is the most widely used photocatalyst, but its limited activity under visible light irradiation has motivated the quest for modified titania materials absorbing visible light. The review starts by justifying how doping with metallic elements is a related strategy, but different, to that leading to the use of Au/TiO(2) in photocatalysis. Data supporting and confirming the photoactivity of gold nanoparticles in colloidal solutions are briefly presented to justify the possibility of gold photosensitization of titania by electron injection into the conduction band. After describing the most common procedures used to prepare Au/TiO(2), the central part of this article is focused on the photocatalytic activity reported for Au/TiO(2) for hydrogen generation, dye decoloration, phenol decomposition and carboxylic acid degradation, among other processes. Emphasis is given to the role that parameters like Au loading, particle size, surface area, spatial structuring and others play on the photocatalytic activity. One important issue has been to distinguish those reports using visible light from those other in which direct titania excitation by UV light has been used. These Au/TiO(2) photocatalysts can find real applications in the near future for environmental remediation and for hydrogen generation.     

Photocatalytic activity of a hierarchically macro/mesoporous titania

Light-harvesting macroporous channels have been successfully incorporated into a mesoporous TiO(2) framework to increase its photocatalytic activity. This bimodal porous material was characterized by X-ray diffractometry in both low-angle and wide-angle ranges, N(2) adsorption-desorption analysis, scanning and transmission electron microscopy, FT-IR, and diffuse reflectance spectroscopy. Ethylene photodegradation in gas-phase medium was employed as a probe reaction to evaluate the photocatalytic reactivity of the catalysts. The results reveal that sintering temperature significantly affects the structural stability and photocatalytic activity of titania. The catalyst which calcined at 350 degrees C possessed an intact macro/mesoporous structure and showed photocatalytic reactivity about 60% higher than that of commercial P25 titania. When the sample was calcined at 500 degrees C, the macroporous structure was retained but the mesoporous structure was partly destroyed. Further heating at temperatures above 600 degrees C destroyed both macro- and mesoporous structures, accompanied by a loss in photocatalytic activity. The high photocatalytic performance of the intact macro/mesoporous TiO(2) may be explained by the existence of macrochannels that increase photoabsorption efficiency and allow efficient diffusion of gaseous molecules.     

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.     

Synthesis and characterization of Nano titania particles embedded in mesoporous silica with both high photocatalytic activity and adsorption capability

TiO(2)-xSiO(2) composites with a high specific surface area (up to 645 m(2)/g), large pore volume, and narrow distribution with average pore sizes ranging from 15 to 20 A have been synthesized by the sol-gel method. The results of characterization by XRD, BET, TEM, FTIR, and DRUV reveal that these TiO(2)-xSiO(2) composites exhibit a core/shell structure of a nano titania/Ti-O-Si species modified titania embedded in mesoporous silica. As compared to pure anatase, the embedding of nano titania particles into the mesoporous silica matrix results in a substantial blue shift of absorption edge from 3.2 to 3.54 eV and higher UV absorption intensity, which are attributed to the formation of the Ti-O-Si species modified titania in the interface between titania and silica. The as-synthesized TiO(2)-xSiO(2) composites exhibit both much higher absorption capability of organic pollutants and better photocatalytic activity for the photooxidation of benzene than pure titania. The better photocatalytic activity of as-synthesized TiO(2)-xSiO(2) composites than pure titania is attributed to their high surface area, higher UV absorption intensity, and easy diffusion of absorbed pollutants on the absorption sites to photogenerated oxidizing radicals on the photoactive sites.     

Bismuth-doped ordered mesoporous TiO2: visible-light catalyst for simultaneous degradation of phenol and chromium

A controllable and reproducible synthesis of highly ordered two-dimensional hexagonal mesoporous, crystalline bismuth-doped TiO(2) nanocomposites with variable Bi ratios is reported here. Analyses by transmission electron microscopy, X-ray diffraction, Raman, and X-ray photoelectron spectroscopy reveal that the well-ordered mesostructure is doped with Bi, which exists as Bi(3+) and Bi((3+x+)). The Bi-doped mesoporous TiO(2) (ms-TiO(2)) samples exhibit improved photocatalytic activities for simultaneous phenol oxidation and chromium reduction in aqueous suspension under visible and UV light over the pure ms-TiO(2), P-25, and conventional Bi-doped titania. The high catalytic activity is due to both the unique structural characteristics and the Bi doping. This new material extends the spectral response from UV to the visible region, and reduces electron-hole recombination, which renders the 2.0% Bi-doped ms-TiO(2) photocatalyst highly responsive to visible light.     

