Nanoparticles Engineering for Lithium‐Ion Batteries

Lithium‐ion batteries (LIBs) have been extensively investigated due to the ever‐increasing demand for new electrode materials for electric vehicles (EVs) and clean energy storage. A wide variety of nano/microstructured LIBs electrode materials are hitherto created via self‐assembly, ranging from 0D nanospheres; 1D nanorods, nanowires, or nanobelts; and 2D nanofilms to 3D nanorod array films. Nanoparticles can be utilized to build up integrated architectures. Understanding of nanoparticles’ self‐assembly may provide information about their organization into large aggregates through low‐cost, high‐efficiency, and large‐scale synthesis. Here, the focus is on the recent advances in preparing hierarchically nano/microstructured electrode materials via self‐assembly. The hierarchical electrode materials are assembled from single component, binary to multicomponent building blocks via different driving forces including diverse chemical bonds and non‐covalent interactions. It is expected that nanoparticle engineering by high‐efficient self‐assembly process will impact the development of high‐performance electrode materials and high‐performance LIBs or other rechargeable batteries.     

Engineered inorganic core/shell nanoparticles

It has been for a long time recognized that nanoparticles are of great scientific interest as they are effectively a bridge between bulk materials and atomic structures. At first, size effects occurring in single elements have been studied. More recently, progress in chemical and physical synthesis routes permitted the preparation of more complex structures. Such structures take advantages of new adjustable parameters including stoichiometry, chemical ordering, shape and segregation opening new fields with tailored materials for biology, mechanics, optics magnetism, chemistry catalysis, solar cells and microelectronics. Among them, core/shell structures are a particular class of nanoparticles made with an inorganic core and one or several inorganic shell layer(s). In earlier work, the shell was merely used as a protective coating for the core. More recently, it has been shown that it is possible to tune the physical properties in a larger range than that of each material taken separately. The goal of the present review is to discuss the basic properties of the different types of core/shell nanoparticles including a large variety of heterostructures. We restrict ourselves on all inorganic (on inorganic/inorganic) core/shell structures. In the light of recent developments, the applications of inorganic core/shell particles are found in many fields including biology, chemistry, physics and engineering. In addition to a representative overview of the properties, general concepts based on solid state physics are considered for material selection and for identifying criteria linking the core/shell structure and its resulting properties. Chemical and physical routes for the synthesis and specific methods for the study of core/shell nanoparticle are briefly discussed.     

Nanoparticle decoration with surfactants: Molecular interactions,assembly, and applications

Nanostructures of diverse chemical nature are used as biomarkers, therapeutics, catalysts, and structural reinforcements. The decoration with surfactants has a long history and is essential to introduce specific functions. The definition of surfactants in this review is very broad, following its lexical meaning “surface active agents”, and therefore includes traditional alkyl modifiers, biological ligands, polymers, and other surface active molecules. The review systematically covers covalent and non-covalent interactions of such surfactants with various types of nanomaterials, including metals, oxides, layered materials, and polymers as well as their applications. The major themes are (i) molecular recognition and noncovalent assembly mechanisms of surfactants on the nanoparticle and nanocrystal surfaces, (ii) covalent grafting techniques and multi-step surface modification, (iii) dispersion properties and surface reactions, (iv) the use of surfactants to influence crystal growth, as well as (v) the incorporation of biorecognition and other material-targeting functionality. For the diverse materials classes, similarities and differences in surfactant assembly, function, as well as materials performance in specific applications are described in a comparative way. Major factors that lead to differentiation are the surface energy, surface chemistry and pH sensitivity, as well as the degree of surface regularity and defects in the nanoparticle cores and in the surfactant shell. The review covers a broad range of surface modifications and applications in biological recognition and therapeutics, sensors, nanomaterials for catalysis, energy conversion and storage, the dispersion properties of nanoparticles in structural composites and cement, as well as purification systems and classical detergents. Design principles for surfactants to optimize the performance of specific nanostructures are discussed. The review concludes with challenges and opportunities.     

