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At least 469 records · Page 26

Examining Metal Identity and Proximity Effects on Acetylene Hydrogenation with Azolate-Based MOFs

Liquid organic hydrogen carriers (LOHCs) are an attractive fuel source due to their compatibility with existing transportation methods and ease of use. However, they suffer from sluggish (de)hydrogenation kinetics. One promising platform for developing next-generation catalysts is metal–organic frameworks (MOFs), which can enable systematic interrogation into the influence of metal identity and spatial arrangement. In this study, the effect of the coordination environment was investigated using Ni- and Co-based azolate MOFs: MFU-4l-OH (M x Zn 5–x (OH) 4 (BTDD) 3 ; x = 4 for M = Co and x = 3 for M = Ni, H 2 BTDD = bis(1H-1,2,3-triazolo[4,5-b][4′,5′-i])dibenzo[1,4]dioxin), composed of single-site nodes, and M(OH) 2 BBTA (M = Ni, Co; H 2 BBTA = 1H,5H-benzo(1,2-d:4,5-d’)bistriazole), composed of extended chain-type nodes. The catalysts were characterized by isotherms, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and X-ray photoelectron spectroscopy (XPS) analysis. Acetylene hydrogenation activity under steady state conditions (150 °C, 1:1 C 2 H 2 :H 2 ) revealed higher turnover frequencies (TOFs) up 1.17 × 10 –2 mol C 2 H 2 mol −1 Ni min −1 and 1.98 × 10 –3 mol C 2 H 2 mol −1 Co min −1 for Ni-MFU-4l-OH and Co-MFU-4l-OH, respectively, compared to their BBTA analogues. However, the Co-based MOFs, particularly Co 2 (OH) 2 -BBTA, exhibited greater selectivity (up to 19%) for the fully hydrogenated ethane product. Isosteric heat of adsorption (Q st ) measurements for ethylene and ethane revealed that the BBTA framework had stronger binding to the products than MFU-4l. Furthermore, these findings demonstrate that metal identity and coordination environment may modulate acetylene hydrogenation performance, leading to design principles for tuning LOHC hydrogenation catalysts.

catalysts↗

A Comparison of Candidate Seal Designs for Future Docking Systems

NASA is developing a new docking system to support future space exploration missions to low Earth orbit, the Moon, and other destinations. A key component of this system is the seal at the main docking interface which inhibits the loss of cabin air once docking is complete. Depending on the mission, the seal must be able to dock in either a seal-on-flange or seal-on-seal configuration. Seal-on-flange mating would occur when a docking system equipped with a seal docks to a system with a flat metal flange. This would occur when a vehicle docks to a node on the International Space Station. Seal-on-seal mating would occur when two docking systems equipped with seals dock to each other. Two types of seal designs were identified for this application: Gask-O-seals and multi-piece seals. Both types of seals had a pair of seal bulbs to satisfy the redundancy requirement. A series of performance assessments and comparisons were made between the candidate seal designs indicating that they meet the requirements for leak rate and compression and adhesion loads under a range of operating conditions. Other design factors such as part count, integration into the docking system tunnel, seal-on-seal mating, and cost were also considered leading to the selection of the multi-piece seal design for the new docking system. The results of this study can be used by designers of future docking systems and other habitable volumes to select the seal design best-suited for their particular application.

Dunlap, Patrick, H., Jr.↗

Application of symbolic and algebraic manipulation software in solving applied mechanics problems

