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At least 1,297 records · Page 72

Atmospheric ice nucleation

Atmospheric ice nucleation is crucial for global precipitation and affects the structure, lifetime and reflectivity of clouds, thereby impacting climate. Ice nucleates in various ways from aerosol particles, termed ice-nucleating particles, over an extensive temperature and humidity range. Quantifying the kinetic and thermodynamic regimes of nucleation is necessary to relate fundamental physics to theoretically based predictions of ice formation for implementation in cloud and climate models. We review how the molecular picture of ice nucleation has advanced in recent years and consequential impacts on the interpretation and parameterization of ice nucleation. Advances include the role of interfacial free energy and pressure on ice nucleation rates, mobility regions of water that generate the critical ice nucleus, classical and non-classical pathways of nucleation, the type of ice polymorph that forms, the impact of solutes on freezing and the role of nanopores as surface features promoting ice nucleation. We also introduce currently debated and evaluated freezing parameterizations for application in model environments. Finally, we outline what we believe are the current needs for improving predictive understanding of ice nucleation.

54 ENVIRONMENTAL SCIENCES↗

Single-particle detection of enhanced polarizability in Au-decorated semiconducting nanorods via scanning dielectric microscopy

Hybrid nanostructures that combine semiconducting and metallic components offer great potential for photothermal therapy, optoelectronics, and sensing, by integrating tunable optical properties with enhanced light absorption and charge transport. Boosting the integrated performance of these hybrid systems demands techniques capable of probing local variations of the physical properties inaccessible to bulk analysis. Here, we report the single-particle dielectric characterization of hybrid, semiconducting bismuth sulfide (Bi 2 S 3 ) nanorods (NR) decorated with metallic Au nanoparticles (NP), employing scanning dielectric microscopy, which uses electrostatic force microscopy in combination with finite-element numerical simulations. We reveal a pronounced enhancement in the local dielectric response of Bi2S3 upon Au decoration, attributed to interfacial polarization and electron transfer from Au to the Bi 2 S 3 matrix, thus suggesting a enhanced metallic-like polarizability at the single-particle level. Numerical simulations show that the response is dominated by the vertical component of the permittivity and that the decorating metallic Au NP produce only moderate shielding of the semiconductor Bi 2 S 3 NR core, indicating that the large increase in the dielectric response originates primarily from intrinsic modifications within the NR. Overall, these findings provide direct insight into structure–property relationships at the single-particle level, supporting the rational design of advanced hybrid nanostructures with tailored electronic functionalities.

36 MATERIALS SCIENCE↗

Molecular Mechanisms of Sorbed Ion Effects during Boehmite Particle Aggregation

Classical theories of particle aggregation, such as Derjaguin–Landau–Verwey–Overbeek (DLVO), do not explain recent observations of ion-specific effects or the complex concentration dependence for aggregation. Thus, here, we probe the molecular mechanisms by which selected alkali nitrate ions (Na + , K + , and NO 3 –) influence aggregation of the mineral boehmite (γ-AlOOH) nanoparticles. Nanoparticle aggregation was analyzed using classical molecular dynamics (CMD) simulations coupled with the metadynamics rare event approach for stoichiometric surface terminations of two boehmite crystal faces. Calculated free energy landscapes reveal how electrolyte ions alter aggregation on different crystal faces relative to pure water. Consistent with experimental observations, we find that adding an electrolyte significantly reduces the energy barrier for particle aggregation (~3–4×). However, in this work, we show this is due to the ions disrupting interstitial water networks, and that aggregation between stoichiometric (010) basal–basal surfaces is more favorable than between (001) edge–edge surfaces (~5–6×) due to the higher interfacial water densities on edge surfaces. The interfacial distances in the interlayer between aggregated particles with electrolytes (~5–10 Å) are larger than those in pure water (a few Ångströms). Together, aggregation/disaggregation in salt solutions is predicted to be more reversible due to these lower energy barriers, but there is uncertainty on the magnitudes of the energies that lead to aggregation at the molecular scale. By analyzing the peak water densities of the first monolayer of interstitial water as a proxy for solvent ordering, we find that the extent of solvent ordering likely determines the structures of aggregated states as well as the energy barriers to move between them. Further, the results suggest a path for developing a molecular-level basis to predict the synergies between ions and crystal faces that facilitate aggregation under given solution conditions. Such fundamental understanding could be applied extensively to the aggregation and precipitation utilization in the biological, pharmaceutical, materials design, environmental remediation, and geological regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Feedback in the Self-Assembly and Function of Air–Liquid Interfaces: Insight into the Bottlenecks of CO 2 Direct Air Capture

