Au, Ag and Au:Ag colloidal nanoparticles synthesized by pulsed laser ablation as SERS substrates

Chemically pure colloidal suspensions of gold and silver nanoparticles were synthesized using pulsed laser ablation.The dependence of laser fl uence on the surface plasmon characteristics of the nanoparticles was investigated.Au:Ag colloidal suspensions were prepared by mixing highly monodisperse Au and Ag nanocolloids.The plasmon band of these mixtures was found to be highly sensitive to Au:Ag concentration ratio and wavelength of the laser beam used in the ablation process.The Au:Ag mixture consists of almost spherical shaped nanostructures with a tendency to join with adjacent ones.The surface enhanced Raman scattering activity of the Au,Ag and Au:Ag colloidal suspensions was tested using crystal violet as probe molecules.Enhancement in Raman signal obtained with Au:Ag substrates was found to be promising and strongly depends on its plasmon characteristics.     

中空银纳米球的制备及其性能研究

新型的金属纳米粒子因为独特的由表面等离子体共振诱导(SPR)的光学性质和很多的潜在应用而受到社会广泛的关注。在具有SPR效应的贵金属纳米粒子中,中空纳米结构有一个很高的散射系数,其共振频率通过改变中空核的尺寸和壳的厚度可以很容易地被控制。本论文中拟采用电化学方法结合电偶置换法在高定向热解石墨(HOPG)及金膜表面制备不同尺寸具有中空结构的银纳米阵列,研究了中空银纳米阵列的局域表面等离子效应(L-SPR),为其在SPR定性和定量研究中的应用提供理论指导。     

局域表面等离子体研究进展

阐述了局域表面等离子体特性,金属纳米粒子的常用制备方法,以及不同形状、尺寸等因素对局域表面等离子体光谱和灵敏度的影响,分析了表面增强拉曼散射的增强因子与金属纳米粒子的等离子共振波长和拉曼激发波长之间的关系,介绍了局域表面等离子体在生物传感方面的应用.     

金银合金纳米粒子的制备

以柠檬酸钠为稳定剂,利用硼氢化钠还原AgNO3和HAuCl4混合溶液制备了Au-Ag合金纳米粒子,UV-Vis光谱谱图只观察到一个位于纯银和纯金之间的表面等离子体共振峰,且该表面等离子体共振峰的最大吸收波长与合金中Au的摩尔分数成线性关系.TEM结果表明:Au-Ag合金纳米粒子的粒径大约为43 nm,且颜色均一,没有明...     

Quantum plasmon resonances of individual metallic nanoparticles

The plasmon resonances of metallic nanoparticles have received considerable attention for their applications in nanophotonics, biology, sensing, spectroscopy and solar energy harvesting. Although thoroughly characterized for spheres larger than ten nanometres in diameter, the plasmonic properties of particles in the quantum size regime have been historically difficult to describe owing to weak optical scattering, metal-ligand interactions, and inhomogeneity in ensemble measurements. Such difficulties have precluded probing and controlling the plasmonic properties of quantum-sized particles in many natural and engineered processes, notably catalysis. Here we investigate the plasmon resonances of individual ligand-free silver nanoparticles using aberration-corrected transmission electron microscope (TEM) imaging and monochromated scanning TEM electron energy-loss spectroscopy (EELS). This technique allows direct correlation between a particle's geometry and its plasmon resonance. As the nanoparticle diameter decreases from 20 nanometres to less than two nanometres, the plasmon resonance shifts to higher energy by 0.5 electronvolts, a substantial deviation from classical predictions. We present an analytical quantum mechanical model that describes this shift due to a change in particle permittivity. Our results highlight the quantum plasmonic properties of small metallic nanospheres, with direct application to understanding and exploiting catalytically active and biologically relevant nanoparticles.     

