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At least 847 records · Page 47

Membrane-induced hydroelastic migration of a particle surfing its own wave

While coupling between fluid flow and soft elastic surfaces is common in biology and engineering, an analytical description is challenging as it often involves non-linear dynamics. Here we show using theory and experiments that a small particle moving along an elastic membrane through a viscous fluid is repelled from the membrane due to hydroelastic forces. The flow field produces an elastic disturbance in the membrane leading to particle–wave coupling. We derive an analytic expression for the particle trajectory and find that the normal migration velocity of the particle is quadratic in its speed and depends on a combination of the tension and bending resistance of the membrane. Experimentally, we measure the normal displacement of spheres sedimenting under gravity along a suspended elastic membrane and find quantitative agreement with the theoretical predictions with no fitting parameters. We experimentally demonstrate that the effect is strong enough for separation and sorting of particles on the basis of both their size and density. We discuss the significance of our results for particles interacting with biological membranes, and propose the use of our model for membrane elasticity measurements.

catalysis (homogeneous), solar (photovoltaic), bio↗

Three-dimensional migration behavior of juvenile salmonids in reservoirs and near dams

To acquire 3-D tracking data on juvenile salmonids, Juvenile Salmon Acoustic Telemetry System (JSATS) cabled hydrophone arrays were deployed in the forebays of two dams on the Snake River and at a mid-reach reservoir between the dams. The depth distributions of fish were estimated by statistical analyses performed on large 3-D tracking data sets from ~33,500 individual acoustic tagged yearling and subyearling Chinook salmon and juvenile steelhead at the two dams in 2012 and subyearling Chinook salmon at the two dams and the mid-reach reservoir in 2013. This research investigated the correlation between vertical migration behavior and passage routes. The depth distributions of fish within the forebays of the dams were significantly different from fish passing the mid-reach reservoir. Fish residing deeper in the forebay tended to pass the dam using deeper powerhouse routes. This difference in depth distributions indicated that the depth distribution of fish at the mid-reach reservoir was not related to behaviors of fish passing through certain routes of the adjacent dams. For fish that were detected deeper than 17.5 m in the forebays, the probability of powerhouse passage (i.e., turbine) increased significantly. Another important finding was the variation in depth distributions during dam passage associated with the diel period, especially the crepuscular periods.

59 BASIC BIOLOGICAL SCIENCES↗

Enhance indigenous agricultural systems to reduce migration

Changes in social and environmental conditions in the Western Highlands of Guatemala undermine food security and job opportunities. Here, we describe how targeted assistance can build upon traditional agricultural systems to increase adaptive capacity, improve nutrition, provide jobs and thereby reduce pressures to migrate.

54 ENVIRONMENTAL SCIENCES↗

Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction

Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions.

Yang, Yao↗

In situ study of defect migration kinetics in nanoporous Ag with enhanced radiation tolerance

Defect sinks, such as grain boundaries and phase boundaries, have been widely accepted to improve the irradiation resistance of metallic materials. However, free surface, an ideal defect sink, has received little attention in bulk materials as surface-to-volume ratio is typically low. Here by using in situ Kr ion irradiation technique in a transmission electron microscope, we show that nanoporous (NP) Ag has enhanced radiation tolerance. Besides direct evidence of free surface induced frequent removal of various types of defect clusters, we determined, for the first time, the global and instantaneous diffusivity of defect clusters in both coarse-grained (CG) and NP Ag. Opposite to conventional wisdom, both types of diffusivities are lower in NP Ag. Such a surprise is largely related to the reduced interaction energy between isolated defect clusters in NP Ag. Determination of kinetics of defect clusters is essential to understand and model their migration and clustering in irradiated materials.

NANOSCIENCE AND TECHNOLOGY↗

Arrested α-hydride migration activates a phosphido ligand for C–H insertion

Bulky tris(carbene)borate ligands provide access to high spin iron(II) phosphido complexes. The complex PhB(MesIm) 3 FeP(H)Ph is thermally unstable, and we observed [PPh] group insertion into a C–H bond of the supporting ligand. An arrested α-hydride migration mechanism suggests increased nucleophilicity of the phosphorus atom facilitates [PPh] group transfer reactivity.

Hickey, Anne K.↗

The effects of cation–anion clustering on defect migration in MgAl 2 O 4

Magnesium aluminate spinel (MgAl 2 O 4 ), like many other ceramic materials, offers a range of technological applications, from nuclear reactor materials to military body armor. For many of these applications, it is critical to understand both the formation and evolution of lattice defects throughout the lifetime of the material. We use the Speculatively Parallel Temperature Accelerated Dynamics (SpecTAD) method to investigate the effects of di-vacancy and di-interstitial formation on the mobility of the component defects. From long-time trajectories of the state-to-state dynamics, we characterize the migration pathways of defect clusters, and calculate their self-diffusion constants across a range of temperatures. We find that the clustering of Al and O vacancies drastically reduces the mobility of both defects, while the clustering of Mg and O vacancies completely immobilizes them. For interstitials, we find that the clustering of Mg and O defects greatly reduces O interstitial mobility, but has only a weak effect on Mg. Lastly, these findings illuminate important new details regarding defect kinetics relevant to the application of MgAl 2 O 4 in extreme environments.

