Thermal Stability of High-Entropy Alloy Nanoparticles Evaluated by In Situ TEM Observations.

High-entropy alloy (HEA) nanoparticles (NPs) have attracted attention in several fields because of their fascinating properties. The high mechanical strength, good thermal stability, and superior corrosion resistance of HEAs, which are derived from their high configurational entropy, are attractive features. Herein, we investigated the thermal stability of FeCoNiCuPd HEA NPs on reduced graphene oxide via in situ transmission electron microscopy observations at elevated temperatures. The HEA NPs maintained their structure, size, and composition at 700 °C, and their size gradually decreased accompanied by the preferential sublimation of Cu. On the contrary, the deterioration of the monometallic Pd NPs begins at temperatures greater than 700 °C according to Ostwald ripening, which involves the migration of adatoms or mobile molecular species. Theoretical calculations revealed that the detachment of adatoms from clusters (i.e., the first step of Ostwald ripening) was suppressed in the case of HEA NPs because of the high-configuration-entropy effect.

Multicrystalline Informatics Applied to Multicrystalline Silicon for Unraveling the Microscopic Root Cause of Dislocation Generation.

A comprehensive analysis of optical and photoluminescence images obtained from practical multicrystalline silicon wafers is conducted, utilizing various machine learning models for dislocation cluster region extraction, grain segmentation, and crystal orientation prediction. As a result, a realistic 3D model that includes the generation point of dislocation clusters is built. Finite element stress analysis on the 3D model coupled with crystal growth simulation reveals inhomogeneous and complex stress distribution and that dislocation clusters are frequently formed along the slip plane with the highest shear stress among twelve equivalents, concentrated along bending grain boundaries (GBs). Multiscale analysis of the extracted GBs near the generation point of dislocation clusters combined with ab initio calculations has shown that the dislocation generation due to the concentration of shear stress is caused by the nanofacet formation associated with GB bending. This mechanism cannot be captured by the Haasen-Alexander-Sumino model. Thus, this research method reveals the existence of a dislocation generation mechanism unique to the multicrystalline structure. Multicrystalline informatics linking experimental, theoretical, computational, and data science on multicrystalline materials at multiple scales is expected to contribute to the advancement of materials science by unraveling complex phenomena in various multicrystalline materials.

Sub-nanometric High-Entropy Alloy Cluster: Hydrogen Spillover Driven Synthesis on CeO2 and Structural Reversibility.

High-entropy alloy (HEA) nanoparticles (NPs) have attracted significant attention as promising catalysts owing to the various unique synergistic effects originating from the nanometer-scale, near-equimolar mixing of five or more components to produce single-phase solid solutions. However, the study of sub-nanometer HEA clusters having sizes of less than 1 nm remains incomplete despite the possibility of novel functions related to borderline molecular states with discrete quantum energy levels. The present work demonstrates the synthesis of CeO2 nanorods (CeO2-NRs) on which sub-nanometer CoNiCuZnPd HEA clusters were formed with the aid of a pronounced hydrogen spillover effect on readily reducible CeO2 (110) facets. The CoNiCuZnPd HEA sub-nanoclusters exhibited higher activity during the reduction of NO by H2 even at low temperatures compared with the corresponding monometallic catalysts. These clusters also showed a unique structural reversibility in response to repeated exposure to oxidative/reductive conditions, based on the sacrificial oxidation of the non-noble metals. Both experimental and theoretical analyses established that multielement mixing in quantum-sized regions endowed the HEA clusters with entirely novel catalytic properties.

Chondrule-like objects and Ca-Al-rich inclusions in Ryugu may potentially be the oldest Solar System materials.

