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At least 289 records · Page 16

Structural Evolution of Mixed-Addenda Keggin Polyoxometalate Anions with Atom-by-Atom Substitution

Polyoxometalates (POMs) are molecular metal oxides with distinctive electronic properties that make them promising materials for applications in energy, sensors, and memory devices. One of the most promising methods of tuning the stability, photochromic, redox, and electron-spin properties of POMs is through the substitution of the metal “addenda” atoms that, along with oxygen, constitute their cage-like structures. Because traditional synthesis methods typically produce a distribution of POMs, the isolation and characterization of multimetallic POMs with predetermined stoichiometry remains challenging. The presence of multiple energetically accessible isomers further complicates the experimental characterization and theoretical modeling of multimetallic POMs. Herein, we leverage the distinguishing mass-selection capabilities of ion soft landing to prepare stoichiometrically selected Keggin PMo x W 12-x O 40 3- (x = 0 – 6, 8, 10, and 12) POMs on self-assembled monolayer surfaces free of the solvent molecules and counterions that often confound characterization of complex species at interfaces. The structures of the supported POMs are characterized with atom-by-atom precision using in situ infrared (IR) reflection absorption spectroscopy complemented by detailed density functional theory calculations. Our joint experimental and theoretical results reveal an almost linear shift in the positions of the IR bands towards lower wavenumbers with an increase in the number of lighter molybdenum atoms compared to heavier W atoms in PMoxW 12-x O 40 3- . The theoretical calculations also indicate that numerous isomeric structures may be populated at the experimental conditions and, consequently, contribute to the overall IR spectra. In conclusion, our findings indicate that in addition to the number of substituted addenda atoms and the presence of multiple isomeric structures, interactions with the surface play an important role in determining the IR spectra and structure of supported bimetallic POMs.

Prabhakaran, Venkateshkumar [Pacific Northwest Nat↗

Uptake of N 2 O 5 by aqueous aerosol unveiled using chemically accurate many-body potentials

The reactive uptake of N 2 O 5 to aqueous aerosol is a major loss channel for nitrogen oxides in the troposphere. Despite its importance, a quantitative picture of the uptake mechanism is missing. Here we use molecular dynamics simulations with a data-driven many-body model of coupled-cluster accuracy to quantify thermodynamics and kinetics of solvation and adsorption of N 2 O 5 in water. The free energy profile highlights that N 2 O 5 is selectively adsorbed to the liquid–vapor interface and weakly solvated. Accommodation into bulk water occurs slowly, competing with evaporation upon adsorption from gas phase. Leveraging the quantitative accuracy of the model, we parameterize and solve a reaction–diffusion equation to determine hydrolysis rates consistent with experimental observations. We find a short reaction–diffusion length, indicating that the uptake is dominated by interfacial features. The parameters deduced here, including solubility, accommodation coefficient, and hydrolysis rate, afford a foundation for which to consider the reactive loss of N 2 O 5 in more complex solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Observation of Photoexcited Charge Carrier Dynamics and Electrostatic Fields at Photocatalytic Semiconductor/liquid Interfaces

Photoelectrochemical conversion of solar energy to fuels at semiconductor-liquid interfaces involves a complex set of processes, which include band bending, built-in electric fields, surface recombination of photoexcited carriers, and ultimately charge transfer to the ions in solution, in which the electrostatic fields within the depletion region of the semiconductor plays an important role. There are loss mechanisms associated with each of these key components in the overall photoelectrochemical conversion efficiency. Direct probe of these elementary processes is key to the rational improvement of photoeletrochemical cells and electrodes. In this collaborative project, Tianquan Lian at Emory University, Steve Cronin at University of Southern California and their students and postdoctoral fellows carried out a series of studies that are aimed at direct observation of photoexcited charge carrier dynamics at photocatalytic semiconductor/liquid interfaces. The collaborative work led to the development of transient reflectance spectroscopy as a tool for in situ probing of carrier dynamics in planar photoelectrode/electrode interface; and the demonstration that this tool can be used to study oxide protected GaP to identify key efficiency limiting factors in these photoelectrodes. This work has led to the development a tool for in situ probing of carrier dynamics in planar photoelectrodes, which will facilitate the mechanistic study of photoelectrochemical cells. This work informs the development of better photoelectrode materials for solar water splitting and CO 2 reduction. This work has contributed to the training of three PhD students in the area of photoelectrochemistry, ultrafast spectroscopy and solar energy conversion

