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At least 415 records · Page 23

Functional CeO x nanoglues for robust atomically dispersed catalysts

Single-atom catalysts make exceptionally efficient use of expensive noble metals and can bring out unique properties. However, applications are usually compromised by limited catalyst stability, which is due to sintering. Although sintering can be suppressed by anchoring the metal atoms to oxide supports, strong metal–oxygen interactions often leave too few metal sites available for reactant binding and catalysis, and when exposed to reducing conditions at sufficiently high temperatures, even oxide-anchored single-atom catalysts eventually sinter. Here we show that the beneficial effects of anchoring can be enhanced by confining the atomically dispersed metal atoms on oxide nanoclusters or ‘nanoglues’, which themselves are dispersed and immobilized on a robust, high-surface-area support. We demonstrate the strategy by grafting isolated and defective CeO x nanoglue islands onto high-surface-area SiO 2 ; the nanoglue islands then each host on average one Pt atom. Further, we find that the Pt atoms remain dispersed under both oxidizing and reducing environments at high temperatures, and that the activated catalyst exhibits markedly increased activity for CO oxidation. We attribute the improved stability under reducing conditions to the support structure and the much stronger affinity of Pt atoms for CeO x than for SiO 2 , which ensures the Pt atoms can move but remain confined to their respective nanoglue islands. The strategy of using functional nanoglues to confine atomically dispersed metals and simultaneously enhance their reactivity is general, and we anticipate that it will take single-atom catalysts a step closer to practical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On FIRE mode in KSTAR

We report on the status of Fast Ion Regulated Enhancement (FIRE) mode experiments in the Korea Superconducting Tokamak Advanced Research. This regime is being developed for high-performance, steady-state operation which features a stationary ion internal transport barrier, enabling a central ion temperature approaching 10 keV to be sustained for up to 50 s, without the need for delicate profile control and with no significant impurity accumulation. As its key novelty lies in the significant contribution of fast ions that stabilize core turbulence, the regime has been named FIRE mode. To achieve this regime, neutral beam injection is applied at moderate power levels near the L–H power threshold, while maintaining low plasma density to avoid the L–H transition. The scenario is typically established in diverted magnetic configurations. The core features of FIRE mode were investigated through power balance analysis and fluctuation measurements, revealing a clear transport bifurcation in the ion channel. At the plasma edge, FIRE mode occasionally exhibits I-mode characteristics, particularly in unfavorable magnetic null configurations with q 95 ∼ 4, including the presence of weakly coherent modes. In terms of MHD activity, sawtooth oscillations are observed but appear to be stabilized during the high-performance phase. Fast ion-driven Alfvénic eigenmodes (AEs), indicated by strong frequency chirping near 200 kHz, are also observed. Additionally, lower-frequency MHD activities, distinct from the fast ion-driven AEs, are present and have some influence on plasma performance. The enhancement of core confinement is primarily attributed to fast ion effects, which were evaluated with respect to dilution, alpha stabilization, and resonant interactions with turbulence using gyrokinetic analyses. Among these, the dilution effect was found to be the most dominant. The characteristics of FIRE mode were compared with those of other hot ion plasma scenarios, such as supershot and hot ion mode. While they share many similarities, FIRE mode is distinguished by the accessibility to conditions with T i ≈ T e , presence of I-mode edge features, and its long-duration sustainment. Predictive simulations of FIRE mode were performed using integrated transport modeling with TRIASSIC, employing the TGLF anomalous transport model. These simulations confirmed the critical role of fast ions in achieving this regime. The future prospect of FIRE mode for application in fusion reactors is discussed, with an emphasis on possibly extending the regime to higher density operation.