Chondrule-like objects and Ca-Al-rich inclusions (CAIs) are discovered in the retuned samples from asteroid Ryugu. Here we report results of oxygen isotope, mineralogical, and compositional analysis of the chondrule-like objects and CAIs. Three chondrule-like objects dominated by Mg-rich olivine are 16O-rich and -poor with Δ17O (=δ17O - 0.52 × Î´18O) values of ~ -23‰ and ~ -3‰, resembling what has been proposed as early generations of chondrules. The 16O-rich objects are likely to be melted amoeboid olivine aggregates that escaped from incorporation into 16O-poor chondrule precursor dust. Two CAIs composed of refractory minerals are 16O-rich with Δ17O of ~ -23‰ and possibly as old as the oldest CAIs. The discovered objects (<30 µm) are as small as those from comets, suggesting radial transport favoring smaller objects from the inner solar nebula to the formation location of the Ryugu original parent body, which is farther from the Sun and scarce in chondrules. The transported objects may have been mostly destroyed during aqueous alteration in the Ryugu parent body.

Maximizing noble metal utilization in solid catalysts by control of nanoparticle location.

Maximizing the utilization of noble metals is crucial for applications such as catalysis. We found that the minimum loading of platinum for optimal performance in the hydroconversion of n-alkanes for industrially relevant bifunctional catalysts could be reduced by a factor of 10 or more through the rational arranging of functional sites at the nanoscale. Intentionally depositing traces of platinum nanoparticles on the alumina binder or the outer surface of zeolite crystals, instead of inside the zeolite crystals, enhanced isomer selectivity without compromising activity. Separation between platinum and zeolite acid sites preserved the metal and acid functions by limiting micropore blockage by metal clusters and enhancing access to metal sites. Reduced platinum nanoparticles were more active than platinum single atoms strongly bonded to the alumina binder.

Large phonon drag thermopower boosted by massive electrons and phonon leaking in LaAlO3/LaNiO3/LaAlO3 heterostructure.

An unusually large thermopower (S) enhancement is induced by heterostructuring thin films of the strongly correlated electron oxide LaNiO3. The phonon-drag effect, which is not observed in bulk LaNiO3, enhances S for thin films compressively strained by LaAlO3 substrates. By a reduction in the layer thickness down to three unit cells and subsequent LaAlO3 surface termination, a 10 times S enhancement over the bulk value is observed due to large phonon drag S (Sg), and the Sg contribution to the total S occurs over a much wider temperature range up to 220 K. The Sg enhancement originates from the coupling of lattice vibration to the d electrons with large effective mass in the compressively strained ultrathin LaNiO3, and the electron-phonon interaction is largely enhanced by the phonon leakage from the LaAlO3 substrate and the capping layer. The transition-metal oxide heterostructures emerge as a new playground to manipulate electronic and phononic properties in the quest for high-performance thermoelectrics.

Hydrogen spillover-driven synthesis of high-entropy alloy nanoparticles as a robust catalyst for CO2 hydrogenation.

High-entropy alloys (HEAs) have been intensively pursued as potentially advanced materials because of their exceptional properties. However, the facile fabrication of nanometer-sized HEAs over conventional catalyst supports remains challenging, and the design of rational synthetic protocols would permit the development of innovative catalysts with a wide range of potential compositions. Herein, we demonstrate that titanium dioxide (TiO2) is a promising platform for the low-temperature synthesis of supported CoNiCuRuPd HEA nanoparticles (NPs) at 400 °C. This process is driven by the pronounced hydrogen spillover effect on TiO2 in conjunction with coupled proton/electron transfer. The CoNiCuRuPd HEA NPs on TiO2 produced in this work were found to be both active and extremely durable during the CO2 hydrogenation reaction. Characterization by means of various in situ techniques and theoretical calculations elucidated that cocktail effect and sluggish diffusion originating from the synergistic effect obtained by this combination of elements.

Wound Healing Promotion by Hyaluronic Acid: Effect of Molecular Weight on Gene Expression and In Vivo Wound Closure.

Hyaluronic acid (HA) has been known to play an important role in wound healing process. However, the effect of molecular weight (MW) of exogenously administered HA on the wound healing process has not been fully understood. In this study, we investigated HA with different MWs on wound healing process using human epidermal keratinocytes and dermal fibroblasts. Cell proliferation and migration ability were assessed by water soluble tetrazolium (WST) assay and wound scratch assay. We examined the effect of HA addition in a full-thickness wound model in mice and the gene expression related to wound healing. Proliferation and migration of HaCaT cells increased with the increase of MW and concentration of HA. Interleukin (IL-1ß), IL-8 and vascular endothelial growth factor (VEGF) as well as matrix metalloproteinase (MMP)-9 and MMP-13 were significantly upregulated by high molecular weight (HMW) HA in keratinocytes. Together with VEGF upregulation and the observed promotion of HaCaT migration, HA with the MW of 2290 kDa may hold potential to improve re-epithelialization, a critical obstacle to heal chronic wounds.

