基于二氧化钛光催化剂生物质转化制备氢气和化学品的研究进展

随着化石能源的枯竭和环境问题的日益严重,发展可再生资源变得越来越重要.太阳能和生物质是自然界中的两大可再生资源.利用太阳能转化生物质制备H2和化学品可以缓解对化石能源的依赖,是解决能源和环境问题的途径之一.本文作者概述了基于TiO2催化剂的光催化生物质制备H2和化学品的研究进展;着重介绍了甲醇、乙醇、甘油和葡萄糖的光催化反应选择性问题和机理研究,分析了存在的问题和可能的解决措施,并就其发展趋势进行了展望.     

超声波-二氧化钛光催化耦合法降解高效氯氰菊酯

采用超声波-TiO2光催化耦合法降解高效氯氰菊酯,考察了高效氯氰菊酯初始浓度、降解时间、溶液pH、催化剂用量等对高效氯氰菊酯农药残留的降解效果,并利用水果进行了实物模拟.结果表明:利用超声波-TiO2光催化耦合法能够有效地降解高效氯氰菊酯农药残留.在弱酸环境中,当纳米TiO2投放量为1.2g/L时,经2h超声催化降解,不同浓度的高效氯氰菊酯农药稀释液均被有效降解,降解率最高可达98.3%.     

Titanium dioxide photocatalysis of adamantane

TiO₂ photocatalysis of adamantane in oxygen equilibrated MeCN yields 1- and 2-adamantanol and adamantanone with limited degradation and preference for functionalization at the 1 position, particularly in the presence of silver salts. Oxidation in CH₂Cl₂ is less selective. The oxidation of cyclohexane and cyclododecane is slower. In N₂-flushed solutions with Ag⁺ as a sacrificial acceptor, products from the trapping of both 1-adamantyl radical (adamantyl methyl ketone) and cation (N-adamantylacetamide) are obtained. Furthermore, alkylation of an electrophilic alkene (isopropylydenmalononitrile) has been obtained, though in a low yield.     

Fabrication of electrospun polyethersulfone/titanium dioxide (PES/TiO2) composite nanofibers membrane and its application for photocatalytic degradation of phenol in aqueous solution

The main objective of this research is to use the photocatalytic properties of PES/TiO₂ nanofibers membranes to remove the phenol as a toxic pollutant in various effluents. The uniform fibers in terms of minimum bead formation and fibers diameter were fabricated. Therefore, more TiO₂ catalysts are on the surface of the fibers which increase the active surface area of nanoparticles and consequently improve the phenol degradation efficiency. The effects of TiO₂ concentration on hydrophilicity, mechanical properties, porosity, mean pore size, and water flux of membranes were studied. The PES/TiO₂ nanofibers were evaluated for phenol degradation under UVA irradiation through a transparent membrane module. The amount of removable phenol was analyzed with high‐performance liquid chromatography. Central composite design was used as a statistical experimental design. Finally, the effect of TiO₂ content in nanofibers and initial phenol concentrations were investigated as well as pH values in synthetic wastewater, on phenol degradation. The results from analysis of variance (ANOVA) analysis indicated that TiO₂ content in nanofibers was the most important and effective parameter on phenol degradation. It was also presented that there is no significant interaction between parameters so that the effect of each parameter was investigated separately. Maximum phenol degradation was 43.0 ± 0.3% and found under conditions of TiO₂ content, initial phenol concentration, and pH value of 8%, 120 ppm, and 7, respectively.     

Thick titanium dioxide films for semiconductor photocatalysis

Thick paste TiO₂ films are prepared and tested for photocatalytic and photoinduced superhydrophilic (PSH) activity. The films are effective photocatalysts for the destruction of stearic acid using near or far UV and all the sol–gel films tested exhibited a quantum yield for this process of typically 0.15%. These quantum yields are significantly greater (4–8-fold) than those for titania films produced by an APCVD technique, including the commercial self-cleaning glass product Activ™. The films are mechanically robust and optically clear and, as photocatalysts for stearic acid removal, are photochemically stable and reproducible. The kinetics of stearic acid photomineralisation are zero order with an activation energy of ca. 2.5 kJ mol⁻¹. All titania films tested, including those produced by APCVD, exhibit PSH. The light-induced fall, and dark recovery, in the water droplet contact angle made with titania paste films are similar in profile shape to those described by others for thin titania films produced by a traditional sol–gel route.     

Enhancement of titanium dioxide photocatalysis by water-soluble fullerenes

Fullerenes are known for their unique electronic properties including high electron affinity. Although use of fullerenes for scavenging photo-generated electrons from titanium dioxide particles has been demonstrated, no attempts have been made to utilize the unique properties of fullerenes to increase the efficacy of photocatalysis. The present study has demonstrated that a mixture of water-soluble polyhydroxy fullerenes (PHF) and titanium dioxide (anatase polymorph) enhances photocatalytic degradation of organic dye. The PHF molecules adsorbed to the surface of titanium dioxide due to electrostatic forces, with adsorption density being higher at lower pH values. The surface coverage of titanium dioxide nanoparticles by PHF molecules determined the extent of enhancement, with an optimum dosed weight ratio of PHF to titanium dioxide at 0.001. Hydroxylation and concomitant solubilization of fullerenes allow their unique electronic properties to be harnessed for photocatalysis.     

