Centrally Coordinated Cobalt Porphyrin Monolayers on the Surface of TiO2 Nanoparticles

Aminopropyltrimethoxysilane (APTS) on the surface of TiO₂ nanoparticles was used to bind cobalt(II) 5,10,15,20-tetra-(4-trimethylaminophenyl)porphyrin iodide (CoTAPPI). The binding involved coordination of amino-group in the APTS to cobalt(II) ion in the center of the porphyrin. The absorption and fluorescence spectra of the products showed that there existed the electron transfer among TiO₂, APTS, and CoTAPPI. The polarized fluorescence spectra were used to evaluate the coordination constants of the porphyrin and APTS. The molecular geometry and binding energy of the TiO₂-APTS-CoTAPPI assembly were calculated with the molecular mechanics approach (MM2).     

球形TiO2-Al2O3的制备、结构和理化性能研究

将Ti(SO₄)₂溶于稀盐酸合成酸性钛溶胶，再将其与铝溶胶和六次甲基四胺溶液混合后采用油柱成型法制备了球形TiO₂-Al₂O₃复合氧化物。通过XRD、低温氮吸附-脱附与NH₃-TPD等手段对样品进行表征，结果表明600 ℃焙烧得到的球形TiO₂-Al₂O₃中TiO₂以无定型形式存在;随TiO₂含量的增加，球形TiO₂-Al₂O₃的比表面积、孔容和平均孔径呈增加趋势;TiO₂的引入没有对球形TiO₂-Al₂O₃的强酸和弱酸中心的强度产生影响，弱酸中心数量显著增加，强酸中心数量稍有增加;球形TiO₂-Al₂O₃的堆密度和压碎强度随TiO₂含量的增加而减小，颗粒直径基本保持不变。     

Structure of TiO2 in TiO2-SiO2 prepared by a complexing agent-assisted sol-gel procedure

Many types of TiO₂-SiO₂ (Ti:Si=50:50 mol%) were prepared by the sol-gel procedure with and without 2-methyl-2, 4-pentanediol (MPD) as an organic ligand. The effect of MPD on the gel structure and the properties of the TiO₂ crystals were studied by XRD and raman spectroscopy, and the effect of the sol standing time on the properties of the TiO₂ crystals were also studied by XRD spectroscopy. In the gels with MPD, anatase of TiO₂ appeared at approximately 580°C, and the crystal structures were similar despite the difference in the gel preparation procedure. The titania gels with MPD were presumed to be dispersed in the silica gel matrix without any Ti-O-Si bond. In the presence of MPD, the formation of titania gels is controlled and the specified TiO₂ crystal is produced.     

Evaluation of the Photocatalytic Properties of Copper Oxides/Graphene/TiO2 Nanoparticles Composites

Easy and cost-efficient modifications of titanium dioxide nanoparticles that improve their efficiency in the visible light domain represent a continuous and challenging research topic. In addition, the effect of graphene on the overall photocatalytic process is still debated. Consequently, herein, we prepared a series of TiO₂ nanoparticle-based composites with different copper oxide mass content (1–3%) and co-doped with graphene of different oxidation degrees. Different characterization techniques were used to analyze the structural and physico-chemical properties of the obtained composites: Scanning Electron Microscopy (SEM)/Transmission Electron Microscopy (TEM)/Energy-dispersive X-ray spectroscopy (EDX) analysis, X-ray powder diffraction (XRD), Fourier-transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic performance was evaluated by the degradation of methylene blue under both UVA and visible light irradiation. The nanocomposites show very good photocatalytic activity independent of the presence of reduced graphene oxide, due to the Cu₂O/CuO-TiO₂ heterojunctions. This finding has been confirmed by the very efficient visible-light-driven degradation of amoxicillin and ciprofloxacin.     

