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At least 91 records · Page 5

Interface‐Controlled Redox Chemistry in Aqueous Mn 2 ⁺/MnO₂ Batteries

Manganese dioxide (MnO 2 ) deposition/dissolution (Mn 2+ /MnO 2 ) chemistry, involving a two-electron-transfer process, holds promise for safe and eco-friendly large-scale energy storage. However, challenges like electrode/electrolyte interface environment fluctuations (H + and H 2 O activity), irreversible Mn degradation, and limited understanding of degradation mechanisms hinder the reversibility of the Mn 2+ /MnO 2 conversion. This study demonstrates a vanadyl/pervanadyl (VO 2+ /VO 2 + ) redox-mediated interface designed for high-energy Mn 2+ /MnO 2 batteries. Unlike flow systems, this work uncovers, for the first time, the mechanism of a static redox-mediated interface in regulating interfacial H + and H 2 O activities. Significantly, the VO 2+ /VO 2 + chemical redox mediation targets Mn 3+ intermediates, suppressing their hydrolysis and enabling 100% Mn 2+ /MnO 2 conversion. The redox-mediated interface enhances the Mn redox electron transfer process, achieving a stable ≈95% coulombic efficiency and ultrahigh capacity of 100 mAh cm −2 with an areal energy density of 111 mWh cm −2 , outperforming flow systems. The electrode also exhibits an average specific capacity of 593 mAh g −1 , approaching the theoretical limit of 616 mAh g −1 , and a specific energy density of 721 Wh kg −1 at high MnO 2 loadings (50–150 mg cm −2 ). Furthermore, the findings highlight the critical role of interfacial redox mediation in regulating H + and H 2 O activities and underscore the significance of interface dynamics.

Xue, Xinzhe [University of California, Santa Cruz,↗

Long‐Range Non‐Coulombic Coupling at the LaAlO 3 /SrTiO 3 Interface

The LaAlO 3 /SrTiO 3 interface hosts a plethora of gate‐tunable electronic phases. Gating of LaAlO 3 /SrTiO 3 interfaces is usually assumed to occur electrostatically. However, increasing evidence suggests that non‐local interactions can influence and, in some cases, dominate the coupling between applied gate voltages and electronic properties. Here, quasi‐1D ballistic electron waveguides are sketched at the LaAlO 3 /SrTiO 3 interface as a probe to understand how gate tunability varies as a function of spatial separation. Gate tunability measurements reveal the scaling law to be at odds with the pure electrostatic coupling observed in traditional semiconductor systems. The non‐Coulombic gating at the interface is attributed to a long‐range nanoelectromechanical coupling between the gate and electron waveguide, possibly mediated by the ferroelastic domains in SrTiO 3 . The long‐range interactions at the LaAlO 3 /SrTiO 3 interface add unexpected richness and complexity to this correlated electron system.

36 MATERIALS SCIENCE↗

The atomic-level structure and stability of interfaces of Pt nanoparticles in alumina: An experimental and computational evaluation

The atomic-level structure of interfaces between Pt and a transition form of Al2O3 were studied using a combination of electron microscopy and first principles calculations. A model system of Pt nanoprecipitates in Al2O3 were formed in sapphire wafers via high-energy ion implantation of Pt followed by thermal annealing at 1000 °C in air. The Pt nanoparticles took the form of tetrahedra and truncated tetrahedra primarily bound by {111}Pt facets. The high prevalence of these facets motivated the development of density functional theory (DFT) based models of (111)Pt interfaces with six different chemical terminations of ( 2 ¯ 01 ) θ-alumina. The atomic-level structure of the Pt/Al2O3 interfaces was characterized with aberration-corrected scanning transmission electron microscopy (STEM) and the experimental images were compared to STEM image simulations of the DFT models. The model interface with Pt bonded to oxygen-terminated θ-Al2O3, with the Pt located on top of the O and with an underlying layer of octahedral Al, provided the best match to the experimental images. This interfacial termination is also the most stable for the thermal annealing conditions used based on thermodynamic calculations of the interfacial energy as a function of temperature and oxygen partial pressure. This experimentally verified model provides a basis for improving models of Pt/γ-alumina interfaces.

