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DOE OSTI2024

Decoupling first-cycle capacity loss mechanisms in sulfide solid-state batteries

Solid-state batteries (SSBs) promise more energy-dense storage than liquid electrolyte lithium-ion batteries (LIBs). However, first-cycle capacity loss is higher in SSBs than in LIBs due to interfacial reactions. The chemical evolution of key interfaces in SSBs has been extensively characterized. Electrochemically, however, we lack a versatile strategy for quantifying the reversibility of solid electrolyte (SE) redox for established and next-generation SSB electrolytes. In this work, we perform tailored electrochemical tests and operando X-ray diffraction to disentangle reversible and irreversible sources of capacity loss in positive electrodes composed of Li 6 PS 5 Cl SE, Li(Ni 0.5 Mn 0.3 Co 0.2 )O 2 (NMC), and carbon conductive additives. We leverage an atypically low voltage cutoff (2.0 V vs. Li/Li + ) to quantify the reversibility of SE redox. Using slow (5.5 mA g NMC −1 ) cycling paired with >100 h low-voltage holds, our cells achieve a surprising 96.2% first-cycle coulombic efficiency, which is higher than previously reported (mean: 72%, maximum: 91.6% across surveyed literature). We clarify that sluggish NMC relithiation kinetics have been historically mistaken for permanently irreversible capacity loss. In conclusion, through systematic decoupling of loss mechanisms, we uncover the unexpected reversibility of SE redox and isolate the major contributors to capacity loss, outlining a strategy for accurate assessment of next-generation SE materials and interface modifications.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS1994

Brief Communication: A Simplified Approach to Transient Convective Droplet Evaporation and Burning

Empirical correlations for evaporation rates from single fuel droplets have existed since the 1930s. These correlations, which will be referred to in this article as Froessling/Ranz-Marshall types of correlations, are appropriate to the special cases of steady-state evaporation in the absence of chemical reaction. In a previous article by the authors, the quasi-steady evaporation and burning processes associated with a fuel drop in a convective environment are examined through a droplet model based on the boundary layer approach. For droplet Reynolds numbers of practical interest, this model produces very reasonable steady state as well as quasi-time-dependent droplet simulations, requiring relatively short computational times and yielding good agreement with the above-mentioned empirical correlations. The steady-state case, however, is usually relevant to practical combustor situations only when the drop has reached a nearly uniform temperature since the heating process of the drop cannot be considered to be quasi-steady. In the present study, the transient heating process of the droplet interior during evaporation and/or burning is taken into account, and thus calculations pertaining to the entire life-time of the droplet are carried out. It is of particular interest here to obtain simplified correlations to describe the transient behavior of evaporating and burning droplets; these may be incorporated with greater ease into spray calculations. Accordingly, we have chosen to use stagnation conditions in the present model in a modification of the Froessling/Ranz-Marshall correlations. These modified correlations, incorporating an effective transfer number, produce a fairly accurate representation of droplet evaporation and burning, while requiring only one tenth the computational effort used in a full boundary layer solution.

Madooglu, K.↗

DOE OSTI2022

Core-Shell Heterostructures as Functional Materials for Solid Oxide Fuel Cell (SOFC) Electrodes

The principal objective of this project was to synthesize core-shell heterostructures for solid oxide fuel cell cathodes using a molten salt solvent. In doing so, the main goals were split into a) to elucidate and understand the influence of molten salt chemistries to expeditiously synthesize perovskite type oxides for solid oxide fuel cells, b) provide a chemical framework for future molten salt syntheses of energy relevant ceramic materials, c) demonstrate and investigate the required parameters for the optimal core-shell synthesis and yield of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) – La 0.8 Sr 0.2 MnO 3 (shell), and d) demonstrate improved cathode performance of core-shell LSCF-LSM compared to an LSCF cathode on symmetric cells. The results clearly show that a) the influence of the molten salt cation outweighs the anion in regards to product stoichiometry, b) molten salts should be tailored to balance cationic and anionic acidity for high product yield, c) high yield of core-shell nanoparticles can be achieved by optimal mass ratio between core to shell, dwell time in the salt, size ratio between core to shell, and mass ratio between overall powder to salt, and d) the core-shell LSCF-LSM cathodes have lower polarization resistances than LSCF at higher temperatures. More work is required to optimize core-shell cathode performance at lower temperatures. However, this work thus provided justification for using the molten salt synthesis for SOFC cathodes and provided insights into future material modifications for improved performance.

