Towards Electrochemiluminescence Microscopy Exploration of Plasmonic-Mediated Phenomena at the Single-Nanoparticle Level

The rational design of functional plasmonic metasurfaces and metamaterials requires the development of high-throughput characterization techniques compatible with operando conditions and capable of addressing single-nanostructures. In their work, Wei et al. demonstrate the use of electrochemiluminescence microscopy to investigate the mechanism behind plasmon-enhanced luminescence induced by gold nanostructures. The use of gold plasmonic arrays was exploited to achieve the rapid spectroscopic evaluation of all the individual nanostructures, and the correlation of the results with high- resolution electron microscopy analysis, guaranteeing a strict one-to-one correspondence. The authors were able to identify two different mechanisms for the enhancement of [Ru(bpy)₃]²⁺-tri-n-propylamine electrochemiluminescence mediated by single gold nanoparticles and by small plasmonic clusters. In the future, the proposed characterization could be used for the rapid and in situ spectroscopic analysis of more complex plasmonic nanostructures and metasurfaces.     

Electrode-Potential-Driven Dissociation of N-Heterocycle/BF3 Adducts: A Possible Manifestation of the Electro-Inductive Effect

Recently, non-Faradaic effects were used to modify the electronic structure and reactivity of electrode-bound species. We hypothesize that these electrostatic perturbations could influence the chemical reactivity of electrolyte species near an electrode in the absence of Faradaic electron transfer. A prime example of non-Faradaic effects is acid-base dissociation near an interface. Here, we probed the near-electrode dissociation of N-heterocycle-BF₃ Lewis adducts upon electrode polarization, well outside of the redox potential window of the adducts. Using scanning electrochemical microscopy and confocal fluorescence spectroscopy, we detected a potential-dependent depletion of the adduct near the electrode. We propose an electro-inductive effect where a more positive potential leads to electron withdrawal on the N-heterocycle. This study takes a step forward in the use of electrostatics at electrochemical interfaces for field-driven electrocatalytic and electro-synthetic processes.     

Fast Li-ion Storage and Dynamics in TiO2 Nanoparticle Clusters Probed by Smart Scanning Electrochemical Cell Microscopy

Anatase TiO₂ is a promising material for Li-ion (Li⁺) batteries with fast charging capability. However, Li⁺ (de)intercalation dynamics in TiO₂ remain elusive and reported diffusivities span many orders of magnitude. Here, we develop a smart protocol for scanning electrochemical cell microscopy (SECCM) with in situ optical microscopy (OM) to enable the high-throughput charge/discharge analysis of single TiO₂ nanoparticle clusters. Directly probing active nanoparticles revealed that TiO₂ with a size of ≈50 nm can store over 30 % of the theoretical capacity at an extremely fast charge/discharge rate of ≈100 C. This finding of fast Li⁺ storage in TiO₂ particles strengthens its potential for fast-charging batteries. More generally, smart SECCM-OM should find wide applications for high-throughput electrochemical screening of nanostructured materials.     

Atom-probe investigations of fine-scale features in intermetallics

Intermetallics have been studied by means of Atom Probe Field Ion Microscopy. Atom-Probe techniques have been used to determine the phase composition and to study the role and the influence of additional elements. The use of the Tomographic Atom Probe makes it possible to map out the distribution of chemical species in a small volume of the material at a near atomic scale. This has been particularly used in order to study segregation of additional elements at interfaces or planar and linear defects in TiAl base and FeAl base alloys.     

