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At least 397 records · Page 22

Explainable machine learning for incipient anomaly detection in compact molten salt heat exchanger with overlapping feature distributions

High-temperature molten salt-cooled reactors (MSCRs) are a promising next-generation nuclear technology option, offering efficient power conversion and inherent safety features. However, the reliability of these systems depends on the robust operation of heat exchangers (HXs), which are susceptible to failure due to temperature gradients and channel plugging caused by fluid freezing. Conventional monitoring methods, relying on inlet and outlet measurements, lack the spatial resolution needed to detect early-stage faults. We propose a novel design of a compact salt-to-salt matrix-type HX design consisting of interleaved arrays of parallel tubes, with integrated synthetic fiber optic distributed temperature sensing (DTS) to enable localized detection of incipient faults. To evaluate performance of this design, we generate high-fidelity synthetic data using heat transfer computational modeling to simulate channel plugging, and introduce sensor noise for realistic modeling of measurements. The dataset comprises of 97% normal operation and 3% anomaly cases, with each anomaly class representing 1% of the data. These early anomalies result in overlapping temperature profiles between normal and faulty channels, producing a non-separable dataset that challenges traditional classification techniques. We benchmark eight supervised machine learning (ML) models and demonstrate that XGBoost achieves the highest performance. To improve transparency, we develop an explainability framework combining Shapley values and partially ordered sets (POSETs) to quantify and structurally analyze feature importance. This approach identifies both dominant predictors and ambiguous feature relationships, enhancing trust and interpretability. Our results highlight the potential of combining DTS and explainable ML with intelligent feature selection to improve predictive maintenance and ensure operational resilience in advanced nuclear systems.

Prantikos, Konstantinos [Argonne National Laborato↗

NASA Tech Briefs, February 2003

opics covered include: Integrated Electrode Arrays for Neuro-Prosthetic Implants; Eroding Potentiometers; Common/Dependent-Pressure-Vessel Nickel-Hydrogen Batteries; 120-GHz HEMT Oscillator With Surface-Wave-Assisted Antenna; 80-GHz MMIC HEMT Voltage-Controlled Oscillator; High-Energy-Density Capacitors; Microscale Thermal-Transpiration Gas Pump; Instrument for Measuring Temperature of Water; Improved Measurement of Coherence in Presence of Instrument Noise; Compact Instruments Measure Helium-Leak Rates; Irreversible Entropy Production in Two-Phase Mixing Layers; Subsonic and Supersonic Effects in Bose-Einstein Condensate; Nanolaminate Mirrors With "Piston" Figure-Control Actuators; Mixed Conducting Electrodes for Better AMTEC Cells; Process for Encapsulating Protein Crystals; Lightweight, Self-Deployable Wheels; Grease-Resistant O Rings for Joints in Solid Rocket Motors; LabVIEW Serial Driver Software for an Electronic Load; Software Computes Tape-Casting Parameters; Software for Tracking Costs of Mars Projects; Software for Replicating Data Between X.500 and LDAP Directories; The Technical Work Plan Tracking Tool; Improved Multiple-DOF SAW Piezoelectric Motors; Propulsion Flight-Test Fixture; Mechanical Amplifier for a Piezoelectric Transducer; Swell Sleeves for Testing Explosive Devices; Linear Back-Drive Differentials; Miniature Inchworm Actuators Fabricated by Use of LIGA; Using ERF Devices to Control Deployments of Space Structures; High-Temperature Switched-Reluctance Electric Motor; System for Centering a Turbofan in a Nacelle During Tests; Fabricating Composite-Material Structures Containing SMA Ribbons; Optimal Feedback Control of Thermal Networks; Artifacts for Calibration of Submicron Width Measurements; Navigating a Mobile Robot Across Terrain Using Fuzzy Logic; Designing Facilities for Collaborative Operations; and Quantitating Iron in Serum Ferritin by Use of ICP-MS.

