The effect of titanium alkoxides in the synthesis of heterobimetallic complexes by titanocene(III) alkoxide-induced metal-metal bond cleavage of metal carbonyl dimers

A series of titanocene(III) alkoxides L₂Ti(III)OR where L = Cp, R = Et(1b), ^tBu(1a), 2,6-Me₂C₆H₃(1c), 2,6-^tBu₂-4-Me-C₆H₂(1d), or L = Cp*, R = Me(2e), ^tBu(2a), Ph(2f) was synthesized and subjected to reaction with [CpM(CO)₃]₂ [M = Mo, W], [CpRu(CO)₂]₂, and Co₂(CO)₈. The Ti(III) precursors 1a, 1c, 2a, 2e, and 2f reacted with [CpM(CO)₃]₂ [M = Mo, W] to form heterobimetallic complexes L₂Ti(OR)(μ-OC)(CO)₂MCp [M = Mo, W], of which Ti and M are linked by an isocarbonyl bridge. Reactions of these Ti(III) complexes with Co₂(CO)₈ resulted in formation of Ti-Co₁ heterobimetallic complexes, from 2a, 2e, or 2f, or Ti-Co₃ tetrametallic complexes, Cp₂Ti(O^tBu)(μ-OC)Co₃(CO)₉ from 1a, 1b, or 1c. The products were characterized by NMR, IR, and X-ray crystallography. Reaction mechanisms were proposed from these results, in particular, from steric/electronic effects of titanium alkoxides.     

Pt/K2La2Ti3O10催化剂的合成及其光催化分解甲醇水溶液制氢

用高温固相法合成了具有类钙钛矿型结构的层状化合物K₂La₂Ti₃O₁₀, 用XRD, UV-DRS对其进行表征. 利用不同还原方法制备了Pt/K₂La₂Ti₃O₁₀光催化剂, 并且用脉冲氢氧滴定法(HOT)测定了K₂La₂Ti₃O₁₀表面Pt的分散度. 考察了Pt/K₂La₂Ti₃O₁₀光催化分解甲醇水溶液制氢的活性. 比较了负载Pt与负载Ni和纯的K₂La₂Ti₃O₁₀的光催化活性. 研究了Pt负载量、不同还原方法对光催化分解水制氢反应活性的影响. 在最佳的Pt负载量2%(质量百分比)下, 产氢速率达到233.88 mmol·h^&;#8722;1. 讨论了该催化剂的能带结构及反应机理.     

Ti,Na与O2反应机理的理论研究

基于MP2/6-311+G(d)水平, 分别对过渡金属Ti和碱金属Na与O2的反应机理进行了研究. 比较了Ti和Na分别以垂直O—O键和沿着O—O键的方向逼近O2, 以及中性体系Ti/Na+O2和带1个负电荷的体系(Ti/Na+O2)-的情况. 详细分析了不同反应路径的结合能和电荷变化的曲线, 预测了最佳反应方式. 结果表明, 垂直接近方式要比水平接近方式更具有优势; 体系带一个负电荷(Ti/Na+O2)-有利于金属与O2的结合. 同时, 计算结果表明在Ti+O2和(Ti+O2)-体系中Ti容易与单态的O2结合; 在中性体系中Na也容易与单态O2结合, 而在(Na+O2)-体系中Na与三态O2的结合更稳定. 在CCSD(T)/6-311++G(3df)//MP2/6-311+G(d)水平下, 计算了Ti+O2和(Ti+O2)-的反应势能面.     

Co3O4 Decorated Ti/TiO2 Nanotubes for Photogenerated Cathodic Protection of 304 Stainless Steel

The Co₃O₄ decorated TiO₂ nanotube arrays(NTAs) coatings are fabricated by the combination of anodization and impregna-ting methods. It is found that the introduction of Co₃O₄ can reduce the diffraction intensity of (101) plane of the TiO₂ and accelerate the separation of photogenerated electron/hole pairs. In addition, the open circuit potential(OCP) and the corrosion potential of 304 stainless steel(304SS) with or without Co₃O₄ decorated TiO₂ NTAs were measured under visible light, which indicated the 304SS coupled with Co₃O₄ decorated TiO₂ NTAs had better anticorrosion performance than that of the 304SS or the 304SS coupled with pure TiO₂ NTAs. The enhancement of the cathodic protection performance of the Co₃O₄ decorated TiO₂ NTAs can be ascribed to the matched energy levels and strong interaction between Co₃O₄ and TiO₂ NTAs, and the improvement of light absorption.     

良性前列腺增生组织对钛宝石激光的吸收和散射特性

研究了经尿道等离子体双极电切除术(PKRP)切除和经尿道前列腺电切术(TURP)切除的前列腺增生(BPH)组织对640, 660, 680, 700, 720, 740, 760, 780, 800, 820, 840, 860和880 nm波长的钛宝石激光的光学特性及其差异,实验采用双积分球测量系统以及反向倍增法获取BPH组织的吸收和散射特性参数。结果表明：PKRP和TURP切除的BPH组织对这1３个不同波长的激光的吸收系数和约化散射系数都是随着激光波长增大而明显减小的,PKRP切除的BPH组织对这同一波长的激光的吸收系数和约化散射系数都明显较TURP切除的BPH组织对相应的波长的激光的吸收系数和约化散射系数要小,PKRP和TURP切除的BPH组织的吸收系数以及约化散射系数的最大值都在640 nm,其值分别为(0.885±0.022)和(0.955±0.024)mm-1以及(1.564±0.039)和(1.658±0.042)mm-1,其差异分别为7.91%以及6.01%,其最小值都在880 nm,其值分别为(0.443±0.011)和(0.455±0.011)mm-1以及(1.117±0.028)和(1.197±0.030)mm-1,其差异分别为2.71%以及7.16%。PKRP和TURP切除的BPH组织对660 nm的吸收系数的差异最大,其值为8.95%,其差异最小在860 nm,其值为1.75%,PKRP和TURP切除的BPH组织对800 nm的约化散射系数的差异最大,其值为9.13%,其差异最小在640 nm,其值为6.01%。     

