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     

可见光照射下染料茜素红的光催化降解机理

研究了 可见光（ ≥４２ ０ ｎ ｍ ） 照射下 染料茜素 红在空气 饱和 的 Ｔｉ Ｏ２ 水溶 液中 发生 的光 催化降解过 程． 借 助紫外 、核磁、顺 磁、红外 、色质 联用等手 段,发现 染料茜素 红的光 催化 降解 过程 符合 Ｌａｎｇ ｍ ｕｉｒ Ｈｉｎｓｈｅｌｗ ｏｏｄ 模型,在 降解过程 中产 生了 过氧 化 物． 核磁 、红 外和 色质联 用等 结 果证 实,主要降解 中间产 物为邻苯 二甲酸 ． Ｃ Ｏ Ｄ 测试 结 果表 明, 其矿 化产 率 达３ ０ ％ , Ｅ Ｓ Ｒ 结 果证 实, 在降解过程 中有 ⒒ Ｏ Ｈ 自由基 生成,说 明其与 染料的降 解机理有 密切联 系．     

聚乙烯/聚己内酯-聚乙二醇共聚物共混物组分相容性及其光水双降解的研究

用动态力学振簧仪、DSC、FT IR、光辐照、浸水降解法研究了马来酸酐化线型低密度聚乙烯 (MPE) /聚己内酯 聚乙二醇共聚物 (PCE)共混物的组分相容性、晶区的熔化和结晶行为以及降解特性 .结果表明 ,马来酸酐化是发生在LLDPE短支链的甲基末端上并通过马来酸酐与PCE的羟基形成氢键相互作用 ,使两组分存在部分相容性 ,PCE的主转变与MPE支链的 β转变发生内移现象 .在共混物中加入乙烯 丙烯酸共聚物(EAA)可以起增容作用 ,同时使MPE和PCE组分的熔点和熔化热进一步下降 .对不同含量PCE的MPE/PCE/EAA共混物的降解特性的研究表明 ,PCE的加入使体系发生光、水降解 ,且随PCE含量的增加降解速度加快 .光 水联合作用的降解速度比单一光或水降解更快 .     

用于结构信息数值化的电负性拓扑指数方法

本文提出了一种用于结构信息数值化的电负性拓朴指数（ETI）方法．此法是用基团电负性（ETIO）来表达原子及其相邻键的结构信息，这一表达较E－state模型中的本征状态项Ii更为合理．基干ETIO建立的ETI方法可用来在原子水平上直接表达分子的结构信息．应用实例表明，用ETI指数表达结构信息，进而用多元回归及人工神经网络相结合建立结构一活性关系模型适用于某些体系．1结构信息数值化方法中的“直接法”结构信息数值化是应用各种数学及人工智能方法建立QSAR模型的必要前提．其方法大体上可分为两类．一类是通过结构的物化参数来实…     

多孔二氧化钛对三氯甲烷光催化氧化的影响

报道 了以多孔 二氧化钛 为光催 化剂光催 化降解 水环境中 三氯甲烷 的一些 结果． 在所选定的实验 条件下 经１５ ｈ 光照, Ｃ Ｈ Ｃｌ３ 光催 化分解率 可达８０ ％ 左右 ． 此 结果 有利 于今 后进 一步 开展实用性 光催化 净化反应 器的研制     

纤维素中钛的分光光度测定法

研究用分光光度法测定纤维素中钛含量的最佳条件。本法不用高温燃烧炉灰化样品,而用浓硫酸水解样品,测定结果重复性良好,准确度高,测定误差为±0.03％。实验结果表明,此方法可用于化纤和造纸工业中钛含量的测定。     

4-n-壬基酚的激光闪光光解和紫外光降解

采用266nm激光闪光光解瞬态吸收光谱和254nm紫外光降解,研究了乙腈及乙腈-水混合溶液中4-n-壬基酚（4-n-NP）的各种光解行为,考察了不同物理化学体系对4-n-NP光解行为的影响规律.实验发现,在266nm激光闪光光解下,4-n-NP既发生光电离又发生光激发,获得了4-n-NP光电离生成的阳离子自由基,以及光激发生成的激发三重态的瞬态特征吸收谱.由S2O82-光分解产生的SO4·-可快速氧化4-n-NP,测得反应速率常数为2.85×109M-1s-1,判定4-n-NP阳离子自由基在pH高于2.2条件下会转变成脱质子中性自由基.研究发现,使用254nm紫外光直接降解4-n-NP比较困难,UV结合添加H2O2可提高其降解效率,UV结合添加K2S2O8可极大提高4-n-NP降解效率,3.5min的光照即可使1×10-4M的4-n-NP完全降解.本文就4-n-NP在各种条件下的光解机理进行了探讨,为此类具有生物激素效应的非离子表面活性剂光降解奠定了基础.     

