Preparation and Characterization of Nanocrystalline Fe-Doped TiO2 Film on Different Substrates and Its Application in Degrading Dyeing Water

TiO₂ and Fe-doped TiO₂ thin films were prepared on the substrates (glass plates and glass microballs) after dipped in colloid and calcined at 500°C. The films have been characterized by UV-absorption, x-ray diffraction and atomic force microscopy (AFM). The investigated Fe-doped TiO₂ (A nominal 10 wt% Fe₂O₃ was impregnated) thin films were obtained by sol-gel method. The characterization results suggest that the calcined thin films primarily consist of TiO₂ anatase. And the light absorption curve of the TiO₂ films modified with Fe showed that red shift had happened by the dope of Fe. TiO₂/beads as photocatalyst were used to degrade the simulated dyeing water which contains reactive deep-blue dye (K-R). Through the degradation experiment, we found that the dope of Fe promoted the photocatalytic activities. The results showed that the dyeing water can be decomposed more effectively by the photocatalytic oxidation of Fe/TiO₂ film on glass micro-balls than glass plates.     

铁铈复合氧化物催化剂SCR脱硝的改性研究

利用共沉淀法制备了铁铈催化剂,考察添加钛、锆、钨和钼对其SCR脱硝的改性规律。结果表明,钨和钼的添加提高了铁铈催化剂高温脱硝性能,却使其低温活性有所降低;钛的添加对铁铈催化剂脱硝性能具有促进作用,尤其提高了其低温活性,并拓宽了其完全转化温度窗口,为最佳改性物。当钛的物质的量比逐渐由0.10增至0.40,铁铈钛催化剂低温脱硝效率先增大后减小,但其高温脱硝效率逐渐增大至100%,钛的最佳物质的量比为0.15。XRD和N₂吸附分析结果表明,钛能优化铁铈催化剂的孔隙结构,增大其比表面积和比孔容,细化其孔径,并与催化剂中铁、铈氧化物形成良好的固溶体,从而提高了铁铈催化剂的SCR脱硝性能。Fe_0.8Ce_0.05Ti_0.15O_z催化剂在150～400℃取得了高于90%的NO_x转化率。     

Titanium complexes bearing carbamato ligands as catalytic precursors for propylene polymerization reactions

This report describes propylene polymerization reactions with titanium complexes bearing carbamato ligands, Ti(O₂CNMe₂)Cl₂ ( I ) and Ti(O₂CR₂)₄ [R₂ = NMe₂ ( II ), NEt₂ ( III ) and ( IV )]. Combinations of these complexes and MAO form catalysts for the synthesis of atactic polypropylene, as confirmed by FT‐IR, DSC and ¹³C NMR analysis. Effects of main reaction parameters on the catalyst activity were studied including the type of complex, solvent, temperature, and the [Al]/[Ti] molar ratio. The highest activity was observed when chlorobenzene was used as a solvent and AlMe₃‐depleted MAO was employed as a cocatalyst. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4095–4102     

Direct Observation of the Binding Mode of the Phosphonate Anchor to Nanosized Polyoxotitanate Clusters

The structures of three newly synthesized phosphonate‐substituted polyoxotitanates are reported. The Ti/O core of [Ti₄O(OEt)₁₂(PhenylPO₃)] ( 1 ) is the building block for two larger phosphonate‐substituted nanoclusters, [Ti₂₅O₂₆(OEt)₃₆(PhenylPO₃)₆] ( 2 ) and [Ti₂₆O₂₆(OEt)₃₉(PhenylPO₃)₆]Br ( 3 ). All compounds exhibit a not previously recognized triply bridging binding mode of the phosphonate anchor with short connecting Ti? O bonds, the average of which is 2.010(7) Å. Comparison with previously reported work suggests that the binding mode of the phosphonate anchor is strongly dependent on the structure of the underlying substrate.     

大比表面积钛黑颜料的制备和表征

本文首次通过pH值控制沉淀法制备前驱物丁二酸钛肼复盐,并进一步热分解制备大比表面积钛黑颜料-黑色钛氧化物。通过比表面积(BET)、电子能谱(EDS)、X射线光电子能谱分析(XPS)、X射线粉末衍射(XRD)、场发射扫描电子显微镜(HRSEM)、物理吸附仪、激光粒度仪和Color i5型台式分光测色仪对黑色钛氧化物进行了表征,确定了黑色钛氧化物的组成为2TiO2·Ti2O3,其表面积为53.854 4 m2·g-1。并考察了酸源、水合肼用量、酸钛比、反应时间、pH、NaOH浓度和煅烧温度等各种反应参数对黑色钛氧化物的颗粒尺寸、分布均匀性和黑色度的影响。用元素分析仪和等离子体光谱仪测定了前驱物组成,确定其组成为[Ti(C4H4O4)2]0.85·2Ti2O3·6N2H4·3H2O,并探讨了黑色钛氧化物形成机理,为新型混合价材料黑色钛氧化物的制备提供重要参考依据。     

Research of Fluorination Process of Rutile Concentrate

The brief review of industrial technologies of titanium-containing concentrates processing has been carried out. Drawbacks of the existing titanium manufacture schemes are shown and the necessity of the essentially new fluoride technologies development has been proved. The reactions proceeding during the fluorination of rutile concentrate with element fluoride are described in the given work. The thermodynamic research of the process has been carried using ASTRA software. Dependence of mass concentration change of titanium tetrafluoride has been investigated in products of reaction on the temperature of the process, and the choice of optimum excess of fluoride has been proved.     

