Role of the Precursor Composition in the Synthesis of Metal Ferrite Nanoparticles

Ternary oxide nanoparticles have attracted much interest because of their intriguing properties, which are not exhibited by binary oxide nanoparticles. However, the synthesis of ternary oxide nanoparticles is not trivial and requires a fundamental understanding of the complicated precursor chemistry that governs the formation mechanism. Herein, we investigate the role of the chemical composition of precursors in the formation of ternary oxide nanoparticles via a combination of mass spectrometry, electron microscopy with elemental mapping, and thermogravimetric analysis. Mn2+, Co2+, and Ni2+ ions easily form bimetallic-oxo clusters with Fe3+ ions with a composition of MFe2O(oleate)(6) (M = Mn, Co, Ni). The use of clusters as precursors leads to the successful synthesis of monodisperse metal ferrite nanoparticles (MFe2O4). On the contrary, zinc- or copper-containing complexes are formed independently from iron-oxo clusters in the precursor synthesis. The mixture of complexes without a bimetallic-oxo core yields a mixture of two different nanoparticles. This study reveals the importance of the precursor composition in the synthesis of ternary oxide nanoparticles.

Early Stage Li Plating by Liquid Phase and Cryogenic Transmission Electron Microscopy

Li metal anodes are among the most promising options for next-generation batteries, exhibiting the highest theoretical capacity. However, irregular Li electrodeposition, which raises safety concerns, is a major obstacle in practical applications. Therefore, a fundamental understanding of the beginning phases of Li plating, such as nucleation and early growth, which have a decisive influence on the dendritic growth of Li, is essential. In this study, we investigated the early stage of Li plating at the single-particle level and its correlation with the solid-electrolyte interphase (SEI) using in situ liquid phase transmission electron microscopy (TEM) and cryogenic TEM. We observed contrasting nucleation dynamics and particle growth patterns in two electrolytes (1 M LiPF6 in ethylene carbonate/diethyl carbonate and 1 M LiTFSI in 1,3-dioxolane/dimethoxy ethane), which originate from different chemical and physical properties of the SEIs. Based on our findings, we propose a mechanism of nucleation and initial growth of Li dictated by the SEI. © 2022 American Chemical Society.11Nsciescopu

Atopic dermatitis and risk of gastroesophageal reflux disease: A nationwide population-based study.

BackgroundAs atopic dermatitis (AD) has been found to be related to various comorbidities as well as substantial patient burden, questions of a possible relationship between AD and nonallergic diseases beyond allergic diseases have also been raised.ObjectiveThe aim of this nationwide matched cohort study was to evaluate whether AD would increase the development of gastroesophageal reflux disease (GERD).MethodsPatients diagnosed with AD were identified from the National Health Insurance Service-National Sample Cohort (NHIS-NSC) 2.0 database in South Korea from 2002 to 2015. Finally, 9,164 adults with AD (≥20 years old) and age, sex, household income, region of residence, disability, and baseline year-matched 9,164 controls were included in the analysis. Hazard ratio (HR) with 95% confidence interval (CI) for the development of GERD was estimated using a Cox proportional hazard regression model.ResultsOverall, 12.3% of the patients in the AD group developed GERD, whereas 10.4% of the individuals in the control group developed GERD. The results of the adjusted model revealed that patients with AD had a significantly increased risk of developing GERD (adjusted HR, 1.15; 95% CI, 1.06-1.26) compared with the matched controls. Increased risk of developing GERD was consistent in subgroup analyses by sex or age groups under 60 years old as well as all the sensitivity analyses performed.ConclusionsThis study suggested that appropriate management should be considered in adults with AD to prevent GERD, because AD was found to be associated with an increased risk of subsequent GERD

Direct Observation of Off-Stoichiometry-Induced Phase Transformation of 2D CdSe Quantum Nanosheets

