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

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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Sharp-tip enhanced catalytic CO oxidation by atomically dispersed Pt 1 /Pt 2 on a raised graphene oxide platform

Revealing structure–activity relationships of graphene-supported atomically dispersed transition metal catalysts is of key importance in catalysis chemistry and materials science. In this work, we report a first-principles theoretical study on O 2 activation and CO oxidation catalyzed by atomically dispersed Pt 1 /Pt 2 anchored on a raised graphene (Gr) platform. The unique sharp-tip structure of the protuberant graphene platform (carbon-tip) can collect extra polarization electrons on the Pt-tip, promoting electron transfer between the catalyst and adsorbates, and greatly enhancing the chemical activity. Higher carbon-tips on defective graphene oxide with a carbon vacancy (Gr-V) produce more polarization electrons, a more localized electric field, and a larger up-shift of the d-orbital center of the Pt-tip, resulting in better catalytic performance. The carbon-tip enhancement reduces the energy barrier for the CO oxidation on Pt 1 O 2 /Gr-V from 1.19 eV to 0.56 eV compared with Pt 1 on planar Gr. In addition, CO poisoning is significantly alleviated, with the CO poisoning rate Γ θ reduced from 2.00 eV to 0.52 eV. Moreover, a linear relationship between the activation barrier and the binding energy of adsorbates is found for various atomically dispersed Pt-tip catalysts on the raised graphene oxide platform. Importantly, the order of catalytic activity is consistent with the carbon-tip enhancement, i.e., Pt 1 O 2 /Gr-V > Pt 2 O 4 /Gr-V > Pt 1 O 2 /Gr > Pt 2 O 4 /Gr. These findings provide important guidance for rational design of atomically dispersed catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Clouds and chemistry on Mars

Variation in the O3 abundance on Mars with changes in cloud opacities has been analyzed theoretically. Particular attention is given to the efficiency of reflectance spectroscopy for observing O3 abundances on Mars.

Lindner, Bernhard L.↗
DOE OSTI2025

Theoretically Informed Kinetics (ThInK): Establishing a modern C 0 -C 3 mechanism for combustion modeling

In contrast to the adage “Models are to be used, not believed”, combustion kinetics models have been intended to be predictive in nature. Theoretical chemical kinetics is now understood to provide a firm foundation for the reaction parameters, thereby facilitating predictive simulations of chemical reactivity, even in regimes that are poorly characterized by chemical kinetic and/or combustion experiments. In this study, we describe a theory-informed kinetics model (ThInK) for small molecule combustion chemistry (H 2 and C 1 – C 3 species) that is based on the prodigious use of theoretical predictions for reaction rate coefficients, thermochemistry, and transport parameters. The distinct features of this kinetics model, which was developed over the course of several decades, are illustrated through simulations of flame propagation and auto-ignition.

Energy transfer↗
DOE OSTI2024

Phase Transitions in Organic and Organic/Inorganic Aerosol Particles

The phase state of aerosol particles can impact numerous atmospheric processes, including new particle growth, heterogeneous chemistry, cloud condensation nucleus formation, and ice nucleation. In this article, the phase transitions of inorganic, organic, and organic/inorganic aerosol particles are discussed, with particular focus on liquid-liquid phase separation (LLPS). The physical chemistry that determines whether LLPS occurs, at what relative humidity it occurs, and the resultant particle morphology is explained using both theoretical and experimental methods. The known impacts of LLPS on aerosol processes in the atmosphere are discussed. Finally, potential evidence for LLPS from field and chamber studies is presented. By understanding the physical chemistry of the phase transitions of aerosol particles, we will acquire a better understanding of aerosol processes, which in turn impact human health and climate.