Clauser, A L↗

Multi-material ALE remap with interface sharpening using high-order matrix-free finite element methods

The arbitrary Lagrangian-Eulerian (ALE) technique involves remapping field quantities from a Lagrangian mesh to an optimized mesh in a conservative, accurate and bounds-preserving manner. For methods based on arbitrary order finite elements, as described in a reference, material volume fractions are advected in pseudo-time using flux-corrected transport (FCT) without any form of interface reconstruction. In practice, this can lead to excessive propagation of small volume fractions throughout the domain. In addition, this method requires assembly of a global advection matrix to compute the bounds-preserving low-order FCT solution. In this work, we introduce a new approach for ALE remap using a high-order matrix-free technique which incorporates a flux modification to sharpen material interfaces in a conservative manner. Our approach begins with computing a bounds-preserving low-order solution to the ALE remap equations at the element level. We then compute a sharp interface solution (not guaranteed to be bounds-preserving) which comes from solving an augmented version of the ALE remap equations with a conservative flux modification which acts to sharpen material volume fractions based on their gradients and transport directions. Using the sharp interface solution, we make global corrections to the bounds-preserving solution while maintaining preservation of bounds. By blending with the sharpened solution at the global level we are able to globally conserve mass without hindering the remap pseudo-time step. This new interface-aware ALE remap method is based entirely on partial assembly techniques where globally assembled matrix operators are no longer needed, resulting in a globally matrix-free FCT method for multi-material, multi-field ALE remap with high performance on GPU architectures. We present results of our new remap method on 1D, 2D and 3D benchmarks and describe the algorithmic tailoring for GPU architectures that was developed.

Vargas, Arturo [Lawrence Livermore National Labora↗

Establishing the Role of Metal, Interface, and Vacancy Sites in Pt/TiO 2 -Catalyzed Acetic Acid Hydrodeoxygenation

Catalytic hydrodeoxygenation (HDO) following catalytic fast pyrolysis (CFP) offers an approach to convert the vapor-phase product of biomass pyrolysis to a stable bio-oil product by reducing the oxygen content. Fundamental insights into the HDO of carboxylic acids, which are a corrosive and acidic CFP product, on promising catalyst materials, such as Pt/TiO 2 , are needed to inform the design of multifunctional HDO catalysts with improved carbon efficiency. In this contribution, density functional theory (DFT) calculations were used to assess the role of Pt-metal and Pt-TiO 2 -interface sites on acetic acid HDO (AA-HDO), and to determine the effect of interfacial oxygen vacancies at the Pt-TiO 2 interface, by calculating the reaction energetics for key AA-HDO surface intermediates and elementary steps on each site type. Pt-metal sites, modeled via Pt(111), preferred to form undesired decarboxylation products (CH 4 and CO 2 ), whereas Pt-TiO 2 -interface sites, modeled via an anatase-supported Pt nanowire, favored the formation of desired deoxygenation products (acetaldehyde and ethane). Interfacial-vacancy sites lowered the activation energy barrier for the first C-O bond-scission step in AA-HDO, predicted to be the rate-limiting step for AA-HDO at the Pt-TiO 2 interface in the absence of a vacancy. These atomistic insights reveal the importance of metal-metal oxide interface sites in AA-HDO selectivity and can be used to inform the rational design of improved HDO catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO 2 Adsorption and Hydrogenation on Inverse InO x /Cu(111) Catalysts: Active Role of the Oxide–Metal Interface

