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Up to 17 GPa, the crystalline phases of N2 are characterized by pronounced orientational disorder, whereas the higher-pressure phases of molecular N2 are ordered. This raises the question about long-term relaxation of orientational disorder within the low- to intermediate-pressure regime. Here, this question is addressed by comparing synthetic with natural, chemically pure, solid N2 that resides as inclusions in diamonds at 300 K for about 108 years at pressures up to 11 GPa. It is shown that disorder prevails at 8.7 GPa, 300 K, where both synthetic and natural N2 assume the same structure. However, at 10.8 GPa, natural solid N2 exhibits monoclinic distortion and partial orientational ordering of the molecules, both of which are not observed in synthetic material. This difference is interpreted as the result of long-term structural relaxation. The ordering mechanism is examined and placed into the context of the δ- to ε-N2 transition. We present explanations for the absence of complete ordering of δ-N2. [ABSTRACT FROM AUTHOR]

A unique on-chip method for the direct correlation of optical properties, with atomic-scale chemical–structural characteristics for a single quantum dot (QD), is developed and utilized in various examples. This is based on performing single QD optical characterization on a modified glass substrate, followed by the extraction of the relevant region of interest by focused-ion-beam–scanning electron microscope processing into a lamella for high resolution scanning transmission electron microscopy (STEM) characterization with atomic scale resolution. The direct correlation of the optical response under an electric field with STEM analysis of the same particle allows addressing several single particle phenomena: first, the direct correlation of single QD photoluminescence (PL) polarization and its response to the external field with the QD crystal lattice alignment, so far inferred indirectly; second, the identification of unique yet rare few-QD assemblies, correlated directly with their special spectroscopic optical characteristics, serving as a guide for future designed assemblies; and third, the study on the effect of metal island growth on the PL behavior of hybrid semiconductor–metal nanoparticles, with relevance for their possible functionality in photocatalysis. This work, therefore, establishes the use of the direct on-chip optical–structural correlation method for numerous scenarios and timely questions in the field of QD research. [ABSTRACT FROM AUTHOR]

Developing high performance catalysts for electrochemical water splitting is critical for an efficient and sustainable route to hydrogen production. For this, single-atom catalysts (SACs) are the best candidates, as they offer the highest atom efficiency. However, current methods to produce SACs involve a complex synthesis, often requiring multiple lengthy and expensive steps and yielding an insufficient density of single atoms. Here, we report a one-step chemical vapor deposition (CVD) synthesis to produce free-standing (FS) electrodes with Ni SACs on a matrix of sulfur-doped carbon nanofibers (CNFs), referred to as SACs@nanocarbon. The mechanism is based on a temperature-controlled delamination of thin films, with Au in contact with a SiO2 substrate, leading to the nucleation and growth of SACs@nanocarbon. Advanced characterization methods indicate the presence of Ni and Au single atoms and larger gold aggregates on the CNF matrix surface. These non-platinum group metal (non-PGM) electrodes showed exceptional performance for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). They performed for over 20 000 cycles with negligible change in overpotential at higher currents, with low onset overpotentials of 305 mV at 10 mA cm−2 for the OER and 40 mV at 17 mA cm−2 for the HER. The overpotential decreased to 195 mV at a current density of 100 mA cm−2. Remarkably, the electrode performance improved over cycling, while gold was dissolving in the electrolyte. This novel synthesis yielding SACs@nanocarbon could pave the way for the development of non-PGM, high performance electrodes for many other electrocatalytic applications. Additionally, the new paradigm of temperature-controlled delamination of thin films could be used to synthesize new materials. [ABSTRACT FROM AUTHOR]

The coarsening of supported nanoparticles is an inevitable process that has a significant impact on the properties of materials. However, due to the limitation of experimental techniques, the atomistic kinetic mechanisms of coarsening remain largely unknown. In this work, we simulated the coarsening process of supported nanoparticles using the phase-field crystal (PFC) model in 2D and examined the influence of substrates' lattice structure on the kinetics of coarsening. The simulation results show that the particle size distribution (PSD) is consistent with mean field methods for the coarsening of triangular structured particles on the fcc(111) face, while the PSD is of a log-normal type for the coarsening on the fcc(110) and fcc(100) faces, which is consistent with the contact model of coarsening. The coarsening of supported nanoparticles is diffusion controlled, and the order of coarsening rate is K(111) > K(110) > K(100). Also, we investigated the influence of lattice mismatch on the coarsening process and found that the coarsening rate decreases with the lattice mismatch. In addition, we observed a superlattice on the surface of the particles using the PFC model, which is similar to previous experimental results, and analyzed the effect of the superlattice on the coarsening of the nanoparticles. [ABSTRACT FROM AUTHOR]