Chemistry↗
DOE OSTI2020

Surface Termination of CsPbBr 3 Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy

Cesium lead halide perovskite quantum dots (QDs) have gained significant attention as next-generation optoelectronic materials; however, their properties are highly dependent on their surface chemistry. The surfaces of cuboidal CsPbBr 3 QDs have been intensively studied by both theoretical and experimental techniques, but fundamental questions still remain about the atomic termination of the QDs. The surface binding sites and modes of ligands at the surface remain unproven. Herein, we demonstrate that solid-state NMR spectroscopy allows the unambiguous assignment of organic surface ligands via 1 H, 13 C, and 31 P NMR. Surface-selective 133 Cs solid-state NMR spectra show the presence of an additional 133 Cs NMR signal with a unique chemical shift that is attributed to Cs atoms terminating the surface of the particle and which are likely coordinated by carboxylate ligands. Dipolar dephasing curves that report on the distance between the surface ammonium ligands and Cs and Pb were recorded using double resonance 1 H{ 133 Cs} and 1 H{ 207 Pb} RESPDOR experiments. Model QD surface slabs with different possible surface terminations were generated from the CsPbBr 3 crystal structure and theoretical RESPDOR dipolar dephasing curves considering all possible 1 H- 133 Cs/ 207 Pb spin pairs were then calculated. Comparison of the calculated and experimental RESPDOR curves indicates the particles are CsBr terminated (not PbBr 2 terminated) with alkylammonium ligands substituting into some surface Cs sites, consistent with the surface-selective 133 Cs NMR experiments. Lastly, these results highlight the utility of high-resolution solid-state NMR spectroscopy for studying ligand binding and the surface structure of nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

A universal co-solvent dilution strategy enables facile and cost-effective fabrication of perovskite photovoltaics

Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (<0.5 M) while retaining similar film quality and device performance as a high concentration (>1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2022

A New Low-Temperature Approach for Efficient and Low-Cost Group V Doping in CdTe Thin Film Solar Cells (Final Technical Report)

The goal of this project is to develop a highly efficient low-temperature ex-situ Group V diffusion doping approach in the CdCl 2 treated polycrystalline CdTe film using the group V chlorides (i.e., PCl 3 , AsCl 3 , SbCl 3 , and BiCl 3 ) as dopants source. For the first time, our innovative doping strategies through the low-temperature ex-situ Group V doping process in polycrystalline CdSeTe successfully demonstrated a promising power conversion efficiency of ~19% compared to the Cu-doped counterparts. Our newly developed low-temperature ex-situ group V doping allows dedicated control of group V diffusion amount, generates a desirable depth profile, and is completely compatible with commercial CdTe module manufacturing. We built the partnership with the largest CdTe solar module manufacturing in the US, e.g., First Solar, Inc to further develop these low-temperature diffusion doped CdSeTe solar cells. Our technology was granted US Patent No. US11257977B2. In this project, we systematically investigate and characterize the new ex-situ group V doping mechanisms, defect chemistry, microstructure, and device physics in CdTe solar cells by combining experimental and theoretical means to pave the way to achieve lower cost toward $\$$0.02/kWh and higher power conversion efficiency (PCE) toward 25% in polycrystalline CdTe solar technology. This project will benefit the public by providing more affordable solar electricity and provide an effective way to address climate change.

14 SOLAR ENERGY↗
NASA NTRS1992

NASA's upper atmosphere research satellite: A program to study global ozone change

The Upper Atmosphere Research Satellite (UARS) is a major initiative in the NASA Office of Space Science and Applications, and is the prototype for NASA's Earth Observing System (EOS) planned for launch in the 1990s. The UARS combines a balanced program of experimental and theoretical investigations to perform diagnostic studies, qualitative model analysis, and quantitative measurements and comparative studies of the upper atmosphere. UARS provides theoretical and experimental investigations which pursue four specific research topics: atmospheric energy budget, chemistry, dynamics, and coupling processes. An international cadre of investigators was assembled by NASA to accomplish those scientific objectives. The observatory, its complement of ten state of the art instruments, and the ground system are nearing flight readiness. The timely UARS program will play a major role in providing data to understand the complex physical and chemical processes occurring in the upper atmosphere and answering many questions regarding the health of the ozone layer.

Luther, Michael R.↗
NASA NTRS1986

Interstellar isomers

Both observational and theoretical studies of molecular clouds are hindered by many difficulties. One way to partially circumvent the difficulties of characterizing the chemistry within these objects is to study the relative abundances of isomers which are synthesized from a common set of precursors. Unfortunately, only one such system has been confirmed, the HCN/HNC pair of isomers. While the basic outlines of its chemistry have been known for some years, there are still many aspects of the chemistry which are unclear. Another potential pair of isomers is HCO+/HOC+; HCO+ is an abundant instellar molecule and a tentative identification of HOC+ has been made in Sgr B2. This identification is being challenged, however, based on theoretical and laboratory evidence that HOC+ reacts with H2. Another potential pair of interstellar isomers is methyl cyanide (CH3CN, acetonitrile) and methyl isocyanide (CH3NC). The cyanide is well known, however the isocyanide has yet to be observed despite theoretical predictions that appreciable quantities should be present.