载钛中孔二氧化硅分子筛的光催化性能研究

分别 以单一 Ｔｉ Ｏ２ 纳米粒 子及不 同 Ｔｉ Ｏ２ 覆 盖率的中 孔分 子筛（ Ｔｉ Ｏ２／ Ｈ Ｍ Ｓ） 和微 孔分 子筛（ Ｔｉ Ｏ２／ Ｎａ Ｙ） 为光催 化剂,以２ ,４ ,６三氯苯 酚（ Ｔ Ｃ Ｐ） 为 降解对象 ,考察了 两类分子 筛担 载 Ｔｉ Ｏ２ 的光催化性 能． 结 果表明 ： 在钛 含量相 同的 条 件下 , Ｔｉ Ｏ２／ Ｈ Ｍ Ｓ 的光 催 化活 性 高于 Ｔｉ Ｏ２／ Ｎａ Ｙ 和 单一 Ｔｉ Ｏ２ 的光催 化活性; Ｔｉ Ｏ２ 负载量 较低时 , Ｔｉ Ｏ２／ Ｈ Ｍ Ｓ 即可 显示 有高 的光 催化 活性, 且其 光催 化活性随着 中孔分 子筛孔径 的增大而 升高     

A sonochemical approach to hierarchical porous titania spheres with enhanced photocatalytic activity

A novel sonochemical approach has been developed to prepare hierarchical porous titania spheres in the presence of a triblock copolymer; it was found that textural meso- and macro-porosity could enhance the photocatalytic activity of mesoporous TiO2.     

Preparation, characterization, and photocatalytic activity of sulfate-modified titania for degradation of methyl orange under visible light

Hydrated titania was prepared by a sol-gel method, taking tetraisopropyl orthotitanate as starting material, and then promoted with different weight percentages of sulfate by an incipient wetness impregnation method. The materials were characterized by various advanced techniques such as PXRD, BET surface area, N(2) adsorption-desorption measurements, FTIR, and SEM. Analytical results demonstrated that TiO(2) is mesoporous in nature, and sulfate modification could inhibit the phase transformation and enhance the thermal stability of TiO(2). It was also found that sulfate modification could reduce the crystallite size and increase the specific surface area of the catalysts. The degradation of methyl orange under solar radiation was investigated to evaluate the photocatalytic activity of these materials. Effects of different parameters such as pH of the solution, amount of catalyst, additives, and kinetics were investigated. At 2.5 wt% sulfate loading, the average percentage of degradation of methyl orange was nearly two times than that of neat TiO(2). The photocatalytic degradation followed first-order kinetics.     

TiO~2修饰的介孔分子筛MCM-41的合成、表征及光 催化性研究

首次以三种不同的含钛有机物为氧化钛的前驱体,合成了三种TiO~2呈单层分散状态的TiO~2修饰的介孔分子筛MCM-41,并以XRD,FT-IR,液氮温度下N~2吸附-脱附曲线,固体UV-vis漫反射等表征手段对其结构特征和氧化钛分散状态进行了研究。TiO~2在介孔分子筛MCM-41孔道中分散,MCM-41仍能保持骨架结构,没有晶相TiO~2生成;TiO~2与MCM-41孔道表面的≡Si－OH以化学键连接,生成Si－O－Ti键;TiO~2在MCM-41内孔壁呈均匀单层分散状态;TiO~2粒子的减小使其对紫外光的吸收发生明显的蓝移现象。并以苯酚降解反应为模型检验合成的具有光催化性的TiO~2修饰的MCM-41的光催化活性。     

Influence of Excitation Wavelength (UV or Visible Light) on the Photocatalytic Activity of Titania Containing Gold Nanoparticles for the Generation of Hydrogen or Oxygen from Water

Gold nanoparticles supported on P25 titania (Au/TiO(2)) exhibit photocatalytic activity for UV and visible light (532 nm laser or polychromatic light λ > 400 nm) water splitting. The efficiency and operating mechanism are different depending on whether excitation occurs on the titania semiconductor (gold acting as electron buffer and site for gas generation) or on the surface plasmon band of gold (photoinjection of electrons from gold onto the titania conduction band and less oxidizing electron hole potential of about -1.14 V). For the novel visible light photoactivity of Au/TiO(2), it has been determined that gold loading, particle size and calcination temperature play a role in the photocatalytic activity, the most active material (Φ(H2) = 7.5% and Φ(O2) = 5.0% at 560 nm) being the catalyst containing 0.2 wt % gold with 1.87 nm average particle size and calcined at 200 °C.     