Molecular Assembly by Sequential Ionic Adsorption of Nanocrystalline TiO2 and a Conjugated Polymer

Abstract

Cationic nanocrystalline TiO₂ particles have been synthesized for which the size and composition of the nanoparticles were analyzed by a transmission emission microscopy and energy dispersive x‐ray spectrometer (EDXS). Multilayered films have been fabricated by sequential adsorption of TiO₂ nanoparticles and poly(3‐thiophene acetic acid) (PTAA). Each layer of the nanoparticles and PTAA in the thin film has also been characterized by x‐ray photoelectron spectroscopy, atomic force microscopy, and UV‐visible spectroscopy. These types of multilayered nanocomposite films may find applications in the fabrication of efficient light harvesting photovoltaic cells.     

Application of the Composite of TiO2 Nanoparticles and Carbon Nanotubes to the Photo-Reduction of Cr(VI) in Water

The composite of carboxyl-modified multi-walled carbon nanotubes (MWNT-COOH) and TiO₂ nanoparticles was prepared in a solvothermal process. The x-ray diffraction (XRD), transmission electron microscope (TEM) and UV-vis spectrum were used to characterize the products. The results showed that the MWNT-COOH was dispersed uniformly in the composite and coated with TiO₂ nanoparticles. The photo-reduction of Cr(VI) to Cr(III) in water catalyzed by the composite was investigated at room temperature. The photocatalytic activity of the composite markedly increased by a factor of approximately 2.2 in comparison with pure TiO₂ (P25). Furthermore, the mechanism of the photocatalytic activity enhancement of the MWNT-COOH/TiO₂ nanoparticles composite for the photo-reduction of Cr(VI) was discussed.     

Thermally effected structural and surface transformations of sulfated TiO2, ZrO2 and TiO2-ZrO2 catalysts

Preparations were characterized by specific surface area, thermogravimetry, and X-ray diffractometry. Thermal effects observed were (a) sulfur loss, (b) sintering, (c) crystallization and transformation of the crystalline phase(s). Thermoanalytical curves indicate that decomposition of the sulfate occurs in two distinct steps. Decrease of surface area due to (b) and (c) is concomitant to decomposition of sulfate. Sulfate was found to hinder sintering, crystallization and phase transformations of ZrO₂ and TiO₂. In low-titania and -zirconia sulfated TiO₂-ZrO₂ the minor component enhances the effect of sulfate. In equimolar TiO₂-ZrO₂ sulfate decomposition is accompanied by rapid formation of crystalline TiZrO₄.This work was supported by the MOL Rt., Hungary, which is gratefully acknowledged.     

Comparison of CO2 Reduction Performance with NH3 and H2O between Cu/TiO2 and Pd/TiO2

The aim of this study is to clarify the effect of doped metal type on CO₂ reduction characteristics of TiO₂ with NH₃ and H₂O. Cu and Pd have been selected as dopants for TiO₂. In addition, the impact of molar ratio of CO₂ to reductants NH₃ and H₂O has been investigated. A TiO₂ photocatalyst was prepared by a sol-gel and dip-coating process, and then doped with Cu or Pd fine particles by using the pulse arc plasma gun method. The prepared Cu/TiO₂ film and Pd/TiO₂ film were characterized by SEM, EPMA, TEM, STEM, EDX, EDS and EELS. This study also has investigated the performance of CO₂ reduction under the illumination condition of Xe lamp with or without ultraviolet (UV) light. As a result, it is revealed that the CO₂ reduction performance with Cu/TiO₂ under the illumination condition of Xe lamp with UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:1:1 while that without UV light is the highest when the molar ratio of CO₂/NH₃/H₂O = 1:0.5:0.5. It is revealed that the CO₂ reduction performance of Pd/TiO₂ is the highest for the molar ratio of CO₂/NH₃/H₂O = 1:1:1 no matter the used Xe lamp was with or without UV light. The molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp with UV light was 10.2 μmol/g, while that for Pd/TiO₂ was 5.5 μmol/g. Meanwhile, the molar quantity of CO per unit weight of photocatalyst for Cu/TiO₂ produced under the illumination condition of Xe lamp without UV light was 2.5 μmol/g, while that for Pd/TiO₂ was 3.5 μmol/g. This study has concluded that Cu/TiO₂ is superior to Pd/TiO₂ from the viewpoint of the molar quantity of CO per unit weight of photocatalyst as well as the quantum efficiency.     

