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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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All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Th-230 - U-238 series disequilibrium of the Olkaria rhyolites Gregory Rift Valley, Kenya: Petrogenesis

Positive correlations of (U-238/Th-230) versus Th show the rhyolites to be products of partial melting. Positive correlations of U and Cl and U and F show that the U enrichment in the rhyolites is associated with the halogen contents which may be related to the minor phenocryst phase fractionation. Instantaneous Th/U ratios exceed time integrated Th/U ratios providing further evidence of the hydrous nature of the Olkaria rhyolite source. Excess (U-238/Th-230) in the subduction related rocks has been associated to the preferential incorporation of uranium in slab derived fluids, but no evaluation of the size of this flux has been made. The majority of the Naivasha samples show a (U-238/Th-230) less than 1 and plot close to the subduction related samples indicating the Naivasha rhyolites may also have been influenced by fluids during their formation. In general samples with high (U-238/Th-230) ratios reflecting recent enrichment of uranium relative to thorium have high thorium contents, thereby the high (U-238/Th-230) ratios are restricted to the most incompatible element enriched magmas and, hence, are a good indication that the rhyolites were formed by partial melting. If a fluid phase had some influence on the formation of the rhyolites then the uranium and thorium may have some correlation with F and Cl contents which can be mirrored by the peralkalinity. Plots of uranium against F and Cl contents are shown. The positive correlation indicates that the uranium enrichments are associated with the halogen contents. There seems to be a greater correlation for U against Cl than F indicating that the U may be transported preferentially as Cl complexes.

Black, S.↗
NASA NTRS1981

Flammability and Photo-Stability of Selected Polymer Systems

A systematic approach to the improvement of the flammability of epoxy resins, bisphenol-A polycarbonate poly(butylene terephthalate), and Nylon 6.6 by introducing halogens and loop functionality into the flame retardants is described. The phthalides (the loop functionality containing molecules) include 3,3-bis(4-bromophenyl)-phthalide, 3,3-bis(4-chlorophenyl)phthalide, and phenolphthalein. The phthalide containing epoxy resins are synthesized and characterized in comparison with the bisphenol-A epoxy resins in terms of flammability in the copolymer systems. The resins include diglycidyl ethers of phenolphthalein, bisphenol-A. tetrabromobisphenol-A, and tetraoromophenolphthalein. The vaporization of the phthalide additive in the polymers is observed in Thermal Gravimetric Analysis. The flame retardancy is primarily due to the presence of halogens. In the poly(butylene terephthalate) system, the cleavage of the C(sub aromatic) -B bond of the flame retardant additive enhances the crosslinking react ions between the aromatic rings resulting in an increase of char formation. In the epoxy resin systems, loop functionality contributes to char formation to a larger extent. The interaction between the epoxy resin and poly-(butylene terephthalate) follows the mechanism of insertion of the oxirane ring into the ester bond. This mechanism is studied by FT-IR. The investigation of the thermal properties of the char-forming phenol-formaldehyde resins is conducted to provide information for the systematic design of high temperature flame-resistant phenolics. NMR and FT-IR are used to characterize the oligomeric resins and the cured resins. The curing agents used in the study include formaldehyde, s-trioxane and terephthaloyl chloride. The brominated phenolic resins are found to have higher oxygen indices with lower char yields.