As its name implies, symbolic and algebraic manipulation is an operational tool which not only can retain symbols throughout computations but also can express results in terms of symbols. This report starts with a history of symbolic and algebraic manipulators and a review of the literatures. With the help of selected examples, the capabilities of symbolic and algebraic manipulators are demonstrated. These applications to problems of applied mechanics are then presented. They are the application of automatic formulation to applied mechanics problems, application to a materially nonlinear problem (rigid-plastic ring compression) by finite element method (FEM) and application to plate problems by FEM. The advantages and difficulties, contributions, education, and perspectives of symbolic and algebraic manipulation are discussed. It is well known that there exist some fundamental difficulties in symbolic and algebraic manipulation, such as internal swelling and mathematical limitation. A remedy for these difficulties is proposed, and the three applications mentioned are solved successfully. For example, the closed from solution of stiffness matrix of four-node isoparametrical quadrilateral element for 2-D elasticity problem was not available before. Due to the work presented, the automatic construction of it becomes feasible. In addition, a new advantage of the application of symbolic and algebraic manipulation found is believed to be crucial in improving the efficiency of program execution in the future. This will substantially shorten the response time of a system. It is very significant for certain systems, such as missile and high speed aircraft systems, in which time plays an important role.

Tsai, Wen-Lang↗

Impacts of the IBM Cell Processor to Support Climate Models

NASA is interested in the performance and cost benefits for adapting its applications to the IBM Cell processor. However, its 256KB local memory per SPE and the new communication mechanism, make it very challenging to port an application. We selected the solar radiation component of the NASA GEOS-5 climate model, which: (1) is representative of column physics (approximately 50% computational time), (2) has a high computational load relative to transferring data from and to main memory, (3) performs independent calculations across multiple columns. We converted the baseline code (single-precision, Fortran) to C and ported it with manually SIMDizing 4 independent columns and found that a Cell with 8 SPEs can process 2274 columns per second. Compared with the baseline results, the Cell is approximately 5.2X, approximately 8.2X, approximately 15.1X faster than a core on Intel Woodcrest, Dempsey, and Itanium2, respectively. We believe this dramatic performance improvement makes a hybrid cluster with Cell and traditional nodes competitive.

Zhou, Shujia↗

Cartesian equivariant representations for learning and understanding molecular orbitals

Qualitative and quantitative orbital properties such as bonding/antibonding character, localization, and orbital energies are critical to how chemists understand reactivity, catalysis, and excited-state behavior. Despite this, representations of orbitals in deep learning models have been very underdeveloped relative to representations of molecular geometries and Hamiltonians. Here, we apply state-of-the-art equivariant deep learning architectures to the task of assigning global labels to orbitals, namely energies characterizations, given the molecular coefficients from Hartree–Fock or density functional theory. The architecture we have developed, the Cartesian Equivariant Orbital Network (CEONET), shows how molecular orbital coefficients are readily featurized as equivariant node features common to all graph-based machine-learned potentials. We find that CEONET performs well at predicting difficult quantitative labels such as the orbital energy and orbital entropy. Furthermore, we find that the CEONET representation provides an intuitive latent space for differentiating orbital character for the qualitative assignment of e.g. bonding or antibonding character. In addition to providing a useful representation for further integrating deep learning with electronic structure theory, we expect CEONET to be useful for automatizing and interpreting the results of advanced electronic structure methods such as complete active space self-consistent field theory. In particular, the ability of CEONET to infer multireference character via the orbital entropy paves the way toward the machine-learned selection of active spaces.

chemical reactions↗

Sinter‐Resistant Platinum Catalyst Supported by Metal–Organic Framework

Abstract Single atoms and few‐atom clusters of platinum are uniformly installed on the zirconia nodes of a metal‐organic framework (MOF) NU‐1000 via targeted vapor‐phase synthesis. The catalytic Pt clusters, site‐isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few‐atom clusters that depend upon synthesis conditions. Operando X‐ray absorption spectroscopy and X‐ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size‐selected clusters, including noble metals, on a high surface area support.