14 SOLAR ENERGY↗

Tocopherol controls D1 amino acid oxidation by oxygen radicals in Photosystem II

Photosystem II (PSII) is an intrinsic membrane protein complex that functions as a light-driven water:plastoquinone oxidoreductase in oxygenic photosynthesis. Electron transport in PSII is associated with formation of reactive oxygen species (ROS) responsible for oxidative modifications of PSII proteins. In this study, oxidative modifications of the D1 and D2 proteins by the superoxide anion (O 2 •- ) and the hydroxyl (HO•) radicals were studied in WT and a tocopherol cyclase (vte1) mutant, which is deficient in the lipid-soluble antioxidant α-tocopherol. In the absence of this antioxidant, high-resolution tandem mass spectrometry was used to identify oxidation of D1: 130 E to hydroxyglutamic acid by O 2 •- at the Pheo D1 site. Additionally, D1: 246 Y was modified to either tyrosine hydroperoxide or dihydroxyphenylalanine by O 2 •- and HO • , respectively, in the vicinity of the nonheme iron. We propose that α-tocopherol is localized near PheoD1 and the nonheme iron, with its chromanol head exposed to the lipid–water interface. This helps to prevent oxidative modification of the amino acid’s hydrogen that is bonded to PheoD1 and the nonheme iron (via bicarbonate), and thus protects electron transport in PSII from ROS damage.

59 BASIC BIOLOGICAL SCIENCES↗

The Molybdenum Oxide Interface Limits the High-Temperature Operational Stability of Unencapsulated Perovskite Solar Cells

Here, we report on the improved operational stability of unencapsulated perovskite solar cells (PSCs) aged in an ambient atmosphere at elevated temperatures (70 °C) for >1000 h under constant illumination and bias at 30–50% relative humidity. We identify a previously unseen interfacial degradation mechanism concerning the use of a MoO x interlayer, which was originally added to increase operational stability. Specifically, the hole-transport layer/MoO x interface buckles under illumination at 70 °C, which leads to delamination and rapid losses of short-circuit current density corresponding to an average $t_{80}$ of ~55 h. By judiciously evaluating various hole-transport layers, interlayers, and contacts, we find that replacing the MoO x with a VO x interlayer, regardless of the other components in the solar cell, alleviates this buckling issue due to its higher activation barrier toward crystallization, leading to significant gains in PSC operational stability. Unencapsulated devices aged in an ambient atmosphere with a VO x interlayer retain 71% of their initial PCE on average after constant illumination and bias at 70 °C for 1100 h ($t_{80}$ ~ 645 h). Currently, this is the highest temperature reported for the operational stability of unencapsulated n-i-p PSCs aged in air. Identification of a new facet of the complex degradation mechanisms in PSCs will allow for targeted acceleration testing to speed the deployment of low-cost, long-lasting electricity generation under realistic operating temperatures.

14 SOLAR ENERGY↗

Triiodide Attacks the Organic Cation in Hybrid Lead Halide Perovskites: Mechanism and Suppression

Molecular I 2 can be produced from iodide-based lead perovskites under thermal stress; triiodide, I 3 − , is formed from this I 2 and I − . Triiodide attacks protic cation MA + - or FA + -based lead halide perovskites (MA + , methylammonium; FA + , formamidinium) as explicated through solution-based nuclear magnetic resonance (NMR) studies: triiodide has strong hydrogen-bonding affinity for MA + or FA + , which leads to their deprotonation and perovskite decomposition. Triiodide is a catalyst for this decomposition that can be obviated through perovskite surface treatment with thiol reducing agents. In contrast to methods using thiol incorporation into perovskite precursor solutions, no penetration of the thiol into the bulk perovskite is observed, yet its surface application stabilizes the perovskite against triiodide-mediated thermal stress. Thiol applied to the interface between FAPbI 3 and Spiro-OMeTAD (“Spiro”) prevents oxidized iodine species penetration into Spiro and thus preserves its hole-transport efficacy. Surface-applied thiol affects the perovskite work function; it ameliorates hole injection into the Spiro overlayer, thus improving device performance. It helps to increase interfacial adhesion (“wetting”): fewer voids are observed at the Spiro/perovskite interface if thiols are applied. Perovskite solar cells (PSCs) incorporating interfacial thiol treatment maintain over 80% of their initial power conversion efficiency (PCE) after 300 h of 85 °C thermal stress.