The direct conversion of carbon dioxide (CO 2 ) into methanol via hydrogenation is essential for industrial applications. Recent studies on catalysts that contain an inverse oxide/metal configuration have shown very good catalytic performance for the CO 2 hydrogenation to methanol process. Here, in this study, we investigated the behavior of indium oxide-Cu(111) interfaces under pure CO 2 and CO 2 /H 2 mixtures using synchrotron-based ambient-pressure X-ray photoelectron spectroscopy (AP-XPS). Initially, a single layer of copper oxide (Cu x O) was grown on the Cu(111) surface by controlled oxidation. On this surface, indium was deposited at room temperature. Oxygen atoms transferred from Cu x O/Cu(111) to the indium metal upon deposition, forming In-O-Cu bonds and active interfaces. Although Cu(111) is not very active for the binding and activation of CO 2 , the formed InO x -Cu(111) interfaces had no problem adsorbing and dissociating the molecule at room temperature. Reaction of CO 2 with H 2 on InO x -Cu(111) yielded surface-bound H 3 CO, CO 2 δ− , CO 3 , and CH x species that are typical intermediates in the production of methanol and other oxygenates. The InO x -Cu(111) interface underwent dynamic chemical changes under reaction conditions, forming In-Cu alloys at low indium coverages (< 0.05 monolayer), while at higher indium coverages a mixture of an In-Cu and InO x was detected in XPS. These findings indicate that InO x /In-Cu interfaces can play a key role in processes aimed at the trapping and valorization of CO 2 .

36 MATERIALS SCIENCE↗

The Role of Nonequilibrium Solvent Effects in Enhancing Direct CO 2 Capture at the Air–Aqueous Amino Acid Interface

Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO 2 from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling ab initio molecular dynamics simulations. Here, we elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH 2 ], facilitating S N 2-based CO 2 conversion to a zwitterion, which then releases a proton via overhydration of [-NH 2 ]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO 2 capture kinetics via control of solvation and ion paring.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the effect of heterogeneities across the electrode|multiphase polymer electrolyte interfaces in high-potential lithium batteries

Polymer electrolytes hold great promise for safe and high-energy batteries comprising solid or semi-solid electrolytes. Multiphase polymer electrolytes, consisting of mobile and rigid phases, exhibit fast ion conduction and desired mechanical properties. However, fundamental challenges exist in understanding and regulating interactions at the electrode|electrolyte interface, especially when using high-potential layered oxide active materials at the positive electrode. Here we demonstrate that depletion of the mobile conductive phase at the interface contributes to battery performance degradation. Molecular ionic composite electrolytes, composed of a rigid-rod ionic polymer with nanometric mobile cations and anions, serve as a multiphase platform to investigate the evolution of ion conductive domains at the interface. Chemical and structural characterizations enable the visualization of concentration heterogeneity and spatially resolve the interfacial chemical states over a statistically significant field of view for buried interfaces. We report that concentration and chemical heterogeneities prevail at electrode|electrolyte interfaces, leading to phase separation in polymer electrolytes. In conclusion, understanding the hidden roles of interfacial chemomechanics in polymer electrolytes enables us to design an interphase tailoring strategy based on electrolyte additives to mitigate the interfacial heterogeneity and improve battery performance.

36 MATERIALS SCIENCE↗

Influence of misfit dislocations on ionic conductivity at oxide interfaces

Mismatched complex oxide thin films and heterostructures have gained significant traction for use as electrolytes in intermediate temperature solid oxide fuel cells, wherein interfaces exhibit variation in ionic conductivity as compared to the bulk. Although misfit dislocations present at interfaces in these structures impact ionic conductivity, the fundamental mechanisms responsible for this effect are not well understood. To this end, a kinetic lattice Monte Carlo (KLMC) model was developed to trace oxygen vacancy diffusion at misfit dislocations in SrTiO 3 /BaZrO 3 heterostructures and elucidate the atomistic mechanisms governing ionic diffusion at oxide interfaces. The KLMC model utilized oxygen vacancy migration energy barriers computed using molecular statics. While some interfaces promote oxygen vacancy diffusion, others impede their transport. Fundamental factors such as interface layer chemistry, misfit dislocation structure, and starting and ending sites of migrating ions play a crucial role in oxygen diffusivity. Molecular dynamics (MD) simulations were further performed to support qualitative trends for oxygen vacancy diffusion. Overall, the agreement between KLMC and MD is quite good, though MD tends to predict slightly higher conductivities, perhaps a reflection of nuanced structural relaxations that are not captured by KLMC. The current framework comprising KLMC modeling integrated with molecular statics offers a powerful tool to perform mechanistic studies focused on ionic transport in thin film oxide electrolytes and facilitate their rational design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shock-driven three-fluid mixing with various chevron interface configurations