08 HYDROGEN↗

DOE OSTI2021

Computational design and analysis of modular cells for large libraries of exchangeable product synthesis modules

Microbial metabolism can be harnessed to produce a large library of useful chemicals from renewable resources such as plant biomass. However, it is laborious and expensive to create microbial biocatalysts to produce each new product. To tackle this challenge, we have recently developed modular cell (ModCell) design principles that enable rapid generation of production strains by assembling a modular (chassis) cell with exchangeable production modules to achieve overproduction of target molecules. Previous computational ModCell design methods are limited to analyze small libraries of around 20 products. In this study, we developed a new computational method, named ModCell-HPC, that can design modular cells for large libraries with hundreds of products with a highly-parallel and multi-objective evolutionary algorithm and enable us to elucidate modular design properties. We demonstrated ModCell-HPC to design Escherichia coli modular cells towards a library of 161 endogenous production modules. From these simulations, we identified E. coli modular cells with few genetic manipulations that can produce dozens of molecules in a growth-coupled manner with different types of fermentable sugars. These designs revealed key genetic manipulations at the chassis and module levels to accomplish versatile modular cells, involving not only in the removal of major by-products but also modification of branch points in the central metabolism. We further found that the effect of various sugar degradation on redox metabolism results in lower compatibility between a modular cell and production modules for growth on pentoses than hexoses. To better characterize the degree of compatibility, we developed a method to calculate the minimal set cover, identifying that only three modular cells are all needed to couple with up 85 compatible production modules. By determining the unknown compatibility contribution metric, we further elucidated the design features that allow an existing modular cell to be re-purposed towards production of new molecules. Altogether, ModCell-HPC is a useful tool for understanding modularity of biological systems and guiding more efficient and generalizable design of modular cells that help reduce research and development cost in biocatalysis.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2002

Opportunities for nutritional amelioration of radiation-induced cellular damage

The closed environment and limited evasive capabilities inherent in space flight cause astronauts to be exposed to many potential harmful agents (chemical contaminants in the environment and cosmic radiation exposure). Current power systems used to achieve space flight are prohibitively expensive for supporting the weight requirements to fully shield astronauts from cosmic radiation. Therefore, radiation poses a major, currently unresolvable risk for astronauts, especially for long-duration space flights. The major detrimental radiation effects that are of primary concern for long-duration space flights are damage to the lens of the eye, damage to the immune system, damage to the central nervous system, and cancer. In addition to the direct damage to biological molecules in cells, radiation exposure induces oxidative damage. Many natural antioxidants, whether consumed before or after radiation exposure, are able to confer some level of radioprotection. In addition to achieving beneficial effects from long-known antioxidants such as vitamins E and C and folic acid, some protection is conferred by several recently discovered antioxidant molecules, such as flavonoids, epigallocatechin, and other polyphenols. Somewhat counterintuitive is the protection provided by diets containing elevated levels of omega-3 polyunsaturated fatty acids, considering they are thought to be prone to peroxidation. Even with the information we have at our disposal, it will be difficult to predict the types of dietary modifications that can best reduce the risk of radiation exposure to astronauts, those living on Earth, or those enduring diagnostic or therapeutic radiation exposure. Much more work must be done in humans, whether on Earth or, preferably, in space, before we are able to make concrete recommendations.

Review↗

NASA NTRS2014

Investigating the Sensitivity of Surface-Level Nitrate Seasonality in Antarctica to Primary Sources Using a Global Model

Determining the sources of total nitrate (TNIT NO-3 + HNO3) reaching Antarctica is a long-standing challenge. Here we analyze the monthly sensitivity of surface-level TNIT in Antarctica to primary sources using a global 3-D chemical transport model, GEOS-Chem, and its adjoint. Modeled seasonal variation of TNIT concentrations shows good agreement with several measurement studies, given that the lack of post-depositional processing in the model leads to an expected underestimate of maximum values in November through January. Remote NOx sources have the greatest impact May-July, during when the model background concentrations are sensitive to NOx emissions from fossil fuel combustion, soil, and lightning originating from 25S to 65S. In this season, NOx is transported to Antarctica as TNIT, which is formed above continental source regions at an altitude of 5-11 km. In other seasons, more NOx is transported as a reservoir species (e.g., peroxyacetyl nitrate, PAN) through the free troposphere, transforming into TNIT within a cone of influence that extends to 35S and above 4 km altitude. Photolysis of PAN over Antarctica is the main driver of modeled NOx seasonality. Stratospheric production and loss of tracers are relatively unimportant in monthly sensitivities in GEOS-Chem, driving only a few percent of surface level variability of TNIT. A small peak concentration in August is captured by the model, although some measured values in August fall outside the range of simulated concentrations. Modifications to the model to represent sedimentation of polar stratospheric clouds (PSCs) lead to increased surface level August TNIT concentrations. However, this simple representation does not explicitly account for PSC particle deposition or disappearance of the tropopause in the middle of winter, and thus the influence of stratospheric nitrate sources estimated in this study is likely a lower bound.