Source record↗

Flare Energy Release in the Lower Solar Atmosphere near the Magnetic Field Polarity Inversion Line

We study flare processes in the solar atmosphere using observational data for an M1-class flare of 2014 June 12, obtained by the New Solar Telescope (NST/BBSO) and Helioseismic Magnetic Imager (HMI/SDO). The main goal is to understand triggers and manifestations of the flare energy release in the photosphere and chromosphere using high-resolution optical observations and magnetic field measurements. We analyze optical images, HMI Dopplergrams, and vector magnetograms, and use nonlinear force-free field (NLFFF) extrapolations for reconstruction of the magnetic topology and electric currents. The NLFFF modeling reveals the interaction of two magnetic flux ropes with oppositely directed magnetic fields in the polarity inversion line (PIL). These flux ropes are observed as a compact sheared arcade along the PIL in the high-resolution broadband continuum images from NST. In the vicinity of the PIL, the NST Hα observations reveal the formation of a thin three-ribbon structure corresponding to a small-scale photospheric magnetic arcade. The observational results are evidence in favor of the primary energy release site located in the chromospheric plasma with strong electric currents concentrated near the PIL. In this case, magnetic reconnection is triggered by the interacting magnetic flux ropes forming a current sheet elongated along the PIL.

79 ASTRONOMY AND ASTROPHYSICS↗

The Cauchy Problem for Boltzmann Bi-linear Systems: The Mixing of Monatomic and Polyatomic Gases

Abstract From a unified vision of vector valued solutions in weighted Banach spaces, this paper establishes the existence and uniqueness for space homogeneous Boltzmann bi-linear systems with conservative collisional forms arising in complex gas dynamical structures. This broader vision is directly applied to dilute multi-component gas mixtures composed of both monatomic and polyatomic gases. Such models can be viewed as extensions of scalar Boltzmann binary elastic flows, as much as monatomic gas mixtures with disparate masses and single polyatomic gases, providing a unified approach for vector valued solutions in weighted Banach spaces. Novel aspects of this work include developing the extension of a general ODE theory in vector valued weighted Banach spaces, precise lower bounds for the collision frequency in terms of the weighted Banach norm, energy identities, angular or compact manifold averaging lemmas which provide coerciveness resulting into global in time stability, a new combinatorics estimate for p -binomial forms producing sharper estimates for the k -moments of bi-linear collisional forms. These techniques enable the Cauchy problem improvement that resolves the model with initial data corresponding to strictly positive and bounded initial vector valued mass and total energy, in addition to only a $$2^+$$ 2 + moment determined by the hard potential rates discrepancy, a result comparable in generality to the classical Cauchy theory of the scalar homogeneous Boltzmann equation.

Physics↗

Characterizing the uppermost 100 m structure of the San Jacinto fault zone southeast of Anza, California, through joint analysis of geological, topographic, seismic and resistivity data

We present results from complementary geological, topographic, seismic and electrical resistivity surveys at the Sagebrush Flat (SGB) site along the Clark fault (CF) strand of the San Jacinto fault zone trifurcation area southeast of Anza, California. Joint interpretation of these data sets, each with unique spatiotemporal sensitivities, allow us to better characterize the shallow (<100 m) fault zone at this structurally complex site. Geological mapping at the surface shows the CF has three main subparallel strands within a <100 m zone with varying degrees of rock damage. These strands intersect units of banded gneiss and tonalite, and various sedimentary units. Near the surface, the weathered but more intact tonalite and gneiss to the southwest have relatively high VP. The low-lying flat sedimentary basins around the two southwestern-most CF strands and elevated damaged gneiss to the northeast have lowest VP <500 m s–1. The high relief of the northeast gneiss unit may in part be explained by its extensive damage and inferred increased relative rock uplift. Resistivity imaging shows the unconsolidated dry basin sediments (maximum >1300 Ohm.m) contrasted against the compacted fine-grained (potentially wet) materials within the CF core and the Bautista Formation (minimum <40 Ohm.m), which is slightly elevated above the flat basins. The inverse relationship between VP (increases) and resistivity (decreases) in the uppermost ~15 m can be characterized as log–log linear with slopes of –2.6 to –4. At depths >30 m, the velocity heterogeneity near the surface merges into larger-scale structures that are generally slower on the northeast side of the CF core compared to the southwest side (as much as ~40 per cent reduction in average VP). A previous study revealed a 20–37 per cent variability in peak ground velocities across the SGB site from local earthquakes. The upper end of that range is associated with the near-surface unconsolidated sedimentary basins and northeast damaged gneiss unit. Preliminary analysis of time-dependent topography mostly shows effects of changing vegetation and anthropogenic activity.

