Effect of Carbon Dioxide on the Degradation of Chemical Warfare Agent Simulant in the Presence of Zr Metal Organic Framework MOF-808
Abstract not provided
Plonka, Anna M.↗
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PySIDT: Subgraph Isomorphic Decision Trees for Molecular Property Prediction
Accurate molecular property prediction is important across all fields of chemistry. Deep neural networks (DNNs) have become increasingly popular due to their ability to train automatically, avoiding the incredibly tedious process of constructing and extending traditional property estimation schemes. However, DNNs require large amounts of training data, are challenging to interpret, require large amounts of memory to load even during inference, and have severe difficulties incorporating qualitative chemical knowledge, which are often desired for molecular property prediction tasks. Here, in this study, we present PySIDT (https://github.com/zadorlab/PySIDT), a software for training and running inference on Subgraph Isomorphic Decision Trees (SIDTs). SIDTs are graph-based decision trees made of nodes associated with molecular substructures. Inference is done by descending target molecular structures down the decision tree to nodes with matching subgraph isomorphic substructures and making predictions based on the final (most specific) nodes matched. SIDTs scale down well to dataset sizes much smaller than is feasible for DNNs. As trees of molecular substructures, SIDTs are inherently readable and easy to visualize, making them easy to analyze. They are also straightforward to extend and retrain, facilitate uncertainty estimation, and enable easy integration of expert knowledge. We demonstrate the SIDT approach discussing its application to a diverse range of molecular prediction tasks: rate coefficient estimation, diffusion coefficient estimation, thermochemistry estimation, transition state bond stretch prediction, p K a prediction, stability of molecular structures, stability of surface structures, and prediction of surface lateral interaction energetics. Additionally, we demonstrate the power of the SIDT algorithms in two direct learning curve vanilla comparisons with the popular DNN-based software Chemprop and the popular gradient boosted trees-based software XGBoost on enthalpy of formation and rate coefficient prediction tasks. In particular, in the enthalpy of formation case, vanilla PySIDT is able to outperform vanilla Chemprop and XGBoost across the full range of training/validation set sizes out to 11,560 data points.
Johnson, Matthew Sean [Sandia National Laboratorie↗
Structure and Thermodynamic Stability of Zeolitic Imidazolate Framework Surfaces
Extensive efforts over the last several decades have focused on the possibility of “crystal engineering” metal–organic framework (MOF) materials with bulk properties tailored toward specific applications. However, beyond their bulk structure, MOF interfaces and surfaces can also play an important role in governing the materials properties relevant to many applications, including both interfacial mass and/or charge transport. We presently examine the diversity of stable surface structures/terminations of zeolitic imidazolate frameworks (ZIFs), a subclass of MOFs, under a variety of conditions that are characteristic of either gas-phase, “post-synthetic” conditions (relevant to many MOF applications) or solution-phase conditions (typical of those used during MOF synthesis). We construct surface phase diagrams to predict the most stable ZIF surface terminations as a function of external parameters (including temperature, adsorbate pressures, and pH), making explicit comparison against prior experimental observations, when possible. Overall, we find that the resulting phase diagrams can be used to explain the results of prior experimental studies of ZIF terminations across a variety of conditions and provide important insights into the factors that govern the structure of ZIF interfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tunable Stabilization of Cuprous Ions via Kinetic and Thermodynamic Control of Cu Electrodeposition in Non-Aqueous Media
In this work, significant stabilization of Cu + ions is achieved in non-aqueous electrolytes containing TFSI - and Cl - anions with diglyme as solvent. When Cl - is absent, stabilization of Cu + occurs due to the very low stability constant of Cu 2+ in diglyme. However, in the presence of relatively low Cl - concentrations (i.e., equimolar relative to Cu 2+ ), both Cu + and Cu 2+ form extremely stable Cu 2+ / + [Cl - ] complexes resulting in a similar to 1200 mV negative shift of the Cu + /0 redox couple relative to that of more easily reduced Cu + [TFSI - ][Cl - ] complexes. Furthermore, these results suggest that the lower solvation energies and wider electrochemical stability windows of non-aqueous solvents relative to water enable anions to play a much more significant role in guiding complexation behavior-providing new possibilities for (electro)chemical stabilization of reactive intermediates and highlighting the wealth of unexplored opportunities for electrolyte design in non-aqueous systems.
