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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

The Iterative Processing Framework: A New Paradigm for Automatic Event Building

Abstract In a traditional data-processing pipeline, waveforms are acquired, a detector makes the signal detections (i.e., arrival times, slownesses, and azimuths) and passes them to an associator. The associator then links the detections to the fitting-event hypotheses to generate an event bulletin. Most of the time, this traditional pipeline requires substantial human-analyst involvement to improve the quality of the resulting event bulletin. For the year 2017, for instance, International Data Center (IDC) analysts rejected about 40% of the events in the automatic bulletin and manually built 30% of the legitimate events. Here, we introduce an iterative processing framework (IPF) that includes a new data-processing module that incorporates automatic analyst behaviors (auto analyst [AA]) into the event-building pipeline. In the proposed framework, through an iterative process, the AA takes over many of the tasks traditionally performed by human analysts. These tasks can be grouped into two major processes: (1) evaluating small events with a low number of location-defining arrival phases to improve their formation; and (2) scanning for and exploiting unassociated arrivals to form potential events missed by previous association runs. To test the proposed framework, we processed a two-week period (15–28 May 2010) of the signal-detections dataset from the IDC. Comparison with an expert analyst-reviewed bulletin for the same time period suggests that IPF performs better than the traditional pipelines (IDC and baseline pipelines). The majority of the additional events built by the AA are low-magnitude events that were missed by these traditional pipelines. The AA also adds additional signal detections to existing events, which saves analyst time, even if the event locations are not significantly affected.

58 GEOSCIENCES↗
DOE OSTI2015

Topology-Guided Design and Syntheses of Highly Stable Mesoporous Porphyrinic Zirconium Metal-Organic Frameworks with High Surface Area

Through a topology-guided strategy, a series of Zr-6-containing isoreticular porphyrinic metalorganic frameworks (MOFs), PCN-228, PCN-229, and PCN-230, with ftw-a topology were synthesized using the extended porphyrinic linkers. The bulky porphyrin ring ligand effectively prevents the network interpenetration which often appears in MOFs with increased linker length. The pore apertures of the structures range from 2.5 to 3.8 nm, and PCN-229 demonstrates the highest porosity and BET surface area among the previously reported Zr-MOFs. Additionally, by changing the relative direction of the terminal phenyl rings, this series replaces a Zr-8 cluster with a smaller Zr-6 cluster in a topologically identical framework. The high connectivity of the Zr-6 cluster yields frameworks with enhanced stability despite high porosity and ultralarge linker. As a representative example, PCN-230, constructed with the most extended porphyrinic linker, shows excellent stability in aqueous solutions with pH values ranging from 0 to 12 and demonstrates one of the highest pH tolerances among all porphyrinic MOFs. This work not only presents a successful example of rational design of MOFs with desired topology, but also provides a strategy for construction of stable mesoporous MOFs.

Liu, TF↗
DOE OSTI2017

Structural characterization of framework–gas interactions in the metal–organic framework Co 2 (dobdc) by in situ single-crystal X-ray diffraction

The crystallographic characterization of framework–guest interactions in metal–organic frameworks allows the location of guest binding sites and provides meaningful information on the nature of these interactions, enabling the correlation of structure with adsorption behavior. Here, techniques developed for in situ single-crystal X-ray diffraction experiments on porous crystals have enabled the direct observation of CO, CH 4 , N 2 , O 2 , Ar, and P 4 adsorption in Co2(dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate), a metal–organic framework bearing coordinatively unsaturated cobalt(II) sites. All these molecules exhibit such weak interactions with the high-spin cobalt(II) sites in the framework that no analogous molecular structures exist, demonstrating the utility of metal–organic frameworks as crystalline matrices for the isolation and structural determination of unstable species. Notably, the Co–CH 4 and Co–Ar interactions observed in Co 2 (dobdc) represent, to the best of our knowledge, the first single-crystal structure determination of a metal–CH 4 interaction and the first crystallographically characterized metal–Ar interaction. Analysis of low-pressure gas adsorption isotherms confirms that these gases exhibit mainly physisorptive interactions with the cobalt(II) sites in Co 2 (dobdc), with differential enthalpies of adsorption as weak as –17(1) kJ mol –1 (for Ar). Moreover, the structures of Co 2 (dobdc)·3.8N 2 , Co 2 (dobdc)·5.9O 2 , and Co 2 (dobdc)·2.0Ar reveal the location of secondary (N 2 , O 2 , and Ar) and tertiary (O 2 ) binding sites in Co 2 (dobdc), while high-pressure CO 2 , CO, CH 4 , N 2 , and Ar adsorption isotherms show that these binding sites become more relevant at elevated pressures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Rigidifying Fluorescent Linkers by Metal-Organic Framework Formation for Fluorescence Blue Shift and Quantum Yield Enhancement

