硅杂四元环化合物的合成和反应

硅杂四元环化合物在有机硅化学中是一类非常重要的小分子环系化合物, 广泛应用于有机化学、金属有机化学以及材料化学. 环上只含有一个硅原子的硅杂环丁烷可以通过γ-卤代丙基硅烷的Grignard反应、Si＝C键与烯烃的 [2＋2]环加成反应以及硅杂环丙烷的扩环反应合成, 环上只含有一个硅原子的硅杂环丁烯可以通过格氏试剂或锂试剂参与的Si—C键的关环反应、硅杂环丁烷的转化反应、硅卡宾对C—H键的插入反应、Si＝C键与炔烃的[2＋2]环加成反应以及二炔基硅烷的分子内成环反应等途径合成. 硅杂环丁烷和硅杂环丁烯由于存在环张力和具有一定的Lewis酸性, 能够通过扩环反应生成五元和六元含硅杂环化合物, 也能够通过开环反应生成不同结构的有机硅分子和聚合物, 抑或实现有机反应在温和条件下的转化.     

硅表面嫁接有机单分子膜的研究近况

由于在微电子、化学 /生物化学传感器、纳米技术及太阳能等领域具有潜在的应用价值 ,通过 Si— C键在硅表面上直接嫁接有机单分子膜 ,已成为近几年新开展的研究热点 .对这一研究领域进行了概要综述     

C(sp3)—H键直接催化硅基化反应研究进展

含C(sp3)—Si键的有机硅化合物在材料科学、药物化学和精细化学品合成等研究领域有着广泛的应用.通过C(sp3)—H的直接催化硅基化形成C(sp3)—Si键具有高的原子经济性和步骤经济性特点,近些年己成为含C(sp3)—Si键的新型有机硅分子合成领域的一个研究热点.详细总结了 C(sp3)—H键直接催化硅基化反应的研...     

银纳米颗粒/聚(乙撑二氧噻吩)修饰的硅纳米线阵列的合成及可见光催化性能研究

硅纳米线阵列由于其较强的光吸收能力及硅材料的丰富储量,被认为是最具大规模应用潜力的可见光光催化剂.针对硅材料在水相环境中不稳定这一瓶颈问题,本文提出了对硅纳米线阵列"先稳定、再活化"的修饰策略.通过在硅纳米线表面修饰聚(乙撑二氧噻吩)使其稳定,之后再修饰银纳米颗粒以提高光催化效率,得到了高效、稳定的可见光光催化剂.并通过研究聚(乙撑二氧噻吩)的厚度及银纳米颗粒的担载量对光催化剂性能的影响,得到了最佳的修饰条件.     

聚丙烯酰胺修饰Fe_3O_4磁性纳米粒子的制备与表征

首先通过化学处理在Fe3O4磁性纳米粒子表面引入Si—H键,然后通过选择性的硅氢加成反应制备了一个端基带溴的磁性引发剂,并利用原子转移自由基聚合(ATRP)技术,在该磁性引发剂表面接枝了聚丙烯酰胺高分子,该聚丙烯酰胺高分子展现出分子量高度可控性和窄的分子量分布.经聚丙烯酰胺修饰后Fe3O4磁性纳米粒子的比饱和磁化强度为58.5 emu.g-1,与未修饰纳米Fe3O4相比下降约20%.     

可见光诱导C—N键断裂构建C—C键的研究进展

近年来,可见光促进的光化学有机转化引起了广大有机化学家的兴趣.相比于传统方法,利用可见光作为可再生能源的光氧化还原催化已被证明是一种温和而强大的工具,可以通过单电子转移(SET)过程促进有机分子的活化.在许多天然产物的结构中存在大量的氨基功能团,同时氨基也是一些药物分子和功能材料的重要结构单元.因此,通过对这些物质分子中的C—N键进行活化而进行C—C键形成的偶联反应,则可以对该类化合物进行有效的结构修饰,从而得到具有多种结构及功能化的化合物.因此,这方面的研究现已成为了有机合成的一个重要研究领域.综述了近年来通过可见光促进C—N键断裂及其在C—C键形成反应研究中的应用研究成果,讨论了代表性的例子及其反应机制.     