stratosphere↗

DOE OSTI2025

Metal–Organic Frameworks as Catalysts for (De)Hydrogenation: Progress, Challenges, and Perspectives

Storing hydrogen through chemical bonding in liquid-organic hydrogen carriers (LOHCs) offers a safer and more practical approach for hydrogen transportation compared to physical liquefaction, which is limited by low volumetric efficiency and gas release. The efficiency of LOHC systems is highly dependent on effective catalysts, which are typically composed of transition metals supported on metal oxides. However, these materials often rely upon costly noble metals, and their nonuniform nature limits mechanistic insights and structure–function relationships that could improve catalyst design. Metal–organic frameworks (MOFs) are promising alternatives to existing catalysts due to their crystalline, tunable, and porous nature. However, their use as catalysts for (de)hydrogenation reactions remains largely underexplored. Related to this, we identify two general classes of MOFs reported as catalysts for (de)hydrogenation reactions: MOFs as scaffolds for catalytically active species and MOFs that function as reactive materials themselves. MOF composites anchor reactive nanoparticles or homogeneous species, imparting reactivity to the framework. The confinement effects experienced by the affixed species, combined with favorable substrate adsorption interactions or acid sites provided by the MOF, enhance the stability, selectivity, and activity of these catalysts for (de)hydrogenation reactions. Additionally, catalytically active MOFs often feature open metal sites at the node or undergo postsynthetic modification at either node or linker to impart reactivity. Here, taking inspiration from these materials, we outline the current state and key challenges of utilizing MOFs as (de)hydrogenation catalysts and propose research pathways to advance materials in this field for energy applications.

Catalysts↗

NASA NTRS2010

Electrochemical Hydrogen Peroxide Generator

Two-electron reduction of oxygen to produce hydrogen peroxide is a much researched topic. Most of the work has been done in the production of hydrogen peroxide in basic media, in order to address the needs of the pulp and paper industry. However, peroxides under alkaline conditions show poor stabilities and are not useful in disinfection applications. There is a need to design electrocatalysts that are stable and provide good current and energy efficiencies to produce hydrogen peroxide under acidic conditions. The innovation focuses on the in situ generation of hydrogen peroxide using an electrochemical cell having a gas diffusion electrode as the cathode (electrode connected to the negative pole of the power supply) and a platinized titanium anode. The cathode and anode compartments are separated by a readily available cation-exchange membrane (Nafion 117). The anode compartment is fed with deionized water. Generation of oxygen is the anode reaction. Protons from the anode compartment are transferred across the cation-exchange membrane to the cathode compartment by electrostatic attraction towards the negatively charged electrode. The cathode compartment is fed with oxygen. Here, hydrogen peroxide is generated by the reduction of oxygen. Water may also be generated in the cathode. A small amount of water is also transported across the membrane along with hydrated protons transported across the membrane. Generally, each proton is hydrated with 3-5 molecules. The process is unique because hydrogen peroxide is formed as a high-purity aqueous solution. Since there are no hazardous chemicals or liquids used in the process, the disinfection product can be applied directly to water, before entering a water filtration unit to disinfect the incoming water and to prevent the build up of heterotrophic bacteria, for example, in carbon based filters. The competitive advantages of this process are: 1. No consumable chemicals are needed in the process. The only raw materials needed are water and oxygen or air. 2. The product is pure and can therefore be used in disinfection applications directly or after proper dilution with water. 3. Oxygen generated in the anode compartment is used in the electrochemical reduction process; in addition, external oxygen is used to establish a high flow rate in the cathode compartment to remove the desired product efficiently. Exiting oxygen can be recycled after separation of liquid hydrogen peroxide product, if so desired. 4. The process can be designed for peroxide generation under microgravity conditions. 5. High concentrations of the order of 6-7 wt% can be generated by this method. This method at the time of this reporting is superior to what other researchers have reported. 6. The cell design allows for stacking of cells to increase the hydrogen peroxide production. 7. The catalyst mix containing a diquaternary ammonium compound enabled not only higher concentration of hydrogen peroxide but also higher current efficiency, improved energy efficiency, and catalyst stability. 8. The activity of the catalyst is maintained even after repeated periods of system shutdown. 9. The catalyst system can be extended for fuel-cell cathodes with suitable modifications.