Kim, In Soo↗

Hypercube matrix computation task

The Hypercube Matrix Computation (Year 1986-1987) task investigated the applicability of a parallel computing architecture to the solution of large scale electromagnetic scattering problems. Two existing electromagnetic scattering codes were selected for conversion to the Mark III Hypercube concurrent computing environment. They were selected so that the underlying numerical algorithms utilized would be different thereby providing a more thorough evaluation of the appropriateness of the parallel environment for these types of problems. The first code was a frequency domain method of moments solution, NEC-2, developed at Lawrence Livermore National Laboratory. The second code was a time domain finite difference solution of Maxwell's equations to solve for the scattered fields. Once the codes were implemented on the hypercube and verified to obtain correct solutions by comparing the results with those from sequential runs, several measures were used to evaluate the performance of the two codes. First, a comparison was provided of the problem size possible on the hypercube with 128 megabytes of memory for a 32-node configuration with that available in a typical sequential user environment of 4 to 8 megabytes. Then, the performance of the codes was anlyzed for the computational speedup attained by the parallel architecture.

Calalo, R.↗

Krylov subspace recycling for evolving structures

Krylov subspace recycling is a powerful tool when solving a long series of large, sparse linear systems that change only slowly over time. In PDE constrained shape optimization, these series appear naturally, as typically hundreds or thousands of optimization steps are needed with only small changes in the geometry. In this setting, however, applying Krylov subspace recycling can be a difficult task. As the geometry evolves, in general, so does the finite element mesh defined on or representing this geometry, including the numbers of nodes and elements and element connectivity. This is especially the case if re-meshing techniques are used. As a result, the number of algebraic degrees of freedom in the system changes, and in general the linear system matrices resulting from the finite element discretization change size from one optimization step to the next. Changes in the mesh connectivity also lead to structural changes in the matrices. In the case of re-meshing, even if the geometry changes only a little, the corresponding mesh might differ substantially from the previous one. Obviously, this prevents any straightforward mapping of the approximate invariant subspace of the linear system matrix (the focus of recycling in this work) from one optimization step to the next; similar problems arise for other selected subspaces. In this paper, we present an algorithm to map an approximate invariant subspace of the linear system matrix for the previous optimization step to an approximate invariant subspace of the linear system matrix for the current optimization step, for general meshes. This is achieved by exploiting the map from coefficient vectors to finite element functions on the mesh, combined with interpolation or approximation of functions on the finite element mesh. We demonstrate the effectiveness of our approach numerically with several proof of concept studies for a specific meshing technique.

42 ENGINEERING↗

Kinetic energy classification and smoothing for compact B-spline basis sets in quantum Monte Carlo

Quantum Monte Carlo calculations of defect properties of transition metal oxides have become feasible in recent years due to increases in computing power. As the system size has grown, availability of on-node memory has become a limiting factor. Saving memory while minimizing computational cost is now a priority. The main growth in memory demand stems from the B-spline representation of the single particle orbitals, especially for heavier elements such as transition metals where semi-core states are present. Despite the associated memory costs, splines are computationally efficient. In this paper, we explore alternatives to reduce the memory usage of splined orbitals without significantly affecting numerical fidelity or computational efficiency. We make use of the kinetic energy operator to both classify and smooth the occupied set of orbitals prior to splining. By using a partitioning scheme based on the per-orbital kinetic energy distributions, we show that memory savings of about 50% is possible for select transition metal oxide systems. Finally, for production supercells of practical interest, our scheme incurs a performance penalty of less than 5%.

97 MATHEMATICS AND COMPUTING↗

Chemical and structural characterization of EUV photoresists as a function of depth by standing-wave x-ray photoelectron spectroscopy