As fossil fuels remain a major source of energy throughout the world, developing efficient negative emission technologies, such as direct air capture (DAC), which remove carbon dioxide (CO 2 ) from the air, becomes critical for mitigating climate change. Although all DAC processes involve CO 2 transport from air into a sorbent/solvent, through an air–solid or air–liquid interface, the fundamental roles the interfaces play in DAC remain poorly understood. In this work, we study the interfacial behavior of amino acid (AA) solvents used in DAC through a combination of vibrational sum frequency generation spectroscopy and molecular dynamics simulations. This study revealed that the absorption of atmospheric CO 2 has antagonistic effects on subsequent capture events that are driven by changes in bulk pH and specific ion effects that feedback on surface organization and interactions. Among the three AAs (leucine, valine, and phenylalanine) studied, we identify and separate behaviors from CO 2 loading, chemical changes, variations in pH, and specific ion effects that tune structural and chemical degrees of freedom at the air–aqueous interface. The fundamental mechanistic findings described here are anticipated to enable new approaches to DAC based on exploiting interfaces as a tool to address climate change.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenge-driven printing strategies toward high-performance solid-state lithium batteries

Solid-state lithium batteries (SSLBs) are promising candidates for replacing traditional liquid-based Li-ion batteries and revolutionizing battery systems for electric vehicles and portable devices. However, longstanding issues such as form factors, interfacial contact resistance, balance between ion conductivity and mechanical strength, and manufacturing processability limit their applications. In this review we present how advanced printing technologies can help to mitigate typical problems in main components of SSLBs and improve device performance. Here we first introduce the common printing techniques for energy storage devices, then focus on the issues and corresponding printing strategies for anodes, cathodes, and solid-state electrolytes to guide the construction of energy-dense, free-form SSLBs. The features and effects of the printed structures are emphasized, as well. We conclude by discussing the problems associated with printing technologies and the potential research directions for printed solid-state batteries.

25 ENERGY STORAGE↗

Spin Rectification and Electrically Controlled Spin Transport in Molecular-Ferroelectrics-Based Spin Valves

We report a spin-rectification effect in a spin-valve structure consisting of ferroelectric croconic acid (C 5 H 2 O 5 ) sandwiched between ferromagnetic electrodes La 0.7 Sr 0.3 MnO 3 and Co, which can be switched between a high-resistance (off ) and a low-resistance (on) state by a poling voltage. In the off state, the magnetoresistance (MR) sign reverses with the measurement voltage with a 0.1-V offset, suggesting a spin-rectification behavior, while in the on state the MR remains negative. These observations can be understood in terms of electrically controlled interfacial energy-band alignment either from the electrostatic effect or from the interfacial redox process. In conclusion, the observed spin-rectification effect suggests thepossibility of diodelike devices for spin-polarized current.

36 MATERIALS SCIENCE↗

VTO_2021_APR_LLNL_Ye

Traditional batteries are composed of two-dimensional films that are stacked and/or rolled. Thin film batteries display high power density while their thick film counterparts show good energy density, but it has proven difficult to concurrently achieve both within these planar form factors. In addition, conventional Li-ion batteries based on liquid organic electrolytes or gel polymer electrolytes have raised severe safety concerns due to the intrinsic flammable properties of the organic electrolytes. They are also not ideal for the use of high energy density metallic lithium (Li) anodes due to Li dendrite growth, or sulfur cathodes due to shuttling effects that result in fast capacity fade. There is an urgent need to develop safe, high-performance solid-state batteries (SSBs) with advanced electrolyte and separator technologies. Although in recent years a series of superionic conductors have been developed for electrolytes and separators, their performance does not satisfy demanding criteria due to large impedance from poor solid electrolyte-electrode contact and questionable electrochemical and mechanical stability. Unlike the well-established roll-to-roll fabrication of conventional Li-ion batteries, the processing of SSBs is unique due to the brittleness of solid-state electrolytes (SSEs). The commercially available or lab-developed SSE discs are usually very thick (hundreds of micrometers to millimeters) to overcome their brittle nature, which unfortunately increases the cell impedance and accounts for the majority of the overall cell weight and volume, leading to dramatically decreased power and energy densities. In this project, we will investigate 3D printing techniques to overcome safety, fabrication, mechanical, and electrochemical issues in SSBs. 3D printing builds complex structures in a layer-by-layer fashion, which allows rapid production of hierarchical architectures, gradient and multi-material structures, and multi-component assemblies. 3D printing is an emerging area that could fundamentally transform energy storage devices. For example, 3D printing can produce batteries with arbitrary form factors to fit a product’s specific volume requirements and can create interwoven electrode arrangements over a wide range of length scales to improve transport and increase power density for a given energy density. For SSBs, 3D printing may dramatically reduce the separator thickness from ~1 mm (by hydraulic pressing) to tens of micrometers or less. In addition, the interfacial contact area between the electrolyte and the electrode may be increased via 3D interdigitated designs. Hence, we expect a significant reduction of the overall cell impedance and enhancement of both energy and power densities of SSBs by harnessing an array of 3D printing technologies being developed at Lawrence Livermore National Laboratory (LLNL).