Lo, Jeelin↗
NASA NTRS2000

A Simulation of Bromoform's Contribution to Stratospheric Bromine

Many chlorinated and brominated compounds that are inert in the troposphere are destroyed in the stratosphere and act as an in-situ source of stratospheric reactive chlorine and bromine. Other halogenated compounds that are reactive in the troposphere might contribute to the stratosphere's halogen budget in two ways. First, like their unreactive companions, rapid convective transport might carry them to the upper troposphere and make them available for subsequent advection by the mean circulation into the stratosphere before they are oxidized or photolyzed. Second, it is more likely that they are destroyed in the troposphere, and the chlorine and bromine that is released might then be transported to the stratosphere. We evaluate the relative influence of these processes on stratospheric bromine in a three-dimensional chemistry and transport model which simulates the distribution of bromoform (CHBr3). CHBr3 is parameterized as a short-lived, ocean-surface source gas whose destruction by photolysis and reaction with hydroxyl (OH) in the troposphere and stratosphere yields inorganic bromine (Br(sub y)). Many of the observed features of CHBr3 are simulated well, and comparisons with observations are used to show that the model represents aspects of transport in the upper troposphere and lower stratosphere that are critical to the evaluation. In particular, the model maintains the observed troposphere-stratosphere distinctness in transport pathways and reproduces the observed seasonal dependence of the mixture of air in the middle- and high-latitude lowermost stratosphere. We estimate that adding CHBr3 to models which already include the long-lived organic brominated compounds (halons and methyl bromide) will increase the simulated stratospheric mass of Br(sub y) by about 15 percent. In-situ stratospheric destruction of CHBr3 produces Br(sub y) in amounts which are comparable to that transported into the stratosphere after photolysis and oxidation of CHBr3 in the troposphere. In our simulations the mass of Br(sub y) produced from the destruction of CHBr3 does not exceed the mass of Br(sub y) produced from the destruction of the long-lived compounds at any level in the stratosphere. However, Br(sub y) from the loss of CHBr3 accounts for approximately one-third of the total Br(sub y) in the lowest kilometer of the stratosphere.

Nielsen, J. Eric↗
NASA NTRS2003

TOMS and SBUV Data: Comparison to 3D Chemical-Transport Model Results

We have updated our merged ozone data (MOD) set using the TOMS data from the new version 8 algorithm. We then analyzed these data for contributions from solar cycle, volcanoes, QBO, and halogens using a standard statistical time series model. We have recently completed a hindcast run of our 3D chemical-transport model for the same years. This model uses off-line winds from the finite-volume GCM, a full stratospheric photochemistry package, and time-varying forcing due to halogens, solar uv, and volcanic aerosols. We will report on a parallel analysis of these model results using the same statistical time series technique as used for the MOD data.

Stolarski, Richard S.↗
NASA NTRS1997

Interactions of anesthetics with the water-hexane interface. A molecular dynamics study

The free energy profiles characterizing the transfer of nine solutes across the liquid-vapor interfaces of water and hexane and across the water-hexane interface were calculated from molecular dynamics simulations. Among the solutes were n-butane and three of its halogenated derivatives, as well as three halogenated cyclobutanes. The two remaining molecules, dichlorodifluoromethane and 1,2-dichloroperfluoroethane, belong to series of halo-substituted methanes and ethanes, described in previous studies (J. Chem. Phys. 1996, 104, 3760; Chem. Phys. 1996, 204, 337). Each series of molecules contains structurally similar compounds that differ greatly in anesthetic potency. The accuracy of the simulations was tested by comparing the calculated and the experimental free energies of solvation of all nine compounds in water and in hexane. In addition. the calculated and the measured surface excess concentrations of n-butane at the water liquid-vapor interface were compared. In all cases, good agreement with experimental results was found. At the water-hexane interface, the free energy profiles for polar molecules exhibited significant interfacial minima, whereas the profiles for nonpolar molecules did not. The existence of these minima was interpreted in terms of a balance between the free energy contribution arising from solute-solvent interactions and the work to form a cavity that accommodates the solute. These two contributions change monotonically, but oppositely, across the interface. The interfacial solubilities of the solutes, obtained from the free energy profiles, correlate very well with their anesthetic potencies. This is the case even when the Meyer-Overton hypothesis, which predicts a correlation between anesthetic potency and solubility in oil, fails.

NASA Center ARC↗
NASA NTRS2008

An Overview of the NASA Spring/Summer 2008 Arctic Campaign - ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites)