When a shock wave crosses a density interface, the Richtmyer–Meshkov instability causes perturbations to grow. Richtmyer–Meshkov instabilities arise from the deposition of vorticity from the misaligned density and pressure gradients at the shock front. In many engineering applications, microscopic surface roughness will grow into multi-mode perturbations, inducing mixing between the fluid on either side of an initial interface. Applications often have multiple interfaces, some of which are close enough to interact in the later stages of instability growth. In this study, we numerically investigate the mixing of a three-layer system with periodic zigzag (or chevron) interfaces, calculating the dependence of the width and mass of mixed material on properties such as the shock timing, chevron amplitude, multi-mode perturbation spectrum, density ratio, and shock mach number. The multi-mode case is also compared with a single-mode perturbation. The Flash hydrodynamic code is used to solve the Euler equations in three dimensions with adaptive grid refinement. Key results include a significant increase in mixed mass when changing from a single-mode to a multi-mode perturbation on one of the interfaces. The mixed width is mainly sensitive to the density ratio and chevron amplitude, whereas the mixed mass also depends on the multi-mode spectrum. In conclusion, steeper initial perturbation spectra have lower mixed mass at early times but a greater mixed mass after the reflected shock transits back across the layer.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Design and performance of AI agents interfacing with an atomic layer deposition tool

In this work, we introduce the design of an atomic layer deposition (ALD) reactor augmented with an AI interface for autonomous materials synthesis. Our modular design encapsulates the particularities of the hardware behind a Python interface that communicates with the ALD control software via transmission control protocol. This interface is compatible with model context protocol interfaces used in agentic frameworks. We have integrated our tool with a simple AI agent that leverages a large language model to transform user-supplied queries into ALD processes that are then run in our reactor. Our approach uses a JavaScript object notation schema to encode ALD processes. Our experimental results show that the AI interface does not impose a significant overhead to our control software, at least within our fastest 10 ms scale. We also carried out a detailed evaluation of the agent performance using leading models in two classes of tasks: basic instruction and process discovery tasks, where the agent is presented with a target material and needs to identify the correct ALD process compatible with the reactor configuration. Despite the simplicity of our agent design, we observed that most of the advanced models excelled at the instruction tasks. However, only recent models, such as o1, o3, GPT-5, and Claude Opus 4, performed well in process discovery tasks. We also observed significant variability in the response for the hardest challenges. While the results obtained are promising, we identify areas where AI research could improve the performance of agents for ALD.

47 OTHER INSTRUMENTATION↗

Quantifying the impact of the Si/O interface in CCSN explosions using the Force Explosion Condition

ABSTRACT The explosion mechanism of a core-collapse supernova (SN) is a complex interplay between neutrino heating and cooling (including the effects of neutrino-driven convection), the gravitational potential, and the ram pressure of the infalling material. To analyse the post-bounce phase of an SN, one can use the generalized force explosion condition (FEC+), which succinctly formalizes the interplay among these four phenomena in an analytical condition, consistent with realistic simulations. In this paper, we use the FEC+ to study the post-bounce phase of 341 spherically symmetric simulations, where convection is included through a time-dependent mixing-length approach. We find that the accretion of the Si/O interface through the expanding shock can significantly change the outcome of the SN by driving the FEC+ above the explosion threshold. We systematically explore this by (i) artificially smoothing the pre-SN density profile, and (ii) artificially varying the mixing length. In both cases, we find that large-enough density contrasts at the Si/O interface lead to successful shock revival only if the FEC+ is already close to the explosion threshold. Furthermore, we find that the accretion of the Si/O interface has a substantial effect on the critical condition for SN explosions, contributing between 5 and 15 per cent, depending on how pronounced the density contrast at the interface is. Earlier studies showed that convection affects the critical condition by 25–30 per cent, which demonstrates that the accretion of the Si/O interface through the shock can play a nearly comparable role in influencing shock dynamics.