CuWO_4促进金红石TiO_2光催化降解苯酚及其可能机理（英文）

已知金红石光催化降解水中有机物的活性远低于锐钛矿和板钛矿。本文报道,加入少量钨酸铜能显著加快金红石光催化降解水中苯酚。反应速率增加的幅度不仅远高于在相同煅烧温度(600°C)下制得的锐钛矿和板钛矿,而且随金红石煅烧温度(150-800°C)的增加持续增加。这些现象说明通过加入助催化剂钨酸铜,高温焙烧温度合成的金红石所具有的高的固有光催化活性可以被开发出来。此外,在过量苯酚存在下,H_2O_2的生成量随钨酸铜的加入量而先增加后减少,并且该趋势与苯酚降解速率基本一致。钨酸铜的这种正效应归结于固态的钨酸铜,而不是溶于水中的铜离子。(光)电化学测试表明,体系发生了从受光激发的金红石到钨酸铜的电子转移。这将提高光生载流子的分离效率,从而增大了O_2还原和苯酚降解的速率。     

高钛炉渣中Ti(Ⅱ)的测定

高钛炉渣中低价钛的测定,对干认识钒钛矿高炉冶炼过程机理、改善工艺流程都有重要意义。至今低价钛合量及分量的测定仍用Табакова的高价铁盐法,尚未见到Ti(Ⅱ)直接测定的报道,本实验用气体容量法直接测定高钛炉渣中Ti(Ⅱ)含量。     

改性硫酸钛催化合成丙酸酯

固体硫酸钛经不同的高温灼烧制得改性硫酸钛，用改性硫酸钛吸附吡啶后的IR光谱表征其表面酸性；用丙酸与多种醇反应考察其酯化催化活性。结果表明，改性硫酸钛表面存在明显的Broensted酸中心；对酯化反应的催化活性高、反应时间短、催化剂可重复使用多次。     

Titania nanowires as substrates for sensing and photocatalysis of common textile industry effluents

Sensing and photocatalysis of textile industry effluents such as dyes using mesoporous anatase titania nanowires are discussed here. Spectroscopic investigations show that the titania nanowires preferentially sense cationic (e.g. Methylene Blue, Rhodamine B) over anionic (e.g. Orange G, Remazol Brilliant Blue R) dyes. The adsorbed dye concentration on titania nanowires increased with increase in nanowire dimensions and dye solution pH. Electrochemical sensing directly corroborated spectroscopic findings. Electrochemical detection sensitivity for Methylene Blue increased by more than two times in magnitude with tripling of nanowire average length. Photodegradation of Methylene Blue using titania nanowires is also more efficient than the commercial P25-TiO₂ nanopowders. Keeping illumination protocol and observation times constant, the Methylene Blue concentration in solution decreased by only 50% in case of P25-TiO₂ nanoparticles compared to a 100% decrease for titania nanowires. Photodegradation was also found to be function of exposure times and dye solution pH. Excellent sensing ability and photocatalytic activity of the titania nanowires is attributed to increased effective reaction area of the controlled nanostructured morphology.     

Environmental photocatalysis: Perspectives for China

Photocatalysis is based on the double aptitude of the photocatalyst (essentially titania) to simultaneously adsorb reactants and absorb efficient photons. Heterogeneous photocatalysis is able to be efficient in Fine, “Green” and Environmental Chemistry. Photocatalysis induces mild oxidations in the absence of water by generating active neutral atomic O* species. For instance, the oxidation of 4-tert-butyl-toluene is 100% selective in 4-tert-butyl-benzaldehyde. In water treatment, many toxic inorganic ions are oxidized in their harmless upper oxidized state. The elimination of organic pollutants is the main field of water photocatalytic decontamination. Most of aliphatic and aromatic pollutants are totally mineralized into CO₂ and innocuous inorganic anions. More complex molecules, such as pesticides (herbicides, insecticides, fungicides, etc.) or dyes, are totally destroyed. Another example of green chemistry is the total degradation of dyes in water, in particular for the azo-dyes, with 100% selective degradation of -N=N- azo-groups into di-nitrogen. Photocatalysis is also active in the “bio-world” by killing bacteria (E. Coli, streptococcus, etc.) in water without re-growth. Air pollutants can also be destroyed, especially all the VOC’s (volatile organic compounds), providing certain air humidity enabling titania to produce cracking OH^· radicals. For chemical engineering reasons, the photocatalyst has to be fixed on a photo-inert support. In these conditions, UV-irradiated titania-based photocatalysis could be applied to the elimination of air pollutants, VOC’s, solvents, odors, chemicals, etc. Air treatment has to be associated with water and solid waste treatment because of odors. This is conducted by covering water treatment ponds or lagunas by rafts on which large sheets of Ahlstrom paper are deposited, supporting titania associated with activated carbon. Eventually, virus AH5N2, a model virus close to H5N1, responsible for the avian flu could be totally inactivated. Photocatalysis is directly connected with all 12 principles of Green Chemistry defined by Anastas (1998) and possesses open perspectives for China.     