36 MATERIALS SCIENCE↗

Dissolution, migration, and deposition of transition metal ions in Li-ion batteries exemplified by Mn-based cathodes – a critical review

Unlike the revolutionary advances in the anodes of lithium-ion batteries from Li intercalation materials to Li alloy and/or conversion reaction materials, the development of the cathode is still dominated by the Li intercalation compounds. Transition metal ions are essential in these cathodes as the rapid redox reaction centers, and one of the biggest challenges for the TM-based cathodes is the capacity and power fading especially at an elevated temperature, which is directly associated with the dissolution–migration–deposition (DMD) process of TMs from the cathode materials. This process not only alters the surface structure of the cathode materials, but more importantly, changes the SEI composition at the anode side. There is no doubt that the TM-DMD issue should be addressed thoroughly to unlock the potential of these compounds to enable a prolonged battery lifetime. This review article mainly focuses on research activities with regard to the DMD process in TM-based cathode materials. In the first four sections, we choose Mn-based cathodes as an example to discuss how Mn DMD relates to the capacity fade of the cell, and what possible approaches might suppress the DMD process by modification of the electrode or electrolyte. In the fifth section, we discuss the TM DMD process in Ni-, Co-, Fe- and V-containing cathode materials. Furthermore, this article reviews the frontier electrochemical research on TM-based cathodes and summarizes the progress and challenges, thereby helping to advance future R&D of LIBs.

25 ENERGY STORAGE↗

Giant current amplification induced by ion migration in perovskite single crystal photodetectors

A giant current amplification was observed in the lateral organic–inorganic perovskite single crystal photodetectors. It was proposed that photoexcitation and electrical field induced migration and accumulation of ions at respective contacts. The interfacial charging due to ion accumulation offers an effective mechanism to trigger counter charge injection, consequently amplifying the total electrical current.

Wu, Ting↗

Electrochemically induced iodine migration in mixed halide perovskites: suppression through chloride insertion

The role of chloride in improving the stability of mixed halide perovskites (MAPbCl x Br 0.5 (1–x) I 0.5(1–x) ) 3 is probed using spectroelectrochemistry. Here, the injection of holes into mixed halide perovskite films through applied anodic bias results in the selective migration of iodine with ultimate expulsion into the electrolyte. Increasing the Cl content (x = 0 to 0.1) in the mixed halide perovskite suppresses the iodine mobility and thus decreases the rate of its expulsion into the solution. Implications of iodine mobility induced by hole accumulation and its impact on overall stability is discussed.

14 SOLAR ENERGY↗

Voltage bias stress effects in metal halide perovskites are strongly dependent on morphology and ion migration pathways

The solar-to-power power conversion efficiencies (PCEs) of metal halide perovskites (MHP) have improved over the last decade using a wide variety of methods, including composition manipulation, dopant introduction, and interfacial buffers. These methods, however, have taken little regard for the electronic and interfacial effects such alterations may cause within devices under voltage bias stress – a condition required for most device operation. We investigate how halide and cation substitution in MHP structures [specifically, CH 3 NH 3 PbI 2.87 Cl 0.13 and Cs 0.1 (MA 0.17 FA 0.83 ) 0.9 Pb(I 0.83 Br 0.17 ) 3 ] effects the current behavior of devices while under a range of voltage bias stress in both light and dark conditions. Additionally, conducting in depth investigations into the electronic and morphological differences between these two MHP devices, we confirmed their unique voltage bias stress effects are due to intrinsic behavior within the perovskite structure. Importantly, we also determined how crystallite orientation can influence ion migration and therefore alter charge transport and current stability in MHP photovoltaic devices.

36 MATERIALS SCIENCE↗

Cleavage of an aromatic ring and radical migration

The present study undertakes a theoretical evaluation of thermal decomposition of aromatic-ring radicals. Potential energy surfaces and associated reaction rate coefficients were calculated for 1- and 2-naphthalenyl, acetanaphthylenyl, and pyrenyl radicals. Kinetic Monte-Carlo simulations were performed to examine the rates of ring cleavage in two sooting laminar premixed flames of ethylene. The simulations showed that the thermal aromatic-ring cleavage is comparable in rate to oxyradical decomposition in a heavier-sooting flame. The simulation also revealed, unexpectedly, fast internal ring radical migration, comparable in frequency to reaction events of aromatic growth.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coherent ring-current migration of Mg-phthalocyanine probed by time-resolved X-ray circular dichroism

The coherent ring current of Mg-phthalocyanine created by a broad band UV-visible pump pulse shows variation with time, where the ring currents at the corner benzene rings, around the Mg cation and on the outer ring oscillate with different time periods and the current density migrates among these regions. The 7 pairs of E u degenerate excited states populated upon photoexcitation, generate 21 distinct coherent ring currents. We further calculate the time-resolved X-ray circular dichroism (TRXCD) spectrum of the coherences contributing to the ring current obtained by an attosecond X-ray probe pulse resonant with the nitrogen K-edge. A frequency domain TRXCD signal obtained by a Fourier transform of the signal with respect to the pump-probe delay time clearly separates the currents induced by different state pairs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