纳米TiO-2对模型病毒-f2噬菌体的吸附特性

为了提高饮用水处理系统对病毒的去除效果,本研究采用静态实验,研究纳米TiO2对模型病毒—f2噬菌体的吸附去除特性,系统考察TiO2投加浓度、病毒浓度、温度及pH值等因素对吸附效果的影响.实验结果表明：f2噬菌体在纳米TiO2表面的吸附符合准二级吸附动力学模型,遵循化学吸附机理,颗粒内扩散为该吸附过程中的速率控制步骤,但不是唯一控制步骤;纳米TiO2对f2噬菌体的吸附符合Freundlich等温吸附模型（qe=27.4Ce1.24）,属于多层吸附类型;在20~40℃范围内,温度对纳米TiO2的吸附性能影响不大,而酸性条件下更有利于纳米TiO2对f2噬菌体的吸附.     

Research progress of photocatalysis based on highly dispersed titanium in mesoporous SiO2

This paper reviewed the TiO₂-SiO₂ and Ti-SiO₂ mesoporous materials and their applications in photocatalysis.     

The influence of titanium dioxide phase composition on dyes photocatalysis

A comparative study of TiO₂ powders prepared by sol–gel methods is presented. Titanium tetraisopropoxide was used as the precursor for the sol–gel processes. The effects of the annealing treatment on phase, crystallite size, porosity and photodegradation of dyes (methyl orange and methylene blue) were studied. The phase structure, microstructure and surface properties of the films were characterized by using X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The X-ray diffraction was used for crystal phase identification, for the accurate estimation of the anatase–rutile ratio and for the crystallite size evaluation of each polymorph in the samples. It was found that the only TiO₂ anatase phase of the synthesized TiO₂ develops below 500 °C, between 600 and 800 °C the anatase coexist with rutile and above 800 °C only the rutile phase was found in the samples. Attention has been paid not only to crystal structures, but also to the porosity, the particle size and the photocatalytic properties. However, the annealing temperature was found to have significant influence on the photocatalytic properties. Different TiO₂ doctor blade thin films were obtained mixing the sol gel powder (100% anatase) and TiO₂ Aldrich with TiO₂ Degussa P25. The surfactant (Triton X100 or sodium dodecyl sulfate) affects the packing density of the particles during deposition and the photocatalytic degradation efficiency of the dyes. The photocatalytic degradation kinetics of methyl orange and methylene blue using TiO₂ thin film were investigated.     

纳米TiO2光催化分解罗丹明B的动力学分析

锐钛矿型TiO2禁带宽度为3 2eV,在波长小于387nm的紫外辐射激发下,价带电子跃迁到导带,光生电子和空穴分离,与表面接触组分可发生一系列氧化还原反应,可将有机污染物降解为简单的无机化合物[1]。TiO2微粒粒径的降低(几十纳米),吸收光谱发生蓝移,催化活性随粒径的减小而增强[2,3]。纳米TiO2对罗丹明B的光催化分解过程与罗丹明B在TiO2表面的吸附有关[4]。本文采用自制纳米TiO2在4W紫外灯直接照射下,光分解罗丹明B为表观一级反应,反应速率与罗丹明B起始浓度及催化剂用量有关。1　实验部分纳米TiO2 采用sol gel法制备。分别配制不同…     

聚苯胺复合二氧化钛的制备及其降解硝基苯研究

以苯胺和二氧化钛为原料,采用化学氧化法,合成光降解复合材料聚苯胺(PANI)/二氧化钛(TiO2),并对其进行表征.采用该复合材料对50mg·L-1的硝基苯模拟废水进行自然光催化降解研究,实验结果显示,当二氧化钛和苯胺用量摩尔数之比为10:1,在自然光条件下获得最佳的催化效果,同时讨论了不同pH值和投加量对降解效果的影...     

甲醛在TiO_2颗粒物表面的非均相反应

使用漫反射红外傅里叶变换光谱(DRIFTS)原位反应器研究了甲醛在TiO2颗粒物表面的非均相反应,结合离子色谱定量分析了反应的主要产物甲酸盐,甲酸盐是由中间产物二氧亚甲基进一步氧化生成.研究了温度和紫外光照对反应的影响,结果表明升高温度和紫外光照可提高反应速率,推测了暗反应和紫外光照下甲醛在TiO2表面的非均相反应机制.结果表明常温下甲醛在TiO2颗粒物表面的反应级数接近2级,初始反应摄取系数为(0.5～5)×10-8([HCHO]:1×1013～2×1014molecule·cm-3),是甲醛浓度的一次函数,同时测定了表观活化能.     