The success in the miniaturization of the electronic device constituents depends mostly on the photolithographic techniques. Recently, to achieve patterning at the sub-10-nm node, extreme ultraviolet (EUV) lithography has been introduced into high volume production. Continued scaling of EUV via increased numerical aperture to achieve nodes at 3-nm and below requires the development of fundamentally new patterning materials and new characterization methods. Current EUV-resist film thicknesses are in the 20- to 40-nm range, and further thickness reduction is required for the next generation. Therefore, interfaces become exceedingly important, and the properties of the resist film would be dominated by top and bottom interfacial effects. X-ray photoelectron spectroscopy (XPS) combined with standing-wave excitation (SW-XPS), a fairly new method in the EUV lithography field, previously had been largely applied in multilayers and superlattices for characterizing the composition and electronic structure of buried layers and interfaces as a function of depth. We applied the SW-XPS method to organic/inorganic photoresists to provide depth-selective information on their structural and chemical conditions of as a function of temperature, EUV exposure, different underlayers, and other fundamental parameters. As a first attempt, we perform an SW-XPS feasibility study on self-assembled monolayer (SAM) films after exposure to an electron beam. By SW-XPS, we determined that the interface between the Al 2 O 3 underlayer and the SAMs is smooth, with a mean roughness of about 0.2 nm. Moreover, we determined that the SAM chains are, on average, tilted by 1/430 deg off the sample normal. The SW-XPS results also suggest that the SAM is not a perfectly aligned and uniform monolayer, with some areas having thickness higher than a single monolayer. We demonstrated that SW-XPS can provide useful information on ultrathin materials with high potential for being used as a characterization method of organic/inorganic photoresists.

36 MATERIALS SCIENCE↗

Metal–Organic Frameworks as a Tunable Platform to Deconvolute Stereoelectronic Effects on the Catalytic Activity of Thioanisole Oxidation

The local environment of a metal active site plays an important role in affecting catalytic activity and selectivity. In re-cent studies, tailoring the behavior of a molybdenum-based active site via modulation of the first coordination sphere has led to improved thioanisole oxidation performance, but disentangling electronic effects from steric influences that arise from these modifications is nontrivial, especially in heterogeneous systems. To this end, the tunability of metal–organic frameworks (MOFs) makes them promising scaffolds for controlling the coordination sphere of a heterogene-ous, catalytically-active metal site while offering additional, attractive features such as crystallinity and high porosity. Herein, we report a variety of MOF-supported Mo species, which were investigated for catalytic thioanisole oxidation to methyl phenyl sulfoxide and/or methyl phenyl sulfone using tert-butyl hydroperoxide (tBHP) as the oxidant. In particular, MOFs of contrasting node architectures were targeted, presenting a unique opportunity to investigate ste-reoelectronic control of Mo active sites in a systematic manner. A Zr 6 -based MOF, NU-1000, was employed along with its sulfated analog Zr 6 -based NU-1000-SO 4 to anchor a dioxymolybdenum species, which enabled examination of sup-port-mediated active site polarizability on catalytic performance. In addition, a MOF containing a mixed metal node, Mo-MFU-4l, was used to probe the stereoelectronic impact of an N-donor ligand environment on the catalytic activity of the transmetalated Mo center. Furthermore, characterization techniques including single crystal X-ray diffraction, were concomi-tantly used with reaction kinetic profiles to better comprehend the dynamics of different Mo active sites, thus correlat-ing structural change with activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sizing of "Mother Ship and Catcher" Concepts for LEO Small Debris Capture

Most Low Earth Orbit (LEO) debris lies in a limited number of inclination "bands" associated with launch latitudes, or with specific useful orbit inclinations (such as polar orbits). Such narrow inclination bands generally have a uniform spread over all possible Right Ascensions of Ascending Node (RAANs), creating a different orbit plane for nearly every piece of debris. This complicates concept of rendezvous and capture for debris removal. However, a low-orbiting satellite will always phase in RAAN faster than debris objects in higher orbits at the same inclination, potentially solving the problem. Such a base can serve as a single space-based launch facility (a "mother ship") that can tend and then send tiny individual catcher devices for each debris object, as the facility drifts into the same RAAN as the higher object. This presentation will highlight characteristic system requirements of such an architecture, including structural and navigation requirements, power, mass and dV budgets for both the mother ship and the mass-produced common catcher devices that would clean out selected inclination bands. The altitude and inclination regime over which a band is to be cleared, the size distribution of the debris, and the inclusion of additional mission priorities all affect the sizing of the system. It is demonstrated that major LEO hazardous debris reductions can be realized in each band with a single LEO launch of a single mother ship, with simple attached catchers of total mass less than typical commercial LEO launch capability.