Anion Association↗
Essential Role of Spinel ZnFe 2 O 4 Surfaces during Lithiation
Spinel zinc ferrite (ZnFe 2 O 4 ) is a well-known anode material in lithium ion batteries (LIBs) due to its large theoretical capacity. However, the high potentials observed at the initial stage of lithiation observed cannot be captured using a model of Li + intercalation into the stoichiometric ZnFe 2 O 4 bulk. Here, using density functional theory (DFT) we report for the first time that theZnFe 2 O 4 surfaces are responsible for the measured initial potentials. Among the three identified stable surfaces, ZnFeO 2 -terminated ZnFe 2 O 4 (1 1 0), O-terminated ZnFe 2 O 4 (1 1 1) and Zn-terminated ZnFe 2 O 4 (1 1 1), both (1 1 1) surfaces display higher lithiation potentials than the (1 1 0) surface, and the estimated potentials based on Zn-terminated (1 1 1) fit well with the experimental observations, while using the models based on ZnFe 2 O 4 (1 1 0) and previously ZnFe 2 O 4 bulk, the estimated potentials are much lower. In terms of Li + diffusion, the Zn-terminated ZnFe 2 O 4 (1 1 1) surface is the most active, where the energetically favorable saturation of Li + on the surface is able to facilitate the process. Our results provide a new strategy for the design of LIB materials, via controlling the particle shape and the associated surface characteristics thus enhancing the discharging performance.
25 ENERGY STORAGE↗
Pathways for practical high-energy long-cycling lithium metal batteries
Lithium (Li)-ion batteries play a critical role in modern day technologies, but their specific energy (Wh kg-1) and energy density (Wh L-1) are approaching the maximum practically achievable values based on existing manufacturing processes with the conventional cathode and anode materials. Developing the next generation rechargeable batteries with a specific energy higher than 300 Wh kg-1, up to 500 Wh kg-1, is a significant challenge. This paper discusses the pathways to build the next generation 500 Wh kg-1 rechargeable Li battery based on Li metal anode and a high nickel-content lithium nickel-manganese-cobalt oxide (high-Ni NMC) cathode. The fundamental requirements and practical technical approaches will be explored to hopefully address this grand challenge. In particular, we discuss the detailed cell level requirements and parameters to achieve high energy density, as well as the significant scientific challenges and potential solutions, including but not limited to enable the direct utilization of Li metal anode with high efficiency and long-term cycling stability, dendrite-free Li metal deposition, high utilization of the cathode materials with high mass loading and reasonable electrode thickness along with minimum parasitic weight in the cathode side. The cell level understanding and validation of the materials properties for high performance and control of interfacial reactions across the whole cell will be explored. New concepts in emerging multifunctional materials and electrolytes/additives and their implications will also be discussed.