累积轧制Ti／AI复合材料的微观结构演变和力学性能研究

用累积轧制法成功制备了平均晶粒尺寸为200--300nm的超细等轴晶Ti／A1多层复合材料．研究了Ti／A1多层复合材料的微结构变化和力学性能．     

Preparation of BiVO4/MIL‐125(Ti) composite with enhanced visible‐light photocatalytic activity for dye degradation

Because of their desired features, including very specific surface areas and designable framework architecture together with their possibility to be functionalized, Metal Framework (MOF) is a promising platform for supporting varied materials in respect of catalytic applications in water treatment. In this work, a novel visible‐light‐responsive photocatalyst that comprised BiVO₄ together with MIL‐125(Ti), was synthesized by a two‐step hydrothermal approach. The characterization of as‐obtained samples as performed by X‐ray diffraction, scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscope, X‐ray photoelectron spectroscopy and ultraviolet‐visible diffuse reflection spectra. Rhodamine B was selected being a target for the evaluation of the photocatalytic function of as‐developed photocatalyst. The photocatalytic reaction parameters, for example, the content of BiVO₄ as well as initial concentration of Rhodamine B was researched. The composite photocatalyst possessing Bi:Ti molar ratio of 3:2 brought to light the fact that the greatest photocatalytic activity had the ability to degrade 92% of Rhodamine B in 180 min. In addition to that, the BiVO₄/MIL‐125(Ti) composite could keep its photocatalytic activity during the recycling test. The phenomenon of disintegration of the photo‐generated charges in the BiVO₄/MIL‐125(Ti) composite was brought to discussion as well.     

Dephosphatation under UV light of water by Ti-PILC with activation by secondary species (La,Se, and Rb)

Me/Ti-PILC catalysts (Me: La, Se, Rb) were prepared with 60% in weight of Ti-species and 3% in weight of Me-secondary species added under ultrasounds. All materials were characterized by XRF, XPS, XRD, BET, HR-TEM/EDS, FEG-SEM and UV-vis. Three kinds of Ti-oxide nanoparticles were identified: (1) Ti-pillars within the clay layers, (2) rutile nanoflowers, and (3) anatase. In UV-vis spectra, no significant change in the band-gap was observed. In La and Se samples, small variations of the anatase XRD lines are associated with cationic diffusion after deposition of secondary species and calcination. An O1s XPS-peak (533.5 eV) is attributed to oxygen vacancies generated by this diffusion. Phosphate photo-removal in water was studied using phosphoric acid solution (75.97 g L⁻¹). Dephosphatation is significantly improved in the presence of Me-species as La/Ti-PILC > Se/Ti-PILC > Rb/Ti-PILC > Ti-PILC. Partial dephosphatation by adsorption is possible in the dark but is strongly improved by UV irradiation. With a La catalyst and under UV irradiation, phosphates (6.6 × 10⁻³ mol L⁻¹) were recovered in less than 70 min. Therefore, Me/Ti-PILC have a great potential as photocatalysts for the treatment of wastewaters and the recovery of phosphates.     

Zr/Ti摩尔比对锶锆钛复合氧化物在可见光下光催化性能的影响

通过分步沉积法制备了不同Zr/Ti 摩尔比的锶锆钛(SZT)复合氧化物催化剂, 以X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、紫外-可见(UV-Vis)漫反射光谱等表征手段考察不同Zr/Ti 摩尔比下SZT催化剂的结构形态, 以可见光下光催化降解亚甲基蓝为模型反应考察样品的光催化活性. 结果表明: Zr/Ti 摩尔比<1 时SZT催化剂发生Zr⁴⁺与Ti⁴⁺同质替换, 引起晶格缺陷, 光催化活性小幅提高; Zr/Ti 摩尔比≥1 时SZT催化剂产生SrZrO₃/Ti_nO_2n-1 (n=4, 9)的新晶相, Ti_nO_2n-1 (n=4, 9)的存在有利于光生电子-空穴的传导与分离, 可大幅提高催化剂光催化活性. 其中, SZT-5/5 表现出最高的光催化活性, 其一级反应速率常数达到0.2133 min^-1, 是同等光照条件下纯SrTiO₃样品(0.0158 min^-1)的13.5倍.     

Electrochemical behavior in simulated body fluid of TiO2 nanotubes on TiAlNb alloy elaborated in various anodizing electrolyte

The present study is focused on tailoring the morphology of TiO₂ nanotubes obtained on Ti6Al7Nb alloy and evaluating their electrochemical behavior in simulated body fluid. The presence of the α and β phases on the Ti6Al7Nb alloy leads to a two‐scale organization of the nanotubes on the samples – which in turn affects the electrochemical stability. Furthermore, five different types of TiO₂ nanotubes were obtained in various electrolytes (e.g. Generation I, a mixture of Generation II and Generation III, Generation III). Electrochemical behavior analysis of all obtained nanotubes morphologies was composed of Tafel plots, cyclic voltammetry and electrochemical impedance spectroscopy and was correlated with morphology data obtained from SEM (nanotubes diameters from top‐view and nanotube length from cross‐section view). The electrochemical results showed that morphological modifications of the Ti6Al7Nb alloy's surface by electrochemical anodizing have induced changes to the electrochemical behavior of the material, evident in the corrosion rates. Copyright © 2014 John Wiley & Sons, Ltd.