Polymer Composites with Plasmonic Metal Nanoparticles

Summary: A two-phase method has been adapted for the preparation of polymer composites consisting of regioregular poly(3-octylthiophene-2,5-diyl) and Au or Ag nanoparticles. This work compares optical and morphological properties of nanocomposites formed by mixing metal organosols and polymer solution (type I composites) with nanocomposites formed by in-situ reduction in polymer solutions (type II composites). Both types contained very small metal nanoparticles (1–10 nm). Interestingly, more than ten-fold enhancement of Raman scattering of the polymer by the electromagnetic (EM) mechanism of SERS (surface-enhanced Raman scattering) resulted from the coupling of the polymer with plasmonic Au nanoparticles into a nanocomposite system.     

Structural, Electronic, and Optical Properties of Noble Metal Clusters from First Principles

We examine low-energy isomeric forms, static polarizabilities, and optical absorption spectra of Ag _n , n = 2–8, and Au _n , n = 2–3, clusters using first principles computations within the static and time-dependent versions of the density functional theory. The noticeable decrease in the static polarizabilities of Ag₇ and Ag₈ compared to the values characteristic of Ag _n , n = 2–6, is correlated with the transition from two-dimensional to three-dimensional structures at n = 7. The optical spectra computed within the time-dependent local density approximation for the most stable structures are in good agreement with the available experimental data and the results of earlier theoretical studies. Optical spectra of higher-energy isomers typically present features that are not observed in the experimental spectra. The d electrons affect the spectra of noble metal clusters by quenching the oscillator strengths through screening of the s electrons and by getting directly involved in the excitations. Due to the larger s–d hybridization in Au compared to Ag, these effects are more pronounced in Au _n clusters.     

Electrodynamics of Noble Metal Nanoparticles and Nanoparticle Clusters

In this paper we examine the electrodynamics of silver nanoparticles and of clusters of nanoparticles, with an emphasis on extinction spectra and of electric fields near the particle surfaces that are important in determining surface-enhanced Raman (SER) intensities. The particles and clusters are chosen to be representative of what has been studied in recent work on colloids and with lithographically prepared particles. These include spheres, spheroids, truncated tetrahedrons, and clusters of two or three of these particles, with sizes that are too large to be described with simple electrostatic approximations but small compared to the wavelength of light. The electrodynamics calculations are mostly based on the discrete dipole approximation (DDA), which is a coupled-finite element approach which produces exact or nearly exact results for particles of arbitrary size and shape if fully converged. Mie theory results are used to study the validity of the DDA for spherical particles, and we also study the validity of the modified long wavelength approximation (MLWA), which is based on perturbative corrections to the electrostatic limit, and of the single dipole per particle approximation (SDA). The results show how the dipole plasmon resonance properties and the electric field contours around the particle vary with particle shape and size for isolated particles. For clusters of particles, we study the effect of interparticle spacing on plasmon resonance characteristics. We also show that the quadrupole resonance is much less sensitive to particle shape and interparticle interactions than the dipole plasmon resonance. These results provide benchmarks that will be used in future comparisons with experiment.     

Metal Nanoparticle/Polymer Hybrid Particles: The Catalytic Activity of Metal Nanoparticles Formed on the Surface of Polymer Particles by UV-Irradiation

Summary: Polymer particles decorated with metal nanoparticles were prepared by UV-irradiation of polystyrene latex particles incorporating polymethylphenylsilane (PS/PMPS) and P[S-co-NIPAM]/PMPS particles (NIPAM: N-isopropyl acrylamide) in the presence of metal salts. The metal nanoparticle/polymer hybrid particles were used as a catalyst for the reduction of 4-nitrophenol with NaBH₄. The Pd- and Ag-P(S-co-NIPAM)/PMPS hybrid particles had larger metal nanoparticles and the lower catalytic activity than those of Pd- and Ag-PS/PMPS, respectively. The surface functional group of the polymer particles affected the formation of the metal nanoparticles and their catalytic activity.     

Metal Nanoparticle/Polymer Hybrid Particles: The Catalytic Activity of Metal Nanoparticles Formed on the Surface of Polymer Particles by UV-Irradiation

Summary: Polymer particles decorated with metal nanoparticles were prepared by UV-irradiation of polystyrene particles incorporating polymethylphenylsilane (PS/PMPS) and P[S-co-NIPAM]/PMPS particles (NIPAM: N-isopropyl acrylamide) in the presence of metal salts. The metal nanoparticle/polymer hybrid particles were used as a catalyst for the reduction of 4-nitrophenol with NaBH₄. The Pd- and Ag-P(S-co-NIPAM)/PMPS hybrid particles had larger metal nanoparticles and the lower catalytic activity than those of Pd- and Ag-PS/PMPS, respectively. The surface functional group of the polymer particles affected the formation of the metal nanoparticles and their catalytic activity.     