36 MATERIALS SCIENCE↗

Edge-Functionalized Graphene Nanoribbon Encapsulation To Enhance Stability and Control Kinetics of Hydrogen Storage Materials

Hydrogen is a long-term clean energy carrier that enables completely carbon-free energy production. However, practical implementation of hydrogen fuel technologies is restricted because of lack of safe and high-performing storage materials. Here, we report Mg nanocrystals encapsulated by narrow, bottom-up synthesized graphene nanoribbons (GNRs) as environmentally stable and high-capacity hydrogen storage materials. As an encapsulation medium, GNRs offer similar functionalities as reduced graphene oxide to protect the encapsulated Mg nanocrystals from extensive oxidation, while allowing penetrations of hydrogen. In addition, the GNRs can be edge functionalized to tune the (de-)hydrogenation kinetics, in particular for the processes occurred at the GNR–Mg interfaces. In this work, four different types of edge-functional groups were introduced into GNRs with the goal of comparing their cycling performances because of edge functionalization. On the basis of detailed kinetic analysis coupled with first-principles calculations, we propose that edge-functional groups can contribute to the reduction of kinetic barriers for surface hydrogen reactions at the interface with the GNR by stabilizing surface defects. Furthermore, the GNR–Mg composite exhibited higher hydrogen storage capacity (7.1 wt % of hydrogen based on the total composite) compared with the current literature while demonstrating long-term air stability. This work suggests that the rational design of edge-functional groups in graphene derivatives can provide a general and novel paradigm for simultaneous encapsulation and hydrogen storage catalysis in simple metal or complex metal nanocrystals.

08 HYDROGEN↗

Deciphering the Cofilin Oligomers via Intermolecular Disulfide Bond Formation: A Coarse-Grained Molecular Dynamics Approach to Understanding Cofilin’s Regulation on Actin Filaments

Cofilin, a key actin-binding protein, orchestrates the dynamics of the actomyosin network through its actin-severing activity and by promoting the recycling of actin monomers. Recent experimental work suggests that cofilin also forms functionally distinct oligomers through thiol post-translational modification (PTM) that encourages actin nucleation and assembly. Despite these advances, the structural conformations of cofilin oligomers that modulate actin activity remain elusive because there are combinatorial ways to oxidize thiols in cysteines to form disulfide bonds rapidly. This study employs molecular dynamics simulations to investigate human cofilin 1 as a case study for exploring cofilin dimers via disulfide bond formation. Using the free energy profiling, our simulations unveil a range of probable cofilin dimer structures not represented in current Protein Data Bank entries. These candidate dimers are characterized by their distinct population distributions and relative free energies. Of particular note is a dimer featuring an interface between cysteines 139 and 147 residues, which demonstrates stable free energy characteristics and intriguingly symmetrical geometry. In contrast, the experimentally proposed dimer structure exhibits a less stable free energy profile. Here, we also evaluate frustration quantification based on the energy landscape theory in the protein-protein interactions at the dimer interfaces. Notably, the 39-39 dimer configuration emerges as a promising candidate for forming cofilin tetramers, as substantiated by frustration analysis. Additionally, docking simulations with actin filaments further evaluate the stability of these cofilin dimer-actin complexes. Our findings thus offer a computational framework for understanding the role of thiol post-translational modification cofilin proteins in regulating oligomerization, and the subsequent cofilin-mediated actin dynamics in the actomyosin network.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Supercomputing Aspects for Simulating Incompressible Flow

