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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Advancing Pore–Space–Partitioned Metal–Organic Frameworks with Isoreticular Cluster Concept

Trigonal planar M 3 (O/OH) trimers are among the most important clusters in inorganic chemistry and are the foundational features of multiple high-impact MOF platforms. Here we introduce a concept called isoreticular cluster series and demonstrate that M 3 (O/OH), as the first member of a supertrimer series, can be combined with a higher hierarchical member (double-deck trimer here) to advance isoreticular chemistry. We report here an isoreticular series of pore-space-partitioned MOFs called M 3 M 6 pacs made from co-assembly between M 3 single-deck trimer and M 3x2 double-deck trimer. Important factors were identified on this multi-modular MOF platform to guide optimization of each module, which enables the phase selection of M 3 M 6 pacs by overcoming the formation of previously-always-observed same-cluster phases. The new pacs materials exhibit high surface area and high uptake capacity for CO 2 and small hydrocarbons, as well as selective adsorption properties relevant to separation of industrially important mixtures such as C 2 H 2 /CO 2 and C 2 H 2 /C 2 H 4 . Furthermore, new M 3 M 6 pacs materials show electrocatalytic properties with high activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Multi–Stage Optimization of Pore Size and Shape in Pore–Space–Partitioned Metal–Organic Frameworks for Highly Selective and Sensitive Benzene Capture

Compared to exploratory development of new structure types, pushing the limits of isoreticular synthesis on a high-performance MOF platform may have higher probability of achieving targeted properties. Multi-modular MOF platforms could offer even more opportunities by expanding the scope of isoreticular chemistry. However, navigating isoreticular chemistry towards best properties on a multi-modular platform is challenging due to multiple interconnected pathways. Here on the multi-modular pacs (partitioned acs) platform, we demonstrate accessibility to a new regime of pore geometry using two independently adjustable modules (framework-forming module 1 and pore-partitioning module 2). A series of new pacs materials have been made. Benzene/cyclohexane selectivity is tuned, progressively, from 4.5 to 15.6 to 195.4 and to 482.5 by pushing the boundary of the pacs platform towards the smallest modules known so far. The exceptional stability of these materials in retaining both porosity and single crystallinity enables single-crystal diffraction studies of different crystal forms (as-synthesized, activated, guest-loaded) that help reveal the mechanistic aspects of adsorption in pacs materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Computational Investigation of the Catalytic Hydrodeoxygenation of Propanoic Acid over a Cu(111) Surface

Cu-based alloy catalysts have recently been investigated experimentally for the hydrodeoxygenation (HDO) of biomass-derived organic acids. Here, the HDO of propanoic acid (PAc) has been studied over Cu(111) by mean-field microkinetic modeling based on parameters obtained from first-principles calculations. Models were developed for the gas- and liquid-phase HDO in condensed water and 1,4-dioxane. In agreement with experimental observations, the gas-phase PAc conversion rate is low at 573 K and increases in liquid water by 1 order of magnitude. In all reaction environments, the decarboxylation mechanism is dominant at low hydrogen partial pressures less than 0.1 bar, and the C–COO bond dissociation is the rate-controlling elementary step. This observation contrasts with the rate-controlling step identified over most group VIII metal surfaces, which is the C–OH bond dissociation in the decarbonylation mechanism. At high hydrogen (H 2 ) partial pressures greater than 10 bar, the HDO of PAc produces propionaldehyde that can readsorb and further react through decarbonylation to produce C 2 alkane products, which is conceptually different from the low H 2 partial pressure scenario. At high H 2 partial pressures, the initial hydrogenation at the carbonyl carbon of PAc becomes the rate-controlling elementary step.

Catalysts↗
DOE OSTI2020

Photochemical Upconversion in Water Using Cu(I) MLCT Excited States: Role of Energy Shuttling at the Micellar/Water Interface