Mesoporous TiO2 nanostructures: a route to minimize Pt loading on titania photocatalysts for hydrogen production

Mesostructured TiO(2) nanocrystals have been prepared using Pluronic F127 as the structure-directing agent. Platinum nanoparticles at different contents (0.1-1.0 wt%) have been photochemically deposited onto the mesoporous TiO(2). TEM investigation of 0.2 wt% Pt/TiO(2) calcined at 450 °C reveals that the TiO(2) particles are quite uniform in size and shape with the particle sizes of TiO(2) and Pt being 10 and 3 nm, respectively. The photocatalytic activities of the Pt loaded TiO(2) have been assessed and compared with those of nonporous commercial Pt/TiO(2)-P25 by determining the rates and the photonic efficiencies of molecular hydrogen production from aqueous methanol solutions. The results show that the amount of hydrogen evolved on Pt/TiO(2)-450 at low Pt loading (0.2 wt%) is three times higher than that evolved on Pt/TiO(2)-P25 and twelve times higher than that evolved on Pt/TiO(2)-350. Despite the BET surface area of the TiO(2)-450 photocatalyst being 3.5 times higher than that of TiO(2)-P25, a 60% smaller amount of the Pt co-catalyst is required to obtain the optimum photocatalytic hydrogen production activity. The reduced Pt loading on the mesoporous TiO(2) will be important both from a commercial and an ecological point of view.     

Synthesis and photocatalytic activity of mesoporous TiO(2) with the surface area, crystallite size, and pore size

Mesoporous TiO(2) materials with various pore-size distributions were synthesized by using diblock copolymers via a sol-gel process in aqueous solution. The properties of these materials were characterized by FE-SEM, HR-TEM, XRD, DRS, BET, and BJH analysis. All particles have spherical morphology with a diameter range of 1-3 mum. The mesoporous TiO(2) materials calcined at 400 degrees C were found to have different specific surface areas - 186, 210, and 192 m(2) g(-1) - and average pore sizes depending on the type of diblock copolymer-5.1, 6.1, and 6.4 nm-and their crystallite sizes were found to be 8.1, 8.3, and 8.8 nm. The photocatalytic activity of each sample was investigated by measuring the photodecomposition of methylene blue (MB), and the small crystallite size, large surface area, and small pore size were found to exhibit better photocatalytic activities. In addition, the photocatalytic activities of all the mesoporous TiO(2) materials were found to be better than that of commercial TiO(2).     

A simple route for the preparation of Eu, N-codoped TiO2 nanoparticles with enhanced visible light-induced photocatalytic activity

A simple route has been developed for the synthesis of europium, nitrogen-codoped titania photocatalysts under mild conditions (i.e., low temperature, < or = 348 K, and ambient pressure). The as-prepared photocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectra (DRS) analyses. The results showed that the codoped photocatalyst with a spheroidal shape exhibited a smaller size than the undoped titania. The transformation from anatase to rutile was suppressed by doping with Eu and N atoms. Furthermore, the absorbance spectra of Eu, N-codoped TiO(2) exhibited a significant red shift to the visible region. The photocatalytic activity of Eu, N-codoped TiO(2) was evaluated by photodegradation of the dye reactive brilliant red X-3B under visible light. This codoped sample exhibited enhanced photocatalytic activity compared to N-doped TiO(2), pure TiO(2), and P25.     

中孔TUD负载的氧化铬掺杂氧化钛光催化降解苯酚

中孔的TUD-1负载的氧化铬掺杂TiO2(Cr-TiO2)有望用于紫外光照射下光催化降解苯酚的催化剂.低角X射线衍射和红外结果证实该样品中TUD-1存在无定形和中孔硅酸盐框架. TUD-1的中孔结构进一步得到N2吸附-脱附的证实：为IV型等温线,并具有窄的孔径分布(3.9 nm)和高的比表面积(>490 m2/g).透射电镜结果表明,所制样品保持了纳米颗粒和多孔孔道结构. TUD-1中负载Cr-TiO2后使得带隙能量增加.与未负载的Cr-TiO2相比,所有TUD-1负载的Cr-TiO2光催化剂表现出更高的紫外光下降解苯酚的活性.其中Si/Ti摩尔比为30的Cr-TiO2/TUD-1样品的光催化活性最高(82%).苯酚的光催化降解遵循一级Langmuir吸附等温线.     