lithium metal anode, lithium nickel manganese coba↗
Non-iridium-based electrocatalyst for durable acidic oxygen evolution reaction in proton exchange membrane water electrolysis
Iridium-based electrocatalysts remain the only practical anode catalysts for proton exchange membrane (PEM) water electrolysis, due to their excellent stability under acidic oxygen evolution reaction (OER), but are greatly limited by their high cost and low reserves. Here, in this study, we report a nickel-stabilized, ruthenium dioxide (Ni-RuO 2 ) catalyst, a promising alternative to iridium, with high activity and durability in acidic OER for PEM water electrolysis. While pristine RuO 2 showed poor acidic OER stability and degraded within a short period of continuous operation, the incorporation of Ni greatly stabilized the RuO 2 lattice and extended its durability by more than one order of magnitude. When applied to the anode of a PEM water electrolyser, our Ni-RuO 2 catalyst demonstrated >1,000 h stability under a water-splitting current of 200 mA cm -2 , suggesting potential for practical applications. Density functional theory studies, coupled with operando differential electrochemical mass spectroscopy analysis, confirmed the adsorbate-evolving mechanism on Ni-RuO 2 , as well as the critical role of Ni dopants in stabilization of surface Ru and subsurface oxygen for improved OER durability.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Understanding why poly(acrylic acid) works: decarbonylation and cross-linking provide an ionically conductive passivation layer in silicon anodes
Poly(acrylic acid) (PAA) is commonly used as a binder for fabricating silicon (Si) anode active materials in lithium-ion batteries due to its useful properties including high polar solvent solubility, good rheology, and strong adhesive properties. However, the role and evolution of PAA during electrode fabrication, cycling, and calendar aging are not well understood. In this work, we reveal the evolution of PAA during electrode curing and relate its chemical change to the final electrode properties and performance. These studies are made possible using two types of in situ attenuated total reflectance-infrared Fourier transform (ATR-FTIR) spectroscopy: thermal ATR-FTIR to probe the cross-linking reaction, and ATR-FTIR spectroelectrochemistry of three-dimensional composite electrodes, a unique technique developed herein that probes the solvation dynamics of lithium ions at the silicon anode interface under electrochemical polarization. Specifically, we show that PAA undergoes a thermally-mediated, cross-linking decarbonylation reaction to form an ether-based network polymer. To show the importance of the polyether moieties, we synthesize partially esterified PAA analogues that do not undergo this cross-linking decarbonylation reaction and correlate the degree of cross-linking to half-cell performance metrics. Finally, we unveil the mechanism of the polyether binder performance through in situ ATR-FTIR spectroelectrochemistry and show that PAA acts as an interfacial material that conducts lithium-ions, limits solvent molecule access to the Si surface, and stabilizes the electrode against parasitic lithium inventory loss at high state of charge for an extended period of time.
25 ENERGY STORAGE↗
Role of perturbed parallel magnetic field effects in predicting turbulent transport in NSTX
This study presents analysis of gyrokinetic simulations on the National Spherical Torus Experiment (NSTX) to investigate the effects of electromagnetic fields on plasma turbulence and transport. The simulations, performed with varying levels of fidelity using the gyrokinetic CGYRO code, include electrostatic (ES), single-field electromagnetic (EM1), and two-field electromagnetic (EM2) models. A detailed comparison across the simulation database reveals that electromagnetic effects increase both predicted growth rates and quasilinear fluxes, with EM2 simulations producing stronger turbulence than ES and EM1 cases. Quasilinear modeling using QLGYRO demonstrates that while the perturbed parallel magnetic field (δB ∥ ) does not drastically affect the total flux at experimental gradients, it leads to a shift in the dominant instability, altering mode structures from microtearing to kinetic ballooning modes (KBMs). The proximity of the plasma profiles to the KBM threshold is explored, with the experimental conditions being near the onset of KBM-driven transport. The KBM, with its large growth rates, is identified as a potential driver of electron temperature flattening, as it can rapidly transport heat across flux surfaces. Performing stability analysis shows core-localized unstable a low- mode that could contribute to the flattening at the early times of the discharge. TGYRO predictive modeling, incorporating both TGLF and QLGYRO, indicates that the inclusion of δB ∥ significantly improves the accuracy of temperature profile predictions in NSTX high-beta plasmas, although challenges remain in modeling the sharp flux discontinuities caused by KBM-driven instabilities.
70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
Holistic energy landscape management in 2D/3D heterojunction via molecular engineering for efficient perovskite solar cells
Constructing two-dimensional (2D) perovskite atop of 3D with energy landscape management is still a challenge in perovskite photovoltaics. Here, we report a strategy through designing a series of π-conjugated organic cations to construct stable 2D perovskites and to realize delicate energy level tunability at 2D/3D heterojunctions. As a result, the hole transfer energy barriers can be reduced both at heterojunctions and within 2D structures, and the preferable work function shift reduces charge accumulation at interface. Leveraging these insights and also benefitted from the superior interface contact between conjugated cations and poly(triarylamine) (PTAA) hole transporting layer, a solar cell with power conversion efficiency of 24.6% has been achieved, which is the highest among PTAA-based n-i-p devices to the best of our knowledge. The devices exhibit greatly enhanced stability and reproducibility. This approach is generic to several hole transporting materials, offering opportunities to realize high efficiency without using the unstable Spiro-OMeTAD.