ARCTAS (Arctic Research of the Composition of the Troposphere from Aircraft and Satellites) is a major NASA led airborne field campaign being performed in the spring and summer of 2008 at high latitudes (http://cloud1.arc.nasa.gov/arctas/). ARCTAS is a part of the International Polar Year program and its activities are closely coordinated with multiple U. S. (NOAA, DOE), Canadian, and European partners. Observational data from an ensemble of aircraft, surface, and satellite sensors are closely integrated with models of atmospheric chemistry and transport in this experiment. Principal NASA airborne platforms include a DC-8 for detailed atmospheric composition studies, a P-3 that focuses on aerosols and radiation, and a B-200 that is dedicated to remote sensing of aerosols. Satellite validation is a central activity in all these platforms and is mainly focused on CALIPSO, Aura, and Aqua satellites. Major ARCTAS themes are: (1) Long-range transport of pollution to the Arctic including arctic haze, tropospheric ozone, and persistent pollutants such as mercury; (2) Boreal forest fires and their implications for atmospheric composition and climate; (3) Aerosol radiative forcing from arctic haze, boreal fires, surface-deposited black carbon, and other perturbations; and (4) Chemical processes with focus on ozone, aerosols, mercury, and halogens. The spring deployment (April) is presently underway and is targeting plumes of anthropogenic and biomass burning pollution and dust from Asia and North America, arctic haze, stratosphere-troposphere exchange, and ozone photochemistry involving HOx and halogen radicals. The summer deployment (July) will target boreal forest fires and summertime photochemistry. The ARCTAS mission is providing a critical link to enhance the value of NASA satellite observations for Earth science. In this talk we will discuss the implementation of this campaign and some preliminary results.

Jacob, Daniel J.↗
NASA NTRS2010

21st Century Trends in Antarctic Temperature and Polar Stratospheric Cloud (PSC) Area in the GEOS Chemistry-Climate Model

This study examines trends in Antarctic temperature and APSC, a temperature proxy for the area of polar stratospheric clouds, in an ensemble of Goddard Earth Observing System (GEOS) chemistry-climate model (CCM) simulations of the 21st century. A selection of greenhouse gas, ozone-depleting substance, and sea surface temperature scenarios is used to test the trend sensitivity to these parameters. One scenario is used to compare temperature trends in two versions of the GEOS CCM. An extended austral winter season is examined in detail. In May, June, and July, the expected future increase in CO2-related radiative cooling drives temperature trends in the Antarctic lower stratosphere. At 50 hPa, a 1.3 K cooling is expected between 2000 and 2100. Ozone levels increase, despite this robust cooling signal and the consequent increase in APSC, suggesting the enhancement of stratospheric transport in future. In the lower stratosphere, the choice of climate change scenarios does not affect the magnitude of the early winter cooling. Midwinter temperature trends are generally small. In October, APSC trends have the same sign as the prescribed halogen trends. That is, there are negative APSC trends in "grealistic future" simulations, where halogen loading decreases in accordance with the Montreal Protocol and CO2 continues to increase. In these simulations, the speed of ozone recovery is not influenced by either the choice of sea surface temperature and greenhouse gas scenarios or by the model version.

Hurwitz, M. M.↗
NASA NTRS2010

Multimodel Assessment of the Factors Driving Stratospheric Ozone Evolution over the 21st Century

The evolution of stratospheric ozone from 1960 to 2100 is examined in simulations from 14 chemistry-climate models, driven by prescribed levels of halogens and greenhouse gases. There is general agreement among the models that total column ozone reached a minimum around year 2000 at all latitudes, projected to be followed by an increase over the first half of the 21st century. In the second half of the 21st century, ozone is projected to continue increasing, level off, or even decrease depending on the latitude. Separation into partial columns above and below 20 hPa reveals that these latitudinal differences are almost completely caused by differences in the model projections of ozone in the lower stratosphere. At all latitudes, upper stratospheric ozone increases throughout the 21st century and is projected to return to 1960 levels well before the end of the century, although there is a spread among models in the dates that ozone returns to specific historical values. We find decreasing halogens and declining upper atmospheric temperatures, driven by increasing greenhouse gases, contribute almost equally to increases in upper stratospheric ozone. In the tropical lower stratosphere, an increase in upwelling causes a steady decrease in ozone through the 21st century, and total column ozone does not return to 1960 levels in most of the models. In contrast, lower stratospheric and total column ozone in middle and high latitudes increases during the 21st century, returning to 1960 levels well before the end of the century in most models.