Photochemical upconversion (UC) through triplet–triplet annihilation (TTA), which employs a visible absorbing triplet photosensitizer and an annihilator, is a process that generates a high energy photon from two lower energy photons. TTA-UC has been largely developed in pure organic solvents and solid-state polymeric constructs while featuring near exclusive use of rare and expensive metals within the photosensitizer. In this current investigation, we demonstrate that TTA-UC from the long lifetime earth-abundant photosensitizer [Cu(dsbtmp) 2 ](PF) 6 (dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline), abbreviated as Cu-PS, functions in water through encapsulation within a cationic-based assembly. Cetyltrimethylammonium bromide was the surfactant of choice as it electrostatically binds the negatively charged water-soluble 10-phenylanthracene-9-carboxylate (PAC) acceptor/annihilator and ultimately facilitates energy transfer across the interface. Efficient triplet–triplet energy transfer (TTET) from Cu-PS to the PAC acceptor was achieved in this aqueous assembly. Unfortunately, the hindered mobility of the PAC moieties ultimately hampered the annihilation process, and this was reflected in attenuated TTA rates and efficiencies. The combined experimental data illustrated that the water-soluble PAC acceptor was able to vectorially deliver the excited-state energy stored in Cu-PS across the interface into the bulk aqueous solution by engaging in excited-state electron transfer with methyl viologen acceptors. Lastly, these results are important for remotely operating photoredox reactions in water while rendering a photosensitizer spatially isolated in the hydrophobic core of a micelle.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Field Evaluation of Do-It-Yourself Air Filtration Solutions for Evaporative Coolers to Reduce Ambient Particle Infiltration in Homes in Wildfire-Affected Communities

Evaporative coolers (ECs) introduce outdoor air pollutants indoors when operating. This study evaluates the potential of do-it-yourself (DIY) air filtration solutions for ECs to cost-effectively reduce the infiltration of ambient fine particulate matter (PM2.5) in homes with ECs using measurements in 48 homes in wildfire-affected agricultural communities in California. All homes received one portable air cleaner (PAC); 25 homes also received DIY filters (mostly MERV 13) attached to their ECs. PurpleAir monitors measured indoor and outdoor PM2.5 concentrations. PAC operation was monitored in all of the homes. EC usage was monitored in some homes and predicted using relative humidity dynamics in all homes. Conditional analyses between EC likely on and off conditions were used to evaluate the impacts of DIY EC filters on ambient PM2.5 infiltration, including during several wildfire-affected days. Median levels of ambient PM2.5 infiltration increased ∼36-42% in homes with only PAC interventions when ECs were likely operating compared to only ∼10-11% in homes with both PACs and DIY EC filters. Pre/postintervention comparisons in a subset of homes confirmed PM2.5 infiltration reductions. EC filter performance declined after extended use. Results suggest that short-term EC filter deployments are likely a cost-effective way to mitigate wildfire smoke infiltration inside these homes.

Wang, Mingyu↗
DOE OSTI2020

A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C 2 Hydrocarbons and CO 2

Abstract Introduction of pore partition agents into hexagonal channels of MIL‐88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4,4′‐dipyridylsulfide (dps) ligands. One third of open metal sites in the acs net are retained in pacs MOFs; two thirds are used for pore‐space partition. The Co 2 V‐pacs MOFs exhibit near or at record high uptake capacities for C 2 H 2 , C 2 H 4 , C 2 H 6 , and CO 2 among MOFs. The storage capacity of C 2 H 2 is 234 cm 3 g −1 (298 K) and 330 cm 3 g −1 (273 K) at 1 atm for CPM‐733‐dps (the Co 2 V‐BDC form, BDC=1,4‐benzenedicarboxylate). These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low‐energy‐cost adsorbent regeneration. CPM‐733‐dps is stable and shows no loss of C 2 H 2 adsorption capacity following multiple adsorption–desorption cycles.

Wang, Yong↗
DOE OSTI2025

Isoreticular Tolerance and Phase Selection in the Synthesis of Multi‐Module Metal–Organic Frameworks for Gas Separation and Electrocatalytic OER

Abstract Although metal–organic frameworks are coordination‐driven assemblies, the structural prediction and design using metal‐ligand interactions can be unreliable due to other competing interactions. Leveraging non‐coordination interactions to develop porous assemblies could enable new materials and applications. Here, we use a multi‐module MOF system to explore important and pervasive impact of ligand‐ligand interactions on metal‐ligand as well as ligand‐ligand co‐assembly process. It is found that ligand‐ligand interactions play critical roles on the scope or breakdown of isoreticular chemistry. With cooperative di‐ and tri‐topic ligands, a family of Ni‐MOFs has been synthesized in various structure types including partitioned MIL‐88‐acs ( pacs ), interrupted pacs (i‐ pacs ), and UMCM‐1‐muo. A new type of isoreticular chemistry on the muo platform is established between two drastically different chemical systems. The gas sorption and electrocatalytic studies were performed that reveal excellent performance such as high C 2 H 2 /CO 2 selectivity of 21.8 and high C 2 H 2 uptake capacity of 114.5 cm 3 /g at 298 K and 1 bar.