液相激光烧蚀合成TiO2纳米颗粒及其XPS研究

采用液相激光烧蚀法制备了二氧化钛纳米颗粒,研究了二氧化钛纳米颗粒的生长与微结构．XRD、TEM、XPS等表征表明：此方法可在室温条件下一步获得金红石型二氧化钛纳米颗粒胶体,颗粒直径约50nm,尺寸分布窄,分散性好,从而显示出良好的应用前景．结合微观表征与激光诱导的瞬态等离子体分析对TiO2纳米颗粒形成机理进行了探讨．     

双键功能化的金纳米粒子的制备与表征

通过四辛基溴化铵稳定的金纳米粒子(TOAB-Au)与含可聚合双键的二硫化物配体之间的置换反应,制备了四种双键功能化的金纳米粒子,并通过紫外光谱、红外光谱、X-光电子能谱、透射电镜和热重分析对金纳米粒子的形貌和组成进行了表征。结果表明,双键功能化的金纳米粒子能够稳定地分散在氯仿和四氢呋喃溶剂中,粒子直径在4 nm到8 nm之间,表面等离子共振吸收峰随配体的不同在521 nm到532 nm之间改变。四种双键功能化的金纳米粒子的表面配体接枝密度在4.2到6.6之间。     

Near-field coupling and SERS effects of palladium nanoparticle dimers

The linear optical properties and the surface-enhanced Raman scattering (SERS) effect of spherical palladium nanoparticle dimers are analyzed theoretically using generalized Mie theory. The calculation results demonstrate that the near-field coupling effect greatly influences the absorption, scattering and extinction spectra of nanoparticle dimers. The surface plasmon resonance wavelength red-shifts dramatically as the separation between nanoparticles decreases. Because of the near-field coupling between nanoparticles and the size effect, the maximum SERS enhancement factor at the ‘hot spot’ between palladium nanoparticle dimers is as high as 10⁷–10⁸, while the averaged SERS enhancement factor over the entire nanoparticle surface is in the range of 10⁵–10⁶. The deviation between the position of the peak in the extinction spectrum and the wavelength for maximum surface-averaged enhancement for the Pd nanoparticle dimers indicates that localized surface plasmon resonance has different influences on the far and near fields. These theoretical results may help to reveal the relationship between the far and near fields, as well as understand the mechanism of electromagnetic enhancement in the surface-enhanced scattering of transition metals.     

银纳米粒子的消光光谱与粒子形状的关系

先利用离散偶极子近似(Discrete Dipole Approximation,DDA)的方法,分别计算置于空气中的球形、不同长径比的椭球形和棒形银纳米粒子的消光光谱.计算结果表明:球形纳米粒子仅存在单个等离子体共振尖峰;而椭球状和棒状粒子则存在横向和纵向两个等离子体共振峰;并且横向峰的变化不甚明显,而纵向峰会随粒子长径比的增大而线性地红移.再结合Gans的解析理论,分析等离子体共振的机理,并研究纵向等离子体共振峰随着粒子长径比的增大而红移的现象.     

Optical nonlinearity and ultrafast dynamics of ion exchanged silver nanoparticles embedded in soda-lime silicate glass

Ag nanoparticles embedded in soda-lime silicate glass were fabricated by ion-exchange and subse-quently annealing method. Z-scan technique, femtosecond time-resolved optical Kerr effect （OKE） technique and femtosecond pump-probe experiment were used to investigate the effects of laser wavelength and laser pulse duration as well as annealing temperature on the third-order optical nonlinearity and ultrafast dynamics of the composites. It was found that the third-order susceptibility of Ag nanoparticles composite glass measured by 400 nm pulse source is larger than that measured by 800 nm pulse source due to an enhancement effect of local field near surface plasmon resonance of Ag nanoparticles in silicate glass. The third-order optical nonlinearity measured by ns laser source is about two orders of magnitude larger than that measured from fs pulse. The annealing temperature has an important effect on the third-order optical nonlinearity and ultrafast dynamics of the composites. Third-order nonlinear susceptibility up to 10^-l0 esu and fast relaxation process up to 0.2 ps have been obtained in Ag nanoparticles doped glass.     

修正偶应力理论层合薄板自由振动模型及尺度效应

通过引入各向异性的细观尺度复合材料层合板的本构方程,将各向同性修正偶应力理论推广到各向异性,基于虚功原理首次建立了复合材料层合板新修正偶应力理论的自由振动模型.该理论包含不同的两个材料细观参数,偶应力曲率应变不对称.但是,用于各向同性材料与原修正偶应力理论等价,为了便于工程应用,建立了只含一个细观材料参数的偶应力层合薄板理论弯曲和振动的简化模型.算例表明建立的偶应力层合薄板模型能用于分析层合板的自由振动尺度效应.     