n-型多孔Si/TiO2纳米线异质结构的制备及光电化学性能

采用光辅助电化学腐蚀法制备了n-型多孔硅衬底, 再采用水热法在其表面生长TiO₂纳米线制得了三维n-型多孔Si/TiO₂纳米线异质结构. 通过X射线衍射、 扫描电子显微镜和X射线能量散射等表征证实了n-型多孔Si/TiO₂纳米线异质结构的形成. 紫外-可见漫反射光谱测试结果表明, n-型多孔硅与TiO₂纳米线的复合提高了紫外-可见波段的光吸收. 光电性能测试结果表明, 3个样品中n-型多孔Si/TiO₂纳米线异质结作为光电极的光电流最高, 这说明n-型多孔Si/TiO₂纳米线作为光电极具有更高的光电化学分解水性能.     

通过硅烷偶联剂在硅和铟锡氧化物(ITO)表面嫁接寡聚芴分子

通过硅烷偶联剂γ-氨丙基三乙氧基硅烷(3-aminopropyl-triethoxysilane,APTES)的“分子桥梁”作用,采用两种不同的方法,把修饰后的寡聚芴分子键联到硅表面和铟锡氧化物(ITO)表面上。X射线光电子能谱(XPS)、原子力显微镜(AFM)和循环伏安(CV)方法等的表征证实了通过硅烷偶联剂在硅表面和ITO表面嫁接寡聚芴分子可行性。     

硅表面有机单分子膜的新表征方法──界面微分电容测量法

提出一种表征硅表面有机单分子膜的新方法界面微分电容测量法.通过对新制备的H-Si(111)表面和一系列烯烃分子修饰的硅表面/电解液界面的微分电容的研究,建立了硅表面有机膜结构和性质与界面电容之间的联系.实践证明这是一个简便、快速和有效的实验技术,为硅表面化学修饰与功能化研究提供了一个非常有力的工具.     

有机分子修饰硅表面*

硅作为一种重要的半导体材料,在微电子领域发挥着极其重要的作用。有机分子修饰硅表面是近年来硅表面化学领域的一个研究热点,引起了研究者的广泛重视。以共价键嫁接在硅表面的有机单分子层能形成稳定、高质量的杂化连接,将赋予传统的硅材料更多新的功能,具有许多其它表面难以比拟的优点。本文针对有机分子修饰硅表面的方法、单层膜的表征和应用,对近年来的最新研究进展进行了综述,并对该方向的今后的发展进行了展望。     

Mimicking both petal and lotus effects on a single silicon substrate by tuning the wettability of nanostructured surfaces

We describe a new method of fabricating large-area, highly scalable, "hybrid" superhydrophobic surfaces on silicon (Si) substrates with tunable, spatially selective adhesion behavior by controlling the morphologies of Si nanowire arrays. Gold (Au) nanoparticles were deposited on Si by glancing-angle deposition, followed by metal-assisted chemical etching of Si to form Si nanowire arrays. These surfaces were chemically modified and rendered hydrophobic by fluorosilane deposition. Au nanoparticles with different size distributions resulted in the synthesis of Si nanowires with very different morphologies (i.e., clumped and straight nanowire surfaces). The difference in nanowire morphology is attributed to capillary force-induced nanocohesion, which is due to the difference in nanowire porosity. The clumped nanowire surface demonstrated the lotus effect, and the straighter nanowires demonstrated the ability to pin water droplets while maintaining large contact angles (i.e., the petal effect). The high contact angles in both cases are explained by invoking the Cassie-Baxter wetting state. The high adhesion behavior of the straight nanowire surface may be explained by a combination of attractive van der Waals forces and capillary adhesion. We demonstrate the spatial patterning of both low- and high-adhesion superhydrophobicity on the same substrate by the simultaneous synthesis of clumped and straight silicon nanowires. The demonstration of hybrid superhydrophobic surfaces with spatially selective, tunable adhesion behavior on single substrates paves the way for future applications in microfluidic channels, substrates for biologically and chemically based analysis and detection where it is necessary to analyze a particular droplet in a defined location on a surface, and as a platform to study in situ chemical mixing and interfacial reactions of liquid pearls.     