Reversible 3D-2D structural phase transition and giant electronic modulation in nonequilibrium alloy semiconductor, lead-tin-selenide.

Material properties depend largely on the dimensionality of the crystal structures and the associated electronic structures. If the crystal-structure dimensionality can be switched reversibly in the same material, then a drastic property change may be controllable. Here, we propose a design route for a direct three-dimensional (3D) to 2D structural phase transition, demonstrating an example in (Pb1-x Sn x )Se alloy system, where Pb2+ and Sn2+ have similar ns2 pseudo-closed shell configurations, but the former stabilizes the 3D rock-salt-type structure while the latter a 2D layered structure. However, this system has no direct phase boundary between these crystal structures under thermal equilibrium. We succeeded in inducing the direct 3D-2D structural phase transition in (Pb1-x Sn x )Se alloy epitaxial films by using a nonequilibrium growth technique. Reversible giant electronic property change was attained at x ~ 0.5 originating in the abrupt band structure switch from gapless Dirac-like state to semiconducting state.

Phosphonic Acid Modified ZnO Nanowire Sensors: Directing Reaction Pathway of Volatile Carbonyl Compounds.

Surface molecular transformations on nanoscale metal oxides are inherently complex, and directing those reaction pathways is still challenging but important for designing their various applications, including molecular sensing, catalysts, and others. Here, a rational strategy to direct a reaction pathway of volatile carbonyl compounds (nonanal: biomarker) on single-crystalline ZnO nanowire surfaces via molecular modification is demonstrated. The introduction of a methylphosphonic acid modification on the ZnO nanowire surface significantly alters the surface reaction pathway of nonanal via suppressing the detrimental aldol condensation reaction. This is directed by intentionally decreasing the probability of two neighboring molecular activations on the nanowire surface. Spectrometric measurements reveal the correlation between the suppression of the aldol condensation surface reaction and the improvement in the sensor performance. This tailored surface reaction pathway effectively reduces the operating temperature from 200 to 100 °C while maintaining the sensitivity. This is because the aldol condensation product ((E)-2-heptyl-2-undecenal) requires a higher temperature to desorb from the surface. Thus, the proposed facile strategy offers an interesting approach not only for the rational design of metal oxide sensors for numerous volatile carbonyl compounds but also for tailoring various surface reaction pathways on complex nanoscale metal oxides.

Monovalent sulfur oxoanions enable millimeter-long single-crystalline h-WO3 nanowire synthesis.

Here, we discuss a misunderstanding regarding chemical capping, which has intrinsically hindered the extension of the length of hexagonal (h)-WO3 nanowires in previous studies. Although divalent sulfate ions (SO42-) have been strongly believed to be efficient capping ions for directing anisotropic h-WO3 nanowire growth, we have found that the presence of SO42- is highly detrimental to the anisotropic crystal growth of the h-WO3 nanowires, and a monovalent sulfur oxoanion (HSO4-) rather than SO42- only substantially promotes the anisotropic h-WO3 nanowire growth. Ab initio electronic structure simulations revealed that the monovalent sulfur oxoanions were preferentially able to cap the sidewall plane (100) of the h-WO3 nanowires due to the lower hydration energy when compared with SO42-. Based on this capping strategy, using the monovalent sulfur oxoanion (CH3SO3-), which cannot generate divalent sulfur oxoanions, we have successfully fabricated ultra-long h-WO3 nanowires up to the millimeter range (1.2 mm) for a wider range of precursor concentrations. We have demonstrated the feasibility of these millimeter-long h-WO3 nanowires for the electrical sensing of molecules (lung cancer biomarker: nonanal) on flexible substrates, which can be operated at room temperature with mechanical flexibility with bending cycles up to 104 times due to the enhanced textile effect.