Nanoparticles by Laser Ablation

This review concerns nanoparticles collected in the form of nanopowder or a colloidal solution by laser ablating a solid target that lies in a gaseous or a liquid environment. The paper discusses the advantages of the method as compared with other methods for nanoparticle synthesis, outlines the factors on which the properties of the produced nanoparticles depend, explains the mechanisms and models involved in the generation of nanoparticles by laser ablation, clarifies the differences between nanoparticle generation in gaseous and liquid environments, presents some experimental desigins and equipment used by the several groups for nanoparticle generation by laser ablation, describes the techniques used for “tuning” the width of the nanoparticles size distribution, and finally presents a few interesting examples of nanoparticles generated by laser ablation.     

Hierarchical and Complex ZnO Nanostructures by Microwave-Assisted Synthesis: Morphologies,Growth Mechanism and Classification

Zinc Oxide is an important and multi-purpose material in various industries due to its particular chemical and physical properties. Discovering a cheap, fast, clean, safe, and easy to use method, to synthesize this oxide nanoparticle has attracted a lot of attention in recent applications. The unique properties of the microwave and its special heating capabilities have yielded desirable outcomes by combining different synthesis methods. In the recent years, the vast majority of studies focus on the microwave-assisted synthesis of zinc oxide nanoparticles. This review article attempts to go over the recent advancements on the synthesis of zinc oxide nanoparticles with the aid of microwave, different morphologies and applications obtained by this method. Various microwave-assisted synthesis methods are classified, including the solution-based methods such as hydrothermal, sol-gel, and combustion methods. Morphology of the nanoparticles can affect the properties, and subsequently, applications of these nanoparticles. On the other hand, there is great diversity of morphological and synthesis conditions of zinc oxide nanoparticles. Thus, categorizing the synthesis techniques and providing features of them, facilitates the selection of appropriate method for designing new hierarchical structures with potential properties for future applications. Also it is endeavored to focus on the formation mechanisms of these methods. Finally, the various morphologies obtained under microwave radiation and their formation mechanisms are discussed and the effective factors in the synthesis are analyzed and presented. The potential and suitable fields of development and progress in the future studies are also proposed.     

Nanohybridization of Low-Dimensional Nanomaterials: Synthesis,Classification, and Application

Nanomaterials have attracted much attention from academic to industrial research. General methodologies are needed to impose architectural order in low-dimensional nanomaterials composed of nanoobjects of various shapes and sizes, such as spherical particles, rods, wires, combs, horns, and other non specified geometrical architectures. These nanomaterials are the building blocks for nanohybrid materials, whose applications have improved and will continuously enhance the quality of the daily life of mankind. In this article, we present a comprehensive review on the synthesis, dimension, properties, and present and potential future applications of nanomaterials and nanohybrids. Due to the large number of review articles on specific dimension, morphology, or application of nanomaterials, we will focus on different forms of nanomaterials, such as, linear, particulate, and miscellaneous forms. We believe that almost all the nanomaterials and nanohybrids will come under these three categories. Every form or dimension or morphology has its own significant properties and advantages. These low-dimensional nanomaterials can be integrated to create novel nano-composite material applications for next-generation devices needed to address the current energy crisis, environmental sustainability, and better performance requirements. We discuss the synthesis, properties, and morphology of different forms of nanomaterials (building blocks). Moreover, we elaborate on the synthesis, modification, and application of nanohybrids. The applications of these nanomaterials and nanohybrids in sensors, solar cells, lithium batteries, electronic, catalysis, photocatalysis, electrocatalysis, and bio-based applications will be detailed. The time is now ripe to explore new nanohybrids that use individual nanomaterial components as basic building blocks, potentially affording additionally novel behavior and leading to new, useful applications. In this regard, the combination or integration of linear nanorods/nanowires and spherical nanoparticles to produce mixed-dimensionality, higher-level nanocomposites of greater complexity is an interesting theme, which we explore in this review article.     