Multiphase Polymer Dispersions and Nanocomposites by Catalytic/Free Radical Emulsion Polymerization

Summary: Free radical emulsion polymerization of styrene (S) or butyl acrylate (BA) in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization affords colloidally stable multiphase latices. Coagulation of a PE/PS latex affords nanocomposites composed of small PE phases dispersed in a PS matrix, as evidenced by the large supercoolings of PE crystallization (by DSC). TEM of PE/PBA latices indicates a PBA phase around the PE particles under the emulsion polymerization conditions investigated. Films formed from these dispersions exhibit homogeneously dispersed PE particles.

Multiphase latices are obtained by free radical emulsion polymerization of butyl acrylate in the presence of latices of linear polyethylene (PE) prepared by catalytic emulsion polymerization.     

聚苯胺/金属纳米粒子复合物的制备及性能

基于国内外最新研究文献及本课题组研究工作,从发展历史、制备方法、多功能性方面系统综述了近年来发展起来的聚苯胺/金属纳米粒子复合物。在聚苯胺基体中引入金属纳米粒子的方法可归纳为3大类：原位复合法、直接共混法和层层自组装法。所形成的有机聚苯胺和无机金属杂化复合物不仅能保留各自原有的特异性能,而且二组分之间还存在着相互协同作用,能够极大地提升基体聚苯胺材料的性能,电导率最高可提高100倍,电氧化催化电流最高可提高10倍。分散在聚苯胺膜中的极少量铂微粒就能使不锈钢板的腐蚀电位稳定在钝化区域。聚苯胺/金属纳米粒子复合物所表现出的突出的固有电导性、优异的反应催化性和极强的金属防腐性,使其跻身于为数不多的新型高性能复合材料之列,显示出了诱人的应用前景。     

Preparation,Functionality, and Application of Metal Oxide‐coated Noble Metal Nanoparticles

With their remarkable properties and wide‐ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal‐oxide components. In this review, particular attention is given to core–shell type metal oxide‐coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard.

     

A High-Performance Catalytic and Recyclability of Phyto-Synthesized Silver Nanoparticles Embedded in Natural Polymer

The present work deals with phytogenic synthesis of Ag NPs in the natural polymer alginate as support material using Aglaia elaeagnoidea leaf extract as a reducing, capping, and stabilizing agent. Ag nanoparticles embedded in alginate were characterized using UV–Vis absorption spectroscopy, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, transmission electron microscopy techniques and selected area electron diffraction techniques. The formation of AgNPs embedded in the polymer was in spherical shape with an average size of 12 nm range has been noticed. The prepared embedded nanoparticles in polymer were evaluated as a solid heterogeneous catalyst for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) and methylene blue to leuco methylene blue in the liquid phase using sodium borohydride (NaBH₄) as reducing agent. The silver nanoparticles embedded polymer exhibited extraordinary catalytic efficacy in reduction of 4-NP to 4-AP and the rate constant is 0.5054 min^?1 at ambient conditions. The catalyst was recycled and reused up to 10 cycles without significant loss of catalytic activity. The preparation of Ag–CA composite was facile, stable, efficient, eco-friendly, easy to recycle, non-toxic, and cost effective for commercial application.     

有序介孔碳基金属复合材料的制备及催化应用

有序介孔碳基金属复合材料具有较大的比表面积、规整的孔道结构、良好的热稳定性及化学稳定性、活性金属组分分散度高以及粒径尺寸小等特点,广泛应用于非均相催化领域。常用的合成方法包括浸渍法、“一锅”法以及金属组分转移法等。本文综述了近年来有序介孔碳基金属复合材料的制备及其在非均相催化领域中的应用研究进展,重点阐述了介孔碳载体的介观结构调控、表面性质控制及限域效应等对所负载的活性金属组分的分散性、粒径大小,以及对反应物和产物扩散的影响,探讨了其在气相反应、液相反应和光电催化等领域的应用,并对有序介孔碳基复合材料的发展方向和应用前景进行了展望。     

Zero-Birefringence Optical Polymer by Birefringent Crystal and Analysis of the Compensation Mechanism

Summary: We reported a method for compensating the birefringence of optical polymers by doping them with inorganic birefringent crystals. In this method, an inorganic birefringent material is chosen that has the opposite birefringence to the polymer and needle-like shape crystals which are oriented when the polymer chains are oriented. The birefringence of the polymer is thus compensated by the opposing birefringence of the crystal. Orientation behavior of the needle-like crystals and polymers was investigated. The orientation function of the needle-like crystal was increased with an increase in the aspect ratio of the needle-like crystal.     

Optical Properties of Noble Metal Clusters in Ultrathin Solid Films

We report on the optical properties (absorption, Raman response) of thin and ultrathin phthalocyanine and amorphous silicon films with incorporated noble metal clusters. The metal clusters cause the typical absorption features originating from their surface plasmon resonance. In ultrathin films, due to the spatially close interface, the plasmon absorption may be displaced from its resonance frequency in the bulk, and its average position may be controlled by the average thickness of the ultrathin optical film. For example, we observe a shift of the plasmon resonance of silver clusters in amorphous silicon films (on fused silica) from 440 nm to 740 nm, when the silicon thickness increases from zero up to 9 nm. The deposition experiments are accompanied by investigations of the film structure, particularly in order to estimate the silver cluster diameter, which is around 3 nm or less.     