Tennakoon, Charles L. K.↗

NASA NTRS2011

Demonstration/Validation of Environmentally-Preferable Coatings for Launch Facilities

Kennedy Space Center (KSC) is responsible for a number of facilities/structures with metallic structural and non-structural components in a highly corrosive environment. Metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the application of an applied coating system. Applied coating systems work via a variety of methods (barrier, galvanic and/or inhibitor) and adhere to the substrate through a combination of chemical and physical bonds. Maintenance at KSC and other NASA Centers is governed by NASA-STD-50088 (Protective Coating of Carbon Steel, Stainless Steel, and Aluminum on Launch Structures, Facilities, and Ground Support Equipment) which establishes practices for the protective coating of ground support equipment and related facilities used by or for NASA programs and projects. The Standard is for the design of non-flight hardware used to support the operations of receiving, transportation, handling, assembly, inspection, test, checkout, service, and launch of space vehicles and payloads at NASA launch, landing, or retrieval sites. These criteria and practices contained within the Standard may be used for items used at the manufacturing, development, and test sites upstream of the launch, landing, or retrieval sites. The objective of this effort is to demonstrate and validate environmentally-preferable alternatives in accordance with NASA-STD-50088 and KSC requirements which can then be added to the Approved Products List. This Test Protocol contains the critical requirements and tests necessary to qualify alternatives for structural steel applications. These tests were derived from engineering, performance, and operational impact (supportability) requirements defined by a consensus of KSC participants. A Test Report will document the results of the testing as well as any test modifications made during the execution of the testing. Users of this Test Protocol should check the project's Test Report for additional test details or minor modifications that may have been necessary in the execution of the testing. The technical stakeholders will have agreed upon test procedures modifications documented in the Test Report.

Lewis, Pattie↗

NASA NTRS1999

Dynamics and Structure of Dusty Reacting Flows: Inert Particles in Strained, Laminar, Premixed Flames

A detailed numerical study was conducted on the dynamics and thermal response of inert, spherical particles in strained, laminar, premixed hydrogen/air flames. The modeling included the solution of the steady conservation equations for both the gas and particle phases along and around the stagnation streamline of an opposed-jet configuration, and the use of detailed descriptions of chemical kinetics and molecular transport, For the gas phase, the equations of mass, momentum, energy, and species are considered, while for the particle phase, the model is based on conservation equations of the particle momentum balance in the axial and radial direction, the particle number density, and the particle thermal energy equation. The particle momentum equation includes the forces as induced by drag, thermophoresis, and gravity. The particle thermal energy equation includes the convective/conductive heat exchange between the two phases, as well as radiation emission and absorption by the particle. A one-point continuation method is also included in the code that allows for the description of turning points, typical of ignition and extinction behavior. As expected, results showed that the particle velocity can be substantially different than the gas phase velocity, especially in the presence of large temperature gradients and large strain rates. Large particles were also found to cross the gas stagnation plane, stagnate, and eventually reverse as a result of the opposing gas phase velocity. It was also shown that the particle number density varies substantially throughout the flowfield, as a result of the straining of the flow and the thermal expansion. Finally, for increased values of the particle number density, substantial flame cooling to extinction states and modification of the gas phase fluid mechanics were observed. As also expected, the effect of gravity was shown to be important for low convective velocities and heavy particles. Under such conditions, simulations indicate that the magnitude and direction of the gravitational force can substantially affect the profiles of the particle velocity, number density, mass flux, and temperature.