超疏水多孔硅的制备及表面稳定性

在加热条件下采用氢化硅烷化反应对多孔硅表面进行改性, 通过扫描电子显微镜、 红外光谱及元素分析等手段表征了多孔硅改性前后的结构和组成, 研究了不同反应时间对其性能的影响. 结果表明, 反应3 h后制得了超疏水表面的多孔硅, 其在碱性及空气环境中具有良好的稳定性.     

Boosting the Dynamic Range for Electrochemical Sensing of Hydrogen Peroxide by Enhanced Integration of Pd Nanoparticles in 3D Porous Si Framework

Three-dimensional porous silicon framework (3D-pSi) integrated with various nanostructures is highly potential for functional devices usage such as micro fuel cells or sensing chips. For noble metal deposition in highly directional Si nanowire array or porous Si with large aspect ratios, one difficulty is the restriction on the depth of deposition available. Herein, we would like to introduce a facile route to enhance the integration of Pd nanoparticles with anisotropic Si porous structure. By converting Si nanowire array into 3D-pSi, the surface coverage of Pd nanoparticles is effectively improved as shown by scanning electron micrographs and cross-sectional element mapping data. The relative electrochemical active surface area is increased by 3.5 folds. In order to demonstrate the merits brought by this morphological evolution, the electrochemical sensing devices are prepared for detecting H₂O₂ in PBS solution. As shown by differential pulse voltammetry, the upper limit of linear range of detection can be raised from 6.30 mM to 14.95 mM. This approach may indicate an alternative for boosting the performance of future sensing chips with progressively limited die area, especially attractive for those scenarios where large dynamic range is favourable.     

Biomimetic fabrication of lotus-leaf-like structured polyaniline film with stable superhydrophobic and conductive properties

Superhydrophobic surfaces were successfully prepared on Ti/Si substrates via the fabrication of conductive polyaniline (PANI) nanowire film. The PANI nanowire film was synthesized by electrodeposition of aniline into the pores of an anodic aluminum oxide (AAO) template on Ti/Si substrate followed by the removal of the template. The surface showed conductivity and superhydrophobicity, even in many corrosive solutions, such as acidic or basic solutions over a wide pH range. Field emission scanning electron microscopy (FE-SEM) demonstrated that the binary geometric structures at micro- and nanometer scale bestowed the prerequisite roughness on the surfaces. The chemical surface modification made the PANI nanowire film superhydrophobic. The results demonstrated that the PANI nanowire film will have good potential applications in the preparation of conductive superhydrophobic surfaces.     

Chemical surface passivation of 3C‐SiC nanocrystals: A first‐principle study

The effect of the chemical surface passivation, with hydrogen atoms, on the energy band gap of porous cubic silicon carbide (PSiC) was investigated. The pores are modeled by means of the supercell technique, in which columns of Si and/or C atoms are removed along the [001] direction. Within this supercell model, morphology effects can be analyzed in detail. The electronic band structure is performed using the density functional theory based on the generalized gradient approximation. Two types of pores are studied: C‐rich and Si‐rich pores surface. The enlargement of energy band gap is greater in the C‐rich than Si‐rich pores surface. This supercell model emphasizes the interconnection between 3C‐SiC nanocrystals, delocalizing the electronic states. However, the results show a clear quantum confinement signature, which is contrasted with that of nanowire systems. The calculation shows a significant response to changes in surface passivation with hydrogen. The chemical tuning of the band gap opens the possibility plenty applications in nanotechnology. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2455–2461, 2010     

