A Macroscopically Relevant 3D‐Metrology Approach for Nanocatalysis Research

A 3D nanometrological approach, which considers as an unbiased validation criterion the quantitative match between values of properties determined by macroscopic characterization techniques and those determined from the nanoscopic results, is developed to unveil the details of complex nanocatalysts. This approach takes into account both the peculiar characteristics of this type of materials and the large influence of noise in the tilt series. It combines, in an optimized way, the latest experimental developments in high angle annular dark field scanning transmission electron microscopy mode (HAADF‐STEM) tomography, such as batch tomography, image denoising by undecimated wavelet transforms, improved reconstructions by total variation minimization and a more efficient, user‐independent, segmentation scheme. To illustrate the use of this novel approach, the 3D structural characterization of a model nanocatalyst comprising gold nanoparticles dispersed on the surface of CeO₂ nanocubes is performed, and the obtained results used to compute the values of different macroscopic chemical and textural properties. Comparison with values obtained by macroscopic characterization techniques match very closely those obtained by 3D nanometrology. Importantly, the new approach described in this work also illustrates a pipeline for nearly fully automated HAADF‐STEM tomography studies, guaranteeing reliable correlations between nanoscopic and macroscopic properties.     

Diffusion of silver nanoparticles on carbonaceous materials. Cluster mobility as a probe for surface characterization

The effect of support geometry and structure on nanoparticles diffusion, nucleation and coalescence was already shown. In this paper, we focus on an alternative use of the interaction between deposited clusters and the substrate for the characterization of surface properties. The use of clusters deposition as probe for surface states characterization appears as an attractive and remarkable tool.     

Near-field optics and control of photonic crystals

We discuss recent progress and the exciting potential of scanning probe microscopy methods for the characterization and control of photonic crystals. We demonstrate that scanning near-field optical microscopy can be used to characterize the performance of photonic crystal device components on the sub-wavelength scale. In addition, we propose scanning probe techniques for realizing local, low-loss tuning of photonic crystal resonances, based on the frequency shifts that high-index nanoscopic probes can induce. Finally, we discuss prospects for on-demand spontaneous emission control. We demonstrate theoretically that photonic crystal membranes induce large variations in spontaneous emission rate over length scales of 50 nm that can be probed by single light sources, or nanoscopic ensembles of light sources attached to the end of a scanning probe.     

A thermodynamic approach to mechanical stability of nanosized particles

Thermodynamic stability conditions for nanoparticles (resulting from non-negativity of the second variation of the free energy) have been analyzed for two cases: (i) a nonvolatile nanosized particle with the size-dependent surface tension; (ii) the limiting case of larger objects when the surface tension takes its macroscopic value. It has been shown that the mechanical stability of a nanoparticle, i.e. its stability relative to the volume fluctuations, is defined by an interplay between the excess (“surface”) free energy and the volumetric elastic energy. According to the results obtained, noble gas clusters and metal nanoparticles satisfy the mechanical stability condition. At the same time, water nanodrops, as well as nanoparticles presented by nonpolar organic molecules, correspond to the stability limit. Among the investigated systems, the stability condition is not carried out for n-Pentane clusters.     

Selective hydrogenation by polymer-encapsulated platinum nanoparticles prepared by an easy single-step sonochemical synthesis

Polypyrrole-encapsulated platinum nanoparticles (PPy/Pt-NPs) prepared by an easy single-step sonochemical synthesis were used as catalysts for the liquid phase hydrogenation of substituted alkenes in methanol or methanol/water mixtures. Polypyrrole (PPy) coatings on the nanoparticles were able to act as nanoscopic filters for substrates molecules, and consequently substrate selectivity could be controlled in the catalytic processes.     

Effect of pressure on melting and solidification of metal nanoparticles

A thermodynamic model was developed to clarify the dependence of melting temperature on hydrostatic pressure in the nanoscopic scale. It is based on the classic Clausius-Clapeyron relation and the size dependence of the melting entropy. The melting of nanoparticles in matrix with coherent and incoherent boundaries was also under consideration. It was shown that external hydrostatic pressure leads to the appearance of extrema of the melting temperature that was considered as a function of the characteristic size of nanoparticles.     

Tunable interplay between superconductivity and correlations in nanoscopic heterostructures

Artificial heterostructures consisting of the superconducting electrode(s) and the free electron reservoir(s) interconnected through various nanoscopic objects, like: quantum dots, nanowires or molecules enable a fully controllable confrontation of the correlation effects with electron pairing. Discrete energy spectrum of the nanoscopic objects (due to the quantum size effect) strongly depends on the many-body effects. Via the proximity effect, these nanoscopic objects are converted into the superconducting grains. Since the coupling to external electrodes can be varied experimentally, this enables a fully controllable investigation of an interplay between the electron correlations and superconductivity. In this work, we explore the subgap (Shiba) states arising from the induced pairing and analyse their influence on the Kondo-type correlations. This issue is currently widely explored using various nanoscopic devices.     