Egolfopoulos, Fokion N.↗

NASA NTRS1999

Dynamics and Structure of Dusty Reacting Flows: Inert Particles in Strained, Laminar, Premixed Flames

A detailed numerical study was conducted on the dynamics and thermal response of inert spherical particles in strained, laminar, premixed hydrogen/air flames. The modeling included the solution of the steady conservation equations for both the gas and particle phases along and around the stagnation streamline of an opposed-jet configuration, and the use of detailed descriptions of chemical kinetics and molecular transport. For the gas phase, the equations of mass, momentum, energy, and species are considered, while for the particle phase, the model is based on conservation equations of the particle momentum balance in the axial and radial direction, the particle number density, and the particle thermal energy equation. The particle momentum equation includes the forces as induced by drag, thermophoresis, and gravity. The particle thermal energy equation includes the convective/conductive heat exchange between the two phases, as well as radiation emission and absorption by the particle. A one-point continuation method is also included in the code that allows for the description of turning points, typical of ignition and extinction behavior. As expected, results showed that the particle velocity can be substantially different than the gas phase velocity, especially in the presence of large temperature gradients and large strain rates. Large particles were also found to cross the gas stagnation plane, stagnate, and eventually reverse as a result of the opposing gas phase velocity. It was also shown that the particle number density varies substantially throughout the flowfield, as a result of the straining of the flow and the thermal expansion. Finally, for increased values of the particle number density, substantial flame cooling to extinction states and modification of the gas phase fluid mechanics were observed. As also expected, the effect of gravity was shown to be important for low convective velocities and heavy particles. Under such conditions, simulations indicate that the magnitude and direction of the gravitational force can substantially affect the profiles of the particle velocity, number density, mass flux, and temperature.

Egolfopoulos, Fokion N.↗

DOE OSTI2025

Si content in methacrylamide-containing A- b -(B- r -C) block copolymers and its impact on reactive ion etching properties

Block copolymers (BCPs) of an A-block-(B-random-C) architecture have been explored as materials for nanolithography because the composition and chemistry of the random block enables modification of thermodynamic and wetting properties to meet manufacturing criteria. Here, in this study, A-b-(B-r-C) BCPs created by an amidation reaction of polystyrene-block-poly(pentafluorophenyl methacrylate) (PS-b-PPFMA) with controlled amounts of Si add insight to previous conclusions about the dual contributions of BCP chemistry and reactive ion etch (RIE) gas chemistry on etch properties. We focus on two RIE etch characteristics: organosilicon etch resistance in H 2 /N 2 plasma etching and enhanced removal of non-styrenic structures in an Ar/O 2 etch. Consistent with previous studies, higher amounts of Si result in greater etch resistance under H 2 /N 2 RIE, where at least ∼10 wt. % Si is necessary to exhibit sufficient etch resistance. By contrast, Ar/O 2 etching resulted in etch rates independent of Si content. We observe previously unreported surface roughening aligned with morphological domains during the H 2 /N 2 etch of modified PS-b-PPFMA BCPs. Limited in the amount of allowable Si to attain equal surface energy between blocks, these BCPs are further disqualified in forming a Si-containing mask. However, in an Ar/O 2 etch, the same BCPs exhibit suitable etch contrast and smooth domain structures, forming a uniform PS mask. Ultimately, this study uses the chemical flexibility of these materials to demonstrate the mechanisms of interactions between BCP and etch chemistry that must be considered to design effective materials for pattern transfer applications.

Eom, Christopher J. [University of Chicago, IL (Un↗

NASA NTRS2011

Automated Miniaturized Instrument for Space Biology Applications and the Monitoring of the Astronauts Health Onboard the ISS

Human space travelers experience a unique environment that affects homeostasis and physiologic adaptation. The spacecraft environment subjects the traveler to noise, chemical and microbiological contaminants, increased radiation, and variable gravity forces. As humans prepare for long-duration missions to the International Space Station (ISS) and beyond, effective measures must be developed, verified and implemented to ensure mission success. Limited biomedical quantitative capabilities are currently available onboard the ISS. Therefore, the development of versatile instruments to perform space biological analysis and to monitor astronauts' health is needed. We are developing a fully automated, miniaturized system for measuring gene expression on small spacecraft in order to better understand the influence of the space environment on biological systems. This low-cost, low-power, multi-purpose instrument represents a major scientific and technological advancement by providing data on cellular metabolism and regulation. The current system will support growth of microorganisms, extract and purify the RNA, hybridize it to the array, read the expression levels of a large number of genes by microarray analysis, and transmit the measurements to Earth. The system will help discover how bacteria develop resistance to antibiotics and how pathogenic bacteria sometimes increase their virulence in space, facilitating the development of adequate countermeasures to decrease risks associated with human spaceflight. The current stand-alone technology could be used as an integrated platform onboard the ISS to perform similar genetic analyses on any biological systems from the tree of life. Additionally, with some modification the system could be implemented to perform real-time in-situ microbial monitoring of the ISS environment (air, surface and water samples) and the astronaut's microbiome using 16SrRNA microarray technology. Furthermore, the current system can be enhanced substantially by combining it with other technologies for automated, miniaturized, high-throughput biological measurements, such as fast sequencing, protein identification (proteomics) and metabolite profiling (metabolomics). Thus, the system can be integrated with other biomedical instruments in order to support and enhance telemedicine capability onboard ISS. NASA's mission includes sustained investment in critical research leading to effective countermeasures to minimize the risks associated with human spaceflight, and the use of appropriate technology to sustain space exploration at reasonable cost. Our integrated microarray technology is expected to fulfill these two critical requirements and to enable the scientific community to better understand and monitor the effects of the space environment on microorganisms and on the astronaut, in the process leveraging current capabilities and overcoming present limitations.