The primary objective of this research is to support the design of liquid rocket systems for the Advanced Space Transportation System. Since the space launch systems in the near future are likely to rely on liquid rocket engines, increasing the efficiency and reliability of the engine components is an important task. One of the major problems in the liquid rocket engine is to understand fluid dynamics of fuel and oxidizer flows from the fuel tank to plume. Understanding the flow through the entire turbo-pump geometry through numerical simulation will be of significant value toward design. One of the milestones of this effort is to develop, apply and demonstrate the capability and accuracy of 3D CFD methods as efficient design analysis tools on high performance computer platforms. The development of the Message Passage Interface (MPI) and Multi Level Parallel (MLP) versions of the INS3D code is currently underway. The serial version of INS3D code is a multidimensional incompressible Navier-Stokes solver based on overset grid technology, INS3D-MPI is based on the explicit massage-passing interface across processors and is primarily suited for distributed memory systems. INS3D-MLP is based on multi-level parallel method and is suitable for distributed-shared memory systems. For the entire turbo-pump simulations, moving boundary capability and efficient time-accurate integration methods are built in the flow solver, To handle the geometric complexity and moving boundary problems, an overset grid scheme is incorporated with the solver so that new connectivity data will be obtained at each time step. The Chimera overlapped grid scheme allows subdomains move relative to each other, and provides a great flexibility when the boundary movement creates large displacements. Two numerical procedures, one based on artificial compressibility method and the other pressure projection method, are outlined for obtaining time-accurate solutions of the incompressible Navier-Stokes equations. The performance of the two methods is compared by obtaining unsteady solutions for the evolution of twin vortices behind a flat plate. Calculated results are compared with experimental and other numerical results. For an unsteady flow, which requires small physical time step, the pressure projection method was found to be computationally efficient since it does not require any subiteration procedure. It was observed that the artificial compressibility method requires a fast convergence scheme at each physical time step in order to satisfy the incompressibility condition. This was obtained by using a GMRES-ILU(0) solver in present computations. When a line-relaxation scheme was used, the time accuracy was degraded and time-accurate computations became very expensive.

Kwak, Dochan↗

Towards Flange-to-Flange Turbopump Simulations for Liquid Rocket Engines

The primary objective of this research is to support the design of liquid rocket systems for the Advanced Space Transportation System. Since the space launch systems in the near future are likely to rely on liquid rocket engines, increasing the efficiency and reliability of the engine components is an important task. One of the major problems in the liquid rocket engine is to understand fluid dynamics of fuel and oxidizer flows from the fuel tank to plume. Understanding the flow through the entire turbopump geometry through numerical simulation will be of significant value toward design. This will help to improve safety of future space missions. One of the milestones of this effort is to develop, apply and demonstrate the capability and accuracy of 3D CFD methods as efficient design analysis tools on high performance computer platforms. The development of the MPI and MLP versions of the INS3D code is currently underway. The serial version of INS3D code is a multidimensional incompressible Navier-Stokes solver based on overset grid technology. INS3D-MPI is based on the explicit massage-passing interface across processors and is primarily suited for distributed memory systems. INS3D-MLP is based on multi-level parallel method and is suitable for distributed-shared memory systems. For the entire turbopump simulations, moving boundary capability and an efficient time-accurate integration methods are build in the flow solver. To handle the geometric complexity and moving boundary problems, overset grid scheme is incorporated with the solver that new connectivity data will be obtained at each time step. The Chimera overlapped grid scheme allows subdomains move relative to each other, and provides a great flexibility when the boundary movement creates large displacements. The performance of the two time integration schemes for time-accurate computations is investigated. For an unsteady flow which requires small physical time step, the pressure projection method was found to be computationally efficient since it does not require any subiterations procedure. It was observed that the artificial compressibility method requires a fast convergence scheme at each physical time step in order to satisfy incompressibility condition. This was obtained by using a GMRES-ILU(0) solver in our computations. When a line-relaxation scheme was used, the time accuracy was degraded and time-accurate computations became very expensive. The current geometry for the LOX boost turbopump has various rotating and stationary components, such as inducer, stators, kicker, hydrolic turbine, where the flow is extremely unsteady. Figure 1 shows the geometry and computed surface pressure of the inducer. The inducer and the hydrolic turbine rotate in different rotational speed.