Spin and orbital magnetic moments of free nanoparticles

The determination of spin and orbital magnetic moments from the free atom to the bulk phase is an intriguing challenge for nanoscience, in particular, since most magnetic recording materials are based on nanostructures. We present temperature-dependent x-ray magnetic circular dichroism measurements of free Co clusters (N=8-22) from which the intrinsic spin and orbital magnetic moments of noninteracting magnetic nanoparticles have been deduced. An exceptionally strong enhancement of the orbital moment is verified for free magnetic clusters which is 4-6 times larger than the bulk value. Our temperature-dependent measurements reveal that the spin orientation along the external magnetic field is nearly saturated at ~20 K and 7 T, while the orbital orientation is clearly not.     

Confined clustering of AuCu nanoparticles under ambient conditions

The study of bimetallic clusters has been increasing in recent years due to the wide range of novel applications, when compared with monometallic nanoparticles This paper presents a simple method of low toxicity to obtain bimetallic nanoparticle clusters of AuCu. The localized surface plasmon resonance (LSPR) of the nanoalloy was located in a value in between those reported for AuNP and CuNP. Raman bands of nanoparticle clusters of AuCu were observed in the range 130-300 cm^?1. The structural and optical analysis of the synthesized nanoparticles confirmed the presence of the bond Au-Cu, with a particle size ranging from 1 to 2 nm. The geometries and vibrational modes were predicted for small metallic clusters of Au, Cu and bimetallic AuCu. The AgCu nanoparticles have been recently implemented in glasses to study optical properties, as well as antibacterial applications.     

Self-assembled organic templates for the selective adsorption of gold nanoparticles into confined domains

A simple procedure for the fabrication of submicron-sized functional organic templates is demonstrated. Native silicon samples are partially coated in millimolar octadecyltrichlorosilane (OTS) solutions. After coating, atomic force microscopy (AFM) reveals islands with diameters ranging from 0.6 to 1 μm. The hydrocarbon chains of the self-assembled silane entities within these islands subsequently are chemically functionalized following a robust preparation scheme. X-ray photoelectron spectroscopy (XPS) and water contact angle measurements were used for characterization. After functionalization, alkylsiloxane islands provide a versatile means to direct the deposition of nanoscopic components. In particular, citrate-stabilized gold nanoparticles (d = 16 ± 2 nm) are shown to selectively adsorb onto aminated islands, whereas adsorption on areas between these islands is negligible.     

Thermal stability of Pt nanoclusters interacting to carbon sublattice

The catalytic activity of Pt clusters is dependent not only on the nanoparticle size and its composition, but also on its internal structure. To determine the real structure of the nanoparticles used in catalysis, the boundaries of the thermal structure stability of Pt clusters to 8.0 nm in diameter interacting with carbon substrates of two types: a fixed α-graphite plane and a mobile substrate with the diamond structure. The effect of a substrate on the processes melting of Pt nanoclusters is estimated. The role of the cooling rate in the formation of the internal structure of Pt clusters during crystallization is studied. The regularities obtained in the case of “free” Pt clusters and Pt clusters on a substrate are compared. It is concluded that platinum nanoparticles with diameter D ≤ 4.0 nm disposed on a carbon substrate conserve the initial fcc structure during cooling.

     

Infrared imaging of single nanoparticles via strong field enhancement in a scanning nanogap

We demonstrate nanoscale resolved infrared imaging of single nanoparticles employing near-field coupling in the nanoscopic gap between the metal tip of a scattering-type near-field optical microscope and the substrate supporting the particles. Experimental and theoretical evidence is provided that highly reflecting or polariton-resonant substrates strongly enhance the near-field optical particle contrast. Using Si substrates we succeeded in detecting Au particles as small as 8 nm (相似文献   

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold–gold interactions while a Lennard–Jones (L–J) potential is used to describe the gold–GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold–gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the ε_Au–C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order–disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.     

Semiconducting Polymer Nanoparticles as Fluorescent Probes for Biological Imaging and Sensing

In recent years, semiconducting polymer nanoparticles have emerged as a new class of extraordinarily bright fluorescent probes. These polymer nanoparticles, which are primarily composed of π‐conjugated polymers, exhibit a variety of outstanding features, including exceptional fluorescence brightness, fast radiative rate, good photostability, facile surface functionalization, and low cytotoxicity. These advantageous characteristics make polymer nanoparticles highly promising for applications in biological imaging and sensing. This progress report highlights recent advances in the synthesis, characterization, and applications as bio‐labels or sensors of these highly emissive organic nanoparticles.     