Structure and properties of polymer modified TiO2 pillared montmorillonite

With the aim of improving the microstructures and properties of TiO₂ pillared montmorillonite (MMT), a long-chain polymer (polyoxypropylenediamine, PPO-D 2000) was used as a template to synthesize composite pillared MMT. The materials were characterized by X-ray powder diffraction (XRD), Fourier transform infrared (FT-IR) spectrophotometer, Fourier Raman (FT-Raman) spectrophotometer, thermo-gravimeter/differential thermogravimeter (TG/DSC), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) methods. The results show that as compared to low-molecular weight surfactant, this polymer significantly expanded the interlayer spacing and thus more TiO₂ could be intercalated into MMT. The specific surface area of polymer/TiO₂ pillared MMT was increased by 13% with comparison to TiO₂ pillared MMT and rose to 241.52 m²/g. Both the pore diameter and volume are doubled, and thus the pore structure is optimized markedly. The investigation on the photo-catalytic degradation of methyl orange in aqueous solution show that the modulation of polymer molecules raise the adsorption content of montmorillonite and improve the photo-catalytic activity. Therefore, this process provides a novel alternative to design and prepare the advanced eco-catalytic materials with high adsorption capacity and photo-catalytic activity. __________ Translated from Huaxue Tongbao, 2007, 12: 936–941 [译自: 化学通报]     

载有C60的TiO2纳米粒子光催化活性

以水溶性C₆₀和TiO₂粒子为前驱体,采用水热法制备了载有C₆₀的锐钛矿型TiO₂纳米粒子。应用X射线衍射、透射电子显微镜、红外光谱、紫外-可见漫反射光谱、荧光光谱对产物进行了表征。以对-硝基苯酚为模型污染物研究了产物的光催化活性,结果表明适量负载C₆₀可以提高TiO₂纳米粒子的光催化活性,C₆₀起着传输电子、促进TiO₂光生载流子分离的作用,且经7次循环使用后对-硝基苯酚的降解效率仍能达到74%。讨论了载有C₆₀的TiO₂纳米粒子光催化降解对-硝基苯酚的机理。     

The effect of certain promoters on TiO2 crystal structure transformation

The effect of certain promoters on TiO₂ crystal structure transformation was studied by mean thermal and X-ray analyses. It was found that the addition of rutile nuclei and potassium, phosphorus, zinc, magnesium, and aluminium compounds to hydrated titanium dioxide before calcination process influences on the initial temperature and anatase transformation.

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Zusammenfassung Mittels Thermo- und Röntgendiffraktionsanalyse wurde der Einfluß gewisser Beschleuniger für Strukturumwandlungen in TiO₂-Kristallen untersucht. Man fand, daß ein Zusatz von Rutilkernen und Kalium-, Phosphor-, Zink-, Magnesium- und Aluminiumverbindungen zu hydratiertem Titanoxid die Anfangstemperatur und das Ausmaß der Anatas-Umwandlung beeinflussen.

     

水热法合成纳米TiO2及其在Grtzel电池中的应用

By varying the hydrolysis and hydrothermal processing parameters in preparing TiO2 nanoparticles different sizes of TiO2 nanoparticles are obtained.(1) At higher autoclaving temperature,lower pH and longer autoclaving period,larger sizes of TiO2 nanoparticles are prepared.(2) The nanoporous electrodes made from sintering smaller TiO2 nanoparticles show relatively poor IPCE and low absorption in UV Vis spectrum,(3) Higher IPCE can be achieved with TiO2 nanoporous electrodes made from sintering larger TiO2 nanoparticles.These electrodes are suitable for studying behavior of the photoelectrochemistry of dye sensitized nanoporous electrodes.     

