Photochemical synthesis: Using light to build C–C bonds under mild conditions

A review of recent advancements in metal-free arylations via photogenerated triplet aryl cations and decatungstate anion ([W₁₀O₃₂]⁴⁻) photocatalyzed C–C bond formation is reported herein. These approaches are two examples of the great potentialities of photons as green activants in organic synthesis, allowing the functionalization of different chemical substrates under mild conditions (room temperature, aqueous solvents, absence of aggressive and unstable reactants and of expensive transition metal-based catalysts, and chance to use solar light as the energy source).     

Novel Bi2MoO6 Nanosheets/Vertical TiO2 Nanorods Arrays Heterojunction with Enhanced Photoelectrochemical Performance under Visible Light Irradiation

Novel Bi₂MoO₆/TiO₂ heterojunction was fabricated by growing Bi₂MoO₆ nanosheets arrays on the vertically aligned TiO₂ nanorods arrays via a two-step solvothermal method. The obtained Bi₂MoO₆/TiO₂ hierarchical heterojunction showed excellent visible light photoelectrochemical performance. Compared with the pure TiO₂ and Bi₂MoO₆, the photocurrent density of the heterojunction was increased 57 and 29 times, respectively. Furthermore, the hydrogen generation rate of the Bi₂MoO₆/TiO₂ for photoelectrocatalytic water-splitting was about 6 times higher than that of the pure Bi₂MoO₆. The improved performance can be attributed to the synergistic effects of enhanced absorption of visible light, increase of migration rate and separation efficiency of photo-induced carriers.     

Controllable Synthesis of Hexagonal WO3 Nanoplates for Efficient Visible‐Light‐Driven Photocatalytic Oxygen Production

Facilitating charge‐carrier separation and transfer is fundamentally important to improve the photocatalytic performance of semiconductor materials. Herein, two‐dimensional hexagonal WO₃ nanoplates were synthesized by a two‐step route: rapid evaporation and solid‐phase sintering. The as‐prepared WO₃ exhibits an enhanced activity of photocatalytic water oxidation compared to bulk monoclinic WO₃. The electron dynamics analysis reveals that a more efficient charge‐carrier separation in the former can be obtained, the origin of which can be attributed to an increased number of surface defects in hexagonal WO₃ nanoplates. This work not only presents a novel and simple method to produce two‐dimensional hexagonal WO₃ nanoplates, but also demonstrates that surface defects and two‐dimensional geometric structures can promote the charge separation, which may be extended to the design of other efficient photocatalysts.     

Tuning the properties of a black TiO2-Ag visible light photocatalyst produced by a rapid one-pot chemical reduction

A highly efficient black TiO₂-Ag photocatalytic nanocomposite, active under both UV and visible light illumination, was synthesized by decorating the surface of 25 nm TiO₂ particles with Ag nanoparticles. The material was obtained via a rapid, one-pot, simple (surfactant and complexing agent free) chemical reduction method using silver nitrate and formaldehyde as a metal salt and reducing agent, respectively. The nanocomposite shows an increase of over 800% in the rate of photocatalytic methylene blue dye degradation, compared to commercial unmodified TiO_2, under UV-VIS illumination. Unlike pure TiO₂, the nanocomposite exhibits visible light activation, with a corresponding drop in optical reflectance from 100% to less than 10%. The photocatalytic properties were shown to be strongly enhanced by post-reduction annealing heat treatments in air, which were observed to decrease, rather than coarsen, silver particle size, and increase particle distribution. This, accompanied by a variation in the silver surface oxidation states, appear to dramatically affect the photocatalytic efficiency under both UV and visible light. This highly active photocatalyst could have wide ranging applications in water and air pollution remediation and solar fuel production.     

The rheology of suspensions of vinylon fibers in polymer liquids. II. Suspensions in polymer solutions

Summary The rheological properties of vinylon fiber suspensions in polymer solutions were studied in steady shear flow. Shear viscosity, first normal-stress difference, yield stress, relative viscosity, and other properties were discussed. Three kinds of flexible vinylon fibers of uniform length and three kinds of polymer solutions as mediums which exhibited remarkable non-Newtonian behaviors were employed. The shear viscosity and relative viscosity ( _r ) increased with the fiber content and the aspect ratio, and depended upon the shear rate. Shear rate dependence of _r was found only in the low shear rate region. This result was different from that of vinylon fiber suspensions in Newtonian fluids. The first normal-stress difference increased at first slightly with increasing fiber content but rather decreased and showed lower values for high content suspensions than that of the medium. A yield stress could be determined by using a modified equation of Casson type. The flow properties of the fiber suspensions depended on the viscosity of the medium in the suspensions under consideration.With 16 figures and 1 table     

Photoelastic model measurement with rotated principal axes by scattered-light photoelasticity

The method of measurement of a three-dimensional photoelastic model with rotated principal axes has not yet been fully experimentally established. It is known that a three-dimensional photoelastic model can be reduced to an optically equivalent model. In this paper, the optically equivalent model is realized from a stratified model consisting of two layers of the frozen stress model. The secondary principal stress direction and the relative phase retardation of the frozen disk model in the stratified frozen stress model are determined for the entire field from Stokes parameters obtained by scattered-light photoelasticity using unpolarized light. The accuracy of these values is confirmed by a comparison with results only from the frozen stress disk model.     