Oman, L. D.↗
NASA NTRS2014

Alternative, Green Processes for the Precision Cleaning of Aerospace Hardware

Precision cleaning is necessary to ensure the proper functioning of aerospace hardware, particularly those systems that come in contact with liquid oxygen or hypergolic fuels. Components that have not been cleaned to the appropriate levels may experience problems ranging from impaired performance to catastrophic failure. Traditionally, this has been achieved using various halogenated solvents. However, as information on the toxicological and/or environmental impacts of each came to light, they were subsequently regulated out of use. The solvent currently used in Kennedy Space Center (KSC) precision cleaning operations is Vertrel MCA. Environmental sampling at KSC indicates that continued use of this or similar solvents may lead to high remediation costs that must be borne by the Program for years to come. In response to this problem, the Green Solvents Project seeks to develop state-of-the-art, green technologies designed to meet KSCs precision cleaning needs.Initially, 23 solvents were identified as potential replacements for the current Vertrel MCA-based process. Highly halogenated solvents were deliberately omitted since historical precedents indicate that as the long-term consequences of these solvents become known, they will eventually be regulated out of practical use, often with significant financial burdens for the user. Three solvent-less cleaning processes (plasma, supercritical carbon dioxide, and carbon dioxide snow) were also chosen since they produce essentially no waste stream. Next, experimental and analytical procedures were developed to compare the relative effectiveness of these solvents and technologies to the current KSC standard of Vertrel MCA. Individually numbered Swagelok fittings were used to represent the hardware in the cleaning process. First, the fittings were cleaned using Vertrel MCA in order to determine their true cleaned mass. Next, the fittings were dipped into stock solutions of five commonly encountered contaminants and were weighed again showing typical contaminant deposition levels of approximately 0.00300g per part. They were then cleaned by the solvent or process being tested and then weighed a third time which allowed for the calculation of the cleaning efficiency of the test solvent or process.Based on preliminary experiments, five solvents (ethanol, isopropanol, acetone, ethyl acetate, and tert-butyl acetate) were down selected for further testing. When coupled with ultrasonic agitation, these solvents removed hydrocarbon contaminants as well as Vertrel MCA and showed improved removal of perfluorinated greases. Supercritical carbon dioxide did an excellent job dissolving each of the five contaminants but did a poor job of removing Teflon particles found in the perfluorinated greases. Plasma cleaning efficiency was found to be dependent on which supply gas was used, exposure time, and gas pressure. Under optimized conditions it was found that breathing air, energized to the plasma phase, was able to remove nearly 100% of the contamination.These findings indicate that alternative cleaning methods are indeed able to achieve precision levels of cleanliness. Currently, our team is working with a commercial cleaning company to get independent verification of our results. We are also evaluating the technical and financial aspects of scaling these processes to a size capable of supporting the future cleaning needs of KSC.

Vertrel MCA↗
NASA NTRS2013

Evaluating Global Emission Inventories of Biogenic Bromocarbons

Emissions of halogenated very short-lived substances (VSLS) are poorly constrained. However, their inclusion in global models is required to simulate a realistic inorganic bromine (Bry) loading in both the troposphere, where bromine chemistry perturbs global oxidizing capacity, and in the stratosphere, where it is a major sink for ozone (O3). We have performed simulations using a 3-D chemical transport model (CTM) including three top-down and a single bottom-up derived emission inventory of the major brominated VSLS bromoform (CHBr3) and dibromomethane (CH2Br2). We perform the first concerted evaluation of these inventories, comparing both the magnitude and spatial distribution of emissions. For a quantitative evaluation of each inventory, model output is compared with independent long-term observations at National Oceanic and Atmospheric Administration (NOAA) ground-based stations and with aircraft observations made during the NSF (National Science Foundation) HIAPER Pole-to-Pole Observations (HIPPO) project. For CHBr3, the mean absolute deviation between model and surface observation ranges from 0.22 (38 %) to 0.78 (115 %) parts per trillion (ppt) in the tropics, depending on emission inventory. For CH2Br2, the range is 0.17 (24 %) to 1.25 (167 %) ppt. We also use aircraft observations made during the 2011 Stratospheric Ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) campaign, in the tropical western Pacific. Here, the performance of the various inventories also varies significantly, but overall the CTM is able to reproduce observed CHBr3 well in the free troposphere using an inventory based on observed sea-to-air fluxes. Finally, we identify the range of uncertainty associated with these VSLS emission inventories on stratospheric bromine loading due to VSLS (Br(VSLS/y)). Our simulations show Br(VSLS/y) ranges from approximately 4.0 to 8.0 ppt depending on the inventory. We report an optimized estimate at the lower end of this range (approximately 4 ppt) based on combining the CHBr3 and CH2Br2 inventories which give best agreement with the compilation of observations in the tropics.