纳米二氧化钛对痕量铅的吸附性能研究

提出了纳米TiO2分离富集, 火焰原子吸收光谱法测定水样中痕量铅的新方法.考察了铅在纳米TiO2上的吸附动力学、最佳酸度和吸附容量.实验结果表明：在最佳实验条件下,纳米TiO2能定量、快速地吸附水中的痕量Pb^2＋,其静态吸附容量为17.90 mg/g.吸附在纳米TiO2上的Pb^2＋可用0.1 mol/L HNO3＋0.1 mol/L CH3COOH完全洗脱.对Pb2＋的检出限为2.57 ng/mL, 相对标准偏差为2.5% （n=11, ρ=0.10 μg/mL）,加标回收率在94.5%～102.5%之间.可用于实际水样中铅的测定.     

N掺杂TiO2对聚乙烯复合薄膜的光催化降解研究

以快速溶胶-凝胶法制备了具有不同N掺杂量的TiO2光催化剂,在室温光照240 h条件下,用于固相光催化降解碳酸钙填充聚乙烯复合材料薄膜;采用X射线光电子能谱仪(XPS)、X射线衍射仪(XRD)、紫外-可见光漫反射仪(UV-Vis)、傅立叶变换红外光谱仪(FTIR)、扫描电子显微镜(SEM)等手段分析了催化剂和薄膜的形貌...     

Synthesis,characterization, and electrophoretic concentration of titanium dioxide nanoparticles in AOT microemulsions

Stable organosols of TiO₂ nanoparticles were prepared by hydrolysis of titanium tetraisopropoxide (TTIP) in microemulsions of sodium bis(2‐ethylhexyl)sulfoxynate (АОТ) in n‐decane with increasing the content of aqueous pseudophase from 0.15 to 0.85 vol.%. As the water content increased, the hydrodynamic diameter of nanoparticles grew from 10 to 225 nm, and the  ζ‐potential, from ‐6 to 18 mV (the surface of TiO₂ nanoparticles was recharged when the water content was 0.45 vol.%). Nonaqueous electrophoresis in a capacitor‐type cell made it possible to concentrate nanoparticles with a diameter of 60 to 225 nm (concentration factor was 10), separate 20 nm and 225 nm particles, and decrease the content of АОТ in organosol by an order of magnitude. Preparation of a concentrate of nanoparticles with a low content (0.015 M) of AOT included the following stages: (i) electrophoresis after synthesis; (ii) sampling of the concentrate and its twenty‐fold dilution with pure n‐decane; and (iii) repeated electrophoresis. In situ laser and spectrophotometric scanning of the interelectrode space showed the formation of a sharp boundary between the raffinate and the layer of moving nanoparticles during electrophoresis.     

机械力化学反应法制备纳米金红石型二氧化钛的研究

以Ti (C4H9O)4 和 C2H2O4·2H2O 为原料在室温下利用机械力化学反应法制备前驱体,利用热重-微商热重法(TG-DTG)决定前驱体的分解温度,通过在特定温度下对前驱体进行热分解得到TiO2.利用XRD,SEM,ZETA 电位粒度分析仪以及紫外光谱仪对所得样品物相,形貌,粒度和光学性能进行分析和表征.结果显示所得粉体微观形貌为球形,其直径(＞ 95%)小于60nm,粒径较小的粉体对紫外线UVA波段的吸收效果较好.     

阳极氧化条件对氧化钛纳米管阵列形貌及光催化性能的影响

以阳极氧化法制备了高度有序的TiO2纳米管阵列,采用扫描电镜观察了不同制备条件下得到的TiO2纳米管阵列的微观形貌,分别考察了电解时间、电压、电解液组成对TiO2纳米管阵列形貌的影响;此外,以酸性红3R染料作为标志物,测定了制得的TiO2纳米管阵列片的光催化性能.结果表明,以0.5%NH4F(质量分数)和乙二醇与水按体积比5∶1混合得到的溶液作为电解液,在15V电压下电解2h,得到的TiO2纳米管阵列的纳米管管径适中(60nm)、大小均一、排列整齐.所制备的TiO2纳米管阵列对染料的降解率显著优于纳米TiO2水溶胶的,且其光催化性能与形貌、电解时间及煅烧温度等密切相关.     

Heterogeneous composite titanium dioxide photocatalysts on phosphate supports

A series of heterogeneous composite photocatalysts was prepared by the deposition of titanium dioxide on porous magnesium phosphate, calcium phosphate, titanium phosphate, zirconium phosphate, and aluminum phosphate supports. The activities of these photocatalysts were compared in the photodecomposition of Rhodamine C dye by the action of UV irradiation. The best functional characteristics were found for the photocatalysts on the magnesium phosphate support treated at 750°C. The use of the photocatalysts on phosphate supports was found to hold promise in photocatalytic water purification. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 1, pp. 36–41, January–February, 2009.