Crystal structures determine material properties, suggesting that crystal phase transformations have the potential for application in a variety of systems and devices. Phase transitions are more likely to occur in smaller crystals; however, in quantum-sized semiconductor nanocrystals, the microscopic mechanisms by which phase transitions occur are not well understood. Herein, the phase transformation of 2D CdSe quantum nanosheets caused by off-stoichiometry is revealed, and the progress of the transformation is directly observed by in situ transmission electron microscopy. The initial hexagonal wurtzite-CdSe nanosheets with atomically uniform thickness are transformed into cubic zinc blende-CdSe nanosheets. A combined experimental and theoretical study reveals that electron-beam irradiation can change the stoichiometry of the nanosheets, thereby triggering phase transformation. The loss of Se atoms induces the reconstruction of surface atoms, driving the transformation from wurtzite-CdSe(112 over bar $\bar{2}$0) to zinc blende-CdSe(001) 2D nanocrystals. Furthermore, during the phase transformation, unconventional dynamic phenomena occur, including domain separation. This study contributes to the fundamental understanding of the phase transformations in 2D quantum-sized semiconductor nanocrystals.11Nsciescopu

Moisture-Induced Degradation of Quantum-Sized Semiconductor Nanocrystals through Amorphous Intermediates

Elucidating the water-induced degradation mechanism ofquantum-sizedsemiconductor nanocrystals is an important prerequisite for theirpractical application because they are vulnerable to moisture comparedto their bulk counterparts. In-situ liquid-phasetransmission electron microscopy is a desired method for studyingnanocrystal degradation, and it has recently gained technical advancement.Herein, the moisture-induced degradation of semiconductor nanocrystalsis investigated using graphene double-liquid-layer cells that cancontrol the initiation of reactions. Crystalline and noncrystallinedomains of quantum-sized CdS nanorods are clearly distinguished duringtheir decomposition with atomic-scale imaging capability of the developedliquid cells. The results reveal that the decomposition process ismediated by the involvement of the amorphous-phase formation, whichis different from conventional nanocrystal etching. The reaction canproceed without the electron beam, suggesting that the amorphous-phase-mediateddecomposition is induced by water. Our study discloses unexploredaspects of moisture-induced deformation pathways of semiconductornanocrystals, involving amorphous intermediates.11Nsciescopu

Insights into structural defect formation in individual InP/ZnSe/ZnS quantum dots under UV oxidation

Abstract InP/ZnSe/ZnS quantum dots (QDs) stand as promising candidates for advancing QD-organic light-emitting diodes (QLED), but low emission efficiency due to their susceptibility to oxidation impedes applications. Structural defects play important roles in the emission efficiency degradation of QDs, but the formation mechanism of defects in oxidized QDs has been less investigated. Here, we investigated the impact of diverse structural defects formation on individual QDs and propagation during UV-facilitated oxidation using high-resolution (scanning) transmission electron microscopy. UV-facilitated oxidation of the QDs alters shell morphology by the formation of surface oxides, leaving ZnSe surfaces poorly passivated. Further oxidation leads to the formation of structural defects, such as dislocations, and induces strain at the oxide-QD interfaces, facilitating In diffusion from the QD core. These changes in the QD structures result in emission quenching. This study provides insight into the formation of structural defects through photo-oxidation, and their effects on emission properties of QDs

Real-space imaging of nanoparticle transport and interaction dynamics by graphene liquid cell TEM

Copyright © 2021 The Authors, some rights reserved;Thermal motion of colloidal nanoparticles and their cohesive interactions are of fundamental importance in nanoscience but are difficult to access quantitatively, primarily due to the lack of the appropriate analytical tools to investigate the dynamics of individual particles at nanoscales. Here, we directly monitor the stochastic thermal motion and coalescence dynamics of gold nanoparticles smaller than 5 nm, using graphene liquid cell (GLC) transmission electron microscopy (TEM). We also present a novel model of nanoparticle dynamics, providing a unified, quantitative explanation of our experimental observations. The nanoparticles in a GLC exhibit non-Gaussian, diffusive motion, signifying dynamic fluctuation of the diffusion coefficient due to the dynamically heterogeneous environment surrounding nanoparticles, including organic ligands on the nanoparticle surface. Our study shows that the dynamics of nanoparticle coalescence is controlled by two elementary processes: diffusion-limited encounter complex formation and the subsequent coalescence of the encounter complex through rotational motion, where surface-passivating ligands play a critical role.11Nsciescopu