Geochemistry & Geophysics↗

Elucidating the Dynamics of Electroweak Symmetry Breaking through Study of High-Multiplicity Boson Final States at the LHC

To understand the full story of the electroweak symmetry breaking (EWSB) and how the universe arrived at today’s universe, the structure of the Higgs potential needs to be probed. We must carefully select and study processes at the LHC that are sensitive to the Higgs potential. In this context, longitudinal vector boson scattering (VBS) processes, V L V L →V L V L , and di-Higgs production, including V L V L →HH at the LHC have been studied for any potential deviation from SM prediction. However, many classes of models beyond the Standard Model (BSM) may result in the 2→2 process being perfectly well-behaved and SM-like but show interesting deviations in 2→3, 2→4, or 2→n(3) processes. If we are to complete the mission objectives the P5 laid out, then a large swath of 2→n(3) must be thoroughly searched and checked. The research supported by this award used data collected at the Compact Muon Solenoid (CMS) detector at the Large Hadron Collider (LHC) to explore VBS produced VVH process in the semi-merged channel. In addition, in the electroweak sector, there are open questions in the multi-gauge boson couplings and the Higgs couplings to the gauge bosons. The research supported by the award also studied the triboson production WWZ process at the LHC, which is a crossed diagram of a VBS process. During the funded period of 9 months, the analysis designs have been finalized.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

The Unusual Multiwavelength Properties of the Gamma-Ray Source PMN J1603-4904

Context. We investigate the nature and classification of PMNJ1603-4904, a bright radio source close to the Galactic plane, which is associated with one of the brightest hard-spectrum gamma-ray sources detected by Fermi/LAT. It has previously been classified as a low peaked BL Lac object based on its broadband emission and the absence of optical emission lines. Optical measurements, however, suffer strongly from extinction and the absence of pronounced short-time gamma-ray variability over years of monitoring is unusual for a blazar. Aims. In this paper, we are combining new and archival multi-wavelength data of PMNJ1603-4904 in order to reconsider the classification and nature of this unusual gamma-ray source. Methods. For the first time, we study the radio morphology of PMNJ1603-4904 at 8.4GHz and 22.3GHz, and its spectral properties on milliarcsecond scales, based on VLBI observations from the TANAMI program. We combine the resulting images with multi-wavelength data in the radio, IR, optical/UV, X-ray, and gamma-ray regimes. Results. PMNJ1603-4904 shows a symmetric brightness distribution at 8.4 GHz on milliarcsecond scales, with the brightest, and most compact component in the center of the emission region. The morphology is reminiscent of a compact symmetric object (CSO). Such objects, thought to be young radio galaxies, have been predicted to produce gamma-ray emission but have not been detected as a class by the Fermi gamma-ray telescope so far. Sparse (u, v)-coverage at 22.3GHz prevents an unambiguous modeling of the source morphology at this higher frequency. Moreover, infrared measurements reveal an excess in the spectral energy distribution (SED), which can be modeled with a blackbody with a temperature of about 1600 K, and which is usually not present in blazar SEDs. Conclusions. The TANAMI VLBI data and the shape of the broadband SED challenge the current blazar classification of one of the brightest gamma-ray sources in the sky. PMNJ1603-4904 seems to be either a highly peculiar BL Lac object or a misaligned jet source. In the latter case, the intriguing VLBI structure opens room for a possible classification of PMNJ1603-4904 as a gamma-ray bright CSO.