糖葫芦状二氧化钛纳米线阵列的制备及其光催化性能

 采用溶胶-电泳技术,在多孔阳极氧化铝(PAA)模板的有序孔洞中制备了高度取向的糖葫芦状TiO2纳米线阵列光催化剂,通过扫描电镜(SEM)和X射线衍射对样品进行了表征. 结果表明, TiO2纳米线为锐钛矿晶型,纳米线直径与PAA模板的孔径一致,且分布均匀. 纳米线取向性极好,每根纳米线都具有周期性凹凸,形似糖葫芦,因此命名为糖葫芦状TiO2纳米线阵列. 以甲基橙的降解反应评价了光催化剂的活性,与相同条件下制备的TiO2/玻璃膜相比, TiO2纳米线阵列在光照1 h时对甲基橙的降解率达到93.6%, 比前者提高了40.2%, 具有很好的光催化活性.     

Theoretic and Experimental Studies on Titania Nanotube Doped with Ag Metal Ions

The electronic state density and energy bands of Ag-doped anatase TiO2 are studied by WIEN2k software package based on DFT. The calculation results show that the band-gap of anatase titania became bigger after doping with Ag metal ions. The band-gap transfers from 2.04 to 2.5 eV, but a new energy band appears among the forbidden band after the Ag atom substitution. The interband width of Ag-TiO2 is 0.17 eV, which is located at –0.07 eV; more excitation and jump routes are opened for the electrons. The lowest excitation energy can achieve 1.2 eV, which may allow the photons with lower energy (at longer wavelength, such as visible light) to be absorbed. Ag ions are implanted into the titania nanotube sample by MEVVA (Metal Vapor Vacuum Arc) implanter. The photo-electrochemical response and photo-degradation experiment of titania nanotube samples implanted with Ag ions are tested under UV and visible light; the results indicated that the performance of implanted titania naotubes is enhanced both under UV and visible light; it is worth mentioning that the photocurrent density can reach 0.145 mA/cm2 under visible light, which is 181 times higher than those of pure TiNT, and the k value of degradation methyl orange can obtain 0.30 h-1, which is 71 times higher than that of pure TiNT. All the experimental results are consistent well with the theoretic ones.     

Aromatic Amines as Co‐sensitizers in Dye Sensitized Titania Solar Cells

Abstract

Solar cells based on titania require the use of sensitizing dyes in order to make the absorption band coincident with the solar spectrum. The most successful sensitizing dyes are based on Ru‐bipyridyls and are chosen for their absorption and redox characteristics. In addition to absorbing visible light, the sensitizing dye injects an electron from its excited state into the band gap of the titania. The injected electron must be conducted through the titania to an electrode upon which the titania is coated. One of the energy wasting pathways available to the injected electron is back transfer to an oxidized dye species on the surface of the titania. We have discovered a simple means of alleviating this energy wasting pathway by anchoring aromatic amines, i.e., co‐sensitizers, at low concentration along with the Ru‐based bipyridyl sensitizing dye to the surface of titania nanoparticles. Our results indicate that there is a significant increase in cell efficiency (～15% at AM 1.5, area ≥1 cm²) primarily due to an increase in current when these species are present on the surface in combination with the dyes. We will report our preliminary results on a series of co‐sensitizers, and we will compare these to literature findings which use similar compounds as either co‐adsorbed species on titania or as substituents on the sensitizing dye molecule itself.     

Titania Nanomaterials Produced from Ti-Salt Flocculated Sludge in Water Treatment

Titania is the most widely used metal oxide for the applications of pigments, paper, solar cells and environmental purification. In order to meet the demand of a large amount of titania, our group has developed a novel process which could significantly lower the cost of waste disposal in water treatment, protect the environment and public health and yield economically valuable titania. Titanium tetrachloride (TiCl₄) or titanium sulfate (Ti(SO₄)₂) as an alternative coagulant in water treatment has been explored for the removal of various pollutants from contaminated water or wastewater. Flocculation efficiencies of the Ti-salts were superior to those of Al- and Fe- salts with additional benefits in that a large amount of titania can be produced by calcinating the flocculated floc. The produced titania showed high photocatalytic activity for the removal of volatile organic compounds. The large amount of titania can be applied to pigments, environment and construction materials which require a lot of titania usages. This review paper presents an historical progress from fundamental to application in terms of the detailed production process, characterization, photoactivity of titania produced from Ti-salt flocculated sludge, and its various applications.     