Plasmonic coupling in single flower-like gold nanoparticle assemblies

Localized surface plasmon resonance (LSPR) arises when light interacts with metallic nanoparticles (NPs). When nanoparticles (NPs) assemble together, the plasmon coupling effect between the NPs often leads to new features in the LSPR of the assembled structure. Understanding the plasmon coupling in the complex assemblies will greatly benefit the development of new plasmonic devices. Here we demonstrate the fabrication of a 3D structure using two different sized Au NPs as building blocks. This 3D structure was achieved by manipulating the binding efficiency of ligands linking the NPs, and proper choice of the NP size. The assembled structure is flower-like structure, with one 130 nm Au NP in the center, and several 40 nm Au NPs attaching as “petals”. Single particle dark-field scattering measurements of the individual assemblies were performed, together with electrodynamics simulations. The experimental and theoretical studies show that, the plasmonic coupling lead to broadening of the LSPR and additional peaks, depending on the number and 3D arrangement of the 40 nm NPs around the center 130 nm NP.     

PVP-assisted laser ablation growth of Ag nanocubes anchored on reduced graphene oxide(rGO) for efficient photocatalytic CO_2 reduction

Metallic nanoparticles loaded graphene nanocomposites have been widely studied for various scientific and technological applications. In this study, a facile method was reported to realize a straightforward growth of shape and size-controllable of metallic nanoparticles, and the subsequent hybridization with graphene in solution by strategically coupling wet-chemical route and laser ablation. By mixing graphene oxide(GO) with a tunable concentration level of polyvinylpyrrolidone(PVP) in aqueous solution, Ag nanocubes with a face-centered cubic crystal structure were generated by pulsed laser ablation and then mounted on GO nanosheets with the assistance of PVP. The preferential adsorption of PVP to Ag(100) crystal face led to the production of Ag nanocubes with exposed(100) facet. The result showed that the morphological yield of spherical particles decreased with the increase in PVP concentration. X-ray diffraction(XRD) and UV–visible spectroscopy analyses confirmed that GO was partially reduced. In the reduction of CO_2 gas, the photocatalytic conversion rate could achieve 133.1 μmol g~(-1) h~(-1) in 6 hrs for cubic Ag-loaded reduced GO composites.     

粒度对吸附影响的量子化学研究

以CO在纳米金刚石表面的吸附为体系,以球形原子簇模拟球形纳米颗粒,用量子化学方法(AM1)研究了吸附剂粒度对吸附影响的规律。结果表明:纳米金刚石的粒径对CO在其表面的吸附影响很大;吸附能的绝对值随粒径的增大而减小,且随着粒径的增大吸附能绝对值减小的趋势逐渐趋于平缓,当粒径很大时,吸附能的绝对值趋于零;吸附能绝对值的对数与粒径成线形关系。这些结论与热力学分析和实验结果相一致,进而说明用量子化学方法来预测和分析纳米粒子的吸附是可行的。     

钠纳米团簇的光吸收和体等离激元:理论分析

指出了体等离激元是一种重要的元激发,在固体里它不能与光波耦合所以无法用光波分波来研究,但是在团簇里由于边界的存在,情况不太一样.此外,光与物质之间的相互作用是非常根本的,但简单金属团簇在紫外光区的光吸收从未被实验研究过,尽管这方面的理论计算非常多.采用光倒空技术对N a20和N a92团簇进行了光吸收实验,覆盖了近紫外部分以及可见光范围(2.0~5.5 eV);实验还研究了其它一些团簇在近紫外范围内的吸收截面.在可见光部分N a20的实验数据与现有的数据非常吻合.除了表面等离激元在可见光区域很强的吸收峰外,还观察到紫外区域明显的光吸收.对吸收截面光谱进行洛伦兹拟合揭示了中心略高于4eV宽峰的存在,这个宽峰的频率与权重均与理论预测非常接近,被确定为纳米团簇"体等离激元"共振.这些吸收光谱是金属纳米团簇由光子激发的"体等离激元"集体电子态的首次实验观测与证实,这种实验现象只存在于有限体系.     