We demonstrate that rigidifying the structure of fluorescent linkers by structurally constraining them in metal-organic frameworks (MOFs) to control their conformation effectively tunes the fluorescence energy and enhances the quantum yield. Thus, a new tetraphenylethylene-based zirconium MOF exhibits a deep-blue fluorescent emission at 470 nm with a unity quantum yield (99.9 +/- 0.5%) under Ar, representing ca. 3600 cm(-1) blue shift and doubled radiative decay efficiency vs the linker precursor. An anomalous increase in the fluorescence lifetime and relative intensity takes place upon heating the solid MOF from cryogenic to ambient temperatures. The origin of these unusual photoluminescence properties is attributed to twisted linker conformation, intramolecular hindrance, and framework rigidity.

Wei, ZW↗
DOE OSTI2014

Comprehensive study of carbon dioxide adsorption in the metal–organic frameworks M 2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Cu, Zn)

Analysis of the CO 2 adsorption properties of a well-known series of metal–organic frameworks M 2 (dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, and Zn) is carried out in tandem with in situ structural studies to identify the host–guest interactions that lead to significant differences in isosteric heats of CO 2 adsorption. Neutron and X-ray powder diffraction and single crystal X-ray diffraction experiments are used to unveil the site-specific binding properties of CO 2 within many of these materials while systematically varying both the amount of CO 2 and the temperature. Unlike previous studies, we show that CO 2 adsorbed at the metal cations exhibits intramolecular angles with minimal deviations from 180°, a finding that indicates a strongly electrostatic and physisorptive interaction with the framework surface and sheds more light on the ongoing discussion regarding whether CO 2 adsorbs in a linear or nonlinear geometry. This has important implications for proposals that have been made to utilize these materials for the activation and chemical conversion of CO 2 . For the weaker CO 2 adsorbents, significant elongation of the metal–O(CO 2 ) distances are observed and diffraction experiments additionally reveal that secondary CO 2 adsorption sites, while likely stabilized by the population of the primary adsorption sites, significantly contribute to adsorption behavior at ambient temperature. In conclusion, density functional theory calculations including van der Waals dispersion quantitatively corroborate and rationalize observations regarding intramolecular CO 2 angles and trends in relative geometric properties and heats of adsorption in the M 2 (dobdc)–CO 2 adducts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Open-Source Framework for Data Storage and Visualization of Real-Time Experiments

Digital real time simulators (DRTS) are increasingly being used for the evaluation of power hardware and controller hardware in the laboratory prior to field deployment. Although DRTS are capable of simulating large models in real-time, it is challenging to visualize the results of large models without overdrawing or confounding the viewer. This paper provides an open-source framework for users to visualize their DRTS-based hardware-in-the-loop (HIL) experimental results in real-time. This proposed framework can be used by experimental test beds that can push data through an internet protocol based network. The proposed framework includes three main components. First, it includes the DRTS that generates and pushes the data to a relay. Second, it includes an application that serves multiple purposes, from data storage, testing, and translation of the data to a publisher/subscriber protocol. Finally, it includes libraries and applications that can be used to visualize the data by subscribing to the relay. This framework is available in open source, and it is tested using the HIL platform developed for testing advanced distribution management systems.

advanced distribution management systems↗
DOE OSTI2021

Siloxyaluminate and Siloxygallate Complexes as Models for Framework and Partially Hydrolyzed Framework Sites in Zeolites and Zeotypes.