FIRE mode↗

Enhancement to Fusion Reactivity in Sheared Flows

Sheared flow increases the reactivity of fusion plasma. In unmagnetized plasma with flow gradients comparable to the mean free path of reacting ions, fusion reactivity can be more than doubled. The effect is of particular relevance to inertial confinement fusion (ICF), where it allows implosion kinetic energy to contribute to the fusion burn even before thermalizing. Finally, because colder fuel stops alpha particles more quickly, ignition is possible in a smaller volume, substantially reducing energy requirements in fast-ignition designs.

fast ignition↗

Pion and kaon parton distribution functions from basis light front quantization and QCD evolution

We investigate the parton distribution functions (PDFs) of the pion and the kaon by combining quantum chromodynamics (QCD) evolution with the basis light front quantization. The initial PDFs result from the light front wave functions obtained by diagonalizing the effective Hamiltonian consisting of the holographic QCD confinement potential, a complementary longitudinal confinement potential, and the color-singlet Nambu–Jona-Lasinio interactions. The valence-quark PDF of the pion, after QCD evolution, is consistent with the result from the E-0615 experiment at Fermilab. Meanwhile, the pion structure function calculated from the PDFs agrees with the ZEUS and the H1 experiments at DESY-HERA for large x. Additionally, the ratio of the up quark PDF of the kaon to that of the pion is in agreement with the NA-003 experiment at CERN. Finally, we also present the cross section for the pion-nucleus induced Drell-Yan process with the obtained pion PDFs supplemented by the PDFs of the target nuclei.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Engineering Functionalized 2D Metal-Organic Frameworks Nanosheets with Fast Li + Conduction for Advanced Solid Li Batteries

Solid-state batteries can ensure high energy density and safety in lithium metal batteries, while polymer electrolytes are plagued by slow ion kinetics and low selective transport of Li + . Metal-organic frameworks (MOFs) are proposed as emerging fillers for solid-state poly(ethylene oxide)(PEO) electrolytes, however, developing functionalized MOFs and understanding their roles on ion transfer has proven challenging. Herein, combining computational and experimental results, the functional group regulation in MOFs can effectively change surficial charge distribution and limit anion movement is revealed, providing a potential solution to these issues. Specifically, functionalized 2D MOF sheets are designed through molecular engineering to construct high-performance composite electrolytes, where the electron-donating effect of substituents in 2D-MOFs effectively limits the movement of ClO 4 - and promotes mechanical properties and ion migration numbers (0.36 up to 0.64) of PEO. As a result, Li/Li cells with composite electrolyte exhibit superior cyclability for 1000 h at a current density of 0.2 mA cm -2 . Meanwhile, the solid LiFePO 4 /Li battery delivers highly reversible capacities of 148.8 mAh g -1 after 200 cycles. In conclusion, these findings highlight a new approach for anion confinement through the use of functional group electronic effects, leading to enhanced ionic conductivity, and a feasible direction for high-performance solid-state batteries.

25 ENERGY STORAGE↗

Quantum-Confined Lifshitz Transition on Weyl Semimetal T d -MoTe 2

Adsorption of alkali atoms onto material surfaces is widely utilized for controlling electronic properties and is particularly effective for two-dimensional materials. While tuning the chemical potential and band gap and creating quantum-confined states are well established for alkali adsorption on semiconductors, the effects on semimetallic systems remain largely elusive. Here, utilizing angle-resolved photoemission spectroscopy measurements and density functional theory calculations, we disclose the creation of two-dimensional electron gas and the quantum-confined Lifshitz transition at the surface of a Weyl semimetal T d -MoTe 2 by potassium adsorption. Electrons from potassium adatoms are shown to be transferred mainly to the lowest unoccupied band within the gapped part of the Brillouin zone, which, in turn, induces strong surface band bending and quantum confinement in the topmost layer. The quantum-confined topmost layer evolves from a semimetal to a strong metal with a Lifshitz transition departing substantially from the bulk band. The present finding and its underlying mechanism can be exploited for the creation of electronic heterojunctions in van der Waals semimetals.