bromocarbons↗
NASA NTRS2016

Calibration of the Fluorine, Chlorine and Hydrogen Content of Apatites With the ChemCam LIBS Instrument

Determining the composition of apatites is important to understand the behavior of volatiles during planetary differentiation. Apatite is an ubiquitous magmatic mineral in the SNC meteorites. It is a significant reservoir of halogens in these meteorites and has been used to estimate the halogen budget of Mars. Apatites have been identified in sandstones and pebbles at Gale crater by ChemCam, a Laser-Induced Breakdown Spectroscometer (LIBS) instrument onboard the Curiosity rover. Their presence was inferred from correlations between calcium, fluorine (using the CaF molecular band centered near 603 nm, whose detection limit is much lower that atomic or ionic lines and, in some cases, phosphorus (whose detection limit is much larger). An initial quantification of fluorine, based on fluorite (CaF2)/basalt mixtures and obtained at the LANL laboratory, indicated that the excess of F/Ca (compared to the stoichiometry of pure fluorapatites) found on Mars in some cases could be explained by the presence of fluorite. Chlorine was not detected in these targets, at least above a detection limit of 0.6 wt% estimated from. Fluorapatite was later also detected by X-ray diffraction (with CheMin) at a level of approx.1wt% in the Windjana drill sample (Kimberley area), and several points analyzed by ChemCam in this area also revealed a correlation between Ca and F. The in situ detection of F-rich, Cl-poor apatites contrasts with the Cl-rich, F-poor compositions of apatites found in basaltic shergottites and in gabbroic clasts from the martian meteorite NWA 7034, which were also found to be more Cl-rich than apatites from basalts on Earth, the Moon, or Vesta. The in situ observations could call into question one of the few possible explanations brought forward to explain the SNC results, namely that Mars may be highly depleted in fluorine. The purpose of the present study is to refine the calibration of the F, Cl, OH and P signals measured by the ChemCam LIBS instrument, initiated for F, for Cl in soils, for P, and estimate their limit of detection. For this purpose, different types of apatites and mixtures of basalt powder and apatites were analyzed using ChemCam Engineering Qualification Model (EQM) at IRAP, Toulouse. The present abstract presents the initial results from the laboratory analyses. Differences between the response function of the EQM and the Flight Model of ChemCam are still to be refined to apply these new results to the Martian dataset.

Meslin, P.-Y.↗
NASA NTRS2018

Evidence for a Continuous Decline in Lower Stratospheric Ozone Offsetting Ozone Layer Recovery

Ozone forms in the Earth's atmosphere from the photodissociation of molecular oxygen, primarily in the tropical stratosphere. It is then transported to the extratropics by the Brewer-Dobson circulation (BDC), forming a protective "ozone layer" around the globe. Human emissions of halogen-containing ozone-depleting substances (hODSs) led to a decline in stratospheric ozone until they were banned by the Montreal Protocol, and since 1998 ozone in the upper stratosphere is rising again, likely the recovery from halogen-induced losses. Total column measurements of ozone between the Earth's surface and the top of the atmosphere indicate that the ozone layer has stopped declining across the globe, but no clear increase has been observed at latitudes between 60degS and 60degN outside the polar regions (60-90deg). Here we report evidence from multiple satellite measurements that ozone in the lower stratosphere between 60degS and 60degN has indeed continued to decline since 1998. We find that, even though upper stratospheric ozone is recovering, the continuing downward trend in the lower stratosphere prevails, resulting in a downward trend in stratospheric column ozone between 60degS and 60degN. We find that total column ozone between 60degS and 60degN appears not to have decreased only because of increases in tropospheric column ozone that compensate for the stratospheric decreases. The reasons for the continued reduction of lower stratospheric ozone are not clear; models do not reproduce these trends, and thus the causes now urgently need to be established.