Hybrid polymer-inorganic materials: multiscale hierarchy

The paper describes a new approach to producing hybrid composite materials with multiscale morphologies. We doped polymer submicrometer spheres with semiconductor or metal (CdS or Ag, respectively) nanoparticles and used these doped microspheres as the functional building blocks in production of hybrid periodically structured materials. The preparation of hybrid polymer particles included the following stages: (i) synthesis of monodisperse polymer microspheres, (ii) in situ synthesis of the inorganic nanoparticles either on the surface, or in the bulk of the polymer beads, and (iii) encapsulation of hybrid microspheres with a hydrophobic shell. We demonstrated that by changing the composition of the polymer beads good control could be achieved over the size of the nanoparticles.     

In Situ Synchrotron X‐Ray Techniques for Real‐Time Probing of Colloidal Nanoparticle Synthesis

Solution‐phase synthesis of colloidal nanoparticles with precisely tailored properties is one of the fastest growing research topic and represents the most critical foundation to implant nanotechnology in a variety of areas to boost performance of traditional systems. Comprehensive understanding of the nucleation and growth mechanisms involved in the formation of colloidal nanoparticles is very important to realize rational design and synthesis of well‐tailored nanoparticles and requires appropriate in situ techniques to probe the kinetics of the synthetic reactions. Synchrotron hard X‐rays represent a class of promising probes for solution‐phase reactions due to their strong penetration in ambient environment and solutions. This review completely summarizes the in situ synchrotron X‐ray techniques emerged in the recent years for real‐time probing nanophase evolution of colloidal nanoparticles. Typical examples of colloidal nanoparticle syntheses are discussed in detail to shed the light on the advantages and disadvantages of individual techniques.     

Composition-Controlled Laser-Induced Alloying of Colloidal Au–Cu Hetero Nanoparticles

Due to their optical properties (localized surface plasmon resonance, LSPR), colloidally dispersed metal nanoparticles are well suited for selective heating by high-energy laser radiation above their melting point without being limited by the boiling point of the solvent, which represents an excellent complement to wet-chemical nanoparticle synthesis. By combining wet-chemical synthesis and postsynthesis laser treatment, the advantages of both methods can be used to specifically control the properties of nanoparticles. Especially in the colloidal synthesis of nanoalloys consisting of two or more metals with different redox potentials, wet-chemical synthesis quickly reaches its limits in terms of composition control and homogeneity. For this reason, the direct synthesis path is divided into two parts to take the strengths of both methods. After preparing Au–Cu hetero nanoparticles by wet-chemical synthesis, nanoalloys with previous adjusted composition can be formed by postsynthesis laser treatment. The formation of these nanoalloys can be followed by different characterization methods, such as transmission electron microscopy (TEM), where the fusion of both metal domains and the formation of spherical and homogeneous Au–Cu nanoparticles can be observed. Moreover, the alloy formation can be followed by different shifts of X-ray diffraction (XRD) reflections and LSPR maxima depending on the composition.     

Aerosol processing for nanomanufacturing

Advances in nanoparticle synthesis are opening new opportunities for a broad variety of technologies that exploit the special properties of matter at the nanoscale. To realize this potential will require the development of new technologies for processing nanoparticles, so as to utilize them in a manufacturing context. Two important classes of such processing technologies include the controlled deposition of nanoparticles onto surfaces, and the application of chemically specific coatings onto individual nanoparticles, so as to either passivate or functionalize their surfaces. This paper provides an overview of three technologies related to these objectives, with an emphasis on aerosol-based methods: first, the deposition of nanoparticles by hypersonic impaction, so as so spray-coat large areas with nanoparticles; second, the use of aerodynamic lenses to produce focused beams of nanoparticles, with beam widths of a few tens of microns, so as to integrate nanoparticle-based structures into microelectromechanical systems; and third, the coating of individual nanoparticles by means of photoinduced chemical vapor deposition (photo-CVD), driven by excimer lamps. We also discuss the combination of these technologies, so that nanoparticle synthesis, together with multiple processing steps, can be accomplished in a single flow stream.     