Bacon, John B.↗

Time and Energy, Exploring Trajectory Options Between Nodes in Earth-Moon Space

The Global Exploration Roadmap (GER) was released by the International Space Exploration Coordination Group (ISECG) in September of 2011. It describes mission scenarios that begin with the International Space Station and utilize it to demonstrate necessary technologies and capabilities prior to deployment of systems into Earth-Moon space. Deployment of these systems is an intermediate step in preparation for more complex deep space missions to near-Earth asteroids and eventually Mars. In one of the scenarios described in the GER, "Asteroid Next", there are activities that occur in Earth-Moon space at one of the Earth-Moon Lagrange (libration) points. In this regard, the authors examine the possible role of an intermediate staging point in an effort to illuminate potential trajectory options for conducting missions in Earth-Moon space of increasing duration, ultimately leading to deep space missions. This paper will describe several options for transits between Low Earth Orbit (LEO) and the libration points, transits between libration points, and transits between the libration points and interplanetary trajectories. The solution space provided will be constrained by selected orbital mechanics design techniques and physical characteristics of hardware to be used in both crewed missions and uncrewed missions. The relationships between time and energy required to transfer hardware between these locations will provide a better understanding of the potential trade-offs mission planners could consider in the development of capabilities, individual missions, and mission series in the context of the ISECG GER.

Martinez, Roland↗

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. Lastly, these results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.

36 MATERIALS SCIENCE↗

Insights into regulatory T-cell and type-I interferon roles in determining abacavir-induced hypersensitivity or immune tolerance

Introduction Clinical use of several small molecule drugs may lead to severe T-cell-mediated idiosyncratic drug hypersensitivity reactions (iDHR) linked to HLA alleles, including abacavir (ABC) with HLA-B*57:01. Due to study limitations in humans, pathogenic networks in iDHR remain elusive. HLA transgenic murine models have been proposed to bridge knowledge gaps in tolerance and susceptibility to drugs. Methods Mice expressing HLA-B*57:01 and Foxp3-DTR/EGFP were generated to selectively deplete regulatory T-cells (Treg) with diphtheria toxin. ABC was administered for 8 days alone or together with cell- and cytokine-depleting antibodies. Cellular and transcriptomic responses were analyzed by RNA, flow cytometry and fluorescence methods. Results While CD8 + T-cell responses to ABC require HLA presentation, ABC also triggered mitochondrial stress in macrophagesin vitro, independently of HLA.In vivo, Treg were the primary mechanism of drug tolerance controlling HLA presentation and costimulation by antigen presenting cells. Treg ablation uncovered immune adverse events linked to activation and proliferation of both drug-specific and bystander CD8 + T-cells through CD28-mediated pathways with support from CD4 + non-Treg. Type-I interferon (IFN-I) and cellular-stress pathways influenced the fate of lymph node cells responding to ABC, implicating innate immune cells such as macrophages and plasmacytoid dendritic cells in the development of T-cell responses against the drug. IFN-I and IL-2 were necessary for CD8 + T-cell differentiation and ABC-induced adverse reactions. Conclusions This study unveils novel immune mechanisms driven by drug and host-related factors required forin vivoreactions and sheds light on potential biomarker and therapeutic targets for managing and preventing severe and life-threatening iDHR.

Immunology↗

Comparison of Communication Architectures for Spacecraft Modular Avionics Systems

This document is a survey of publicly available information concerning serial communication architectures used, or proposed to be used, in aeronautic and aerospace applications. It focuses on serial communication architectures that are suitable for low-latency or real-time communication between physically distributed nodes in a system. Candidates for the study have either extensive deployment in the field, or appear to be viable for near-term deployment. Eleven different serial communication architectures are considered, and a brief description of each is given with the salient features summarized in a table in appendix A. This survey is a product of the Propulsion High Impact Avionics Technology (PHIAT) Project at NASA Marshall Space Flight Center (MSFC). PHIAT was originally funded under the Next Generation Launch Technology (NGLT) Program to develop avionics technologies for control of next generation reusable rocket engines. After the announcement of the Space Exploration Initiative, the scope of the project was expanded to include vehicle systems control for human and robotics missions. As such, a section is included presenting the rationale used for selection of a time-triggered architecture for implementation of the avionics demonstration hardware developed by the project team