Influence of Gemini Surfactant with Modified TiO2 Nanoparticles on the Interfacial Tension of Oil/Water

The research on the impacts of modified TiO₂ nanoparticles (NPs) on interfacial tension (IFT) is in its infancy. Our work focuses on the IFT of the modified TiO₂ and Gemini surfactant N,N,N′,N′-tetramethyl-N,N′-dimyristyl-1,2-ethane diammonium dichlone (YND1233) complex solutions for reservoir stimulation purposes. The factors of YND1233, modified TiO₂ NPs, temperature, aging stability, adsorption loss, and mineralized degree were explored with the comparison of unmodified TiO₂ NPs and YND1233 as contrast samples. The results indicate that the dynamic IFTs decrease and then increase with the concentrations of YND1233 and modified TiO₂ NPs, and the minimum IFT appears at 0.200 and 0.010 wt%, respectively. YND1233/modified TiO₂ complex solutions show lower and more stable IFTs, better temperature resistance, longer aging time, and lower adsorption on the surface of quartz sand. The modified TiO₂ NPs and YND1233 in the YND1233/modified TiO₂ complex solution can be adsorbed to the interface and decrease the IFTs through synergistic effect. A mixed diffusion-kinetic mechanism is provided for the adsorption and interactions with Ca²⁺/Mg²⁺ involved in YND1233/modified TiO₂ complex solution.     

Visible Light Photocatalytic Activity of Porphyrin Tin(IV) Sensitized TiO2 Nanoparticles for the Degradation of 4-Nitrophenol and Methyl Orange

A stable metalloporphyrin sensitized TiO₂ (Degussa P25) photocatalyst was prepared by using trans-dihydroxo[5,10,15,20-tetraphenylporphyrin]tin(IV) (SnP) as a sensitizer in a simple impregnation process. The solid diffuse reflectance ultraviolet-visible (UV-vis) spectrum of the SnP sensitized TiO₂ photocatalyst (SnP-TiO₂) indicated that there existed interaction between SnP and TiO₂. It was found that SnP-TiO₂ exhibited an enhanced visible light photocatalytic activity as compared with that over P25 for the degradation of 4-nitrophenol (4-NP) and methyl orange (MO) in aqueous solutions. The mechanism exploration showed that the degradation of MO and 4-NP experienced two different ways, that is, MO was photodegraded by reactive oxygen species and 4-NP was directly photodegraded by the excited state of SnP. Furthermore, it was found that the loading content of SnP had an important influence on the photocatalytic activity of TiO₂. The maximum photocatalytic efficiency was achieved when the contents of SnP were 25 mg and 30 mg per gram TiO₂ for MO and 4-NP, respectively. Importantly, SnP-TiO₂ was particularly stable and the photocatalytic activity was hardly decreased after being recycled seven times in the presence of oxygen, which could be attributed to the easy reductive regeneration of SnP.     

Sol-Gel Derived TiO2-SiO2 Fibres

TiO₂−SiO₂ fibres with 0, 5, 10 and 20 volume % SiO₂ have been prepared by drawing from a gel followed by sintering at different temperatures. Nearly one meter long fibres can be drawn easily in conditions of about 50% relative humidity. Addition of SiO₂ inhibits the crystallisation of TiO₂ and also the anatase → rutile transformation and improves the strength of the fibres. While the pure TiO₂ fibres are brittle, those with 5, 10 and 20 volume % SiO₂ are flexible and strong. Tensile strength values as high as 3 GPa have been achieved in the 10 volume % SiO₂−TiO₂ fibres. Fibres heated above 900°C are brittle. The shape of the cross section of the fibres is found to depend on their diameters.     