Anionic molecular models for nonhydrolyzed and partially hydrolyzed aluminum and gallium framework sites on silica, M[OSi(OtBu) 3 ] 4 - and HOM[OSi(OtBu) 3 ] 3 - (where M=Al or Ga), were synthesized from anionic chlorides Li{M[OSi(OtBu) 3 ] 3 Cl} in salt metathesis reactions. Sequestration of lithium cations with [12]crown-4 afforded charge-separated ion pairs composed of monomeric anions M[OSi(OtBu) 3 ] 4 - with outer-sphere [([12]crown-4) 2 Li] + cations, and hydroxides {HOM[OSi(OtBu) 3 ] 3 } with pendant [([12]crown-4)Li] + cations. These molecular models were characterized by single-crystal X-ray diffraction, vibrational spectroscopy, mass spectrometry and NMR spectroscopy. Upon treatment of monomeric [([12]crown-4)Li]{HOM[OSi(OtBu) 3 ] 3 } complexes with benzyl alcohol, benzyloxide complexes were formed, modeling a possible pathway for the formation of active sites for Meerwin-Ponndorf-Verley (MPV) transfer hydrogenations with Al/Ga-doped silica catalysts.

Dombrowski, James P↗
DOE OSTI2014

Increasing the Stability of Metal-Organic Frameworks

Metal-organic frameworks (MOFs) are a new category of advanced porous materials undergoing study by many researchers for their vast variety of both novel structures and potentially useful properties arising from them. Their high porosities, tunable structures, and convenient process of introducing both customizable functional groups and unsaturated metal centers have afforded excellent gas sorption and separation ability, catalytic activity, luminescent properties, and more. However, the robustness and reactivity of a given framework are largely dependent on its metal-ligand interactions, where the metal-containing clusters are often vulnerable to ligand substitution by water or other nucleophiles, meaning that the frameworks may collapse upon exposure even to moist air. Other frameworks may collapse upon thermal or vacuum treatment or simply over time. This instability limits the practical uses of many MOFs. In order to further enhance the stability of the framework, many different approaches, such as the utilization of high-valence metal ions or nitrogen-donor ligands, were recently investigated. This review details the efforts of both our research group and others to synthesize MOFs possessing drastically increased chemical and thermal stability, in addition to exemplary performance for catalysis, gas sorption, and separation.

Bosch, Mathieu↗
DOE OSTI2015

A generalized reconstruction framework for unconventional PET systems

Purpose: Quantitative estimation of the radionuclide activity concentration in positron emission tomography (PET) requires precise modeling of PET physics. The authors are focused on designing unconventional PET geometries for specific applications. This work reports the creation of a generalized reconstruction framework, capable of reconstructing tomographic PET data for systems that use right cuboidal detector elements positioned at arbitrary geometry using a regular Cartesian grid of image voxels. Methods: The authors report on a variety of design choices and optimization for the creation of the generalized framework. The image reconstruction algorithm is maximum likelihood-expectation–maximization. System geometry can be specified using a simple script. Given the geometry, a symmetry seeking algorithm finds existing symmetry in the geometry with respect to the image grid to improve the memory usage/speed. Normalization is approached from a geometry independent perspective. The system matrix is computed using the Siddon’s algorithm and subcrystal approach. The program is parallelized through open multiprocessing and message passing interface libraries. A wide variety of systems can be modeled using the framework. This is made possible by modeling the underlying physics and data correction, while generalizing the geometry dependent features. Results: Application of the framework for three novel PET systems, each designed for a specific application, is presented to demonstrate the robustness of the framework in modeling PET systems of unconventional geometry. Three PET systems of unconventional geometry are studied. (1) Virtual-pinhole half-ring insert integrated into Biograph-40: although the insert device improves image quality over conventional whole-body scanner, the image quality varies depending on the position of the insert and the object. (2) Virtual-pinhole flat-panel insert integrated into Biograph-40: preliminary results from an investigation into a modular flat-panel insert are presented. (3) Plant PET system: a reconfigurable PET system for imaging plants, with resolution of greater than 3.3 mm, is shown. Using the automated symmetry seeking algorithm, the authors achieved a compression ratio of the storage and memory requirement by a factor of approximately 50 for the half-ring and flat-panel systems. For plant PET system, the compression ratio is approximately five. The ratio depends on the level of symmetry that exists in different geometries. Conclusions: This work brings the field closer to arbitrary geometry reconstruction. A generalized reconstruction framework can be used to validate multiple hypotheses and the effort required to investigate each system is reduced. Memory usage/speed can be improved with certain optimizations.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