Dehydrative cyclocondensation reactions on hydrogen-terminated Si(100) and Si(111): an ex situ tool for the modification of semiconductor surfaces

Dehydrative cyclocondensation processes for semiconductor surface modification can be generally suggested on the basis of well-known condensation schemes; however, in practice this approach for organic functionalization of semiconductors has never been investigated. Here we report the modification of hydrogen-terminated silicon surfaces by cyclocondensation. The cyclocondensation reactions of nitrobenzene with hydrogen-terminated Si(100) and Si(111) surfaces are investigated and paralleled with selected cycloaddition reactions of nitro- and nitrosobenzene with Si(100)-2x1. Infrared spectroscopy is used to confirm the reactions and verify an intact phenyl ring and C-N bond in the reaction products as well as the depletion of surface hydrogen. High resolution N 1s X-ray photoelectron spectroscopy (XPS) suggests that the major product for both cyclocondensation reactions investigated is a nitrosobenzene adduct that can only be formed following water elimination. Both IR and XPS are augmented by density functional theory (DFT) calculations that are also used to investigate the feasibility of several surface reaction pathways, which are insightful in understanding the relative distribution of products found experimentally. This novel surface modification approach will be generally applicable for semiconductor functionalization in a highly selective and easily controlled manner.     

Using Si and Ge nanostructures as substrates for surface-enhanced Raman scattering based on photoinduced charge transfer mechanism

The possibility of utilizing the Si and Ge nanostructures to promote surface-enhanced Raman scattering (SERS) is discussed. The vibronic coupling of the conduction band and valence band states of Si or Ge with the excited and ground states of the target molecule during the charge transfer (CT) process could enhance the molecular polarizability tensor. Using H-terminated silicon nanowire (H-SiNW) and germanium nanotube (H-GeNT) arrays as substrates, significant Raman enhancement of the standard probes, Rodamine 6G (R6G), dye (Bu(4)N)(2)[Ru(dcbpyH)(2)-(NCS)(2)] (N719), and 4-aminothiophenol (PATP), are demonstrated. The abundant hydrogen atoms terminated on the surface of SiNW and GeNT arrays play a critical role in promoting efficient CT and enable the SERS effect.     

Synthesis of bifunctional polymer nanotubes from silicon nanowire templates via atom transfer radical polymerization

As a way to control the surface properties of nanowires and nanotubes, we present a method for growing polymer from the surface of silicon/silica core/shell nanowires. After modification of nanowire surfaces with polymer initiators, Atom Transfer Radical Polymerization (ATRP) was used to grow methacrylate polymer chains from the surface. The resulting structures were characterized by SEM, TEM, and EELS. After etching the silicon cores, the resulting polymer-coated nanotubes will have hydrophilic silica cores with hydrophobic polymer shells.     

Investigation of the effect of finite-sized ions on the nanowire field-effect transistor in electrolyte concentration using a modified Poisson–Boltzmann model

One-dimensional (1D) nanowire field-effect transistors (FETs) have recently played a major role in sensing applications. Due to charging of the surface functional chemical groups with protonation and deprotonation, the transport properties of these nanowire transistors affect the aqueous environment, altering the electrical double layer (EDL) potential drops and charge distributions in the electrolyte concentration. In this work, we have implemented the simple modified Poisson–Boltzmann (MPB) theory in a 1D silicon nanowire FET, and the effect of the various finite sizes of ions in z:z symmetric electrolyte concentration was investigated. For a given ionic concentration and surface charge, the EDL potential drop, accumulation of charges and the charge distributions of NaCl and CsCl ions were studied. From the MPB model results with the nanowire FET, it was observed that the potential drop of the EDL depends on the size of the ions in the electrolyte. The study of various electrostatic investigations of finite-sized ions was successfully done by implementing the MPB model on a silicon nanowire FET. It can be used in both chemical and biological sensors.