Multiwavelength↗

Statistical Analysis in Support of Fuel Temperature Control in the Advanced Gas Reactor Experiments

There are four completed tests among a series of Advanced Gas Reactor (AGR) irradiation experiments that are being conducted within the Advanced Reactor Technologies (ART) Fuel Development and Qualification Program. The main objectives of the fuel experimental campaigns are to provide the necessary data on fuel performance to support fuel process development, qualify a fuel design and fabrication process for normal operation and hypothetical accident conditions, and support development and validation of fuel performance and fission product transport models and codes. Since this tri-structural isotropic fuel is qualified to be used in high temperature gas-cooled reactors (HTGRs), it is essential that the testing conditions of fuel irradiations are designed to mimic those in the conceptual gas reactors. As a result, temperatures of the AGR test fuel have to be maintained within a specified range that is typical of the HTGRs. In each AGR capsule, the test fuel temperature is controlled independently using a variable fraction neon and helium gas mixture that fills the gap volume for each capsule. The temperature as measured by a thermocouple (TC) terminated in the graphite holder (which houses fuel compacts) is used as a feedback for the gas flow controllers. Direct temperature measurement for fuel compacts is not possible because contact between a TC head and fuel particle could lead to undesirable failures. Therefore, an ABAQUS-based finite element thermal model was created to predict the daily average fuel temperatures during the entire irradiation period. It is well-known that extended exposure to neutron irradiation and high temperatures leads to changes in geometries of fuel compacts and graphite holder, which results in changes of the gas gap, leading to a change in the relationship between TC and fuel temperatures. In addition, TCs are expected to drift and sometimes fail under irradiation conditions. These facts make maintaining test fuel temperature within a specified range challenging. This paper describes how the regression analysis methods are used in conjunction with calculated fuel temperatures from early irradiation periods (when the irradiation effect is relatively small) to effectively control fuel temperature for the remaining irradiation (when the irradiation effect became profound). This is particularly important in the event when all TCs in a capsule fail.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

AGR-5/6/7 Ceramography Report

The Advanced Gas Reactor (AGR) Fuel Development and Qualification Program was established in 2002 to conduct research and development on tri-structural isotropic (TRISO)-coated particle fuel for High Temperature Gas-cooled Reactors (HTGRs). All AGR irradiations have been completed: AGR-1 (Collin 2015), AGR-2 (Collin 2014), AGR-3/4 (Collin 2016) and AGR-5/6/7 (Pham 2021). The objectives of each program are presented in Figure 1.1. The purpose of the AGR-5/6/7 program was to provide a baseline fuel qualification data set to support licensing, deployment, and operation of HTGRs in the United States. To achieve these goals, the program includes fuel fabrication, irradiations of TRISO fuels and high-temperature materials, safety testing and post-irradiation examination (PIE), fuel performance modeling, and fission product (FP) transport (Sharp 2020). The AGR-5/6/7 work continues as a final irradiation program of the Advanced Reactor Technologies (ART) program, that began in February 2018 and ended in July 2020. The AGR-5/6/7 fuel compacts were irradiated for a total of approximately 360.9 effective full power days (EFPDs) (Stempien 2023), resulting in final burn-up values, on a per-compact basis, ranging from 5.66% to 15.26% fissions per initial heavy metal atom (FIMA), and fast fluence values ranging from 1.62×1025 n/m2 to 5.55×1025 n/m2 (E >0.18 MeV) (Stempien 2022)

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High resolution CO images of Seyfert Galaxies

The CO (J = 1-0) emission of three Seyfert galaxies, NGC 3227, NGC 7469, and NGC 5033 was imaged. The CO emission in NGC 3227 and NGC 7469 appears as compact structures centered on the active nuclei, containing substantial fractions of the single-dish flux. In NGC 3227, 10 percent of the CO flux detected by the interferometer is contained within the ionized narrow-line region. The unresolved molecular gas concentrations in the nucleus of NGC 3227 imply a CO mass of 65 million solar masses concentrated within a diameter less than 50 pc. The CO emission in NGC 5033 is not detected at this resolution, implying a CO structure size of 20 to 60 arcsec. Continuum emission at 2.7 mm is not detected in any of the three galaxies. In the center of NGC 7469, the H2 mass is comparable to the dynamical mass. Kinematic studies of the detected gas reveal a rotational motion of the gas in NGC 3227 and NGC 7469, allowing identification of the gas in NGC 7469 with a nuclear starburst. These data are consistent with the idea that interactions between galaxies cause gas to concentrate in their nuclei thereby feeding starburst and Seyfert activity.