Boccioli, Luca (ORCID:000000024819310X)↗

Spectral Similarity Masks Structural Diversity at Hydrophobic Water Interfaces

The air-water and graphene-water interfaces represent quintessential examples of the liquid-gas and liquid-solid boundaries, respectively. While the sum-frequency generation (SFG) spectra of these interfaces show similarities, a consensus on their signals and interpretations has yet to be reached. Leveraging deep learning, we computed first-principles SFG spectra for both systems, addressing experimental discrepancies. Here, our findings reveal that similarities in SFG signals do not translate into comparable interfacial microscopic properties. Instead, graphene-water and air-water interfaces exhibit fundamental differences in SFG-active thicknesses, hydrogen-bonding networks, and surface dynamics. These distinctions underscore roughness suppression and electronic interactions present at the solid-liquid interface but absent at the gas-liquid interface.

Wang, Yong [Princeton Univ., NJ (United States)] (↗

Emergent Phenomena at Mott Interfaces – a Time- and Depth-Resolved Approach (Final Technical Report)

This is the final technical report for Award DE-SC0019297, Emergent Phenomena at Mott Interfaces – a Time- and Depth-Resolved Approach. This research program aimed to address the scientific questions related to the emergence and control of non-equilibrium electronic phases of matter in strongly correlated Mott oxides and their interfaces. We were focusing specifically on exploiting the interfaces in heterostructures and superlattices, containing Mott oxides CaMnO 3 and LaNiO 3 because in such systems, precise control of electronic and magnetic structure in the ground state can be achieved through dimensionality, heterostructuring, interface termination, and lattice strain. We utilized advanced x-ray spectroscopic and scattering techniques, to investigate these phenomena. Additionally, we used intense THz electric-field pulses generated by a femtosecond laser to directly modify the electronic structure and magnetic states of the ultrathin LaNiO 3 and CaMnO 3 layers in such heterostructures, with the objectives of disentangling, understanding, and harnessing control over the intricate competing interactions responsible for two-dimensional magnetism and metal-insulator transition at the interfaces.

36 MATERIALS SCIENCE↗

Amphiphilic Baskets for Supramolecular Nanoarchitectures at Interfaces: Inverted Monolayer Formation on Water

Interfacial chemistry of molecular baskets remains poorly understood despite their promise for supramolecular applications of detection and sequestration of toxic molecules including those of illicit drugs, organophosphorus compounds, and anticancer agents. We present a fundamental investigation of the interfacial behavior of three amphiphilic supramolecular baskets (ASB 4, 8, and 12), having increasingly longer yet linear alkyl chains at the top of their bowl-shaped cavity. The studies were completed at the air−water interface to elucidate surface activity, interfacial stability, self-assembly, and monolayer organization that drive inverted monolayer formation, in which the molecular arms orient toward the aqueous phase in a configuration opposite to that typically observed for lipids. Herein, surface pressure−area isotherms of ASB 4, 8, 12, deposited on a water surface, were performed in tandem with nonequilibrium relaxation experiments to quantify surface activity, thermodynamic stability, and monolayer compressibility of the baskets’ monolayer assembly. Brewster angle microscopy enabled direct visualization of morphological evolution, aggregation, and packing at the interface. We show that systematic extension of the hydrocarbon arms, from four to 12 methylene groups, progressively modifies intermolecular packing, drives distinct two-dimensional aggregation pathways, and increases number densities at the air−water interface. Atomistic molecular dynamics simulations corroborate many of these experimentally observed trends and provide mechanistic detail on the cooperative roles of basket topology and interfacial concentration in regulating the hydration structure and dynamics within the cavities generated by surface-adsorbing baskets, consistent with observed variations in surface activity and packing. Our results establish how the topology of these unique supramolecules and their concentration govern interfacial organization and offer a rational framework for designing amphiphiles with predictable behavior at soft interfaces.