Xiao, Yuchen [Department of Chemistry University o↗
DOE OSTI2025

Isoreticular Tolerance and Phase Selection in the Synthesis of Multi‐Module Metal–Organic Frameworks for Gas Separation and Electrocatalytic OER

Abstract Although metal–organic frameworks are coordination‐driven assemblies, the structural prediction and design using metal‐ligand interactions can be unreliable due to other competing interactions. Leveraging non‐coordination interactions to develop porous assemblies could enable new materials and applications. Here, we use a multi‐module MOF system to explore important and pervasive impact of ligand‐ligand interactions on metal‐ligand as well as ligand‐ligand co‐assembly process. It is found that ligand‐ligand interactions play critical roles on the scope or breakdown of isoreticular chemistry. With cooperative di‐ and tri‐topic ligands, a family of Ni‐MOFs has been synthesized in various structure types including partitioned MIL‐88‐acs ( pacs ), interrupted pacs (i‐ pacs ), and UMCM‐1‐muo. A new type of isoreticular chemistry on the muo platform is established between two drastically different chemical systems. The gas sorption and electrocatalytic studies were performed that reveal excellent performance such as high C 2 H 2 /CO 2 selectivity of 21.8 and high C 2 H 2 uptake capacity of 114.5 cm 3 /g at 298 K and 1 bar.

Xiao, Yuchen [Department of Chemistry University o↗
DOE OSTI2023

Application of Cell Painting for chemical hazard evaluation in support of screening-level chemical assessments

‘Cell Painting’ is an imaging-based high-throughput phenotypic profiling (HTPP) method in which cultured cells are fluorescently labeled to visualize subcellular structures (i.e., nucleus, nucleoli, endoplasmic reticulum, cytoskeleton, Golgi apparatus / plasma membrane and mitochondria) and to quantify morphological changes in response to chemicals or other perturbagens. HTPP is a high-throughput and cost-effective bioactivity screening method that detects effects associated with many different molecular mechanisms in an untargeted manner, enabling rapid in vitro hazard assessment for thousands of chemicals. Here, 1201 chemicals from the ToxCast library were screened in concentration-response up to ~100 μM in human U-2 OS cells using HTPP. A phenotype altering concentration (PAC) was estimated for chemicals active in the tested range. PACs tended to be higher than lower bound potency values estimated from a broad collection of targeted high-throughput assays, but lower than the threshold for cytotoxicity. In vitro to in vivo extrapolation (IVIVE) was used to estimate administered equivalent doses (AEDs) based on PACs for comparison to human exposure predictions. AEDs for 18/412 chemicals overlapped with predicted human exposures. Phenotypic profile information was also leveraged to identify putative mechanisms of action and group chemicals. Of 58 known nuclear receptor modulators, only glucocorticoids and retinoids produced characteristic profiles; and both receptor types are expressed in U-2 OS cells. Thirteen chemicals with profile similarity to glucocorticoids were tested in a secondary screen and one chemical, pyrene, was confirmed by an orthogonal gene expression assay as a novel putative GR modulating chemical. Most active chemicals demonstrated profiles not associated with a known mechanism-of-action. However, many structurally related chemicals produced similar profiles, with exceptions such as diniconazole, whose profile differed from other active conazoles. Overall, the present study demonstrates how HTPP can be applied in screening-level chemical assessments through a series of examples and brief case studies.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2024

Tailoring Interface Energies via Phosphonic Acids to Grow and Stabilize Cubic FAPbI 3 Deposited by Thermal Evaporation