Meixner, M.↗

Design of a shipping fixture for a compact cryomodule hermetic assembly

In support of the development of a conduction-cooled 915MHz superconducting radio frequency (SRF) cryomodule, this study highlights the design of a shipping fixture for transporting the hermetic assembly 4500 km from Jefferson Lab to General Atomics in San Diego, California. The hermetic assembly consists of a 2-cell 915 MHz SRF cavity, a coaxial fundamental power coupler and warm-to-cold transition beam tubes. The two-part shipping assembly consists of an inner frame, providing direct mounting of the components, and an outer frame mounted to the ground transport vehicle. The inner frame is then connected to the outer frame by way of wire-rope isolators. Accelerometer data from ground transportation of previous projects at Jefferson Lab provides the baseline for the expected frequency and magnitude of vibrational and shock events during transit. Modal analyses were carried out in ANSYS on the inner frame assembly and critical components to identify an appropriate wire-rope isolator configuration such that peak loads are mitigated and the incurred frequencies do not correspond with the fundamental modes of the structures.

Accelerator Physics↗

Gravitational waves and galaxies cross-correlations: a forecast on GW biases for future detectors

ABSTRACT Gravitational waves (GWs) have rapidly become important cosmological probes since their first detection in 2015. As the number of detected events continues to rise, upcoming instruments like Einstein Telescope (ET) and Cosmic Explorer (CE) will observe millions of compact binary mergers. These detections, coupled with galaxy surveys by instruments such as the Dark Spectroscopic Energy Instrument (DESI), Euclid, and the Vera Rubin Observatory, will provide unique information on the large-scale structure of the universe by cross-correlating GWs with the distribution of galaxies hosting them. In this paper, we focus on how cross-correlations constrain the clustering bias of GWs emitted by the coalescence of binary black holes (BBHs). This parameter links BBHs to the underlying dark matter distribution, hence informing us how they populate galaxies. Using a multitracer approach, we forecast the precision of these measurements under different survey combinations. Our results indicate that current GW detectors will have limited precision, with measurement errors as high as $\displaystyle \sim 50~{{\ \rm per\ cent}}$. However, third-generation detectors like ET, when cross-correlated with Legacy Survey of Space and Time (LSST) data, can improve clustering bias measurements to within 2.5 per cent. Furthermore, we demonstrate that these cross-correlations can enable a per cent-level measurement of the magnification lensing effect on GWs. Despite this, there is a degeneracy between magnification and evolution biases, which hinders the precision of both. This degeneracy is most effectively addressed by assuming knowledge of one bias or targeting an optimal redshift range of $\displaystyle 1 \lt z \lt 2.5$. Our analysis opens new avenues for studying the distribution of BBHs and testing the nature of gravity through large-scale structure.