Injection of synthesized FePt nanoparticles in hole-patterns for bit patterned media

FePt nanoparticles of uniform sizes, compositions, and crystal structures can be obtained by chemical synthesis. Additionally, the nanoparticles can be well dispersed by the adsorption of a surfactant on the nanoparticle surface. Previously, the immobilization of FePt nanoparticles on a thermal oxide Si substrate was carried out by chemical synthesis, utilizing the Pt-S bonding between the -SH functional group in (3-mercaptopropyl)trimethoxysilane, MPTMS and Pt in FePt nanoparticles. However, controlling FePt nanoparticle arrays by this synthesis method was very difficult. In the present study, we attempted to control the distortion of the arrangement of FePt nanoparticles using an MPTMS layer modified with a silane coupling reaction and a geometrical structure prepared by ultraviolet nanoimprint lithography (UV-NIL). In this study, the hole-patterns used for the geometrical structure on Si(1 0 0) were 200 nm wide, 40 nm deep, and had a 500 nm pitch. The 5.6 nm FePt nanoparticles were used to coat the hole-patterns by using a picoliter pipette. An XHR-SEM image clearly revealed that the FePt nanoparticles were successfully arranged as a single layer with an average pitch of 10.0 nm by Pt-S bonding in the hole-patterns on Si(1 0 0).     

Structural and optical properties of novel surfactant-coated Yb@TiO<Subscript>2</Subscript> nanoparticles

In this paper a novel hybrid approach to synthesise composite nanoparticles is presented. It is based on the laser ablation of a bulk target (Yb) immersed in a reversed micellar solution which contains nanoparticles of a different host material (TiO₂ nanoparticles) previously synthesised by chemical method. This approach thus exploits the advantages of the chemical synthesis through reversed micellar solution (size control, nanoparticle stabilisation), and of the laser ablation (“clean” synthesis, no side reactions). Central role is played by the microscopic processes controlling the deposition of the ablated Yb atoms onto the surface of TiO₂ nanoparticles which actually behave as nucleation seeds. The structural features of the resulting Yb@TiO₂ composite nanoparticles have been studied by Transmission Electron Microscopy, whereas their peculiar optical properties have been explored by UV–Vis spectroscopy and steady-state fluorescence. Results consistently show the formation of Yb and TiO₂ glued nanodomains to form nearly spherical and non-interacting nanoparticles with enhanced photophysical properties.     

Polymer-supported metals and metal oxide nanoparticles: synthesis,characterization, and applications

Metal and metal oxide nanoparticles exhibit unique properties in regard to sorption behaviors, magnetic activity, chemical reduction, ligand sequestration among others. To this end, attempts are being continuously made to take advantage of them in multitude of applications including separation, catalysis, environmental remediation, sensing, biomedical applications and others. However, metal and metal oxide nanoparticles lack chemical stability and mechanical strength. They exhibit extremely high pressure drop or head loss in fixed-bed column operation and are not suitable for any flow-through systems. Also, nanoparticles tend to aggregate; this phenomenon reduces their high surface area to volume ratio and subsequently reduces effectiveness. By appropriately dispersing metal and metal oxide nanoparticles into synthetic and naturally occurring polymers, many of the shortcomings can be overcome without compromising the parent properties of the nanoparticles. Furthermore, the appropriate choice of the polymer host with specific functional groups may even lead to the enhancement of the properties of nanoparticles. The synthesis of hybrid materials involves two broad pathways: dispersing the nanoparticles (i) within pre-formed or commercially available polymers; and (ii) during the polymerization process. This review presents a broad coverage of nanoparticles and polymeric/biopolymeric host materials and the resulting properties of the hybrid composites. In addition, the review discusses the role of the Donnan membrane effect exerted by the host functionalized polymer in harnessing the desirable properties of metal and metal oxide nanoparticles for intended applications.     

Gold and gold–silver core-shell nanoparticle constructs with defined size based on DNA hybridization

Nanoparticles represent versatile building blocks in material science and nanotechnology. Thereby, the defined assembly of nanostructures (13 and 56 nm in diameter, respectively) is of significant importance. Short DNA sequences can be bound to the nanoparticle surface thus enabling highly specific DNA hybridization-driven events that direct the formation of nanoparticle constructs. In this paper, examples for the defined formation of gold nanoparticle constructs are demonstrated. In addition, gold–silver core-shell nanoparticles are introduced as further building blocks for the hybridization-controlled formation of nanoparticle constructs.     