Coevaporation of formamidinium lead iodide (FAPbI 3 ) is a promising route for the fabrication of highly efficient and scalable optoelectronic devices, such as perovskite solar cells. However, it poses experimental challenges in achieving stoichiometric FAPbI 3 films with a cubic structure (α-FAPbI 3 ). In this work, we show that undesired hexagonal phases of both PbI 2 and FAPbI 3 form during thermal evaporation, including the well-known 2H-FAPbI 3 , which are detrimental for optoelectronic performance. We demonstrate the growth of α-FAPbI 3 at room temperature via thermal evaporation by depositing phosphonic acids (PAc) on substrates and subsequently coevaporating PbI 2 and formamidinium iodide. We use density-functional theory to develop a theoretical model to understand the relative growth energetics of the α and 2H phases of FAPbI 3 for different molecular interactions. Experiments and theory show that the presence of PAc molecules stabilizes the formation of α-FAPbI 3 in thin films when excess molecules are available to migrate during growth. This migration of molecules facilitates the continued presence of adsorbed organic precursors at the free surface throughout the evaporation, which lowers the growth energy of the α-FAPbI 3 phase. Our theoretical analyses of PAc molecule–molecule interactions show that ligands can form hydrogen bonding to reduce the migration rate of the molecules through the deposited film, limiting the effects on the crystal structure stabilization. Our results also show that the phase stabilization with molecules that migrate is long-lasting and resistant to moist air. These findings enable reliable formation and processing of α-FAPbI 3 films via vapor deposition.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Jacobian-free pseudo-arclength continuation method for phase transitions in inhomogeneous thermodynamic systems

Developing phase diagrams for inhomogeneous systems in thermodynamics is difficult, in part, due to the large phase space and the possibility of unstable and metastable solutions arising from first-order phase transitions. Pseudo-arclength continuation (PAC) is a method that allows one to trace out stable and unstable solutions of nonlinear systems. Typically, PAC utilizes the Jacobian in order to implement Newton (or quasi-Newton) steps. In this work, we present a Jacobian-free PAC method that is amenable to the usual workflows in inhomogeneous thermodynamics. We demonstrate our method in systems that have first-order phase transitions, including a novel example of polyelectrolyte complex coacervation in confinement, where multiple surface phase transitions occur and can overlap with one another.

Chemistry↗
DOE OSTI2022

Successive neutron alignments in the yrast, negative-parity band of oblate-deformed Tl 199

The negative-parity band structure built on the proton h 9/2 state in 199 Tl has been established up to an excitation energy of 7 MeV and spin of (51/2) ℏ. The level scheme has been extended with the inclusion of fourteen new transitions de-exciting levels at high spin. The ΔI = 1 γ rays are found to be more prominently visible in the spectra when comparing to Δ I = 2 transitions. Rotation alignments are evident at frequencies of 0.22 and 0.30 MeV with both being attributed to the breaking of pairs of neutrons in the i 13/2 subshell. Since 199 Tl is expected to have weak oblate deformation, and lies in a transitional region where competing contributions to the spin are expected from collective rotation and the angular momentum of high-j nucleons, calculations using both the principal axis cranking (PAC) and tilted axis cranking (TAC) formalisms have been performed to understand its structure. Both the PAC and TAC calculations are found to provide a satisfactory description of the evolution of excitation energies with spin. The PAC calculations give a good account of the experimental crossing frequencies and associated spins. Furthermore, the structure of the yrast, negative-parity band in 199 Tl may be primarily understood in terms of the collective rotation of a moderately deformed oblate nucleus, along with contributions to the angular momentum from two pairs of rotation-aligned i 13/2 neutrons.

190 ≤ A ≤ 219↗
NASA NTRS1985

Demonstration of relaxed static stability on a commercial transport

The application of relaxed static stability was studied under a program to determine ways of improving the energy efficiency in current and future transport aircraft. Pitch active control systems (PACs) were developed for application in the near term to current aircraft and in the next generation to advanced aircrft of the future. Analyses identified potential drag benefits of: (1) 2% for current transport aircraft with neutral stability; and (2) as much as 17% for next generation aircraft with high aspect ratio supercritical wings which must operate 10 to 15% statistically unstable to achieve optimum performance. Flight test evaluations of the near-term PACs were conducted to a 3% mean aerodynamic chord (MAC) negative static margin on a Lockheed L-1011 aircraft. The advanced PACs was demonstrated to a 20% MAC negative static margin on a piloted visual motion simulator at the NASA Langley Research Center. Test results for both systems showed flying qualities characteristics as good as current conventional aircraft.