25 ENERGY STORAGE↗

03.02.02.45: Energy Efficiency Improvement Approaches in Ice Related Processes

The primary objective of this project was to facilitate the dislocation of the interfacial ice layer by employing advanced materials and ultrasonic vibration to reduce ice adhesion strength. This work employed two technical approaches that were thoroughly investigated and previously reported. The effectiveness of these approaches, both individually and in combination, has been quantified, demonstrating notable energy savings. The projected payback period for these enhancements is approximately 2.2 years or less, contingent upon specific energy costs. Furthermore, these advancements hold significant promise for reducing carbon emissions across various equipment scales. This study particularly focused on the ultrasonic deicing technique for diverse structures, utilizing numerical simulations to evaluate performance and potential benefits.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Freeze Casting of LAGP for 3D Textured Solid-State Structural Electrolytes

In this study, all-solid-state structural lithium-ion batteries, a type of load bearing electrochemical energy storage that provides systems-level weight savings is being pursued for the realization of inherently safe next generation hybrid-electric and all-electric green aerospace propulsion systems. Currently investigated all-solid-state batteries do not meet the requirements for specific power and mechanical stability. To address these issues, freeze casting of lithium aluminum germanium phosphate (LAGP) electrolyte material has been explored for the creation of a textured 3D electrolyte scaffold with large interfacial surface area for high power discharge and hierarchical porosity for accommodation of active material volume changes during electrochemical cycling. We report the effects of freeze casting processing parameters on the microstructural development and mechanical performance of the scaffolds, characterized through scanning electron microscopy and ring-on-ring mechanical testing. Slurry composition and casting parameters such as solids loading, casting speed, tape angle, and temperature gradients have been modified to determine the impact on density, lamellar morphology, and final load-bearing performance.

ceramics↗

Ultrafast Formation of Charge Transfer Trions at Molecular‐Functionalized 2D MoS 2 Interfaces

In this work, we investigate trion dynamics occurring at the heterojunction between organometallic molecules and a monolayer transition metal dichalcogenide (TMD) with transient electronic sum frequency generation (tr-ESFG) spectroscopy. By pumping at 2.4 eV with laser pulses, we have observed an ultrafast hole transfer, succeeded by the emergence of charge-transfer trions. This observation is facilitated by the cancellation of ground state bleach and stimulated emission signals due to their opposite phases, making tr-ESFG especially sensitive to the trion formation dynamics. The presence of charge-transfer trion at molecular functionalized TMD monolayers suggests the potential for engineering the local electronic structures and dynamics of specific locations on TMDs and offers a potential for transferring unique electronic attributes of TMD to the molecular layers.

Time-resolved↗

Structural inversion asymmetry in epitaxial ultrathin films of Bi(111)/InSb(111)B

Bismuth (Bi) films hold potential for spintronic devices due to strong spin-orbit coupling. Understanding the growth, surface states, and interactions with the substrate is key to their functionalization. Large-area high-quality (111) Bi ultrathin films were grown on InSb (111)B substrates by molecular beam epitaxy (MBE). Strong film-substrate interactions epitaxially stabilize the (111) orientation and lead to nonequivalent interface potentials. Analysis of angle-resolved photoemission spectroscopy (ARPES) measurements, employed to characterize the evolution of the surface states with film thickness, indicate a crossing at the $\overline{M}$ point, suggesting a topologically trivial phase in the thin film. In conclusion, the results show the presence of interfacial bonds to the substrate breaks inversion symmetry, preventing the semimetal-to-semiconductor transition predicted for freestanding bismuth layers, highlighting the importance of controlled functionalization and surface passivation of two-dimensional materials.