Selective solid-phase microextraction of polycyclic aromatic hydrocarbons in water based on oriented phosphorus-containing titanium oxide nanofibers grown on titanium support prior to high-performance liquid chromatography with ultraviolet detection

A novel solid-phase microextraction coating of phosphorous-containing titanium oxide composite was developed using titanium fiber as a support and a titanium source by hydrothermal oxidation in a phosphoric acid solution containing hydrogen peroxide. The morphology of the fiber coatings was controlled by the conditions of the hydrothermal oxidation reaction. The oriented nanofiber coating was employed to extract several types of representative aromatic analytes. The experimental results demonstrated that the as-prepared fiber exhibited excellent extraction efficiency toward polycyclic aromatic hydrocarbons. Combined with high-performance liquid chromatography with ultraviolet detection, main extraction conditions were optimized, including pH, ionic strength, extraction temperature, stirring rate, extraction time and desorption time. The established method presented good linearity from 0.05 to 200 μg/L with limit of detection ranging from 0.012 to 0.126 μg/L. This convenient and green procedure was suitable for the selective extraction and determination of typical polycyclic aromatic hydrocarbons in environmental water samples. The relative recoveries of 85.8–112% were obtained for the determination of target polycyclic aromatic hydrocarbons in water samples spiked with 5.0 and 15.0 μg/L. Moreover, the as-prepared fiber showed at least 210 extraction/desorption cycles due to its high mechanical and chemical stability.     

Sulfanyl Porphyrazines with Morpholinylethyl Periphery—Synthesis,Electrochemistry, and Photocatalytic Studies after Deposition on Titanium(IV) Oxide P25 Nanoparticles

The syntheses, spectral UV–Vis, NMR, and electrochemical as well as photocatalytic properties of novel magnesium(II) and zinc(II) symmetrical sulfanyl porphyrazines with 2-(morpholin-4-yl)ethylsulfanyl peripheral substituents are presented. Both porphyrazine derivatives were synthesized in cyclotetramerization reactions and subsequently embedded on the surface of commercially available P25 titanium(IV) oxide nanoparticles. The obtained macrocyclic compounds were broadly characterized by ESI MS spectrometry, 1D and 2D NMR techniques, UV–Vis spectroscopy, and subjected to electrochemical studies. Both hybrid materials, consisting of porphyrazine derivatives embedded on the titanium(IV) oxide nanoparticles’ surface, were characterized in terms of particle size and distribution. Next, they were subjected to photocatalytic studies with 1,3-diphenylisobenzofuran, a known singlet oxygen quencher. The applicability of the obtained hybrid material consisting of titanium(IV) oxide P25 nanoparticles and magnesium(II) porphyrazine derivative was assessed in photocatalytic studies with selected active pharmaceutical ingredients, such as diclofenac sodium salt and ibuprofen.     

响应面法优化Co2+掺杂TiO2制备工艺研究

利用共沉淀-水热法制备了钴掺杂二氧化钛光催化剂,以催化降解水中草甘膦效率为指标,采用响应面法对钴掺杂二氧化钛光催化剂的制备条件进行优化。结果表明,钴掺杂二氧化钛光催化剂的最佳制备工艺为:水热反应温度139.64℃、水热反应时间23.75h、煅烧温度408.17℃和煅烧时间4.04h。利用最佳制备条件下制得的钴掺杂二氧化钛光催化剂催化降解水中草甘膦,降解效率接近80%,与纯二氧化钛相比,催化降解效率有较大幅度提升。     

摩擦点火Ti-V-Cr阻燃钛合金燃烧产物的组织特征

采用摩擦氧浓度实验方法, 结合原位观察、扫描电镜、能谱仪和X-射线衍射分析, 系统研究Ti-V-Cr 阻燃钛合金燃烧产物的微观组织形貌、燃烧反应过程的合金元素分布规律及微观机理. 结果表明: Ti-V-Cr 阻燃钛合金燃烧过程发出闪亮耀眼的白光, 具有典型金属燃烧的火焰特征. 燃烧产物主要有TiO₂, V₂O₅和Cr₂O₃三种氧化物, 该混合氧化物以分散颗粒和致密连续体存在. 分散颗粒为规则的球形; 致密连续燃烧产物的微观组织具有分区特征, 从合金基体至燃烧表面依次为过渡区、热影响区、熔凝区和燃烧区. 其中, 过渡区存在一些微小的颗粒状凸起, 且有一定方向性; 热影响区中形成大量V基固溶体相和少量的Ti基固溶体相, V基固溶体相上存在Ti的含量远高于基体的针状析出物; 熔凝区中, 大量的Ti基固溶体中存在少量的V基固溶体; 燃烧区主要为Ti, V和Cr的氧化物混合物. 热影响区的V基固溶体相降低了Ti元素向熔凝区的迁移速率, 减慢了燃烧区Ti与O的优先反应; 燃烧区形成的TiO₂, V₂O₅和Cr₂O₃混合氧化物和熔凝区O在Ti中大量固溶共同终止了O向合金基体的继续扩散, 从而使Ti-V-Cr阻燃钛合金表现出优异的阻燃功能性.