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Dealloying typically occurs via the chemical dissolution of an alloy component through a corrosion process. In contrast, here we report an atomic-scale nonchemical dealloying process that results in the clustering of solute atoms. We show that the disparity in the adatom-substrate exchange barriers separate Cu adatoms from a Cu-Au mixture, leaving behind a fluid phase enriched with Au adatoms that subsequently aggregate into supported clusters. Using dynamic, atomic-scale electron microscopy observations and theoretical modeling, we delineate the atomic-scale mechanisms associated with the nucleation, rotation and amorphization-crystallization oscillations of the Au clusters. We expect broader applicability of the results because the phase separation process is dictated by the inherent asymmetric adatom-substrate exchange barriers for separating dissimilar atoms in multicomponent materials.

High-resolution transmission electron microscopy (HRTEM) examination of nanoparticles requires their placement on some manner of support - either TEM grid membranes or part of the material itself, as in many heterogeneous catalyst systems - but a systematic quantification of the practical imaging limits of this approach has been lacking. Here we address this issue through a statistical evaluation of how nanoparticle size and substrate thickness affects the ability to resolve structural features of interest in HRTEM images of metallic nanoparticles on common support membranes. The visibility of lattice fringes from crystalline Au nanoparticles on amorphous carbon and silicon supports of varying thickness was investigated with both conventional and aberration-corrected TEM. Over the 1-4nm nanoparticle size range examined, the probability of successfully resolving lattice fringes differed significantly as a function both of nanoparticle size and support thickness. Statistical analysis was used to formulate guidelines for the selection of supports and to quantify the impact a given support would have on HRTEM imaging of crystalline structure. For nanoparticles ≥1nm, aberration-correction was found to provide limited benefit for the purpose of visualizing lattice fringes; electron dose is more predictive of lattice fringe visibility than aberration correction. These results confirm that the ability to visualize lattice fringes is ultimately dependent on the signal-to-noise ratio of the HRTEM images, rather than the point-to-point resolving power of the microscope. This study provides a benchmark for HRTEM imaging of crystalline supported metal nanoparticles and is extensible to a wide variety of supports and nanostructures.

High-power electronics, such as GaN high electron mobility transistors (HEMTs), are expected to perform reliably in high-temperature conditions. This study aims to gain an understanding of the microscopic origin of both material and device vulnerabilities to high temperatures by real-time monitoring of the onset of structural degradation under varying temperature conditions. This is achieved by operating GaN HEMT devices in situ inside a transmission electron microscope (TEM). Electron-transparent specimens are prepared from a bulk device and heated up to 800 °C. High-resolution TEM (HRTEM), scanning TEM (STEM), energy-dispersive x-ray spectroscopy (EDS), and geometric phase analysis (GPA) are performed to evaluate crystal quality, material diffusion, and strain propagation in the sample before and after heating. Gate contact area reduction is visible from 470 °C accompanied by Ni/Au intermixing near the gate/AlGaN interface. Elevated temperatures induce significant out-of-plane lattice expansion at the SiNx/GaN/AlGaN interface, as revealed by geometry-phase GPA strain maps, while in-plane strains remain relatively consistent. Exposure to temperatures exceeding 500 °C leads to almost two orders of magnitude increase in leakage current in bulk devices in this study, which complements the results from our TEM experiment. The findings of this study offer real-time visual insights into identifying the initial location of degradation and highlight the impact of temperature on the bulk device's structure, electrical properties, and material degradation. [ABSTRACT FROM AUTHOR]