A Workshop on Writing Letters to the Editor.

This article was migrated. The article was marked as recommended. Background: Writing letters to the editor based on critical appraisal can serve as the first step in scholarly activity. The workshop in this study focused on educating physicians about the best ways to write letters to the editor. Methods: We conducted a 90-minute workshop as a part of scientific conference. Participants were physicians and medical students who chose to join this workshop. We developed the following learning outcomes for participants: 1) to be able to explain falsificationism; 2) to be able to explain how to check author instructions; 3) to be able to explain how to write a letter to the editor. Results: Twenty-eight participants, including three medical students, attended the workshop. Participants' satisfaction with the workshop had a mean of 4.5 points out of 5 (standard deviation: 0.5). Nearly 80% of participants achieved the learning outcomes. Four participants' groups submitted letters within a month after the workshop, and all four were published. These four groups encompassed a total of 13 authors. In addition, none of the first author of each letter had previously written a clinical research paper. Findings and Discussion: This workshop improved not only the participants' knowledge but it also led to the concrete result of four published letters. Japanese physicians would be able to use this framework to write letters to the editor.

Impact of the Spatial Organization of Bifunctional Metal-Zeolite Catalysts on the Hydroisomerization of Light Alkanes.

Improving product selectivity by controlling the spatial organization of functional sites at the nanoscale is a critical challenge in bifunctional catalysis. We present a series of composite bifunctional catalysts consisting of one-dimensional zeolites (ZSM-22 and mordenite) and a γ-alumina binder, with platinum particles controllably deposited either on the alumina binder or inside the zeolite crystals. The hydroisomerization of n-heptane demonstrates that the catalysts with platinum particles on the binder, which separates platinum and acid sites at the nanoscale, leads to a higher yield of desired isomers than catalysts with platinum particles inside the zeolite crystals. Platinum particles within the zeolite crystals impose pronounced diffusion limitations on reaction intermediates, which leads to secondary cracking reactions, especially for catalysts with narrow micropores or large zeolite crystals. These findings extend the understanding of the "intimacy criterion" for the rational design of bifunctional catalysts for the conversion of low-molecular-weight reactants.

Synthesis of Monodispersedly Sized ZnO Nanowires from Randomly Sized Seeds.

We demonstrate the facile, rational synthesis of monodispersedly sized zinc oxide (ZnO) nanowires from randomly sized seeds by hydrothermal growth. Uniformly shaped nanowire tips constructed in ammonia-dominated alkaline conditions serve as a foundation for the subsequent formation of the monodisperse nanowires. By precisely controlling the sharp tip formation and the nucleation, our method substantially narrows the distribution of ZnO nanowire diameters from σ = 13.5 nm down to σ = 1.3 nm and controls their diameter by a completely bottom-up method, even initiating from randomly sized seeds. The proposed concept of sharp tip based monodisperse nanowires growth can be applied to the growth of diverse metal oxide nanowires and thus paves the way for bottom-up grown metal oxide nanowires-integrated nanodevices with a reliable performance.

Substantial Narrowing on the Width of "Concentration Window" of Hydrothermal ZnO Nanowires via Ammonia Addition.

A crystal growth of hydrothermal ZnO nanowires essentially requires a concentration control within so-called "concentration window", where the anisotropic crystal growth of ZnO nanowires preferentially occurs. Although understanding what exactly determines the width of "concentration window" is important to tailor the anisotropic crystal growth process, the fundamental knowledge as to "concentration window" is still scarce. Here we report the effect of ammonia addition on the width of "concentration window" using conventional hydrothermal ZnO nanowire growth. We found that the ammonia addition substantially narrows the width of "concentration window". Within the narrow range of zinc complex concentration, we found a significant increase of growth rate (up to 2000 nm/h) of ZnO nanowires. The narrowed "concentration window" and the resultant increased growth rate by the ammonia addition can be understood in terms of synchronized effects of both (1) a reduction of zinc hydroxide complex (precursor) concentration and (2) a fast rate limiting process of ligand exchange between different zinc complexes. Thus, the present knowldege as to "concentration window" will accelerate further tailoring an anisotropic crystal growth of hydrothermal ZnO nanowires.