Human space travelers↗

DOE OSTI2024

Spin-Controllable Dynamics in Defect-Engineered Carbon Nanotubes as Single Photon Emitters: Data-Driven Modeling and Computations

Quantum technologies, such as quantum computing and sensing, require efficient single-photon emission (SPE) sources that operate at room temperature in telecom wavelengths. While several materials can serve as SPE sources, no single platform meets all the criteria for efficiency, ambient operation, and scalability. Single-walled carbon nanotubes (SWCNTs) with covalently attached molecules offer a promising solution. Their SPE can be easily tuned via modifications of the SWCNT's diameter, chirality, and bonded molecules, enabling emission across near-IR to telecom wavelengths at ambient conditions. However, to fully realize the potential of SWCNTs and unlock their quantum capabilities, a deeper understanding of how structural defects from molecular adducts affect their emission and competing photoexcited processes is essential. To address this gap in our knowledge, this project combined quantum chemistry calculations with data-driven methods of cheminformatics (QSAR) and machine learning (ML). The developed computational approaches have provided several design strategies for covalent functionalization of SWCNTs to improve their optical response. The collaboration with Los Alamos National Lab (LANL) enabled direct comparison of computational and experimental data, facilitating method validation. This partnership was enhanced through access to LANL's Center for Integrated Nanotechnologies (CINT) utilizing User Facility Program and summer internships, which provided three NDSU graduate students with hands-on experience at LANL. The outcomes of this project included (1) Advancing the current stage of computational methods in accurate modeling of non-adiabatic spin-dependent photoexcited dynamics and its applicability to nanosystems consisting of thousands of atoms, realized as open-access codes linked to existing DFT-based software; (2) Establishing the relationship between the structure of adducts and SWCNTs and intrinsic excitonic and spin properties of defect states for guiding novel synthetic strategies and experimental probes of chemically functionalized SWCNTs as near-IR emitting materials; (3) Generating virtual libraries of hypothetical functionalized SWCNTs for virtual screening of their chemical structures and optical properties, leveraging new functionalities of SWCNTs; (4) Offering a unique experience for NDSU graduate students that prepared them for future scientific careers related to materials modeling and big data processing. These results were summarized in 12 published journal papers and 3 recently submitted papers. One of a key finding is that the position of defect sites on the SWCNT surface primarily drives the emission redshift (up to 100 meV), while the polarity of the defect-inducing molecules has a much smaller effect (~10 meV). However, the electron-donating or withdrawing properties of a molecule influence selecting reactivity of defect sites. These insights important for optimizing synthetic protocols for desired emissions in SWCNTs. We also revealed that the interaction between two defects at various positions on the SWCNT enhances the redshift and optical activity of states, favoring strong near-IR emission. This suggests that manipulations in defect concentrations is a promising strategy for controlling efficient emission. Mostly important, the defect position was found controllable by the spin states of photoexcited intermediates: Excited aromatic molecules form ortho defects with SWCNTs at their singlet states in the presence of oxygen, while oxygen-free conditions favor para defects via the triplet-state mechanism. Additionally, a heat-activated [2+2] cycloaddition reaction facilitates divalent defect formation with fewer bonding positions that narrows emission bands. These groundbreaking findings have been experimentally validated and significantly advance our understanding of defect chemistry in SWCNTs. Using a novel encoding technique and 3D-MoRSE descriptors, we developed highly accurate ML/QSAR models to predict both the 3D structure and optical properties of SWCNTs with chemical defects. This model enabled the creation of a virtual library of 125,556 structures, providing new insights into the relationship between SWCNT-defect structure and emission.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