Zazzera, Stefano (ORCID:0000000158979221)↗

Freely Expanding Knots of X-Ray-emitting Ejecta in Kepler’s Supernova Remnant

We report measurements of proper motion, radial velocity, and elemental composition for 14 compact X-ray-bright knots in Kepler’s supernova remnant (SNR) using archival Chandra data. The knots with the highest speed show both large proper motions ( μ ∼ 0.″11–0.″14 yr{sup −1}) and high radial velocities ( v ∼ 8700–10,020 km s{sup −1}). For these knots the estimated space velocities (9100 km s{sup −1} ≲ v {sub 3D} ≲ 10,400 km s{sup −1}) are similar to the typical Si velocity seen in supernovae (SNe) Ia near maximum light. High-speed ejecta knots appear only in specific locations and are morphologically and kinematically distinct from the rest of the ejecta. The proper motions of five knots extrapolate back over the age of Kepler’s SNR to a consistent central position. This new kinematic center agrees well with previous determinations, but is less subject to systematic errors and denotes a location about which several prominent structures in the remnant display a high degree of symmetry. These five knots are expanding at close to the free expansion rate (expansion indices of 0.75 ≲ m ≲ 1.0), which we argue indicates either that they were formed in the explosion with a high density contrast (more than 100 times the ambient density) or that they have propagated through regions of relatively low density ( n {sub H} < 0.1 cm{sup −3}) in the ambient medium. X-ray spectral analysis shows that the undecelerated knots have high Si and S abundances, a lower Fe abundance, and very low O abundance, pointing to an origin in the partial Si-burning zone, which occurs in the outer layer of the exploding white dwarf for models of SNe Ia. Other knots show lower speeds and expansion indices consistent with decelerated ejecta knots or features in the ambient medium overrun by the forward shock. Our new accurate location for the explosion site has well-defined positional uncertainties, allowing for a great reduction in the area to be searched for faint surviving donor stars under non-traditional single-degenerate SNe Ia scenarios; because of the lack of bright stars in the search area the traditional scenario remains ruled out.

79 ASTRONOMY AND ASTROPHYSICS↗

Lunar near-surface structure

Seismic refraction data obtained at the Apollo 14, 16, and 17 landing sites permit a compressional wave velocity profile of the lunar near surface to be derived. Beneath the regolith at the Apollo 14 Fra Mauro site and the Apollo 16 Descartes site is material with a seismic velocity of about 300 m/sec, believed to be brecciated material or impact-derived debris. Considerable detail is known about the velocity structure at the Apollo 17 Taurus-Littrow site. Seismic velocities of 100, 327, 495, 960, and 4700 m/sec are observed. The depth to the top of the 4700-m/sec material is 1385 m, compatible with gravity estimates for the thickness of mare basaltic flows, which fill the Taurus-Littrow valley. The observed magnitude of the velocity change with depth and the implied steep velocity-depth gradient of more than 2 km/sec/km are much larger than have been observed on compaction experiments on granular materials and preclude simple cold compaction of a fine-grained rock powder to thicknesses of the order of kilometers.

Cooper, M. R.↗

Pulse-Timing Studies of X Ray Pulsars

The pulse-timing projects supported by NASA Grant NAG8-695 were motivated in large part by our long-standing interest in the physics of rotating neutron stars and particularly the variations in rotation due to internal and external fluctuating torques. For accretion-powered pulsars, observed as compact galactic X-ray sources, our work has been motivated by questions regarding the physics of matter accretion, mass transfer, and mass loss in these X-ray binary systems. For rotation-powered pulsars using X-ray, optical, and radio observations, we have examined the internal structure of neutron stars and mechanisms for secular spin-down. These issues are still central to the continuing process of understanding the complex behavior of these fascinating systems. The work supported by this grant is based mainly on Ginga observations of three pulsating X-ray sources. We observed two of these sources (Her X-1 and SMC X-1) within the framework of a NASA-ISAS program for U.S.-Japan collaborations to obtain and analyze Ginga observations. In addition, we joined with members of the Ginga team to apply our pulse-timing methods to PSR 0540-69 data obtained as a collateral benefit of the regular monitoring by Ginga of SN 1987A. In addition to these Ginga observations, there exist other relevant data on all three of these sources. The direction of our investigations has been affected by the necessity of including these supporting data in our analyses, and setting up the necessary collaborations has sometimes entailed extra work that was not anticipated in our proposals. Indeed, we have often taken the initiative in establishing these joint projects.