DESCQA: An Automated Validation Framework for Synthetic Sky Catalogs

The use of high-quality simulated sky catalogs is essential for the success of cosmological surveys. The catalogs have diverse applications, such as investigating signatures of fundamental physics in cosmological observables, understanding the effect of systematic uncertainties on measured signals and testing mitigation strategies for reducing these uncertainties, aiding analysis pipeline development and testing, and survey strategy optimization. The list of applications is growing with improvements in the quality of the catalogs and the details that they can provide. Given the importance of simulated catalogs, it is critical to provide rigorous validation protocols that enable both catalog providers and users to assess the quality of the catalogs in a straightforward and comprehensive way. For this purpose, we have developed the DESCQA framework for the Large Synoptic Survey Telescope Dark Energy Science Collaboration as well as for the broader community. The goal of DESCQA is to enable the inspection, validation, and comparison of an inhomogeneous set of synthetic catalogs via the provision of a common interface within an automated framework. Here in this paper, we present the design concept and first implementation of DESCQA. In order to establish and demonstrate its full functionality we use a set of interim catalogs and validation tests. We highlight several important aspects, both technical and scientific, that require thoughtful consideration when designing a validation framework, including validation metrics and how these metrics impose requirements on the synthetic sky catalogs.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2015

Understanding Small-Molecule Interactions in Metal-Organic Frameworks: Coupling Experiment with Theory

Metal-organic frameworks (MOFs) have gained much attention as next generation porous media for various applications, especially gas separations/storage and catalysis. New MOFs are regularly reported; however, to develop better materials in a timely manner for specific applications, the interactions between guest molecules and the internal surface of the framework must first be understood. In this review, we present a combined experimental and theoretical approach that proves essential for the elucidation of small-molecule interactions in a model MOF system known as M 2 (dobdc) (dobdc 4– = 2,5-dioxido-1,4-benzenedicarboxylate; M = Mg, Mn, Fe, Co, Ni, Cu, or Zn), a material whose adsorption properties can be readily tuned via chemical substitution. Here, we additionally show that the study of extensive families like this one can provide a platform to test the efficacy and accuracy of developing computational methodologies in slightly varying chemical environments, a task that is necessary for their evolution into viable, robust tools for screening large numbers of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations for solvent-based carbon capture. Part 2: Chemical absorption across a wetted wall column: Original Research Article: Hierarchical calibration and validation framework of bench-scale computational fluid dynamics simulations

Part 1 of this paper presents a numerical model for non-reactive physical mass transfer across a wetted wall column (WWC). In Part 2, we improved the existing computational fluid dynamics (CFD) model to simulate chemical absorption occurring in a WWC as a bench-scale study of solvent-based carbon dioxide (CO 2 ) capture. In this study, to generate data for WWC model validation, CO 2 mass transfer across a monoethanolamine (MEA) solvent was first measured on a WWC experimental apparatus. The numerical model developed in this work can account for both chemical absorption and desorption of CO 2 in MEA. In addition, the overall mass transfer coefficient predicted using traditional/empirical correlations is conducted and compared with CFD prediction results for both steady and wavy falling films. A Bayesian statistical calibration algorithm is adopted to calibrate the reaction rate constants in chemical absorption/desorption of CO 2 across a falling film of MEA. The posterior distributions of the two transport properties, i.e., Henry's constant and gas diffusivity in the non-reacting nitrous oxide (N 2 O)/MEA system obtained from Part 1 of this study, serves as priors for the calibration of CO 2 reaction rate constants after using the N 2 O/CO 2 analogy method. Finally, the calibrated model can be used to predict the CO 2 mass transfer in a WWC for a wider range of operating conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