现场显微红外光谱电化学技术及超微铂盘电极上的反射吸收光谱测定

本文阐述了一种新的光谱电化学技术——现场显微红外光谱电化学法的反射式方法的技术特点和优势,报告了一种适于水溶剂和非水溶剂的反射式现场显微红外光谱电化学池的设计,并首次在25um直径的超微铂盘工作电极上,对Fe(CN)_6~(4-)/FE(CN)_6~(3-)进行了现场显微红外光谱电化学的测量。     

金属纳米电极的制备、表征及其在电化学测量中的应用

本文简要介绍了各种金属纳米电极的制备及表征方法。结合我们自己的工作,重点介绍了纳米电极在电化学反应动力学参数测量及扫描电化学显微镜(SECM)中的应用,并对其发展前景进行了展望。引用文献78篇。     

The influence of fibre wall thickness on the undissolved residuals in CMC solutions

An industrial calcium sulfite pulp was fractionated in a hydrocyclone to four fractions that differed in dimensions and composition due to differences in density. The intention was to investigate whether the fibre dimensions had any influence on the properties of carboxymethyl cellulose (CMC) produced from the fractions and especially how the properties of the unreacted material differed. It was surprisingly found that the fraction containing thin-walled fibres gave CMC and dissolved residuals in the CMC-solution that had the lowest degree of substitution (DS). It was therefore believed that the thin-walled fibres were collapsed and more closely bound in the fibre network after drying of the pulp and that this impeded the chemical diffusion in the subsequent CMC-process, i.e. the diffusion of the CMC-chemicals into the cell wall was slower. There was thus a correlation between thinner fibres and a lower degree of substitution for CMC made from such fibres. It was also found that tick-walled fibres had a higher degree of substitution than the thin-walled fibres but that the highest degree of substitution was obtained if a mixture of thin- and thick-walled fibres were used.     

Investigation of the resolution ability of an image inversion interferometer

The present paper presents the experimental measurement of the interferometric point spread function of an image inversion interferometer (III). The measurement was realized by scanning a pointlike source in the object plane and integrating the intensity in the image plane for each position of the point source. The achieved results are compared to the theoretical expectations and the results, which we received in a previous work by using a different method. The improved resolution of two neighbouring points in comparison to the conventional image is demonstrated. In addition we propose an explanation concerning the divergences of the values to be expected in theory.     

X-ray fluorescence (conventional and 3D) and scanning electron microscopy for the investigation of Portuguese polychrome glazed ceramics: Advances in the knowledge of the manufacturing techniques

This work shows the first analytical results obtained by X-Ray Fluorescence (XRF) (conventional and 3D) and Scanning Electron Microscopy with Energy Dispersive System (SEM-EDS) on original Portuguese ceramic pieces produced between the 16th and 18th centuries in Coimbra and Lisbon. Experts distinguished these productions based only on the color, texture and brightness, which originates mislabeling in some cases.Thanks to lateral and spatial resolution in the micrometer regime, the results obtained with μ-XRF were essential in determining the glaze and pigment thicknesses by monitoring the profile of the most abundant element in each “layer”. Furthermore, the dissemination of these elements throughout the glaze is different depending on the glaze composition, firing temperature and on the pigment itself. Hence, the crucial point of this investigation was to analyze and understand the interfaces color/glaze and glaze/ceramic support.Together with the XRF results, images captured by SEM and the corresponding semi-quantitative EDS data revealed different manufacturing processes used by the two production centers. Different capture modes were suitable to distinguish different crystals from the minerals that confer the color of the pigments used and to enhance the fact that some of them are very well spread through the glassy matrix, sustaining the theory of an evolved and careful procedure in the manufacturing process of the glaze.     

Critical angles for axial channeling

The critical angle for axial proton channeling has been measured as a function of temperature for a number of different crystals. The results are consistently below the values predicted from simple analytical estimates. The magnitude of this discrepancy does not seem to depend on the specific lattice structure. In point of fact, all the results are consistent with a relationship ψ_1/2 = α(p/a). ψ₁, where ψ₁ is Lindhard's characteristic angle, and α(p/a)is a function of the thermal vibrational amplitude p, measured in units of the Thomas-Fermi screening distance a. A formula for α(p/a), derived by Barrett from computer simulations, on the average predicts the magnitude of α quite well, but the observed functional dependence on p/a is considerably stronger than predicted.