36 MATERIALS SCIENCE↗

Isotope effects on transport in LHD

Abstract Isotope effects are one of the most important issues for predicting future reactor operations. Large helical device (LHD) is the presently working largest stellarator/helical device using super conducting helical coils. In LHD, deuterium experiments started in 2017. Extensive studies regarding isotope effects on transport have been carried out. In this paper, the results of isotope effect studies in LHD are reported. The systematic studies were performed adjusting operational parameters and nondimensional parameters. In L mode like normal confinement plasma, where internal and edge transport barriers are not formed, the scaling of global energy confinement time ( τ E ) with operational parameters shows positive mass dependence ( M 0.27 ; where M is effective ion mass) in electron cyclotron heating plasma and no mass dependence ( M 0.0 ) in neutral beam injection heating plasma. The non-negative ion mass dependence is anti-gyro-Bohm scaling. The role of the turbulence in isotope effects was also found by turbulence measurements and gyrokinetic simulation. Better accessibility to electron and ion internal transport barrier (ITB) plasma is found in deuterium (D) plasma than in hydrogen (H). Gyro kinetic non-linear simulation shows reduced ion heat flux due to the larger generation of zonal flow in deuterium plasma. Peaked carbon density profile plays a prominent role in reducing ion energy transport in ITB plasma. This is evident only in plasma with deuterium ions. New findings on the mixing and non-mixing states of D and H particle transports are reported. In the mixing state, ion particle diffusivities are higher than electron particle diffusivities and D and H ion density profiles are almost identical. In the non-mixing state, ion particle diffusivity is much lower than electron diffusivity. Deuterium and hydrogen ion profiles are clearly different. Different turbulence structures were found in the mixing and non-mixing states suggesting different turbulence modes play a role.

Physics↗

Particle-based modelling of axisymmetric tandem mirror devices

In this work, we describe the use of a 1D-2V quasi-neutral hybrid electrostatic PIC with Monte-Carlo Coulomb collisions and non-uniform magnetic field to model the parallel transport and confinement in an axisymmetric tandem mirror device. End-plugs, based on simple-mirrors, are positioned at each end of the device and fueled with neutral beams (25 and 100 keV) to produce a sloshing ion population and increase the density of the end-plugs relative to the central cell. Results show the formation of a potential difference barrier between the central cell and the end-plugs. This potential confines a large fraction of the low energy thermal ions in the central cell which would otherwise be lost in a simple mirror, demonstrating the advantage of the beam-driven tandem mirror configuration relative to simple mirrors. In addition, we explore the effect of end-plug electron temperature on the confinement time of the device and compare it with theoretical estimates. Finally, we discuss the limitations of the code in its present form and describe the next logical steps to improve its predictive capability such as a fully nonlinear Fokker–Planck collision operator, multiply nested flux surface solutions and modeling the exhaust region up to the wall.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Deposition of ultrathick heavy-metal alloys on rotating substrates by high-power impulse magnetron sputtering: Target erosion effects

Sputter deposition of ultrathick (≈20μm) Au–Ta alloy coatings on sphero-cylindrical substrates is key for the fabrication of hohlraums for magnetically assisted inertial confinement fusion. In this work, we study the deposition of AuTa 4 alloy coatings onto rotating substrates. We use high-power impulse magnetron sputtering (HiPIMS) in a constant peak target voltage mode. Results show that the target erosion state has a strong impact on the dominant crystallographic phase, microstructure, surface morphology, and electrical resistivity of AuTa 4 films. This is due to effects of changes in the confining magnetic field with target erosion on the HiPIMS discharge characteristics and the sputter source output. We quantify these effects via plasma diagnostics and discuss the optimization of HiPIMS deposition of ultrathick films for cases when target erosion effects dominate film properties.