Molecular Self‐Assembly of Multifunctional Nanoparticle Composites with Arbitrary Shapes and Functions: Challenges and Strategies

The assembly of nanoparticles into complicated, anisotropic shapes has much promise for advanced materials and devices. Developing effective and efficient anisotropic mono‐functionalization strategies is an imperative step in realizing this potential. By functionalizing DNA one at a time to the nanoparticle, a DNA‐nanoparticle building block could have distinct DNA sequences at different locations on the surface of the particle. Since this technology could incorporate nanoparticles of different composition, generating toolboxes of various nanoparticle building blocks (“nano‐toolboxes”) with DNA at defined locations and in defined 3D orientations on a nanoparticle, it promises not only complicated shapes, but also the ability to tune the function of the assembly. The challenges of programmable and scalable multifunctional nanostructure self‐assembly with DNA conjugated to nanoparticles are reviewed. The first difficulty is to control the assembly process so that designed products are formed, and unwanted products are minimized. The design problem for nanostructure construction is both physically and computationally complex. Thus, the other major challenge is to devise design methodologies that move nanostructure construction from trial and error to principled approaches. Strategies to overcome these challenges are also presented by realizing greater control over the final shapes and functions of the self‐assembled nanostructures. Finally, the future perspectives of nano‐toolboxes and their promise in applications such as multifunctional, multicolor, and multimodal contrast nanoagents for medical therapy and diagnostics (theranostics) are described.     

适配体纳米金比色分析技术研究进展

核酸适配体作为一种生物识别分子,其本质是一段单链DNA或RNA,折叠形成特定的二级、三级构象后与靶标分子以高亲和力高特异性结合。纳米金具有强烈的粒子间距光学效应,其在分散状态下呈红色,发生凝聚后变为蓝色。适配体可以通过共价偶联或静电吸附与纳米金结合,通过结合靶标来控制纳米金的颜色变化,从而提供了一种简单、快速、灵敏、可以肉眼观察的快速分析技术。综述了适配体纳米金比色分析技术的研究进展,通过对不同方法比较和讨论,提出了未来的研究方向。     

液相法制备金属纳米粒子

液相法是在均相溶液中，利用各种途径引发化学反应，通过均相或异相成核及随后的扩散生长而制备出粒径分布窄且表面功能化的纳米尺度材料．介绍了液-液两相法、反相胶束、高温液相法等制备单分散金属纳米粒子的方法和高温液相法制备金属纳米粒子的影响因素，以及近年来在金属纳米粒子的制备和性能研究上的进展，尤其是Co等多种磁性纳米粒子的制备、磁性研究．     

面向原子制造的框架核酸研究进展

框架核酸是核酸分子通过自组装形成的一维到三维的框架结构,不仅能精准定位功能基元,还可实现在纳米甚至原子级尺度上进行力学、光学和电学等物理性质,以及单分子水平化学与生化反应的精准调控.利用框架核酸对物质进行原子级的人工自组装,可实现基本构筑单元的精准物理排布与功能化集成,进而实现器件制造,有望推动从原子到宏观的精确功能化...     

Size-effects in clusters and free nanoparticles probed by soft X-rays

Recent progress from experiments on clusters and free nanoparticles is reported, where emphasis is put on studies in the soft X-ray regime. We review selected examples on the characterization of free molecular clusters and nanoparticles. Specifically, we discuss recent progress in changes of the local structure in free clusters. Photoemission and particle charging as well as elastic light scattering from free nanoparticles are reported. These approaches permit the characterization of the intrinsic properties of nanoscopic systems as building blocks of nanoscopic matter and possible nanomaterials.     

Dimensionality selection in a molecule-based magnet

Gaining control of the building blocks of magnetic materials and thereby achieving particular characteristics will make possible the design and growth of bespoke magnetic devices. While progress in the synthesis of molecular materials, and especially coordination polymers, represents a significant step towards this goal, the ability to tune the magnetic interactions within a particular framework remains in its infancy. Here we demonstrate a chemical method which achieves dimensionality selection via preferential inhibition of the magnetic exchange in an S=1/2 antiferromagnet along one crystal direction, switching the system from being quasi-two- to quasi-one-dimensional while effectively maintaining the nearest-neighbor coupling strength.