Gold Nanorods: From Synthesis and Properties to Biological and Biomedical Applications

Noble metal nanoparticles are capable of confining resonant photons in such a manner as to induce coherent surface plasmon oscillation of their conduction band electrons, a phenomenon leading to two important properties. Firstly, the confinement of the photon to the nanoparticle's dimensions leads to a large increase in its electromagnetic field and consequently great enhancement of all the nanoparticle's radiative properties, such as absorption and scattering. Moreover, by confining the photon's wavelength to the nanoparticle's small dimensions, there exists enhanced imaging resolving powers, which extend well below the diffraction limit, a property of considerable importance in potential device applications. Secondly, the strongly absorbed light by the nanoparticles is followed by a rapid dephasing of the coherent electron motion in tandem with an equally rapid energy transfer to the lattice, a process integral to the technologically relevant photothermal properties of plasmonic nanoparticles. Of all the possible nanoparticle shapes, gold nanorods are especially intriguing as they offer strong plasmonic fields while exhibiting excellent tunability and biocompatibility. We begin this review of gold nanorods by summarizing their radiative and nonradiative properties. Their various synthetic methods are then outlined with an emphasis on the seed‐mediated chemical growth. In particular, we describe nanorod spontaneous self‐assembly, chemically driven assembly, and polymer‐based alignment. The final section details current studies aimed at applications in the biological and biomedical fields.     

Nonspherical Noble Metal Nanoparticles: Colloid‐Chemical Synthesis and Morphology Control

Metal nanoparticles have been the subject of widespread research over the past two decades. In recent years, noble metals have been the focus of numerous studies involving synthesis, characterization, and applications. Synthesis of an impressive range of noble metal nanoparticles with varied morphologies has been reported. Researchers have made a great progress in learning how to engineer materials on a nanometer length scale that has led to the understanding of the fundamental size‐ and shape‐dependent properties of matter and to devising of new applications. In this article, we review the recent progress in the colloid‐chemical synthesis of nonspherical nanoparticles of a few important noble metals (mainly Ag, Au, Pd, and Pt), highlighting the factors that influence the particle morphology and discussing the mechanisms behind the nonspherical shape evolution. The article attempts to present a thorough discussion of the basic principles as well as state‐of‐the‐art morphology control in noble metal nanoparticles.     

贵金属纳米线的模板法制备及应用研究进展

贵金属纳米线因独特的光学性质吸引了人们的普遍关注,已经被广泛应用于生物传感器、太阳能电池、纳米尺度光电器件领域。其光学性能主要来源于贵金属表面的区域等离子体共振,而区域等离子体共振主要由金属纳米线的形状、尺寸、组成以及电磁常数决定。简要地回顾了模板法合成贵金属纳米线的方法,讨论了影响纳米线光学性质的因素,最后简述了应用前景。     

贵金属纳米粒子及其复合物的非线性光学性能和应用研究进展

具有非线性光学特性的贵金属纳米粒子受到广泛的关注,因为这类金属纳米粒子及其复合物不仅具有重要的理论研究意义而且在非线性光学器件方面具有重要的潜在应用价值.对这类金属纳米粒子的主要制备方法、光学特性以及在激光防护等非线性光学器件方面的应用研究进展进行了综述,并对未来的研究和尚存在的问题进行了分析和展望.     

贵金属纳米颗粒的表面等离子共振研究

通过修正的Mie理论分别对单金属Ag、单金属Cu和Cu核Ag壳纳米颗粒/玻璃复合材料的吸收光谱进行了理论计算.计算结果表明,对单金属Ag纳米颗粒/玻璃复合材料,Ag的吸收峰位于425nm左右,不随颗粒尺寸变化而发生偏移;对单金属Cu纳米颗粒/玻璃复合材料,Cu的吸收峰也不随尺寸变化发生偏移但强度较弱;对Cu核Ag壳纳米...     

Structural and Magnetic Properties of Various Ferromagnetic Nanotubes

The structural and magnetic properties of ferromagnetic nanotubes fabricated by a low cost electrodeposition method are investigated. The fabrication of various elemental ferromagnetic materials are described, such as Fe, Co, and Ni, and ferromagnetic alloys, such as NiFe, CoPt, CoFeB, and CoCrPt nanotube arrays, in aluminum oxide templates and polycarbonate membranes with different diameters, wall thicknesses, and lengths. The structural, magnetic, and magnetization reversal properties of these nanotubes are investigated as a function of the geometrical parameters. The angular dependence of the coercivity indicates a transition from the curling to the coherent mode for the ferromagnetic nanotubes. The results show that nanotube fabrication allows the outer and inner diameter, length, and thickness of the nanotubes to be tuned systematically. The magnetization processes of ferromagnetic nanotubes are influenced by the wall thickness.     