36 MATERIALS SCIENCE↗

Transport coefficient sensitivities in a semi-analytic model for magnetized liner inertial fusion

Performance of magnetized liner inertial fusion (MagLIF) experiments is highly dependent on transport processes including magnetized heat flows and magnetic flux losses. Magnetohydrodynamic simulations used to model these experiments require a choice of model for the transport coefficients, which are the constants of proportionality relating driving terms, such as temperature gradients and currents, to the associated heat and magnetic field transport. The coefficients have been the subject of repeated recalculation using various methods throughout the years. Using a semi-analytic MagLIF model, we compare models for the transport coefficients. The choice of model modifies magnetic-flux losses caused by the Nernst thermoelectric effect and thermal conduction losses. We present simulated results from parameter scans conducted in order to compare the effects of the different models on parameters of interest in MagLIF. In some regions of parameter space, discrepancies of up to 38% are found in integrated quantities like the fusion yield. These results may serve as a guide for experimental validation of the various models, particularly as laser preheat energies and initial axial field strengths are increased on MagLIF experiments.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Ferroelectric Semimetals with α-Bi/SnSe van der Waals Heterostructures and Their Topological Currents

We show that proximity effects can be utilized to engineer van der Waals heterostructures (vdWHs) displaying semimetallic spin-ferroelectricity locking, where ferroelectricity and semimetallic spin states are confined to different layers, but are correlated by means of proximity effects. Our findings are supported by first principles calculations involving α-Bi/SnSe bilayers. We show that such systems support ferroelectrically switchable nonlinear anomalous Hall effect originating from large Berry curvature dipoles as well as direct and inverse spin Hall effects with giant bulk spin-charge interconversion efficiencies. In conclusion, the giant efficiencies are consequences of the proximity-induced semimetallic nature of low energy electron states, which are shown to behave as two-dimensional pseudo-Weyl fermions by means of symmetry analysis and first principles calculations as well as direct angle-resolved photoemission spectroscopy measurements.

2-dimensional systems↗

Structure and dynamics of ethane confined in silica nanopores in the presence of CO 2

Fundamental understanding of the subcritical/supercritical behavior of key hydrocarbon species inside nano-porous matrices at elevated pressure and temperature is less developed compared to bulk fluids, but this knowledge is of great importance for chemical and energy engineering industries. This study explores in detail the structure and dynamics of ethane (C 2 H 6 ) fluid confined in silica nanopores, with a focus on the effects of pressure and different ratios of C 2 H 6 and CO 2 at non-ambient temperature. Quasi-elastic neutron scattering (QENS) experiments were carried out for the pure C 2 H 6 , C 2 H 6 :CO 2 = 3:1, and 1:3 mixed fluids confined in 4-nm cylindrical silica pores at three different pressures (30 bars, 65 bars, and 100 bars) at 323 K. Two Lorentzian functions were required to fit the spectra, corresponding to fast and slow translational motions. No localized motions (rotations and vibrations) were detected. Higher pressures resulted in hindrances of the diffusivity of C 2 H 6 molecules in all systems investigated. Pore size was found to be an important factor, i.e., the dynamics of confined C 2 H 6 is more restricted in smaller pores compared to the larger pores used in previous studies. Molecular dynamics simulations were performed to complement the QENS experiment at 65 bars, providing supportive structure information and comparable dynamic information. The simulations indicate that CO 2 molecules are more strongly attracted to the pore surface compared to C 2 H 6 . The C 2 H 6 molecules interacting with or near the pore surface form a dense first layer (L1) close to the pore surface and a second less dense layer (L2) extending into the pore center. Both the experiments and simulations revealed the role that CO 2 molecules play in enhancing C 2 H 6 diffusion (“molecular lubrication”) at high CO 2 :C 2 H 6 ratios. The energy scales of the two dynamic components, fast and slow, quantified by both techniques, are in very good agreement. Herein, the simulations identified the fast component as the main contributor to the dynamics. Molecule motions in the L2 region are mostly responsible for the dynamics (fast and slow) that can be detected by the instrument.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystallization of nanopore-confined imidazolium ionic liquids probed by temperature-resolved in situ grazing-incidence wide angle X-ray scattering (GIWAXS)