14 SOLAR ENERGY↗
Rational Selection of Sodium Layered Oxides for High Performance Na-Ion Batteries: P2 vs O3 vs P2-O3 Intergrowths
Sodium ion batteries (NIBs) are gaining importance as an energy storage technology complementary to the Li-ion batteries. In this regard, sodium-based layered oxides are recognized as one of the most suitable positive electrode candidate for NIBs, but vast variety of their chemical compositions and crystal structures complicates the selection of the best material. To shed light on different figures of merit that control the selection of layered oxide material for NIB applications, we compare here a P2, P2-O3 intergrowth and two O3 sodium layered oxides composed of the same transition metals (Ni, Mn, Ti and Zn) but in differing stoichiometries. The results show that the new P2-type Na 0.67 Ni 0.3 Zn 0.03 Mn 0.52 Ti 0.15 O 2 phase reported here combines most of the advantages, such as stability towards moisture, reduced surface reactivity, better thermal stability and high rate capability, which are essential for commercialization, except for a limited capacity (∼125 mAh g −1 ) compared to the O3 NaNi 0.45 Zn 0.05 Mn 0.4 Ti 0.1 O 2 phase (∼180 mAh g −1 ), reported by our group previously. Altogether, this work enlarges the family of attractive Na-based positive electrodes and teaches us that we should not solely be obsessed with the capacity of a material to decide of its applicability.
Electrochemistry↗
Low-energy electron diffraction and photoelectric study of /110/ tantalum as a function of ion bombardment and heat treatment.
Electron diffraction and photoelectric study of crystal surface structure stability of tantalum subjected to ion bombardment and heat treatment
METAL CRYSTAL↗
Longitudinal dynamics of liquid filled elastic shells
Longitudinal dynamics of liquid filled elastic shells - interaction liquid and elastic tank, liquid surface instability, and bubble dynamics
ELASTIC SHELL↗
Impurities and interface states in the SiO2/Si system Final report
Impurities and interface states in silicon dioxide-silicon system
IMPURITY↗
Surface effects in semiconductors due to evaporation techniques
Fabrication induced surface instabilities in semiconductor devices
SEMICONDUCTOR DEVICE↗
Water landing characteristics of a model of a winged reentry vehicle
Proposed manned space shuttle vehicles are expected to land on airport runways. In an emergency situation, however, the vehicle may be required to land on water. A 1/10-scale dynamic model of a winged reentry vehicle was investigated to determine the water landing characteristics. Two configurations of the proposed vehicle were studied. Configuration 1 had a 30 deg negative dihedral of the stabilizer-elevon surface whereas configuration 2 had a 30 deg positive dihedral. Results indicate that the maximum normal accelerations for configurations 1 and 2 when landing in calm water were approximately 8g and 6g, respectively, and the maximum longitudinal accelerations were approximately 5g and 3g, respectively. A small hydroflap was needed to obtain satisfactory calm-water landings with configuration 2, whereas configuration 1 gave good landings without a hydroflap. All landings made in rough water resulted in unsatisfactory motions. For landings made in three different wave sizes, both configurations dived. The maximum normal accelerations for configurations 1 and 2 when landing in waves were -10.1g and -18.7g, respectively, and the maximum longitudinal accelerations for both configurations were approximately 13g.
Stubbs, S. M.↗
Dye penetrant indications caused by superficial surface defects in 2014 aluminum alloy welds.
Demonstration that dye penetrant indications on the heat-affected zone of 2014-T6 aluminum GMA weldments are frequently caused by superficial surface conditions and are less than 0.007 in. deep. The following methods are suggested for minimization of these surface defects: stabilization of the arc, application of dc ?GTA' welding procedures, reduction of the caustic etch time, and use of fine grain materials.
Hocker, R. G.↗
Decision surface estimate of nonlinear system stability domain by Lie series method.
The Lie series recursive algorithm for Zubov's partial differential equation is used to generate two sets of points, where one represents the exact asymptotic stability boundary of an equilibrium state of the nonlinear system under consideration and the other is interior to it. Based on these two sets of data as training samples of two classes, a decision hypersurface can be determined such that it is a close approximation of the asymptotic stability boundary.
Kormanik, J.↗