Deeter, John E.↗

Micro pulse laser radar

An eye safe, compact, solid state lidar for profiling atmospheric cloud and aerosol scattering is disclosed. The transmitter of the micro pulse lidar is a diode pumped micro-J pulse energy, high repetition rate Nd:YLF laser. Eye safety is obtained through beam expansion. The receiver employs a photon counting solid state Geiger mode avalanche photodiode detector. Data acquisition is by a single card multichannel scaler. Daytime background induced quantum noise is controlled by a narrow receiver field-of-view and a narrow bandwidth temperature controlled interference filter. Dynamic range of the signal is limited to optical geometric signal compression. Signal simulations and initial atmospheric measurements indicate that micropulse lider systems are capable of detecting and profiling all significant cloud and aerosol scattering through the troposphere and into the stratosphere. The intended applications are scientific studies and environmental monitoring which require full time, unattended measurements of the cloud and aerosol height structure.

Spinhirne, James D.↗

Nucleophilic Displacement Reactions of Silver-Based Metal–Organic Chalcogenolates

Here, we report nucleophilic displacement reactions that can increase the dimensionality or coordination number of silver-based metal–organic chalcogenolates (MOChas). MOChas are crystalline ensembles containing one-dimensional (1D) or two-dimensional (2D) inorganic topologies with structures and properties defined by the choice of metal, chalcogen, and ligand. MOChas can be readily prepared from a variety of small-molecule ligands and metals or metal ions. Although MOChas offer ligand diversity, most reported examples use relatively small ligands, typically involving short alkyl chains, aryl rings, or molecular cages. This is because larger, more complex molecules often yield poor product morphologies with indeterminate structures. In this study, we overcame this limitation by employing a ligand exchange strategy whereby a 1D MOCha, silver(I) methyl 2-mercaptobenzoate (2MMB), is used as a silver source for preparing 2D examples. The reaction proceeds generally toward products composed of the stronger nucleophile. We show that the reaction prefers displacing 1D topologies to yield 2D ones and replacing thiolates with selenolates. We performed a study to characterize the mechanism by which organic chalcogenols and dichalcogenides exchange with MOChas. The collected data and product analysis support a proposed mechanism of nucleophilic substitution, explaining how both organic chalcogenols and dichalcogenides can displace ligands in MOChas. This work provides a new synthetic route that will enable the preparation of more elaborate MOChas and heterostructures thereof. This approach enabled the preparation of previously inaccessible oligophenyl MOChas, which were successfully solved via small-molecule serial femtosecond crystallography (smSFX) at the SPring-8 Ångström Compact Free Electron LAser (SACLA) facility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

HyMARC Seedling: Optimized Hydrogen Adsorbents via Machine Learning and Crystal Engineering

This final report is presented in two parts: In Part 1, the H 2 capacities of a diverse set of 918,734 metal-organic frameworks (MOFs) sourced from 19 databases is predicted via machine learning (ML). Using only 7 structural features as input, ML identifies 8,282 MOFs with the potential to exceed the capacities of state-of-the-art materials. The identified MOFs are predominantly hypothetical compounds having low densities (<0.31 g/cm3) in combination with high surface areas (>5,300 m2/g), void fractions ($0.90), and pore volumes (>3.3 cm3/g). The relative importance of the input features are characterized, and dependencies on the ML algorithm and training set size are quantified. The most important features for predicting H 2 uptake are pore volume (for gravimetric capacity) and void fraction (for volumetric capacity). The ML models are available on the web, allowing for rapid and accurate predictions of the hydrogen capacities of MOFs from limited structural data; the simplest models require only a single crystallographic feature. In part 2, ways to improve the poor powder packing density of MOFs is discussed. More specifically, a strategy that improves packing efficiency and volumetric hydrogen gas storage density dramatically through engineered morphologies and controlled-crystal size distributions is presented that holds promise for maximizing storage capacity for a given MOF. The packing density improvement, demonstrated for the benchmark sorbent MOF-5, leads to a significant enhancement of volumetric hydrogen storage performance relative to commercial MOF-5. System model projections demonstrate that engineering of crystal morphology/size or use of a bimodal distribution of cubic crystal sizes in tandem with system optimization can surpass the 25 g/L volumetric capacity of a typical 700 bar compressed storage system and exceed the DOE targets 2020 volumetric capacity (30 g/L). Finally, a critical link between improved powder packing density and reduced damage upon compaction is revealed leading to sorbents with both high surface area and high density.

08 HYDROGEN↗