Formation of argentic clusters and small Ag nanoparticles in soda-lime silicate glass

The formation of argentic clusters and very small Ag nanoparticles of 0.5 to 2 nm size in commercial soda-lime glass silver-doped by Ag/Na ion exchange in a mixed nitrate melt has been studied by electron microscopy and EXAFS. Particles formation was induced already during the ion exchange procedure, or by subsequent ion irradiation with 1.5 MeV He⁺ or 3 MeV Au⁺. The presence of nanoparticles was also macroscopically revealed by their surface plasmon resonance. The structural characterization indicates that specific configurations of silver oxide-like structures, so-called argentic clusters, are involved in the initial stage of nanoparticles formation.     

Adsorption at cell surface and cellular uptake of silica nanoparticles with different surface chemical functionalizations: impact on cytotoxicity

Methods for the facile and in-line characterization of size distribution and physical properties of unsupported nanoparticles are of paramount importance for fundamental research and industrial applications. The state-of-the-art free nanoparticle characterization methods do not provide accuracy, high throughput, and operation easiness to support widespread use for routine characterization. In this perspective paper, we describe and discuss the opportunities provided by approaches for nanoparticle characterization based on optical measurements of the field scattered by particles. In particular, we show how insightful is the measure of both the real and the imaginary parts of the field amplitude, a task that has been considered in the past but never had a widespread exploitation. A number of opportunities are generated by this approach, in view of assessing a more efficient characterization and a better understanding of the properties of nanoparticles. We focus our attention on the capability of characterizing nanoparticles of wide interest for applications, considering cases where traditional approaches are not currently effective. Possible exploitations are both in research and in industrial environments: to validate a synthetic process, for example, or for in-line monitoring of a production plant to generate advanced process control tools, as well as decision-making tools for acting in real time during the production.     

Optical properties of sol-gel fabricated Ni/SiO2 glass nanocomposites

Nickel nanoparticles were grown in silica glass by annealing of the sol-gel prepared silicate matrices doped with nickel nitrate. TEM characterization of Ni/SiO₂ glass proves the formation of isolated spherical nickel nanoparticles with mean sizes 6.7 and 20 nm depending on annealing conditions. The absorption and photoluminescence spectra of Ni/SiO₂ glasses were measured. In the absorption spectra, we observed the band related to the surface plasmon resonance (SPR) in Ni nanoparticles. The broadening of SPR was observed with decrease of Ni nanoparticle size. The width of the surface plasmon band decreases 1.5 times at the lowering of temperature from 293 to 2 K because of strong electron-phonon interaction. The spectra proved the creation of nickel oxide NiO clusters and Ni²⁺ ions in silica glass as well.     

Determination of interdiffusion coefficients of liquid zinc and tin under convectionless conditions

In the present work, the production is reported of Cu nanoparticles, with sizes of 2-5 nm, by proton irradiation with a low controlled temperature for the sample. The process yields aggregates over a crystalline matrix of the same element. The structural evolution of the sample is analyzed from macroscopic to nanoscopic scales, using optical and electron microscopy. The grain size and preferential shape-changes of the polycrystalline sheets were obtained by optical chromatic systems. Scanning electron microscopy analysis was used to study the morphology and composition with an Energy Dispersive Spectroscopy (EDS) system, and with the help of transmission electron microscopy the lattice matrix of crystal was solved and the nanoparticles' shape and size were determined. Molecular simulation tools were used to support the analysis of high-resolution elecron microscopic images and the nanoparticles' behavior.     

Femtosecond ionization and fragmentation of free silicon nanoparticles

Femtosecond-laser spectroscopy is used to study the photoionization and photofragmentation of large neutral silicon clusters in a beam. Silicon clusters Si_n with sizes up to n≈6000, corresponding to nanoparticles with diameters up to 6 nm, are generated in a laser vaporization source. Nanosecond- and femtosecond-laser ionization are employed to characterize the free silicon nanoparticles. Excitation with intense femtosecond-laser pulses leads to prompt formation of doubly and triply charged Si_n clusters. Additionally, strong fragmentation of charged clusters occurs by Coulomb explosion, resulting in high released kinetic energies. Multiply charged atoms up to Si⁴⁺ with initial kinetic energies in the range of 500 eV are observed for laser intensities of about 10¹³ W/cm². Pump–probe spectroscopy yields decay times of the intermediate resonances of the nanoparticles. Received: 22 January 2000 / Published online: 7 August 2000