NASA NTRS2014

Mercury's Weather-Beaten Surface: Understanding Mercury in the Context of Lunar and Asteroidal Space Weathering Studies

Mercury's regolith, derived from the crustal bedrock, has been altered by a set of space weathering processes. Before we can interpret crustal composition, it is necessary to understand the nature of these surface alterations. The processes that space weather the surface are the same as those that form Mercury's exosphere (micrometeoroid flux and solar wind interactions) and are moderated by the local space environment and the presence of a global magnetic field. To comprehend how space weathering acts on Mercury's regolith, an understanding is needed of how contributing processes act as an interactive system. As no direct information (e.g., from returned samples) is available about how the system of space weathering affects Mercury's regolith, we use as a basis for comparison the current understanding of these same processes on lunar and asteroidal regoliths as well as laboratory simulations. These comparisons suggest that Mercury's regolith is overturned more frequently (though the characteristic surface time for a grain is unknown even relative to the lunar case), more than an order of magnitude more melt and vapor per unit time and unit area is produced by impact processes than on the Moon (creating a higher glass content via grain coatings and agglutinates), the degree of surface irradiation is comparable to or greater than that on the Moon, and photon irradiation is up to an order of magnitude greater (creating amorphous grain rims, chemically reducing the upper layers of grains to produce nanometer scale particles of metallic iron, and depleting surface grains in volatile elements and alkali metals). The processes that chemically reduce the surface and produce nanometer-scale particles on Mercury are suggested to be more effective than similar processes on the Moon. Estimated abundances of nanometer-scale particles can account for Mercury's dark surface relative to that of the Moon without requiring macroscopic grains of opaque minerals. The presence of nanometer-scale particles may also account for Mercury's relatively featureless visible-near-infrared reflectance spectra. Characteristics of material returned from asteroid 25143 Itokawa demonstrate that this nanometer-scale material need not be pure iron, raising the possibility that the nanometer-scale material on Mercury may have a composition different from iron metal [such as (Fe,Mg)S]. The expected depletion of volatiles and particularly alkali metals from solar-wind interaction processes are inconsistent with the detection of sodium, potassium, and sulfur within the regolith. One plausible explanation invokes a larger fine fraction (grain size less than 45 micron) and more radiation-damaged grains than in the lunar surface material to create a regolith that is a more efficient reservoir for these volatiles. By this view the volatile elements detected are present not only within the grain structures, but also as adsorbates within the regolith and deposits on the surfaces of the regolith grains. The comparisons with findings from the Moon and asteroids provide a basis for predicting how compositional modifications induced by space weathering have affected Mercury's surface composition.

Weathering↗

DOE OSTI2021

Simulation of radon-222 with the GEOS-Chem global model: Emissions, seasonality, and convective transport

Radon-222 (222Rn) is a short-lived radioactive gas naturally emitted from land surface, and has long been used to assess convective transport in atmospheric models. In this study, we simulate 222Rn using the GEOS-Chem chemical transport model with aims to improve our understanding of 222Rn emissions and surface concentration seasonality, and to characterize convective transport associated with two Goddard Earth Observing System (GEOS) meteorological products, MERRA and GEOS-FP. We evaluate four available 222Rn emission scenarios by comparing model results with surface observations at 51 global surface sites. The default emission scenario in GEOS-Chem yields a moderate agreement with global surface observations (< 70% data within a factor of 2) and a large underestimate of wintertime surface 222Rn concentrations at Northern Hemisphere mid- and high-latitudes due to an oversimplified formulation of 222Rn emission fluxes (1 atom cm-2 s-1 over land with a reduction by a factor of 3 under freezing conditions). We compose a new global 222Rn emission scenario based on Zhang et al. (2011) and show its potential to improve simulated surface 222Rn concentrations and seasonality. The regional components of this emission scenario include spatially and temporally varying emission fluxes derived from previous measurements of soil radium content and soil exhalation models, which are key factors to 222Rn emission flux rates. However, large model underestimates of surface 222Rn concentrations still exist in Asia, suggesting unusually high regional 222Rn emissions. We propose a conservative up-scaling factor of 1.2 for 222Rn emission fluxes in China, as also constrained by the observed deposition fluxes of 210Pb (decay daughter of 222Rn). With this modification, the model shows better agreement with the observations in Europe and North America (>80% data within a factor of 2), and reasonable agreement in Asia (close to 70%). Further constraints on 222Rn emissions would require additional observations of surface 222Rn concentrations and emission fluxes in central U.S., Canada, Africa, and Asia. We also compare and assess convective transport in model simulations driven by MERRA and GEOS-FP using observed 222Rn vertical profiles during northern mid-latitude summertime and from two short-term airborne campaigns. While the simulations with both GEOS products are able to capture the observed vertical gradient of 222Rn concentrations in the lower troposphere (0-4 km), neither correctly represents the level of convective detrainment, resulting in biases in the middle and upper troposphere. Compared to GEOS-FP, MERRA leads to stronger convective transport of 222Rn, which is partially compensated by its weaker large-scale vertical advection, resulting in similar global vertical distributions of 222Rn concentrations between the two simulations.