Defrees, D.↗
DOE OSTI2022

Multivalent optical cycling centers: towards control of polyatomics with multi-electron degrees of freedom

Optical control of polyatomic molecules promises new opportunities in precision metrology and fundamental chemistry, as well as quantum information and many-body science. Contemporary experimental and theoretical efforts have mostly focused on cycling photons via excitation of a single electron localized to an alkaline earth (group 2)-like metal center. In this paper, we consider pathways towards optical cycling in polyatomic molecules with multi-electron degrees of freedom, which arise from two or more cycling electrons localized to p-block post-transition metal and metalloid (group 13, 14, and 15) centers. Here, we characterize the electronic structure and rovibrational branching of several prototypical candidates using ab initio quantum chemical methods. Despite increased internal complexity and challenging design parameters, we find several molecules possessing quasi-closed photon cycling schemes with highly diagonal, visible and near-infrared transitions. Furthermore, we identify new heuristics for engineering optically controllable and laser-coolable polyatomic molecules with multi-electron cycling centers. Our results help elucidate the interplay between hybridization, repulsion, and ionicity in optically active species and provide new directions for using polyatomic molecules with complex electronic structure as a resource for quantum science and measurement.

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

Theoretical kinetics predictions for NH 2 + HO 2

Recent modeling studies of NH 3 oxidation, which are motivated by the prospective role of ammonia as a zero-carbon fuel, have indicated significant discrepancies between existing literature mechanisms. In this study high level theoretical kinetics predictions have been obtained for the reaction of NH 2 with HO 2 , which has previously been highlighted as an important reaction with high sensitivity and high uncertainty. The potential energy surface is explored with coupled cluster calculations including large basis sets and high-level corrections to yield high accuracy (~0.2 kcal/mol) estimates of the stationary point energies. Variational transition state theory is used to predict the microcanonical rate constants, which are then incorporated in master equation treatments of the temperature and pressure dependent kinetics. For the radical-radical channels, the microcanonical rates are obtained from variable reaction coordinate transition state theory implementing directly evaluated multireference electronic energies. The analysis yields predictions for the total rate constant as well as the branching to the NH 3 + O 2 , H 2 NO + OH, and HNO + H 2 O channels. Rate constants are also reported for the H 2 NO + OH reaction as they arise naturally from the analysis. The rate constant and branching fraction determined in this work for the NH 2 + HO 2 reaction deviate significantly from values used in most previous modeling studies. The fact that the main product channel is chain terminating, rather than propagating, has strong implications for modeling NH 3 ignition and oxidation, in particular at intermediate temperatures and elevated pressure.

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

A Minimal Information Set To Enable Verifiable Theoretical Battery Research

Batteries are an enabling technology for addressing sustainability through the electrification of various forms of transportation (1) and grid storage. (2) Batteries are truly multi-scale, multi-physics devices, and accordingly various theoretical descriptions exist to understand their behavior (3-5) ranging from atomistic details to techno-economic trends. As we explore advanced battery chemistries (6,7) or previously inaccessible aspects of existing ones, (8-10) new theories are required to drive decisions. (11-13) The decisions are influenced by the limitations of the underlying theory. Advanced theories used to understand battery phenomena are complicated and require substantial effort to reproduce. However, such constraints should not limit the insights from these theories. We can strive to make the theoretical research verifiable such that any battery stakeholder can assess the veracity of new theories, sophisticated simulations or elaborate analyses. We distinguish verifiability, which amounts to “Can I trust the results, conclusions and insights and identify the context where they are relevant?”, from reproducibility, which ensures “Would I get the same results if I followed the same steps?” With this motivation, we propose a checklist to guide future reports of theoretical battery research in Table 1. We hereafter discuss our thoughts leading to this and how it helps to consistently document necessary details while allowing complete freedom for creativity of individual researchers. Given the differences between experimental and theoretical studies, the proposed checklist differs from its experimental counterparts. (14,15) This checklist covers all flavors of theoretical battery research, ranging from atomic/molecular calculations (16-19) to mesoscale (20,21) and continuum-scale interactions, (9,22) and techno-economic analysis. (23,24) Finally, as more and more experimental studies analyze raw data, (25) we feel this checklist would be broadly relevant.