Kiris, Cetin↗

A Theoretical Solid Oxide Fuel Cell Model for Systems Controls and Stability Design

As the aviation industry moves toward higher efficiency electrical power generation, all electric aircraft, or zero emissions and more quiet aircraft, fuel cells are sought as the technology that can deliver on these high expectations. The hybrid solid oxide fuel cell system combines the fuel cell with a micro-turbine to obtain up to 70% cycle efficiency, and then distributes the electrical power to the loads via a power distribution system. The challenge is to understand the dynamics of this complex multidiscipline system and the design distributed controls that take the system through its operating conditions in a stable and safe manner while maintaining the system performance. This particular system is a power generation and a distribution system, and the fuel cell and micro-turbine model fidelity should be compatible with the dynamics of the power distribution system in order to allow proper stability and distributed controls design. The novelty in this paper is that, first, the case is made why a high fidelity fuel cell mode is needed for systems control and stability designs. Second, a novel modeling approach is proposed for the fuel cell that will allow the fuel cell and the power system to be integrated and designed for stability, distributed controls, and other interface specifications. This investigation shows that for the fuel cell, the voltage characteristic should be modeled but in addition, conservation equation dynamics, ion diffusion, charge transfer kinetics, and the electron flow inherent impedance should also be included.

Kopasakis, George↗

Evaluation of microstructure stability at the interfaces of Al-6061 welds fabricated using ultrasonic additive manufacturing

Ultrasonic additive manufacturing (UAM) is a solid-state additive manufacturing process that uses fundamental principles of ultrasonic welding and sequential layering of tapes to fabricate complex three-dimensional (3-D) components. One of the factors limiting the use of this technology is the poor tensile strength along the z-axis. Recent work has demonstrated the improvement of the z-axis properties after post-processing treatments. The abnormally high stability of the grains at the interface during post-weld heat treatments is, however, not yet well understood. In this work we use multiscale characterization to understand the stability of the grains during post-weld heat treatments. Aluminum alloy (6061) builds, fabricated using ultrasonic additive manufacturing, were post-weld heat treated at 180, 330 and 580 °C. The grains close to the tape interfaces are stable during post-weld heat treatments at high temperatures (i.e., 580 °C). This is in contrast to rapid grain growth that takes place in the bulk. Transmission electron microscopy and atom-probe tomography display a significant enrichment of oxygen and magnesium near the stable interfaces. Based on the detailed characterization, two mechanisms are proposed and evaluated: nonequilibrium nano-dispersed oxides impeding the grain growth due to grain boundary pinning, or grain boundary segregation of magnesium and oxygen reducing the grain boundary energy.

36 MATERIALS SCIENCE↗

Surface Chemistry, Passivation, and Electrode Performance in Core–Shell Architectures of LiCoO 2 Nanoplates

Core–shell structures offer opportunities to overcome challenges to the durability of Li-ion batteries with high energy density due to instability at the cathode/electrolyte interface. Achieving complete stability requires fundamental understanding of the role of the shell in providing passivation without compromising carrier transport, by tuning surface chemistry and structural features in a highly conformal barrier layer. Here, individual LiCoO 2 nanoplates were employed as the core, and passivating shells were grown at a tailored thickness and composition, through different Al loadings and annealing temperatures. Depending on the annealing conditions, the sub-5 nm shells were shown to vary from amorphous aluminum oxide layers to LiAl x Co 1–x O 2 gradients, resulting in an Al-rich outer layer on a Co-rich core. This control revealed the differing balance between effective minimization of redox-active Co 3+ at the surface and transport properties of the two types of shell. Based on correlations with electrode performance, the requirements in thickness of the layers were proposed to critically depend on their chemical composition, with epitaxial shells based on surface substitution being favored. As a result, the outcomes of the study simultaneously advance the ability to assemble complex oxides into heterostructures and refine the rules of design for tunable passivation through a barrier layer, so as to maximize electrode properties in practical batteries.