Inbar, Hadass S. [Univ. of California, Santa Barba↗

Structure and Dynamics of CO 2 at the Air–Water Interface from Classical and Neural Network Potentials

The accurate description of the structure and dynamics of CO 2 at the instantaneous air–water interface, along with the effects of surface fluctuations on the CO 2 -transport processes, is essential for the development of negative emission technologies aimed at minimizing climate change. In this study, we performed molecular dynamics simulations of CO 2 at the air–water interface using neural network potentials (NNPs) trained on ab initio data generated through density-functional-theory-based molecular dynamics simulations. We compared these results with classical force fields to assess their performance in modeling interfacial CO 2 behavior. Our findings revealed that the asymmetric interactions, coupled with thermal surface fluctuations at the air–water interface, significantly influence CO 2 transport into the aqueous phase. The simulations demonstrate that classical force fields underestimate both the free energy of CO 2 transport and the strength of its interactions at the interface compared with the neural network potentials. In conclusion, the free energy and the interfacial dynamics of CO 2 are primarily influenced by the distribution of water within the instantaneous interfacial water layer, responsible for creating an asymmetric intermolecular interaction environment within the interfacial region.

Ab initio molecular dynamics↗

Operando methods: A new era of electrochemistry

One of the grand challenges facing electrochemistry is to directly resolve the complex nature of (electro)catalyst active sites and capture real-time “movies” of reaction dynamics, i.e. “watching chemistry in action”. The need for such fundamental understanding has stimulated the development of operando/in situ methods, which have greatly enhanced our ability to identify activity descriptors of electrocatalysts and establish structure–property relationships of energy materials. Here, this review summarizes the frontiers of operando electrochemical liquid-cell scanning transmission electron microscopy and correlative synchrotron X-ray methods, which are complementary tools to comprehensively investigate reaction dynamics across multiple spatiotemporal scales. In an effort to encourage greater adoption of advanced operando methods by the general electrochemistry community, this review points out the need to benchmark electrochemistry in confined and heterogenous liquid environment with minimal beam-induced damage. We anticipate that multimodal operando methods will become indispensable for understanding interfacial reaction mechanisms for the broad chemistry and energy materials communities.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A fresh perspective on the role of band bending, and related contributors, in light-driven production of electricity and chemicals

It is widely known that semiconductor-based solar energy conversion could power our planet. This is in part because high-quality semiconductor structures are unrivalled in their ability to separate photogenerated electrons and holes. One effective approach to achieving this photoinduced charge separation relies on a phenomenon known as “band bending”. But details to justify why band bending results in photoinduced charge separation are more complex than often appreciated. This underappreciation is an impediment to the rational, hypothesis-driven design of next-generation approaches to solar energy conversion. Herein we show, by means of derivations rooted in physical chemistry, that several phenomena – not just band bending – can facilitate photoinduced charge separation, and that each is influenced by nonequilibrium species concentration and a parameter, such as diffusion coefficient or rate coefficient, that introduces dynamics. To help visualize the impact of each phenomenon, we introduce plots that depict their contributions as free energy, force, flux, force constant, and rate. We reveal that spatial dopant distributions that define band bending are predictors of initial photogenerated species transport rates. But charge separation alone does not guarantee high-efficiency operation. A photogenerated change in energy that is freely available to do useful work is also essential, and is strongly dependent on semiconductor optical properties and reaction kinetics. Notably, this information reveals that specificity of interfacial chemical reactions – even when they are not preceded by charge separation elsewhere – can result in efficient solar energy conversion. We expect that this tutorial will guide researchers in their pursuit to uncover new mechanisms for light to perform useful work.

14 SOLAR ENERGY↗

Biologically inspired reinforcement using polydopamine of polymer bound composites

Interfacial strength plays a critical role in the mechanical properties of a composite system. In this work, a proven mock high explosive (HE), 5-iodo-2’-deoxyuridine (IDOX) was coated by the adhesive promoting polymer polydopamine (PDA), then formulated with an Estane binder system to form an improved HE mock composite. An extensive comparison study of mechanical properties was performed to determine the effects, if any, of PDA on the composite system. To aid in interpretation of the mechanical test data, neutron reflectometry experiments were performed to determine the thickness and structure of the as deposited PDA films. The mechanical performance of PDA-treated IDOX was then compared to untreated specimens by compression testing in the Brazilian disk geometry. The results strongly suggested that the structure of PDA consists of two layers: one low in density caused by polymer agglomerates attaching to the substrate during polymerization, and the second high in density caused by controlled linear deposition of polydopamine. Finally, the mechanical testing showed that PDA greatly increased the stiffness and yield strength of IDOX based mocks without causing any disruption to the underlying crystal system.