Supported Noble‐Metal Single Atoms for Heterogeneous Catalysis

Single‐atom catalysts (SACs), with atomically distributed active metal sites on supports, serve as a newly advanced material in catalysis, and open broad prospects for a wide variety of catalytic processes owing to their unique catalytic behaviors. To construct SACs with precise structures and high density of accessible single‐atom sites, while preventing aggregation to large nanoparticles, various strategies for their chemical synthesis have been recently developed by improving the distribution and chemical bonding of active sites on supports, which results in excellent activity and selectivity in a variety of catalytic reactions. Noble‐metal‐based SACs are discussed, and their structural properties, chemical synthesis, and catalytic applications are highlighted. The structure–activity relationships and the underlying catalytic mechanisms are addressed, including the influences of surface species and reducibility of supports on the activity and stability, impact of the unique structural and electronic properties of single‐atom centers modulated by metal/support interactions on catalytic activity and selectivity, and how the modified catalytic mechanism obtained by inhibiting the multiatoms involves catalytic pathways. Finally, the prospects and challenges for development in this field are highlighted.     

Macroscale Colloidal Noble Metal Nanocrystal Arrays and Their Refractive Index‐Based Sensing Characteristics

Colloidal noble metal nanocrystals are promising for a large number of optical and biotechnological applications. Many practical applications require the formation of large‐area, high‐density, and uniformly distributed metal nanocrystal arrays on various substrates, to overcome the limitations brought by the instability of colloidal metal nanocrystal solutions and the high cost of single‐particle spectroscopy characterizations. A method is developed for directly depositing colloidal metal nanocrystals, including Au nanospheres, Au nanorods, Au nanobipyramids, and (Au core)/(Ag shell) nanorods, from their solutions onto different substrates. The resultant nanocrystal arrays are relatively uniform and dense, with the peak extinction value of a single layer reaching 0.3. Their areas are up to 10 cm by 10 cm and can be further increased if larger‐size containers are utilized. The refractive index sensitivities are studied for Au nanorod arrays supported on glass slides, mesoporous silica and titania films, and capped with different molecules. Au nanorods deposited on mesoporous titania films are found to exhibit the highest index sensitivities, comparable to those of the same nanorod sample in solutions. It is expected that this approach will greatly facilitate plasmonic applications that require large‐area arrays of noble metal nanocrystals.     

真空镀膜法制备纳米铝颗粒膜及其表面等离激元共振特性研究

采用直流磁控溅射镀膜技术制备了纳米铝颗粒膜,并尝试通过两种方式获得纳米铝的表面等离激元共振吸收峰,一种是先在室温石英基底上沉积纳米铝,再进行真空退火;另一种是在热石英基底上沉积纳米铝。用透射电镜和扫描电子显微镜、X-射线光电子谱、紫外-可见吸收光谱表征了样品的形貌和晶态结构、成份和吸收特性。采用比对的方式,研究了基底温度、沉积时间对两种方法制备的纳米铝表面等离激元共振的影响。结果表明,先沉积纳米铝,再进行真空退火,不能获得表面等离激元共振吸收峰,而在热基底上沉积纳米铝,可以获得明显的表面等离激元共振吸收峰。通过调控沉积时间和沉积温度实现了纳米铝表面等离激元共振峰从紫外光区到可见光区的可控移动。而且,研究发现对于平均厚度大于3 nm的纳米铝薄膜,由于纳米铝氧化具有自限性,其表面等离激元共振特性在空气中稳定且主要取决于纳米铝颗粒的团聚度。本研究对理解纳米铝表面等离激元共振特性及其应用具有指导意义。     

Size‐Dependent Nonlinear Optical Properties of Atomically Thin Transition Metal Dichalcogenide Nanosheets

Size‐dependent nonlinear optical properties of modification‐free transition metal dichalcogenide (TMD) nanosheets are reported, including MoS₂, WS₂, and NbSe₂. Firstly, a gradient centrifugation method is demonstrated to separate the TMD nanosheets into different sizes. The successful size separation allows the study of size‐dependent nonlinear optical properties of nanoscale TMD materials for the first time. Z‐scan measurements indicate that the dispersion of MoS₂ and WS₂ nanosheets that are 50–60 nm thick leads to reverse saturable absorption (RSA), which is in contrast to the saturable absorption (SA) seen in the thicker samples. Moreover, the NbSe₂ nanosheets show no size‐dependent effects because of their metallic nature. The mechanism behind the size‐dependent nonlinear optical properties of the semiconductive TMD nanosheets is revealed by transient transmission spectra measurements.     

Unraveling Structural Information of Turkevich Synthesized Plasmonic Gold–Silver Bimetallic Nanoparticles

For the synthesis of gold–silver bimetallic nanoparticles, the Turkevich method has been the state‐of‐the‐art method for several decades. It is presumed that this procedure results in a homogeneous alloy, although this has been debatable for many years. In this work, it is shown that neither a full alloy, nor a perfect core–shell particle is formed but rather a core–shell‐like particle with altering metal composition along the radial direction. In‐depth wet‐chemical experiments are performed in combination with advanced transmission electron microscopy, including energy‐dispersive X‐ray tomography, and finite element method modeling to support the observations. From the electron tomography results, the core–shell structure can be clearly visualized and the spatial distribution of gold and silver atoms can be quantified. Theoretical simulations are performed to demonstrate that even though UV–vis spectra show only one plasmon band, this still originates from core–shell type structures. The simulations also indicate that the core–shell morphology does not so much affect the location of the plasmon band, but mainly results in significant band broadening. Wet‐chemistry experiments provide the evidence that the synthesis pathway starts with gold enriched alloy cores, and later on in the synthesis mainly silver is incorporated to end up with a silver enriched alloy shell.