Rising, J. J.↗
NASA NTRS1984

Development of an advanced pitch active control system and a reduced area horizontal tail for a wide-body jet aircraft

The development of an advanced pitch active control system (PACS) and a reduced area horizontal tail for a wide-body jet transport (L-1011) with a flying horizontal stabilizer is discussed. The advanced PACS control law design objectives were to provide satisfactory handling qualities for aft c.g. flight conditions to negative static stability margins of 10 percent and to provide good maneuver control column force gradients for nonlinear stability flight conditions. Validity of the control laws were demonstrated by piloted flight simulation tests on the NASA Langley Visual Motion Simulator. Satisfactory handling qualities were actually demonstrated to a negative 20 percent static stability margin. The PACS control laws were mechanized to provide the system architecture that would be suitable for an L-1011 flight test program to a negative stability margin of 3 percent which represents the aft c.g. limits of the aircraft. Reduced area horizontal tail designs of 30 and 38 percent with respect to the L-1011 standard tail were designed, fabricated and wind tunnel tested. Drag reductions and weight savings of the 30 percent smaller tail would provide an L/D benefit of about 2% and the 38% small tail L/D benefit would be about 3 percent. However, forward c.g. limitations would have to be imposed on the aircraft because the maximum horizontal tail lift goal was not achieved and sufficient aircraft nose-up control authority was not available. This limitation would not be required for a properly designed new aircraft.

Guinn, Wiley A.↗
NASA NTRS1983

Extended flight evaluation of a near-term pitch active control system

Fuel savings can be achieved by moving the center of gravity of an aircraft aft which reduces the static stability margin and consequently the trim drag. However, flying qualities of an aircraft with relaxed static stability can be significantly degraded. The flying qualities can be restored by using a pitch active control system (PACS). This report documents the work accomplished during a follow-on program (see NASA CR-165951 for initial program report) to perform extended flight tests of a near-term PACS. The program included flying qualities analyses, piloted flight simulation tests, aircraft preparation and flight tests to demonstrate that the near-term PACS provided good flying qualities within the linear static stability envelope to a negative 3% static stability margin.

Guinn, Wiley A.↗
NASA NTRS2010

GASPS Photometry of the Tucana-Horologium Association

The GASPS Open Time Key Programme on Herschel represents a new opportunity to sensitively probe protoplanetary and debris disks at far-IR wavelengths. We present preliminary PACS 70 and 160 micron photometry of eighteen stars in the 30 Myr-old Tucana-Horologium association. Of these eighteen, eight were detected in the 70 micron band. Four of these eight were also detected in the 160 micron band. We constructed SEDs for these systems using optical data from Hipparcos (B and V), near-IR data from 2MASS (J, H, and K), mid-IR data from IRAS and Spitzer MIPS (12 and 24 microns, respectively), and the new far-IR data from PACS. For the stars showing IR excess emission, we fit simple single-temperature blackbody curves to the IR excess in order to determine the rough dust abundances and temperatures. Dust observations at these wavelengths will also be important for comparison with upcoming Herschel PACS spectra that will search for gas in the disks. Our goal is to determine or limit the ever-allusive gas-to-dust ratio for these disk systems.

Roberge, Donaldson J.↗
NASA NTRS2012

HD 172555: Detection of 63 micrometers [OI] Emission in a Debris Disc

Context. HD 172555 is a young A7 star belonging to the Beta Pictoris Moving Group that harbours a debris disc. The Spitzer IRS spectrum of the source showed mid-IR features such as silicates and glassy silica species, indicating the presence of a warm dust component with small grains, which places HD 172555 among the small group of debris discs with such properties. The IRS spectrum also shows a possible emission of SiO gas. Aims. We aim to study the dust distribution in the circumstellar disc of HD 172555 and to asses the presence of gas in the debris disc. Methods. As part of the GASPS Open Time Key Programme, we obtained Herschel-PACS photometric and spectroscopic observations of the source. We analysed PACS observations of HD 172555 and modelled the Spectral Energy Distribution (SED) with a modified blackbody and the gas emission with a two-level population model with no collisional de-excitation. Results. We report for the first time the detection of [OI] atomic gas emission at 63.18 micrometers in the HD 172555 circumstellar disc.We detect excesses due to circumstellar dust toward HD 172555 in the three photometric bands of PACS (70, 100, and 160 m). We derive a large dust particle mass of (4.8 plus-minus 0.6)x10(exp -4) Mass compared to Earth and an atomic oxygen mass of 2.5x10(exp -2)R(exp 2) Mass compared to Earth, where R in AU is the separation between the star and the inner disc. Thus, most of the detected mass of the disc is in the gaseous phase.

Riviere-Marichalar, P.↗