The synthesis of two-dimensional van der Waals magnets has paved the way for both technological applications and fundamental research on magnetism confined to ultra-small length scales. Edge magnetic moments in ferromagnets are expected to be less magnetized than in the sample interior because of the reduced amount of neighboring ferromagnetic spins at the sample edge. We recently demonstrated that CrGeTe3 (CGT) flakes thinner than 10 nm are hard ferromagnets; i.e., they exhibit an open hysteresis loop. In contrast, thicker flakes exhibit zero net remnant field in the interior, with hard ferromagnetism present only at the cleaved edges. This experimental observation suggests that a nontrivial interaction exists between the sample edge and the interior. Here, we demonstrate that artificial edges fabricated by focus ion beam etching also display hard ferromagnetism. This enables us to write magnetic nanowires in CGT directly and use this method to characterize the magnetic interaction between the interior and edge. The results indicate that the interior saturation and depolarization fields depend on the lateral dimensions of the sample. Most notably, the interior region between the edges of a sample narrower than 300 nm becomes a hard ferromagnet, suggesting an enhancement of the magnetic exchange induced by the proximity of the edges. Last, we find that the CGT regions amorphized by the gallium beam are nonmagnetic, which introduces a novel method to tune the local magnetic properties of CGT films, potentially enabling integration into spintronic devices. [ABSTRACT FROM AUTHOR]

A detailed and systematic investigation on the effect post heat treatment has on the microstructure evolution and the resultant mechanical properties of the wire arc additive manufacturing processed Mg-5.9Gd-2.8Y-0.7Zr alloy is conducted in this work. The microstructure of the as-built sample is composed mainly of fine equiaxed α-Mg grain and Mg24(Gd, Y)5 phase. The solution heat treatment (400°C × 1 h) has relatively little effect on grain size, but it can effectively reduce the content of the Mg24(Gd, Y)5 phase, which leads to a significantly improved elongation with slightly decreased strength. Further ageing heat treatment at 200°C induces prismatic β' precipitates formation and does not influence other phases and grain size. The samples directly following the peak ageing heat treatment process demonstrate the best tensile properties with yield strength of 227 ± 9 MPa, ultimate tensile strength of 350 ± 4 MPa and elongation of 5.5 ± 0.6%. [ABSTRACT FROM AUTHOR]

Top‐down fabricated nanoantenna architectures of both metallic and dielectric materials show powerful functionalities for Raman and fluorescence enhancement with relevance to single molecule sensing while inducing directionality of chromophore emission with implications for single photon sources. We synthesize the smallest bow‐tie nanoantenna by selective tip‐to‐tip fusion of two tetrahedral colloidal quantum dots (CQDs) forming a dimer. While the tetrahedral monomers emit non‐polarized light, the bow‐tie architecture manifests nanoantenna functionality of enhanced emission polarization along the bow‐tie axis, as predicted theoretically and revealed by single‐particle spectroscopy. Theory also predicts the formation of an electric‐field hotspot at the bow‐tie epicenter. This is utilized for selective light‐induced photocatalytic metal growth at that location, unlike growth on the free tips in dark conditions, thus demonstrating bow‐tie dimer functionality as a photochemical reaction center. [ABSTRACT FROM AUTHOR]

Zinc chalcogenides nanostructures are promising newly‐studied materials for photocatalytic reactions such as water reduction for hydrogen generation and photoinitiation of radical polymerization processes. Herein, we introduced a straightforward synthesis of thin ZnS shell on ZnSe nanorods and characterized the resulting core/shell ZnSe/ZnS nanorods by electron microscopy techniques and X‐ray photoelectron spectroscopy. Then, the photocatalytic activities of the nanorods were studied by gas chromatography for hydrogen generation and by Fourier transform infrared spectroscopy for the photoinitiation capability. While such core/shell systems may limit charge transfer to the solution due to the type‐I band alignment, we find that the photochemical stability and photocatalytic activity of this system is significantly enhanced over pristine ZnSe nanorods. ZnSe/ZnS nanorods with Ni(NO3)2 co‐catalyst are used for hydrogen generation and the effects of the nanorods' surface coating, pH conditions and type of hole scavenger are examined. The best performances were observed for nanorods after ligand stripping with Meerwein′s reagent using ascorbic acid as a hole acceptor at pH 4.5. All three parameters were found to affect the photocatalytic activity. Yet, the surface coating and pH dependence differ from previous reports on cadmium chalcogenides photocatalysts. The origin of their differences is discussed and attributed to the band alignment of the systems and the nature of the co‐catalyst. The stable heavy‐metal free ZnSe/ZnS nanorods system presented here holds promise for various photocatalytic applications. [ABSTRACT FROM AUTHOR]

Abstract: Structural defects, found in gallium-phosphide nanowires, grown from Au catalyst on InP 〈111〉B substrate using metal organic molecular beam epitaxy, were extensively studied using Transmission Electron Microscopy (TEM). Several types of growth were analyzed: pure axial, axial–lateral and self catalyzed. Pure axially grown nanowires were found to be single crystals with wurzite crystal structure and Ga-polarity. These nanowires contained threading edge dislocation along the wire axis. The axial–lateral nanowires grew with zinc blend crystal structure and exhibited polycrystalline nature. Self catalyzed single crystalline nanowires possessed wurzite crystal structure with P-polarity and exhibited threading edge dislocations along their axis. [Copyright &y& Elsevier]