42 ENGINEERING↗

Heavily neodymium doped ceria as an effective barrier layer in solid oxide electrochemical cells

10 mol% gadolinium doped ceria (GDC10) is widely used as a barrier layer between oxygen electrode and electrolyte to prevent interfacial reactions. A 50 mol% neodymium doped ceria (NDC50) barrier layer has been proposed and studied in this paper. Symmetrical cells with NDC50 and GDC10 barrier layers, Nd 2 NiO 4+δ (NNO)–Ce 0.5 Nd 0.5 O 2-δ (NDC50) electrode, and YSZ electrolyte have been systematically studied using impedance spectroscopy (EIS) at various temperatures and oxygen partial pressure (pO 2 ). The NDC50 barrier layer has significantly decreased polarization resistance across a wide temperature and pO 2 range compared to the GDC10 barrier layer. The rare earth C-type structure of the NDC50 barrier layer causes barrier free migration of oxygen ions resulting in improved ionic conductivity compared to GDC10. Finally, distribution of relaxation time (DRT) modeling has been used to obtain insights into the electrode processes.

08 HYDROGEN↗

Ionic liquid mediated one-step perpendicular assembly in block copolymer thin films for ultrafiltration membrane applications

The rapid rise of oil and gas, petrochemical, food processing, and pharmaceutical industries has added a complex mixture of contaminants like oil, particulates, metals, and other organic compounds to wastewater. Multipurpose membranes with precise pore structure can offer a solution to this problem and block copolymers (BCP) can be used to achieve such structures. Achieving vertical assembly of BCP domains provides a perfect template for developing uniform through film channels for separation and transport of material, besides being useful for the rectification of defects in photolithography patterns. Producing such morphologies may require extensive film/substrate processing and is not always feasible for scale-up. With this article, we demonstrate a facile solution casting method to induce vertical domain assembly in as-cast diblock copolymer thin films in the presence of an ionic liquid (IL) additive that preferentially segregates to one block and neutralizes interfacial interactions. We also show the tunability of domain sizes by controlling the additive concentration. These vertically aligned morphologies are important for the development of next-generation lithographic techniques and form excellent templates for ultrafiltration membranes with uniform pore sizes. In conclusion, this article demonstrates how IL additives can be used to obtain stable non-equilibrium morphologies in as-cast BCP films and the effect of BCP molecular mass, block volume fractions, and IL content on self-assembly.

59 BASIC BIOLOGICAL SCIENCES↗

Synergistic Coupling Effect of Electronic Conductivity and Interphase Compatibility on High-Voltage Na 3 V 2 (PO 4 ) 2 F 3 Cathodes

Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has been considered an up-and-coming cathode material candidate for sodium (Na) ion batteries in light of its high specific capacity and working voltage. However, an erratic cathode/electrolyte interface layer is inevitably formed, accompanied by continuous electrolyte decomposition on the NVPF surface, when the voltage exceeds 4.2 V vs Na + /Na. Herein, the interphase features of NVPF are obviously enhanced owing to the ameliorated electronic conductivity obtained by combining it with carbon nanotubes (CNT). The NVPF with 3 wt % CNT (NVPF@3% CNT) reduces the Na + diffusion kinetic energy barrier and electron transport resistance. Furthermore, the conducting network formed by CNT with sturdy structure strength can promptly accommodate the volumetric changes during sequential Na + extraction/insertion and thus effectively improve the long-term cyclic performance of NVPF/hard carbon full cells. The initial discharge capacity approaches 105 mA h g –1 at 0.5C, and it retains 94% capacity retention after 200 cycles at the temperature of –10 °C. The cathode/electrolyte interphase characterization results further demonstrate that the interphase layer on the NVPF@3% CNT cathode is thinner and more compact compared with pristine samples. Here, this research provides a competitive strategy to facilitate the interfacial compatibility between the NVPF and electrolytes and accelerate the commercialization of high-performance Na-ion batteries.

25 ENERGY STORAGE↗