Hydrocarbons↗

Improving Ionic Conformality Across Polymer Electrolyte|Electrode Interfaces

Maintaining uniform ionic transport at electrode|electrolyte interfaces, i.e., ionic conformality, remains challenging in polymer electrolyte (PE)-based solid-state batteries. Morphological conformality does not necessarily imply ionic conformality. In PEs, which typically consist of a mechanically supporting component and distinct ionically conductive components, the rearrangement or depletion of mobile ion-conductive domains at interfaces can disrupt ionic transport pathways. Such localized ionic depletion contributes to interfacial instability and capacity degradation in high-voltage lithium-metal batteries. Herein, an electrolyte design approach aimed at minimizing interfacial heterogeneities is demonstrated through compositional adjustments, characterized by spatially resolved structural and chemical X-ray techniques and NMR diffusometry to elucidate ion transport dynamics. This approach improves ionic conformality at electrode interfaces, enhancing cycling stability in Li||LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NMC811) coin and pouch cells cycled at high voltages. These results contribute to understanding interfacial behaviors in multiphase PEs and inform strategies for improving stability across solid-state battery interfaces.

36 MATERIALS SCIENCE↗

On the Structure–Property Relationship of Semi‐Coherent FeCr 2 O 4 /Cr 2 O 3 Spinel/Corundum Interfaces

Abstract Oxide heterointerfaces are extremely common in both natural and artificial composite structures, including corroded structural materials. Often, key properties such as segregation and atomic transport are dictated by the structure of these interfaces. However, despite this critical link, very few heterointerfaces have been studied in any detail at the atomic scale. Here, one important oxide heterointerface is examined, between spinel and corundum, using the chemical system FeCr 2 O 4 /Cr 2 O 3 as a representative and technologically important case. Using atomistic simulation techniques, it is found that the structure, particularly the local chemistry, of the interface depends on the crystal chemistry at the interface. This atomic and chemical structure further impacts important properties such as defect segregation and mass transport. It is found that defects can nucleate at some regions of these interfaces and migrate back and forth across the corundum layer, suggesting high atomic mobility that may be important for the evolution of spinel/corundum composite structures in extreme conditions.

36 MATERIALS SCIENCE↗

A Versatile Approach to Stabilize Liquid–Liquid Interfaces using Surfactant Self-Assembly

Stabilizing liquid–liquid interfaces, whether between miscible or immiscible liquids, is crucial for a wide range of applications, including energy storage, microreactors, and biomimetic structures. Here, in this study, a versatile approach for stabilizing the water-oil interface is presented using the morphological transitions that occur during the self-assembly of anionic, cationic, and nonionic surfactants mixed with fatty acid oils. The morphological transitions underlying this approach are characterized and extensively studied through small-angle X-ray scattering (SAXS), rheometry, and microscopy techniques. Dissipative particle dynamics (DPD) as a simulation tool is adopted to investigate these morphological transitions both in the equilibrium ternary system as well as in the dynamic condition of the water-oil interface. Such a versatile strategy holds promise for enhancing applications such as liquid-in-liquid 3D printing. Moreover, it has the potential to revolutionize a wide range of fields where stabilizing liquid–liquid interfaces not only offers unprecedented opportunities for fine-tuning nanostructural morphologies but also imparts interesting practical features to the resulting liquid shapes. These features include perfusion capabilities, self-healing, and porosity, which could have significant implications for various industries.

36 MATERIALS SCIENCE↗