手性金属络合物催化不对称Baeyer-Villiger反应

Baeyer-Villiger反应是有机化学基本反应之一,但是催化不对称Baeyer-Villiger反应的研究尚处于起步阶段。本文按手性配体的不同,评述了手性金属络合物催化不对称Baeyer-Villiger反应的研究,特别是由外消旋或前手性酮制备光学活性内酯的研究进展。     

Fast Optical Healing of Crystalline Polymers Enabled by Gold Nanoparticles

A general method for very fast and efficient optical healing of crystalline polymers is reported. By loading a very small amount of gold nanoparticles (AuNPs) in either poly(ethylene oxide) (T_m ≈ 63 °C) or low‐density polyethylene (T_m ≈ 103 °C), the heat released upon surface plasmon resonance (SPR) absorption of 532 nm light by AuNPs can melt crystallites in the interfacial region of two polymer pieces brought into contact; and the subsequent recrystallization of polymer chains on cooling merges the two pieces into one. The fracture strength of such repaired sample can reach the level of the undamaged polymer after 10 s laser exposure. Moreover, in addition to an ability of long‐distance remote and spatially selective healing, the optical method also works for polymer samples immersed in water.

     

Catalytic Activation of Olefins by Metal Triflates and Triflimides: Application to Fragrance Chemistry

Fragrance compounds constitute a wide family of relatively volatile compounds presenting interesting odour properties. Several processes catalysed by metal triflates and triflimides have been recently developed with a view to applications to fragrance chemistry. These reactions, involving the activation of non‐activated olefins, mainly involve inter‐ and intramolecular carbon–carbon, carbon–oxygen and carbon–sulfur bond formation.     

混合金属高分子催化剂及其催化加氢活性的研究

改变金属离子种类和高分子配位体的结构可以改变高分子金属催化剂的催化活性。本文作者在SiO_2为载体的聚乙烯醇缩对N,N-二甲氨苯甲醛—钯单金属高分子催化剂中引入少量第二种金属。离子形成混合金属高分子催化剂。研究结果表明,其中Co~(2+),Ni~(2+)及NaAc的引入对原催化剂具有较好的助催化效果,其中Ni~(i+)的引入使原单金属高分子催化剂对丙烯酸的催化加氢活性可提高75％,此外本文还对混合金属高分子催化剂的其他催化性能进行了研究。     

贵金属纳米粒子/硅纳米线复合纳米材料的制备及其催化性能研究

以十二烷基硫酸钠(SDS)作为保护剂, 利用贵金属阳离子(Mⁿ⁺)与HF处理后的硅纳米线(SiNWs)之间的氧化还原反应, 在SiNWs表面负载了贵金属纳米粒子. 通过调控SDS/Mⁿ⁺物质的量比、反应物浓度、反应温度等实验参数, 制备出了金属纳米粒子粒径均一且负载密集的AuNPs/SiNWs, PtNPs/SiNWs复合材料. 将AuNPs/SiNWs复合材料应用在亚甲基蓝的还原反应, 实验结果显示, 60 min内AuNPs/SiNWs可以将55%的亚甲基蓝还原, 表明AuNPs/SiNWs具有良好的催化活性. 这种复合材料易于从反应溶液中分离出来, 可以实现纳米催化剂的循环使用.     

金属纳米粒子/聚合物体系的稳定性及其机理

金属纳米粒子由于其小的尺寸和大的比表面积等特点,使其具有独特的热性能、电性能、磁性能和光性能,以及很强的团聚趋势。因此金属纳米粒子是否被稳定在纳米尺度内,是它们能否表现出独特性能的关键。本文综述了非离子聚合物、聚电解质、两亲聚合物、双亲水聚合物、树状聚合物对金属纳米粒子的稳定作用及其稳定机理的研究进展。     

Reactive Template Synthesis of Polypyrrole Nanotubes for Fabricating Metal/Conducting Polymer Nanocomposites

Unique nanocomposites of polypyrrole/Au and polypyrrole/Pt hybrid nanotubes are synthesized employing polypyrrole (PPy) nanotubes as an advanced support by solution reduction. The conducting polymer PPy nanotubes are fabricated by using pre‐prepared MnO₂ nanowires as the reactive templates. MnO₂ nanowires induce the 1D polymerization of pyrrole monomers and the simultaneous dissolution of the templates affords the hollow tube‐like structure. The loading content of metal nanoparticles in the nanocomposites could be adjusted by simply changing the amount of metal precursors. This work provides an efficient approach to fabricate an important kind of metal/conducting polymer hybrid nanotubes that are potentially useful for electrocatalyst and sensor materials.