25 ENERGY STORAGE↗
DOE OSTI2020

Phosphorus-rich stars with unusual abundances are challenging theoretical predictions

Almost all chemical elements have been made by nucleosynthetic reactions in various kind of stars and have been accumulated along our cosmic history. Among those elements, the origin of phosphorus is of extreme interest because it is known to be essential for life such as we know on Earth. However, current models of (Galactic) chemical evolution under-predict the phosphorus we observe in our Solar System. Here we report the discovery of 15 phosphorus-rich stars with unusual overabundances of O, Mg, Si, Al, and Ce. Phosphorus-rich stars likely inherit their peculiar chemistry from another nearby stellar source but their intriguing chemical abundance pattern challenge the present stellar nucleosynthesis theoretical predictions. Specific effects such as rotation or advanced nucleosynthesis in convective-reactive regions in massive stars represent the most promising alternatives to explain the existence of phosphorus-rich stars. The phosphorus-rich stars progenitors may significantly contribute to the phosphorus present on Earth today.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Mixed Cationic and Anionic Redox in Ni and Co Free Chalcogen-Based Cathode Chemistry for Li-Ion Batteries

Mixed cationic and anionic redox cathode chemistry is emerging as conventional cationic-redox of transition metal based layered oxides are reaching their theoretical capacity limit. However, these anionic redox in transition metal oxide-based cathodes attained by taking excess lithium has resulted in stability issues due to weak metal - oxygen ligand covalency. Here, we present an alternative approach of improving metal - ligand covalency by introducing less electronegative chalcogen ligand (sulfur) in the cathode structural framework where the metal dband penetration into ligand p-band thereby utilizing reversible mixed anionic and cationic redox chemistry. Through this design strategy, we report possibility of developing a new family of layered cathode materials when partially filled d orbital redox couples like Fe 2+/3+ are introduced in the Li-ion conducting phase (Li 2 SnS 3 ). Further, the electron energy loss spectroscopy (EELS) and X-ray absorption near-edge structure (XANES) analysis are used to qualitatively identify the charge contributors at the metal and ligand sites during Li + extraction. The detailed high-resolution transmission electron microscopy (HR-TEM) and high annular dark field-scanning transmission electron microscopy (HAADF-STEM) investigation reveal the multi redox induced structural modifications and its surface amorphization with nanopore formation during cycling. Findings from this study will shed light on designing Ni and Co free chalcogen cathodes and various functional materials in the chalcogen based dual anionic and cationic redox cathode avenue.

25 ENERGY STORAGE↗
DOE OSTI2020

Reversible redox chemistry in azobenzene-based organic molecules for high-capacity and long-life nonaqueous redox flow batteries

Redox flow batteries (RFBs), often categorized as aqueous and nonaqueous systems, represent a type of large-scale energy storage technology for renewable energy resources. Redox-active organic molecules have recently drawn extensive interests in RFBs as promising active materials due to their elemental abundance, structural diversity and high tunability of properties, but employing organic molecules in nonaqueous systems is far limited in terms of useable capacity and cycling stability. Here we introduce a class of azobenzene-based organic compounds with the azo group as redox-active center in the p-conjugated structure as new active materials to realize high-performance nonaqueous RFBs with long cycling life and high capacity. By screening suitable organic solvents with high solubility and conductivity, the azobenzene organic molecule was capable to achieve a stable long cycling with a low capacity decay of 0.014% per cycle and 0.16% per day over 1000 cycles. And the stable cycling of electrolytes under a high concentration of 1 M was also realized, delivering a high reversible capacity of ~46 Ah L -1 . The unique lithium-coupled redox chemistry accompanied with a voltage increase was observed and revealed by experimental characterization and theoretical simulation. With the reversible two-electron redox activity of azo group in p-conjugated structures, azobenzene as an azo-aromatic molecule represents a class of promising redox-active organics for potential grid-scale energy storage systems.

25 ENERGY STORAGE↗