Gwaltney, D. A.↗

Unraveling Network-induced Memory Contention: Deeper Insights with Machine Learning

Remote Direct Memory Access (RDMA) is expected to be an integral communication mechanism for future exascale systems enabling asynchronous data transfers, so that applications may fully utilize CPU resources while simultaneously sharing data amongst remote nodes. We examine Network-induced Memory Contention (NiMC) on Infiniband networks. We expose the interactions between RDMA, main-memory and cache, when applications and out-of-band services compete for memory resources. We then explore NiMCs resulting impact on application-level performance. For a range of hardware technologies and HPC workloads, we quantify NiMC and show that NiMCs impact grows with scale resulting in up to 3X performance degradation at scales as small as 8K processes even in applications that previously have been shown to be performance resilient in the presence of noise. In addition, this work examines the problem of predicting NiMC's impact on applications by leveraging machine learning and easily accessible performance counters. This approach provides additional insights about the root cause of NiMC and facilitates dynamic selection of potential solutions. Finally, we evaluated three potential techniques to reduce NiMCs impact, namely hardware offloading, core reservation and network throttling.

97 MATHEMATICS AND COMPUTING↗

Circuit and Method for Communication Over DC Power Line

A circuit and method for transmitting and receiving on-off-keyed (OOK) signals with fractional signal-to-noise ratios uses available high-temperature silicon- on-insulator (SOI) components to move computational, sensing, and actuation abilities closer to high-temperature or high-ionizing radiation environments such as vehicle engine compartments, deep-hole drilling environments, industrial control and monitoring of processes like smelting, and operations near nuclear reactors and in space. This device allows for the networking of multiple, like nodes to each other and to a central processor. It can do this with nothing more than the already in-situ power wiring of the system. The device s microprocessor allows it to make intelligent decisions within the vehicle operational loop and to effect control outputs to its associated actuators. The figure illustrates how each node converts digital serial data to OOK 18-kHz in transmit mode and vice-versa in receive mode; though operations at lower frequencies or up to a megahertz are within reason using this method and these parts. This innovation s technique modulates a DC power bus with millivolt-level signals through a MOSFET (metal oxide semiconductor field effect transistor) and resistor by OOK. It receives and demodulates this signal from the DC power bus through capacitive coupling at high temperature and in high ionizing radiation environments. The demodulation of the OOK signal is accomplished by using an asynchronous quadrature detection technique realized by a quasi-discrete Fourier transform through use of the quadrature components (0 and 90 phases) of the carrier frequency as generated by the microcontroller and as a function of the selected crystal frequency driving its oscillator. The detected signal is rectified using an absolute-value circuit containing no diodes (diodes being non-operational at high temperatures), and only operational amplifiers. The absolute values of the two phases of the received signal are then summed and hard limited (digitized) by comparing them to a reference level and are then input into a microprocessor as a serial bit stream. The quasi-discrete Fourier transform is performed in high-temperature components (operational amplifiers, analog switches, resistors, and capacitors). The demodulated signal is a serial data stream that is input to the UART (universal asynchronous receiver transmitter) receiver pin of the microprocessor. The OOK of the carrier frequency uses the output of the UART pin as an enabling signal that drives the gate of the MOSFET. Logic low bits enable the carrier frequency (realized by using the 0 phase signal from the microcontroller, though either phase may be used) to be DC-coupled to the power supply bus through a current-limiting resistor mounted between the MOSFET drain and the supply rail. The presence of logic lows on the power supply rail is realized by carrier bursts while logic highs are realized by the absence of bursts.

Krasowski, Michael J.↗