Stratospheric Ozone↗
NASA NTRS2020

OMI Measurements of Bromine Monoxide and Implications for Missing Sources of Polar Bromine in GEOS-Chem

The OMI satellite instrument provides total column measurements of bromine monoxide (BrO) with daily global coverage. Reactive bromine compounds (Br and BrO) catalytically destroy ozone in both the stratosphere and troposphere. The current emission scheme of brominated source gases in the GEOS-Chem chemical transport model well represents the stratospheric burden of bromine. However, halogen research in GEOS-Chem has largely focused on the influence of halogens on the tropospheric oxidative capacity. In the troposphere, the distribution of brominated compounds is more variable and significant uncertainties remain in the chemical processes governing the sources and sinks of reactive bromine compounds. In this study, we use GEOS-Chem simulated stratospheric columns of BrO to separate the tropospheric signal of BrO from the OMI total column measurements. The resulting tropospheric BrO columns are used to identify seasonal and regional anomalies in tropospheric BrO not currently represented in GEOS-Chem. In particular, periods of elevated tropospheric BrO during polar spring are observable by OMI, and past studies have connected these so-called "bromine explosion" events to near complete removal of surface ozone. Due to significant uncertainties in the springtime polar source of reactive bromine, many global models, including GEOS-Chem, do not simulate these tropospheric ozone depletion events. Consequently, OMI-based tropospheric columns of BrO are useful tool for investigating the impact of bromine explosion events on tropospheric ozone depletion episodes as well as background air quality.

Wales, Pamela↗
DOE OSTI2022

Wet chemical synthesis and properties of argyrodite sulfide solid electrolytes for solid state lithium batteries

The commercialization of the lithium-ion battery (LIB) in 1991 was responsible for the explosion in portable electronic technologies that has been seen over the past 30 years. With the advent of electric vehicles and other high-powered technologies, there is tremendous demand for LIBs with higher energy density and high safety. To achieve this, new electrode materials must be explored. The obvious choice of anode material would be pure metal lithium, which has a theoretical specific capacity of 3860 mAh g-1 . Unfortunately, metal lithium anodes have not been widely commercialized due to their tendency to react violently with the flammable liquid electrolytes used in today’s batteries. Battery safety can best be achieved by adopting solid electrolytes in place of liquid electrolytes. Solid electrolytes are nonvolatile and nonflammable, safely allowing for the combination of high-capacity cathode materials with a Li metal anode. Argyrodite sulfide solid electrolytes such as halogen-doped Li6PS5X (X = Cl, Br, I) are noted for their high ionic conductivity. But before sulfides can be commercially adopted, they possess several disadvantages which must be addressed, including time- and energy-consuming synthesis processes, poor electrochemical stability, and intrinsically poor air stability. This dissertation seeks to address each of these challenges through materials design an synthesis strategies. In this work, we pioneer a solvent-based approach for the synthesis of argyrodite solid electrolytes Li7PS6 and Li6PS5Xinstead of a stringent solid-state synthesis. Nontoxic ethanol is employed as the solvent, enabling a rapid synthetic approach to produce argyrodite solid electrolytes with high phase purity and compositional flexibility. Compared with Li7PS6, halogen doping (i.e. X = F, Cl, Br, I) not only increases the ionic conductivity, but also enhances the electrochemical stability at the interface towards Li metal. Specifically, F-doped argyrodites produce a robust SEI layer containing LiF, contributing to enhanced interfacial stability. Finally, to address the air instability challenge, argyrodite-incorporated composite solid electrolytes (CSEs) are designed and prepared to produce stable and flexible membranes that are demonstrated in solid-state Li metal batteries. These advances push argyrodite sulfide solid electrolyte research further and pave the way for the proliferation of next generation lithium metal batteries.