Efficiency Improvement in Polymer Light‐Emitting Diodes by “Far‐Field” Effect of Gold Nanoparticles

The “far‐field” effect of metal nanoparticles (NPs), when chromophores localized nearby metal NPs (typically the distance >λ/10), is an important optical effect to enhance emission in photoluminescence. The far‐field effect originates mainly from the interaction between origin emission and mirror‐reflected emission, resulting in the increased irradiative rate of chromophores on the mirror‐type substrate. Here, the far‐field effect is used to improve emission efficiency of polymer light‐emitting diodes (PLEDs). A universal performance improvement is achieved for the full visible light (red, green, blue) PLEDs, utilizing gold (Au) NPs to modify the indium tin oxide (ITO) substrates; this is shown by experimental and theoretical simulation to mainly come from the far‐field effect. The optimized distance, between the NPs and chromophores with visible light emission ranging from 400 to 700 nm, is 80–120 nm. Thus the scope of the far‐field may overlap the light‐emitting profile very well to enhance the efficiency of optoelectronic devices. The 30–40% enhancement is obtained for different color‐emitting materials through distance optimization. The far‐field effect is demonstrated to enhance device performance for materials in the full‐visible spectral range, which extends the optoelectric applications of Au NPs.     

基于可调控多肽纳米管和石墨烯复合纳米结构的光吸收催化平台

近年来, 自组装纳米结构因为其容易制备、稳定、环保以及与各种功能基团、粒子等的多样结合能力吸引了科学家们的目光, 成为人们研究的热点课题, 在光电池、光催化、水凝胶、药物缓释等方面的实验科学领域得到了广泛的应用. 尤其是光催化方面, 自组装结构的重复性为激子的传递创造了比较良好的条件, 成为众多激子传递平台中的佼佼者. 本文报道了一种以苯丙氨酸二肽纳米管和羧基石墨烯为基础的自组装光吸收催化平台, 对其结构进行研究, 并使用该体系进行了烟酰胺腺嘌呤二核苷酸到它的还原态的催化实验. 该体系的微观结构由纳米管和石墨烯膜复合而成, 羧基石墨烯的存在能够降低纳米管直径, 实现纳米管的形态操控, 石墨烯与多肽纳米管复合纳米结构的存在实现了多通道协同激子传递, 降低了激子传递的距离, 极大增强了催化中心对于激子的接受和使用效率. 在复合了光敏剂和催化中心之后, 该体系具有较高的稳定性, 均一的分散性, 很强的光能吸收和转化能力等性质. 对于从NADP⁺往NADPH转变的催化实验表明, 该体系有较高的反应速率和催化效率, 并且比两种单一结构催化平台效果之和更好, 实现了一加一大于二的效应, 展现了复合纳米结构光吸收催化平台的巨大潜力和广阔应用前景.     

基于菌紫质F态的永久光存储研究

在线偏振飞秒激光激发下, 菌紫质通过双光子光化学反应可以生成具有永久光致各向异性的蓝移产物F₅₄₀态. 基于F₅₄₀态的永久光致各向异性, 通过调控飞秒激光空间光场分布, 可以在菌紫质薄膜中实现永久光信息存储. 本文使用纯相位型空间光调制器调制飞秒激光光场, 在物镜焦平面上生成光学点阵图案, 可以将信息快速记录在菌紫质薄膜中. 同时, 通过改变入射激光偏振方向, 可以实现偏振复用光存储, 这在高密度光存储和数据加密领域具有潜在应用.     

室温条件下掺铥光纤放大器中光波群速减慢的研究

从掺铥离子光纤的速率方程和传输方程出发,建立了掺铥离子光纤放大器中光速减慢的理论模型,分析并讨论了介质的增益与泵浦光功率之间的关系。当掺铥离子光纤处于吸收区域时,粒子布居振荡导致光脉冲经历了饱和吸收过程,此时光脉冲传输延迟;当掺铥离子光纤处于增益区域时,粒子布居振荡导致光脉冲经历了增益饱和过程,此时脉冲传输超前。依据该理论模型进行了理论仿真计算,同时进行了室温条件下掺铥离子光纤中光波群速减慢传输的研究。