Comparison of rhodamine B degradation under UV irradiation by two phases of titania nano-photocatalyst

Titania (TiO₂) nano-photocatalysts, with different phases, prepared using a modified sol?Cgel process were employed in the degradation of rhodamine at 10?mg?L^?1 concentration. The degradation efficiency of these nano-photocatalysts was compared to that of commercial Degussa P25 titania. It was found that the nanocatalysts calcined at 450?°C and the Degussa P25 titania had similar photoreactivity profiles. The commercial Degussa P25 nanocatalysts had an overall high apparent rate constant of (K _app) of 0.023?min^?1. The other nanocatalyst had the following rate constants: 0.017, 0.0089, 0.003 and 0.0024?min^?1 for 450, 500, 550 and 600?°C calcined catalysts, respectively. This could be attributed to the phase of the titania as the anatase phase is highly photoactive than the other phases. Furthermore, characterisation by differential scanning calorimetry showed the transformation of titania from amorphous to anatase and finally to rutile phase. SEM and TEM characterisations were used to study the surface morphology and internal structure of the nanoparticles. BET results show that as the temperature of calcinations was raised, the surface area reduced marginally. X-ray diffraction was used to confirm the different phases of titania. This study has led to a conclusion that the anatase phase of the titania is the most photoactive nanocatalyst. It also had the highest apparent rate constant of 0.017?min^?1, which is similar to that of the commercial titania.     

Thickness-dependent photocatalytic performance of ZnO nanoplatelets

In this paper, we report the large-scale synthesis of ZnO nanoplatelets as thin as 10 nm. The nanoplatelets show higher efficiency in photodegrading organic dyes than ZnO nanorods do, and for the nanoplatelets, the thinner they are, the higher the performance. The photocatalytic decomposition of organic dyes (eosin B) by ZnO nanoplatelets compares favorably to the performances of ZnS porous nanoparticles and commercial Degussa P25 titania particles. This finding may have significant implications in the environment remediation and the fabrication of functional nanodevices.     

Improvement of the Visible‐Light Photocatalytic Performance of TiO2 by Carbon Mesostructures

An improvement in the photodegradation performance for dyes due to interaction between carbon and titania in a self‐assembled mesoporous C? TiO₂ composite catalyst, even for the difficult degradation of azo dyes, is reported herein. The dye removal process involves adsorption of the dye from water by the mesoporous carbon–titania, followed by photodegradation on the separated dye‐loaded solid. Such adsorption–catalysis cycles can be carried out more than 80 times without discernible loss of photocatalytic activity or the anatase content of the composite. In each run, about 120 mg dye per g catalyst can be degraded. The mesoporous carbon–titania catalyst also exhibits a high capacity for converting methyl orange in aqueous solution under visible light. Characterization by XRD, TEM, and N₂ sorption techniques has revealed that the self‐assembled composite catalyst has an ordered mesostructure, uniform mesopores (4.3 nm), a large pore volume (0.30 cm³ g^?1), and a high surface area (348 m² g^?1). The pore walls are composed of amorphous carbon and anatase nanoparticles of size 4.2 nm, which are well dispersed and confined. X‐ray photoelectron spectroscopy (XPS), surface photovoltage spectroscopy (SPS), and UV/Vis absorption results indicate doping of carbon into the anatase lattice and a change in the bandgap of the semiconductor. The synergistic improvement in the composite catalyst can be attributed to the following features: (1) carbon doping of the anatase lattice modifies its bandgap and enhances its activity under visible light; (2) confinement within carbon pore walls prevents aggregation of tiny anatase nanoparticles, improving their activity and stability; (3) the mesopores provide a confined space for photocatalysis; and (4) the strong adsorption ability of porous carbon for organic substances ensures that large quantities can be processed and inhibits further diffusion of the adsorbed organic substances, thereby enhancing the mineralization on anatase.     

Synthesis,characterization and evaluation of nanocrystalline anatase titania for the degradation of dibutyl phosphate

Degradation of dibutyl phosphate (DBP) in aqueous solution was successfully demonstrated in this paper using nanoparticles of anatase titania. Nanocrystalline anatase titania employed for the degradation study was synthesized in house by solgel route under stirring mode using titanium ethoxide precursor. The catalyst was characterized using XRD, DRS, BET, TEM, TG–DTA and Raman spectroscopy to establish the catalytic activity and surface morphology. A cylindrical photoreactor was used for the photocatalytic experiments. 10 mg of nano anatase titania and 0.5 mL of 30 % H₂O₂ were used as catalysts for the degradation of 1,000 mL of 240 mg/L DBP. Ion chromatographic procedure was used for following the DBP degradation. More than 95 % of DBP degradation could be in less than 45 min and the kinetics of DBP was found to follow pseudo first order. It was demonstrated that the photocatalytic efficiency of the synthesized titania was better than P-25 titania.