Zhang, Bo↗

DOE OSTI2020

A new approach for measuring the carbon and oxygen content of atmospherically relevant compounds and mixtures

Abstract. Due to its complexity, gas- and particle-phase organic carbon in the atmosphere is often classified by its bulk physicochemical properties. However, there is a dearth of robust, moderate-cost approaches to measure the bulk chemical composition of organic carbon in the atmosphere. This is particularly true for the degree of oxygenation, which critically affects the properties and impacts of organic carbon but for which routine measurement approaches are lacking. This gap has limited the understanding of a wide range of atmospheric components, including particulate matter, the mass of which is monitored worldwide due to its health and environmental effects but the chemical characterization of which requires relatively high capital costs and complex operation by highly trained technical personnel. In this work, we demonstrate a new approach to estimate the mass of carbon and oxygen in analytes and mixtures that relies only on robust, moderate-cost detectors designed for use with gas chromatography. Organic compounds entering a flame ionization detector were found to be converted with approximately complete efficiency to CO2, which was analyzed downstream using an infrared detector to measure the mass of carbon analyzed. The ratio of the flame ionization detector (FID) signal generated to CO2 formed (FID∕CO2) was shown to be strongly correlated (R2=0.89) to the oxygen-to-carbon ratio (O∕C) of the analyte. Furthermore, simple mixtures of analytes behaved as the weighted average of their components, indicating that this correlation extends to mixtures. These properties were also observed to correlate well with the sensitivity of the FID estimated by structure activity relationships (quantified as the relative effective carbon number). The relationships between measured FID∕CO2, analyte O∕C, and FID sensitivity allow the estimation of one property from another with <15 % error for mixtures and <20 % error for most individual analytes. The approach opens the possibility of field-deployable, autonomous measurement of the carbon and oxygen content of particulate matter using time-tested, low-maintenance detectors, though such an application would require some additional testing on complex mixtures. With some instrumental modifications, similar measurements on gas-phase species may be feasible. Moreover, the potential expansion to additional gas chromatography detectors may provide concurrent measurement of other elements (e.g., sulfur, nitrogen).

42 ENGINEERING↗

DOE OSTI2023

Surface‐modified Ag@Ru‐P25 for photocatalytic CO 2 conversion with high selectivity over CH 4 formation at the solid–gas interface

Systematic optimization of the photocatalyst and investigation of the role of each component is important to maximizing catalytic activity and comprehending the photocatalytic conversion of CO 2 reduction to solar fuels. A surface-modified Ag@Ru-P25 photocatalyst with H 2 O 2 treatment was designed in this study to convert CO 2 and H 2 O vapor into highly selective CH 4 . Ru doping followed by Ag nanoparticles (NPs) cocatalyst deposition on P25 (TiO 2 ) enhances visible light absorption and charge separation, whereas H 2 O 2 treatment modifies the surface of the photocatalyst with hydroxyl (–OH) groups and promotes CO 2 adsorption. High-resonance transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray absorption near-edge structure, and extended X-ray absorption fine structure techniques were used to analyze the surface and chemical composition of the photocatalyst, while thermogravimetric analysis, CO 2 adsorption isotherm, and temperature programmed desorption study were performed to examine the significance of H 2 O 2 treatment in increasing CO 2 reduction activity. The optimized Ag 1.0 @Ru 1.0 -P25 photocatalyst performed excellent CO 2 reduction activity into CO, CH 4 , and C 2 H 6 with a ~95% selectivity of CH 4 , where the activity was ~135 times higher than that of pristine TiO 2 (P25). For the first time, this work explored the effect of H 2 O 2 treatment on the photocatalyst that dramatically increases CO 2 reduction activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