The crystallization behavior of ionic liquids (ILs) 1-butyl-3-methylimidazolium [BMIM] hexafluorophosphate [PF 6 ] and chloride [Cl] is investigated upon confinement in 2.3 or 8.2 nm diameter silica nanopore arrays, along with the effects of covalently modifying the pore walls with 1-(3-trimethoxysilylpropyl)3-methylimidazolium [TMS-MIM] + groups. In situ grazing-incidence wide angle x-ray scattering (GIWAXS) is performed during heating from as low as -110 °C to room temperature. Partially ordered “nanodomains” are observed in both ILs in the bulk molten state, but they are disrupted by nanoconfinement. Melting point depression consistent with capillary effects is observed for [BMIM][PF 6 ] in 2.3 nm pores. However, the melting point is elevated for [BMIM][PF 6 ] in 8.2 nm pores, which provide sufficient space to stabilize the crystalline phase. For [BMIM][Cl], crystallization is observed only in 8.2 nm bare silica pores, but the melting point is severely depressed. Tethering with IL-like [TMS-MIM + ] also promotes the crystallization of [BMIM][PF 6 ], resulting in elevated melting points. The combined effects of a larger pore size and pore surface tethering on [BMIM][PF 6 ] result in a single stable crystal phase that persists from -140 °C to 25 °C (vs. the bulk melting point of -11 °C). These results show that when ILs are used in confined systems, complex crystallization behavior can emerge depending on the counterion, pore size, and surface modification that require consideration of ion layering in the confined space in addition to surface free energy effects.

He, Yuxin [University of Kentucky, Lexington, KY (↗

Effects of pore size on water dynamics in mesoporous silica

Water confined in mesoporous silica plays a central role in its many uses ranging from gas sorption to nanoconfined chemical reactions. Here in this paper, the influence of pore diameter (2.5–5.4 nm) on water hydrogen bond (H-bond) dynamics in MCM41 and SBA15 mesoporous silicas is investigated using femtosecond infrared vibrational spectroscopy and molecular dynamics simulations on selenocyanate (SeCN-) anions dissolved in the pores. As shown recently, SeCN- spectral diffusion is a reliable probe of surrounding water H-bond structural motions. Additionally, the long CN stretch vibrational lifetime facilitates measurement of the full range of confined dynamics, which are much slower than in bulk water. The simulations shed light on quantitative details that are inaccessible from the spatially averaged observables. The dependence of SeCN- orientational relaxation and that of spectral diffusion on the distance from the silica interface are quantitatively described with an exponential decay and a smoothed step-function, respectively. The distance-dependence of both quantities is found to be independent of the diameter of the pores, and the spatial distribution of SeCN- is markedly non-uniform, reaching a maximum between the interface and the pore center. The results indicate that the commonly invoked two-state, or core–shell, model is a more appropriate description of spectral diffusion. Using these insights, we model the full time-dependence of the measured dynamics for all pore sizes and extract the “core” and “shell” dynamical correlation functions and SeCN- spatial probability distributions. The results are critically compared to those for water confined in reverse micelles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Instability seeding mechanisms due to internal defects in inertial confinement fusion targets

Performance degradation in laser-driven inertial confinement fusion (ICF) implosions is caused by several effects, one of which is Rayleigh–Taylor instability growth. Defects in ICF targets, such as internal voids and surface roughness, create instability seeds in the shell as shocks propagate through the target. A comprehensive understanding of seeding mechanisms is essential to characterize the impact of target defects on inflight shell integrity and mass injection into the central, lower-density vapor region. An analysis of early-time behavior of both single-mode shell mass modulations and isolated voids is performed by examining the evolution of the acoustic waves launched by these target imperfections. A systematic study of localized perturbation growth as a function of defect placement and size is presented. Furthermore, the use of low-density ablator materials (such as foams) is suggested as a potential mitigation strategy to improve target robustness against the impact of defect-initiated growth.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Ion velocity effect governs damage annealing process in defective KTaO 3