同轴静电纺丝法在纳米中空Ti02纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶,钛酸四正丁酯和PVP溶胶,银颗粒为前驱体,以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维.将双组分纤维在200℃下热处理去除乙醇与表面吸附水后,继而在空气气氛中焙烧至600℃.可以得到在内表面上沉积银颗粒的TiO2纳米管,银颗粒的直径为5-40 nm,TiO2纳米管的外径150-300 nm.管臂厚10-20 nm.用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征.中空纤维的直径和管壁可以通过改变电纺参数来调节.与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较,Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

同轴静电纺丝法在纳米中空TiO2纤维中填充Ag的应用

以聚乙烯吡咯烷酮(PVP)溶胶/钛酸四正丁酯和PVP溶胶/银颗粒为前驱体, 以共轴静电纺丝法制备了银填充的TiO2中空纳米纤维. 将双组分纤维在200 ℃下热处理去除乙醇与表面吸附水后, 继而在空气气氛中焙烧至600 ℃, 可以得到在内表面上沉积银颗粒的TiO2纳米管, 银颗粒的直径为5-40 nm, TiO2纳米管的外径150-300 nm, 管臂厚10-20 nm. 用红外吸收光谱(IR)、X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)等测试手段对超细纤维进行了表征. 中空纤维的直径和管壁可以通过改变电纺参数来调节. 与Ag-TiO2纳米纤维、TiO2纳米中空纤维、TiO2纳米纤维及TiO2纳米粉体相比较, Ag颗粒填充的TiO2纳米中空纤维在光分解亚甲基蓝上表现出了更好的光催化性能.     

Synthesis and structure of nanocrystalline TiO2 with lower band gap showing high photocatalytic activity

Nanocrystalline TiO2 was synthesized by the solution combustion method using titanyl nitrate and various fuels such as glycine, hexamethylenetetramine, and oxalyldihydrazide. These catalysts are active under visible light, have optical absorption wavelengths below 600 nm, and show superior photocatalytic activity for the degradation of methylene blue and phenol under UV and solar conditions compared to commercial TiO2, Degussa P-25. The higher photocatalytic activity is attributed to the structure of the catalyst. Various studies such as X-ray diffraction, Raman spectroscopy, Brunauer-Emmett-Teller surface area, thermogravimetric-differential thermal analysis, FT-IR spectroscopy, NMR, UV-vis spectroscopy, and surface acidity measurements were conducted. It was concluded that the primary factor for the enhanced activity of combustion-synthesized catalyst is a larger amount of surface hydroxyl groups and a lowered band gap. The lower band gap can be attributed to the carbon inclusion into the TiO2 giving TiO(2-2x)C(x) VO2**.     

Synthesis, characterization, and photocatalytic activity for hydrogen evolution of nanocrystalline mesoporous titania prepared by surfactant-assisted templating sol-gel process

Nanocrystalline mesoporous titania was synthesized via a combined sol-gel process with surfactant-assisted templating method, treated under various calcination conditions, and evaluated for its photocatalytic activity through photocatalytic hydrogen evolution from an aqueous methanol solution. In this synthetic method, applied surfactant template molecules functioned as both mesopore-forming and gelation-assisting agents. The resulting products were methodically characterized by TG-DTA, XRD, N₂ adsorption-desorption, diffuse reflectance UV-Vis spectra, SEM, and TEM analyses. The partial phase transformation from anatase to rutile occurred beyond calcination temperature of 600 °C and anatase-rutile transition kinetics was also investigated. The calcination conditions and crystalline phases existing in the products exerted significant effect on the photocatalytic hydrogen evolution activity. The activity of the synthesized titania treated under appropriate calcination conditions was considerably higher than that of commercial titania powders, Ishihara ST-01 and Degussa P-25. It is clearly seen that the introduction of mesopore into titania photocatalyst substantially improved the photocatalytic performance.     

非金属元素掺杂及三维花状多级结构对介孔TiO_2可见光催化性能的促进作用

分别以尿素和葡萄糖为氮源和碳源,在温和条件下合成了具有三维花状多级结构的氮/碳掺杂二氧化钛.研究了非金属元素掺杂及三维花状多级结构对介孔TiO_2可见光催化性能的促进作用,结果表明,二者在增强TiO_2在可见光区域的吸收和提高TiO_2材料的光催化活性方面起到了协同促进的作用.