Visualizing Progressive Atomic Change in the Metal Surface Structure Made by Ultrafast Electronic Interactions in an Ambient Environment.

Understanding the atomic and molecular phenomena occurring in working catalysts and nanodevices requires the elucidation of atomic migration originating from electronic excitations. The progressive atomic dynamics on metal surface under controlled electronic stimulus in real time, space, and gas environments are visualized for the first time. By in situ environmental transmission electron microscopy, the gas molecules introduced into the biased metal nanogap could be activated by electron tunneling and caused the unpredicted atomic dynamics. The typically inactive gold was oxidized locally on the positive tip and field-evaporated to the negative tip, resulting in the atomic reconstruction on the negative tip surface. This finding of a tunneling-electron-attached-gas process will bring new insights into the design of nanostructures such as nanoparticle catalysts and quantum nanodots and will stimulate syntheses of novel nanomaterials not seen in the ambient environment.

Reversible gas-solid reaction in an electronically-stimulated palladium nanogap.

We investigated a nanogap between a pair of palladium electrode tips with gas (nitrogen, hydrogen, and oxygen) and a biasing voltage using in situ atomic resolution environmental transmission electron microscopy (ETEM). We found an unexpected gas-solid (nitrogen-palladium) reaction that occurs on the surface of the positive electrode tip. A palladium nitride compound was synthesized with gaseous nitrogen at low pressure at room temperature. The nitridation of palladium was previously reported and predicted to occur only under high pressure and at high temperature. The reaction in ETEM apparatus was reversible with the change in the magnitude of an electric field in the nanogap. Additionally, the asymmetrical surface dynamics on the pair of electrode tips in gas (nitrogen, hydrogen, and oxygen) were revealed by ETEM observation. It is likely that the electrons in the gap induce the reversible reaction. This study has opened a new route toward creating nanoscale materials because the creation, stabilization, and annihilation of the material in a nanogap can be controlled electrically and electronically on demand for various applications.

Rational Method of Monitoring Molecular Transformations on Metal-Oxide Nanowire Surfaces.

Metal-oxide nanowires have demonstrated excellent capability in the electrical detection of various molecules based on their material robustness in liquid and air environments. Although the surface structure of the nanowires essentially determines their interaction with adsorbed molecules, understanding the correlation between an oxide nanowire surface and an adsorbed molecule is still a major challenge. Herein, we propose a rational methodology to obtain this information for low-density molecules adsorbed on metal oxide nanowire surfaces by employing infrared p-polarized multiple-angle incidence resolution spectroscopy and temperature-programmed desorption/gas chromatography-mass spectrometry. As a model system, we studied the surface chemical transformation of an aldehyde (nonanal, a cancer biomarker in breath) on single-crystalline ZnO nanowires. We found that a slight surface reconstruction, induced by the thermal pretreatment, determines the surface chemical reactivity of nonanal. The present results show that the observed surface reaction trend can be interpreted in terms of the density of Zn ions exposed on the nanowire surface and of their corresponding spatial arrangement on the surface, which promotes the reaction between neighboring adsorbed molecules. The proposed methodology will support a better understanding of complex molecular transformations on various nanostructured metal-oxide surfaces.

Oxidation and hydrogenation of Pd: suppression of oxidation by prolonged H2 exposure.

We investigate the phase transition of a Pd surface in both oxidizing and reducing environments by environmental transmission electron microscopy (ETEM). ETEM allows us to study sequential exposure of Pd to O2 and H2 in the same TEM conditions. First, under ETEM observation, oxidation occurs at step edges but it can also occur at terraces. Second, as the most important result, we observed a novel process where previous exposure to H2 suppresses new oxidation of the Pd surface. Third, we show by electron energy loss spectroscopy (EELS) that this process, suppression of oxidation by previous exposure to H2, is not due to the formation of bulk ß-phase Pd hydride. We also demonstrate that this process is not present in Pt. Finally, we discuss the hypothesis to explain this phenomenon: formation of surface-Pd-hydride suppresses the new oxidation. This observation, suppression of oxidation by H2 exposure, may eventually lead to new breakthroughs.