Effects of electronic to nuclear energy losses (S e /S n ) ratio on damage evolution in defective KTaO 3 have been investigated by irradiating pre-damaged single crystal KTaO 3 with intermediate energy O ions (6 MeV, 8 MeV and 12 MeV) at 300 K. By exploring these processes in pre-damaged KTaO 3 containing a fractional disorder level of 0.35, the results demonstrate the occurrence of a precursory stage of damage production before the onset of damage annealing process in defective KTaO 3 that decreases with O ion energy. The observed ionization-induced annealing process by ion channeling analysis has been further mirrored by high resolution transmission electron microscopy analysis. In addition, the reduction of disorder level is accompanied by the broadening of the disorder profiles to greater depth with increasing ion fluence, and enhanced migration is observed with decreasing O ion energy. Since S e (~3.0 keV nm –1 ) is nearly constant for all 3 ion energies across the pre-damaged depth, the difference in behavior is due to the so-called 'velocity effect': the lower ion velocity below the Bragg peak yields a confined spread of the electron cascade and hence an increased energy deposition density. Here, the inelastic thermal spike calculation has further confirmed the existence of a velocity effect, not previously reported in KTaO 3 or very scarcely reported in other materials for which the existence of ionization-induced annealing has been reported. In other words, understanding of ionization-induced annealing has been advanced by pointing out that ion velocity effect governs the healing of pre-existing defects, which may have significant implication for the creation of new functionalities in KTaO 3 through atomic-level control of microstructural modifications, but may not be limited to KTaO 3 .

74 ATOMIC AND MOLECULAR PHYSICS↗

Towards the first plasma-electron screening experiment

The enhancement of fusion reaction rates in a thermonuclear plasma by electron screening of the Coulomb barrier is an important plasma-nuclear effect that is present in stellar models but has not been experimentally observed. Experiments using inertial confinement fusion (ICF) implosions may provide a unique opportunity to observe this important plasma-nuclear effect. Herein, we show that experiments at the National Ignition Facility (NIF) have reached the relevant physical regime, with respect to the density and temperature conditions, but the estimated impacts of plasma screening on nuclear reaction rates are currently too small and need to be increased to lower the expected measurement uncertainty. Detailed radiation hydrodynamics simulations show that practical target changes, like adding readily available high-Z gases, and significantly slowing the inflight implosion velocity, while maintaining inflight kinetic energy, might be able to push these conditions to those where plasma screening effects may be measurable. We also perform synthetic data exercises to help understand where the anticipated experimental uncertainties will become important. But challenges remain, such as the detectability of the reaction products, non-thermal plasma effects, species separation, and impacts of spatial and temporal gradients. This work lays the foundation for future efforts to develop an important platform capable of the first plasma electron screening observation.

inertial confinement fusion↗

Effects of negative triangularity on microinstabilities in a low-recycling lithium-wall spherical tokamak

In this work, we present a linear gyrokinetic study of the impact of negative triangularity (NT) on microinstabilities in the Lithium Tokamak eXperiment-β (LTX-β), a low-recycling spherical tokamak with liquid lithium plasma-facing components that produce flat electron-temperature profiles [Elliott et al., IEEE Trans. Plasma Sci. 48, 1382 (2020)]. While NT is widely recognized as a stabilizing mechanism and often associated with improved confinement in conventional tokamaks, this study reveals that its effect is not universally stabilizing in the parameter regime of LTX-β and is shown to be highly sensitive to local equilibria. Using local linear simulations with the GS2 code [Kotschenreuther et al., Comput. Phys. Commun. 88, 128 (1995)] at ρ=0.3, 0.5, and 0.8 for two representative discharges (#103955 and #109355), and employing the Miller equilibrium model to isolate shaping effects, we find that NT can transition from stabilizing to destabilizing depending on magnetic shear, safety factor, and electron-temperature gradient. In shot #103955, NT reduces growth rates across radii, with strongest stabilization at the edge, whereas in shot #109355, it is stabilizing in the core but destabilizing at mid-radius and edge under experimental conditions. Parametric scans show that flattening the electron-temperature profile, increasing magnetic shear, and reducing the safety factor recover NT stabilization. These results demonstrate that NT stabilization is tunable rather than intrinsic and requires coordinated control of magnetic geometry and gradient drive.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