25 ENERGY STORAGE↗
DOE OSTI2022

Solid additive engineering enables high-efficiency and eco-friendly all-polymer solar cells

Currently, morphology optimization of all-polymer solar cells (all-PSCs) strongly depends on the use of solvent additives, which are usually highly toxic and harmful to the environment and human health. Here, we report a green and volatile solid additive, 2-methoxynaphthalene (2-MN). It was found that the incorporation of 2-MN into a PM6:PY-DT blend can effectively manipulate the aggregations of PM6 and PY-DT during film depositing and thermal annealing processes and results in highly ordered molecular packing and favorable phase-separated morphology. Consequently, a record-high efficiency of 17.32% is achieved for the PM6:PY-DT device. Moreover, 2-MN-processed all-PSCs were fabricated by using non-halogenated solvent. High efficiencies of 17.03% and 16.67% are obtained for all-PSCs fabricated under nitrogen atmosphere and ambient conditions, respectively. Finally, our work shows that the utilization of 2-MN as a green and solid additive is a simple and feasible strategy to optimize the morphology and sheds new light on eco-friendly fabrication and application of all-PSCs.

14 SOLAR ENERGY↗
DOE OSTI2022

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding

In this work, we report the synthesis of five new hybrid materials containing the [PuCl 6 ] 2- anion and charge balancing, non-covalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH) 2 [PuCl 6 ] and 5, (4IPyH) 4 [PuCl 6 ] · 2Cl, exhibit two distinct sheet-like structure types. Structurally relevant non-covalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM) approach. The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory and a hierarchy of acceptor-donor pairings established. In turn, the PuIV-Cl bonds were studied using the QTAIM and natural localized molecular orbital (NLMO) approaches to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. Energy decomposition (ED) and natural ED analyses were also explored to probe the bond mechanism and, more broadly, explore the efficacy of these techniques in studying these anionic systems. The results of the PuIV-Cl bond analyses were compared across composition via analogous treatments of previously reported [PuO 2 Cl 4 ] 2- and [PuCl 3 (H 2 O) 5 ] molecular units. In summary, our study indicates that the Pu-Cl bonds are predominately ionic, yet exhibit small varying degrees of covalent character that increase from [PuCl 3 (H 2 O) 5 ], [PuO 2 Cl 4 ] 2- , to [PuCl 6 ] 2- , while the participation of the Pu based s/d and f orbitals concurrently decrease and increase, respectively.

transuranic↗
DOE OSTI2022

Stability Enhancement and Microstructural Modification of Ni-Rich Cathodes via Halide Doping

In this study, elemental doping is an effective strategy to modify surface and bulk chemistry in NMC cathode materials. By adding small amounts of lithium halide salts during the calcination process, the Ni-rich NMC811 cathode is doped with Br, Cl, or F halogens. The dopant type has a significant impact on the lithiation process and heavily influences the final cathode porosity and surface morphology. Utilizing a variety of electrochemical, surface, and bulk characterization techniques, it is demonstrated that an initial content of 5 mol % LiBr or LiCl in the lithium source is effective in improving capacity retention while also providing excellent rate performance. The improvements are attributed to a substantial increase in specific surface area, the formation of a stable cathode electrolyte interface (CEI) layer, and suppressed surface reconstruction. In addition, the particle microstructure is better equipped to handle cyclic volume changes with increased values of critical crack lengths. Overall, it is demonstrated that anion doping via the addition of lithium halide salts is a facile approach toward Ni-rich NMC modification for enhanced cathode performance.

25 ENERGY STORAGE↗
DOE OSTI2021

Non-Innocent Role of the Ceria Support in Pd-Catalyzed Halophenol Hydrodehalogenation

The hydrodehalogenation (HDH) of halophenols is efficiently catalyzed by palladium supported on high-surface ceria (Pd/CeO2) under mild conditions (35 °C, 1 atm H2). A combination of NMR, diffuse reflectance infrared Fourier transform spectroscopy, Raman spectroscopy, and XPS studies and HDH kinetics of substituted halobenzenes suggests that the reaction proceeds mainly via a sequence of dissociative adsorption of phenolic hydroxyl onto the support, oxidative addition of the C–halogen bond to Pd, and reductive elimination to give phenol and hydrogen halide. The dissociative adsorption of the -OH group onto oxygen vacancies of the ceria support results in an electron-rich intermediate that facilitates the turnover-limiting reductive elimination step. In contrast, the direct pathway catalyzed by Pd without dissociative adsorption of the reactants on the support takes place at a slower rate. The mechanistic insights gained in this study were used to modify the reaction conditions for enabling HDH of recalcitrant halides such as fluorides and iodides.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