Na-B小团簇的密度泛函理论研究

使用Gaussian03程序包,采用密度泛函B3LYP在6-311+G(d)基组水平上对NanBm(n+m＝6)团簇进行理论研究.通过对NanBn团簇的几何结构、能量、最高占据轨道和最低空轨道能隙、振动频率以及原子电荷分布等进行分析.结果表明,随着Na原子数的增加,NanBm团簇的稳定性下降,其化学活性增强.在所有的最...     

碳掺杂pg-C3N4的制备及其光催化性能研究

为了提高单一半导体材料的光催化活性,采用水热法制备高比表面积的多孔石墨相氮化碳(pg-C₃N₄),通过碳掺杂和金纳米粒子(AuNPs)负载对pg-C₃N₄进行改性得到Au/pg-C@C₃N₄复合纳米材料,并对复合材料的组成、微观结构和性能进行表征。结果显示,碳元素的引入并未破坏pg-C₃N₄原有的片层结构,但明显提高了pg-C₃N₄的比表面积（高达158.2 m²/g）;AuNPs引入基体后,AuNPs的等离子共振效应可显著提高基体对可见光的吸收和光生电子-空穴的分离效率;当AuNPs含量为0.5%（质量分数）时,复合纳米材料具有最佳的光催化性能（表观反应速率常数k=0.078 4 s^-1）。因此,通过碳掺杂和纳米Au负载改性pg-C₃N₄可制备高活性复合光催化剂,为今后进一步提高氮化碳基催化剂的催化活性提供了理论基础。     

环形石墨烯纳米结构的等离激元激发

基于含时密度泛函理论,研究了环形石墨烯纳米结构的等离激元激发.在低能共振区,和同尺度大小的石墨烯纳米结构相比,环形石墨烯纳米结构光谱的主要吸收峰发生了红移;体系中有两种主要的等离激元共振模式:低能成键模式和高能反键模式.此外,环形石墨烯纳米结构的等离激元激发对体系尺度的大小也有一定的依赖性.     

PAAm/CMC-Ag纳米复合水凝胶的制备表征及溶胀动力学研究

以N,N-亚甲基双丙烯酰胺(N,N-MBA)为交联剂,过硫酸钾(KPS)为引发剂,合成了聚丙烯酰胺(AAm)-羧甲基纤维素钠盐(CMC)半互穿网络水凝胶.通过傅里叶红外光谱纳米复合水凝胶PAAm/CMC-Ag的结构.紫外可见光谱研究表明,Ag纳米粒子的表面等离子体吸收峰在450 nm范围.溶胀动力学表明,PAAm/CM...     

多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极对CO2的光电催化还原研究

通过溶胶法制备了氢氧化铁溶胶纳米粒子及镧掺杂氢氧化铁溶胶纳米粒子,多壁碳纳米管负载后,化学修饰在碳纤维簇电极上,制备出多壁碳纳米管负载镧掺杂氢氧化铁纳米胶粒修饰碳纤维簇电极,该电极对CO_2有光电催化还原作用。多壁碳纳米管修饰后增加了电极的表面积,氢氧化铁纳米胶粒修饰后还原电流变大增强了电催化还原功能,镧掺杂后起始电位正移增加了光催化还原功能。以MOPAC2012提供的PM7半经验分子轨道方法在设计的铁-氧-氯构成的氢氧化铁分子簇模型上进行半经验分子轨道计算,通过对计算结果的热力学,能级,分子轨道组成以及光谱分析表明,氢氧化铁溶胶纳米粒子及其镧掺杂对CO_2有光电催化还原行为。所设计的分子簇模型是具有热力学稳定的结构,镧掺杂加强了其稳定性。氢氧化铁分子簇具有较好的电子转移性,镧掺杂降低了其费米能级高度,有利于光催化,与实验结果相对应。且催化后的CO_2在键长、分子结构以及红外光谱都发生了较大变化,并具有碳酸的前体结构,实现了对CO_2分子的活化和光电化学催化还原。