25 ENERGY STORAGE↗

X-ray nanodiffraction studies of ionically controlled nanoscale phase separation in cobaltites

Complex oxide heterostructures provide access to emergent functional and structural phases that are not present in the bulk constituent materials. In this Rapid Communication, we focus on $La_{0.67}Sr_{0.33}CoO_3$ (LSCO)/Gd heterostructures due to the high oxygen ion conductivity, as well as the coupled magnetic and electronic properties of LSCO, which are strongly dependent on the oxygen stoichiometry. This combination of properties enables the ionic control of the functional properties of LSCO thin films through the presence of oxygen getter layers such as Gd.We utilize x-ray nanodiffraction to directly image the nanoscale morphology of LSCO thin films as they are progressively transformed from the equilibrium perovskite phase to the metastable brownmillerite (BM) phase with increasing Gd thickness. Our studies show the coexistence of perovskite and BM phases with a critical oxygen vacancy concentration threshold which leads to the formation of extended BM filaments. In addition to lateral phase separation, we observed phase separation within the film thickness possibly due to pinning of the perovskite and BM phases by the substrate/LSCO and LSCO/Gd interface, respectively. Our studies provide a nanoscale survey of the phase separation in the cobaltites and shed light on the formation of the metastable BM phase.

36 MATERIALS SCIENCE↗

Shuttle Propulsion Overview - The Design Challenges

The major elements of the Space Shuttle Main Propulsion System include two reusable solid rocket motors integrated into recoverable solid rocket boosters, an expendable external fuel and oxidizer tank, and three reusable Space Shuttle Main Engines. Both the solid rocket motors and space shuttle main engines ignite prior to liftoff, with the solid rocket boosters separating about two minutes into flight. The external tank separates, about eight and a half minutes into the flight, after main engine shutdown and is safely expended in the ocean. The SSME's, integrated into the Space Shuttle Orbiter aft structure, are reused after post landing inspections. The configuration is called a stage and a half as all the propulsion elements are active during the boost phase, with only the SSME s continuing operation to achieve orbital velocity. Design and performance challenges were numerous, beginning with development work in the 1970's. The solid rocket motors were large, and this technology had never been used for human space flight. The SSME s were both reusable and very high performance staged combustion cycle engines, also unique to the Space Shuttle. The multi body side mount configuration was unique and posed numerous integration and interface challenges across the elements. Operation of the system was complex and time consuming. This paper describes the design challenges and key areas where the design evolved during the program.

Owen, James W.↗

Examination of actinide chemistry at solid-water interfaces to support advanced actinide separations (Final Report)

In this work we have examined the thermodynamics of actinide interactions with solid interfaces in the presence and absence of multi-functional complexing ligands. The term “interactions” is a global term to capture many potential reactions including aqueous complexation, sorption/surface complexation, surface-mediated redox reactions, electrostatic attraction and repulsion, surface passivation, surface precipitation, and counter-ion competition. Each of these potential reactions may control actinide interactions with a solid surface. This work is helping to develop a more fundamental understanding of actinide bonding at solid:water interfaces and examine unique surface mediated oxidation/reduction reactions which are not expected based on the reduction potentials of aqueous species. We place a large emphasis on understanding both sorption and desorption processes as a means of understanding the sorption mechanisms. This work is directly aligned with the DOE BES Heavy Element Chemistry programs interests in understanding “the chemical and physical properties of these elements to determine solution, interfacial and solid-state bonding and reactivity”.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Photoelectrochemical CO 2 Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles

The development of photoelectrochemical systems for converting CO 2 into chemical feedstocks offers an attractive strategy for clean energy storage by directly utilizing solar energy, but selectivity and stability for these systems have thus been limited. Here, we interface silicon nanowire (SiNW) photocathodes with a copper nanoparticle (CuNP) ensemble to drive efficient photoelectrochemical CO 2 conversion to multicarbon products. This integrated system enables CO 2 -to-C 2 H 4 conversion with faradaic efficiency approaching 25% and partial current densities above 2.5 mA/cm 2 at -0.50 V vs RHE, while the nanowire photocathodes deliver 350 mV of photovoltage under 1 sun illumination. Under 50 h of continual bias and illumination, CuNP/SiNW can sustain stable photoelectrochemical CO 2 reduction. In conclusion, these results demonstrate the nanowire/catalyst system as a powerful modular platform to achieve stable photoelectrochemical CO 2 reduction and the feasibility to facilitate complex reactions toward multicarbons using generated photocarriers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