A framework for modeling and optimizing dynamic systems under uncertainty

Algebraic modeling languages (AMLs) have drastically simplified the implementation of algebraic optimization problems. However, there are still many classes of optimization problems that are not easily represented in most AMLs. These classes of problems are typically reformulated before implementation, which requires significant effort and time from the modeler and obscures the original problem structure or context. In this work we demonstrate how the Pyomo AML can be used to represent complex optimization problems using high-level modeling constructs. We focus on the operation of dynamic systems under uncertainty and demonstrate the combination of Pyomo extensions for dynamic optimization and stochastic programming. We use a dynamic semibatch reactor model and a large-scale bubbling fluidized bed adsorber model as test cases.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2014

Oxidation of ethane to ethanol by N 2 O in a metal-organic framework with coordinatively unsaturated iron(II) sites

Enzymatic haem and non-haem high-valent iron–oxo species are known to activate strong C–H bonds, yet duplicating this reactivity in a synthetic system remains a formidable challenge. Although instability of the terminal iron–oxo moiety is perhaps the foremost obstacle, steric and electronic factors also limit the activity of previously reported mononuclear iron(IV)–oxo compounds. In particular, although nature's non-haem iron(IV)–oxo compounds possess high-spin S = 2 ground states, this electronic configuration has proved difficult to achieve in a molecular species. These challenges may be mitigated within metal–organic frameworks that feature site-isolated iron centres in a constrained, weak-field ligand environment. Here, we show that the metal–organic framework Fe 2 (dobdc) (dobdc 4- = 2,5-dioxido-1,4-benzenedicarboxylate) and its magnesium-diluted analogue, Fe 0.1 Mg 1.9 (dobdc), are able to activate the C–H bonds of ethane and convert it into ethanol and acetaldehyde using nitrous oxide as the terminal oxidant. Electronic structure calculations indicate that the active oxidant is likely to be a high-spin S = 2 iron(IV)–oxo species.

Xiao, Dianne J.↗
DOE OSTI2017

Xenon Recovery at Room Temperature using Metal-Organic Frameworks

Xenon is known to be a very efficient anesthetic gas but its cost prohibits the wider use in medical industry and other potential applications. It has been shown that Xe recovery and recycle from anesthetic gas mixture can significantly reduce its cost as anesthetic. The current technology uses series of adsorbent columns followed by low temperature distillation to recover Xe, which is expensive to use in medical facilities. Herein, we propose much efficient and simpler system to recover and recycle Xe from simulant exhale anesthetic gas mixture at room temperature using metal organic frameworks. Among the MOFs tested, PCN-12 exhibits unprecedented performance with high Xe capacity, Xe/N2 and Xe/O2 selectivity at room temperature. The in-situ synchrotron measurements suggest the Xe is occupied in the small pockets of PCN-12 compared to unsaturated metal centers (UMCs). Computational modeling of adsorption further supports our experimental observation of Xe binding sites in PCN-12.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Direct Observation of Xe and Kr Adsorption in a Xe-Selective Microporous Metal–Organic Framework

The cryogenic separation of noble gases is energy-intensive and expensive, especially when low concentrations are involved. Metal organic frameworks containing polarizing groups within their pore spaces are predicted to be efficient Xe/Kr solid state adsorbents but no experimental insights on the nature of the Xe-network interaction is available to date. Here we report a new microporous metal organic framework (designated SBU2) that is selective toward Xe over Kr at ambient conditions, with Xe/Kr selectivity of about 10 and Xe capacity of 37.1 wt% at 298 K. Results of single crystal diffraction show Xe selectivity may be attributed to the specific geometry of the pores, forming cages built with phenyl rings and enriched with polar -OH groups, both serving as strong adsorption sites for polarizable Xe gas. The Xe/Kr separation in SBU2 was investigated with experimental and computational breakthrough methods. These experiments showed that Xe broke through the column after 3 min, followed by Kr at 4.5 min after injection of gases mixture, which confirmed that SBU2 has a real practical potential for separating Xe from Kr. Computational calculations show that SBU2 capacity and adsorption selectivity is comparable to the best-performing unmodified MOFs such as Ni-MOF-74 or Co Formate.

Xenon, Krypton↗