Overcoming slow kinetics and high overpotential in electrocatalytic oxygen evolution reaction (OER) requires innovative catalysts and approaches that transcend the scaling relationship between binding energies for intermediates and catalyst surfaces. Inorganic complexes provide unique, customizable geometries, which can help enhance their efficiencies. However, they are unstable and susceptible to chemical reaction under extreme pH conditions. Immobilizing complexes on substrates creates single‐molecule catalysts (SMCs) with functional similarities to single‐atom catalysts (SACs). Here, an efficient SMC, composed of dichloro(1,3‐bis(diphenylphosphino)propane) nickel [NiCl2dppp] anchored to a graphene acid (GA), is presented. This SMC surpasses ruthenium‐based OER benchmarks, exhibiting an ultra‐low onset and overpotential at 10 mAcm−2 when exposed to a static magnetic field. Comprehensive experimental and theoretical analyses imply that an interfacial charge transfer from the Ni center in NiCl2dppp to GA enhances the OER activity. Spectroscopic investigations reveal an in situ geometrical transformation of the complex and the formation of a paramagnetic Ni center, which under a magnetic field, enables spin‐selective electron transfer, resulting in enhanced OER performance. The results highlight the significance of in situ geometric transformations in SMCs and underline the potential of an external magnetic field to enhance OER performance at a single‐molecule level. [ABSTRACT FROM AUTHOR]

Ga2O3 films were deposited on (100) MgAl2O4 spinel substrates at 550, 650, 750, and 850 ° C using metal-organic chemical vapor deposition and investigated using x-ray diffraction and transmission electron microscopy. A phase-pure γ-Ga2O3-based material having an inverse spinel structure was formed at 850 °C; a mixture of the γ-phase and β-Ga2O3 was detected in films grown at 750 ° C. Only β-Ga2O3 was determined in the films deposited at 650 and 550 ° C. A β- to γ-phase transition occurred from the substrate/film interface during growth at 750 ° C. The growth and stabilization of the γ-phase at the outset of film growth at 850 ° C was affected by the substantial Mg and Al chemical interdiffusion from the MgAl2O4 substrate observed in the energy-dispersive x-ray spectrum. Atomic-scale investigations via scanning transmission electron microscopy of the films grown at 750 and 850 ° C revealed a strong tetrahedral site preference for Ga and an octahedral site preference for Mg and Al. It is postulated that the occupation of these atoms in these particular sites drives the β-Ga2O3 to γ-phase transition and markedly enhances the thermal stability of the latter phase at elevated temperatures. [ABSTRACT FROM AUTHOR]

This document is a correction to a research article titled "Nickel-Based Single-Molecule Catalysts with Synergistic Geometric Transition and Magnetic Field-Assisted Spin Selection Outperform RuO2 for Oxygen Evolution" published in the journal Advanced Energy Materials. The correction addresses an error in Figure S5d of the supporting information, specifically related to the O1s raw spectrum of NiGA. The corrected data is provided in a revised figure. Additionally, the document includes revised sentences in the "Computation Details" section to provide greater clarity about the methodology used in the research. The authors apologize for the error. [Extracted from the article]

Volatile molecules are generated for mass spectral analysis at an electrode placed directly within the ion source. Poly(ethylene) glycol) (PEG, average molecular weight 400) is used as the solvent due to its extremely low volatility, while hexamethylphosphoric triamide (HMPA) provides a wider potential range. A twin, interdigitated electrode pair is used, one side of which is coated with the redox polymer Prussian blue to act as an auxiliary/pseudoreference. Mass spectral peaks characteristic of ferrocene are seen during the reduction of ferrocinium, including the parent at m/z 186. Following the mass spectral signal at m/z 186 as a function of time during electrolysis lends insight into the transport properties of material from the electrode surface to the mass spectral detector. Similar qualitative results are shown for the oxidation of carboxylic acids in PEG and the reduction of dibromododecane in HMPA.

The synthesis of (2(sub 2))(1,5)cyclooctatetraenophane proceeds in 13 steps from the ketone precursor via the annulating capabilities of the Cook-Weiss reaction and the thermal isomerization of semibullvalenes to cyclooctatetraenes. Molecular mechanics computations and X-ray crystallography show that the phane exists in two chiral ground-state conformations, whose interconversions proceed without a change in the double bond locations. Moreover, spectral data show that one conformation dominates the equilibrium.