Fabrication of Ordered TiO2 Porous Thin Films by Sol-Dipping PS Template Method

Monolayer polystyrene spheres (∼400 nm) array templates were assembled orderly on clean glass substrates by dip-drawing method from emulsion of PS and porous TiO₂ thin films were prepared by using sol-dipping template method to fill TiO₂ sol into the interstices among the close-packed PS templates and then annealing to remove the PS templates. The effects of TiO₂ precursor sol concentration and dipping time in sol on the porous structure of the thin films were studied. The results showed pore size of the ordered TiO₂ porous thin film depended mainly on PS size and partly on TiO₂ sol concentration. The shrinkage of pore diameter was about 10% for 0.2 M and 20% for 0.4 M TiO₂ sol concentrations. X-ray diffraction (XRD) spectra indicated the porous thin film was anatase structure. The transmittance spectrum showed that optical transmittance of the porous thin film kept above 70% beyond the wavelength of 430 nm. Optical band-gap of the porous TiO₂ thin film (fired at 550^∘;C) was 3.12 eV.     

偶氮苯聚合物膜的光致高密度存储及其三维微结构的研究

设计、合成及表征了一种偶氮苯聚合物(PGMAA-20)。研究了该偶氮苯聚合物薄膜中的高密度光学存储和三维微结构,并成功地将20套光栅储存在样品中同一个点上,储存密度是已报道的两倍;用简单的2波混频光路在该材料中刻写出长方格子和六角星型的微结构,在制作多重不同周期不同角度的高密度光栅结构的实验过程中,观察到不同周期光栅的刻写顺序对整个微结构形成的最终结果具有决定性的影响。     

B2O3/TiO2-ZrO2的结构表征及其与酸性和催化性能间的关系

采用XRD、N₂吸附、 ¹¹B MAS NMR、NH₃-TPD和催化性能评价等方法研究了B₂O₃/TiO₂-ZrO₂催化剂的结构、酸性及催化环己酮肟气相Beckmann重排反应性能间的关系。结果表明,催化剂中的B₂O₃同时以三配位的BO₃和四配位的BO₄结构单元存在;     

含有偶氮苯和1,3,4-噁二唑结构聚合物的合成及性能

合成了同时含有偶氮苯和1,3,4-噁二唑结构的新型共轭聚合物(LPOXD),采用FT-IR、UV-Vis、1H NMR、GPC、TGA和DSC测试技术对其结构进行了表征。 结果表明,所得共轭聚合物的特性粘数为0.02960 L/g,Mw和分子量分布指数PDI分别为8500 g/mol和1.55。 质量损失5%的温度为290 ℃,Tg为92.8 ℃。 长烷氧基侧链的引入极大地提高了LPOXD在氯仿和四氢呋喃等有机溶剂中的溶解性。 采用紫外-可见吸收光谱、荧光光谱及循环伏安对LPOXD的光电性能进行了研究。 结果表明,在365 nm紫外光照射下,LPOXD中偶氮苯发生反-顺异构化;350 nm光激发下,LPOXD在蓝紫光波长范围内发射荧光;循环伏安测试得出LPOXD最高占有轨道(HOMO)能量和最低空轨道(LUMO)能量分别为-5.96和-3.17 eV。     

Aggregation Behavior of Titanium Dioxide Nanoparticles in Aqueous Environments

We report on the stability of titanium dioxide nanoparticles suspended in various aqueous solutions with and without the presence of a model organic contaminant—salicylic acid. The stability of the suspended nanoparticles was revealed by measuring the isoelectric point by means of zetapotential scans and measuring the growth kinetics of the hydrodynamic particle size by means of dynamic light scattering (DLS) under different pH conditions. Aggregated nanoparticle sizes were also examined using atomic force microscopy. It was found that salicylic acid had a dramatic impact on the aggregation behavior of TiO₂ nanoparticles, suggesting that salicylic acid adsorbs to TiO₂ nanoparticles surfaces.