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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Microkinetic insights into the role of catalyst and water activity on the nucleation, growth, and dissolution during COF-5 synthesis

The chemical pathway for synthesizing covalent organic frameworks (COFs) involves a complex medley of reaction sequences over a rippling energy landscape that cannot be adequately described using existing theories. Even with the development of state-of-the-art experimental and computational tools, identifying primary mechanisms of nucleation and growth of COFs remains elusive. Other than empirically, little is known about how the catalyst composition and water activity affect the kinetics of the reaction pathway. In this work, for the first time, we employ time-resolved in situ Fourier transform infrared spectroscopy (FT-IR) coupled with a six-parameter microkinetic model consisting of ~10 million reactions and over 20 000 species. The integrated approach elucidates previously unrecognized roles of catalyst pK a on COF yield and water on growth rate and size distribution. COF crystalline yield increases with decreasing pK a of the catalysts, whereas the effect of water is to reduce the growth rate of COF and broaden the size distribution. The microkinetic model reproduces the experimental data and quantitatively predicts the role of synthesis conditions such as temperature, catalyst, and precursor concentration on the nucleation and growth rates. Furthermore, the model also validates the second-order reaction mechanism of COF-5 and predicts the activation barriers for classical and non-classical growth of COF-5 crystals. The microkinetic model developed here is generalizable to different COFs and other multicomponent systems.

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

Lithiophilic CoF 2 @C hollow spheres towards spatial lithium deposition for stable lithium metal batteries

Lithium metal (LM) is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential. Nonetheless, side reactions, volume change, and unwanted lithium dendrite growth seriously limit the practical application of LM. Herein, with the aid of a hard template approach, a novel lithiophilic CoF 2 -carbon hollow sphere (CoF 2 @C-HS) composite material is successfully prepared via a facile in-situ fluorination and etching strategy. The lithiophilic CoF 2 acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiF-rich solid electrolyte interphase (SEI), and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition. Theoretical simulations reveal that the synergistic effect of lithiophilic CoF 2 and hollow carbon matrix homogenizes the electric field distribution and Li + flux. Benefiting from these advantages, the CoF 2 @C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency (CE) of 93.7% for 280 cycles at 1 mA cm –2 and 1 mA h cm –2 . The symmetrical cell using CoF 2 @C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 mA cm –2 and an areal capacity of 0.5 mA h cm –2 . Moreover, the Li@CoF 2 @C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95% in LiFePO 4 -based full cell and 110 stable cycles at 1 C in LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811)-based high-voltage full cell. Finally, this work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition, realizing dendrite-free LM anodes and the practical applications of LM batteries.

25 ENERGY STORAGE↗
NASA NTRS1986

COFS 3: Multibody dynamics and control technology

COFS 3 is the third project within the Control of Flexible Structures (COFS) program. It deals with developing multibody dynamics and control technology for large space structures. It differs from COFS 1 and 2 in two respects. First, it addresses a more complex class of structure, and second it is basically a scale model ground test and analysis program while COFS 1 and 2 feature Shuttle flight experiments. The specific technology thrusts within COFS 3 are model sensitivities, test methods, analysis validation, systems identification, and vibration suppression. The COFS 3 project will develop the methods for using dynamically scaled models and analysis to predict the structural dynamics of large space structures. The project uses the space station as a focus because it is typical of the structures of interest and provides the first opportunity to obtain full-scale on-orbit dynamics data.

Letchworth, Robert↗
DOE OSTI2024

Mapping TpPa-1 covalent organic framework (COF) molecular interactions in mixed solvents via atomistic modeling and experimental study

Complex solvent environments continue to limit the widespread adoption of organic solvent nanofiltration (OSN) in many chemical industry applications. In this paper we employ a commercially available covalent organic framework (COF), TpPa-1, and force field models to molecularly map separation performance of TpPa-1 membrane in mixed solvents. To minimize time and length scale mismatch between atomistic modeling and experiments, solvent permeance was normalized with water in modeling and experimental results to enable direct comparison. Model outputs, such as organic solvent permeance and solute rejection rate, matched well with filtration results. Since the atomistic models assume that all mass transfer is via through-pore transport, the discrepancies between modeling and experimental results provide insights on the effect of linear polymer defects, adsorption and interstitial mass transfer on polycrystalline COF membrane performance. In sum, force field models can serve as digital twins of COF membranes to simulate separation processes while capturing the effects of COF structure, chemistry, and crystallinity on membrane performance in complex organic solvent environments. Finally, this approach will provide insight into future COF design and synthesis for persisting separation challenges.

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

Engineering of flat bands and Dirac bands in two-dimensional covalent organic frameworks (COFs): relationships among molecular orbital symmetry, lattice symmetry, and electronic-structure characteristics

Two-dimensional covalent organic frameworks (2D-COFs), also referred to as 2D polymer networks, display unusual electronic-structure characteristics, which can significantly enrich and broaden the fields of electronics and spintronics. In this Focus article, the objective of this report is to lay the groundwork for the conceptual description of the fundamental relationships among the COF electronic structures, the symmetries of their 2D lattices, and the frontier molecular orbitals (MOs) of their core and linker components. We focus on monolayers of hexagonal COFs and use tight-binding model analyses to highlight the critical role of the frontier-MO symmetry, in addition to lattice symmetry, in determining the nature of the electronic bands near the Fermi level. We rationalize the intriguing feature that, when the core unit has degenerate highest occupied MOs [or lowest unoccupied MOs], the COF highest valence band [or lowest conduction band] is flat but degenerate with a dispersive band at a high-symmetry point of the Brillouin zone; the consequences of having such band characteristics are briefly described. Multi-layer and bulk 2D COFs are found to maintain the salient features of the monolayer electronic structures albeit with a reduced bandgap due to the interlayer coupling. This Focus article is thus meant to provide an effective framework for the engineering of flat and Dirac bands in 2D polymer networks.

36 MATERIALS SCIENCE↗
NASA NTRS1988

Control Of Flexible Structures-2 (COFS-2) flight control, structure and gimbal system interaction study

The second Control Of Flexible Structures Flight Experiment (COFS-2) includes a long mast as in the first flight experiment, but with the Langley 15-m hoop column antenna attached via a gimbal system to the top of the mast. The mast is to be mounted in the Space Shuttle cargo bay. The servo-driven gimbal system could be used to point the antenna relative to the mast. The dynamic interaction of the Shuttle Orbiter/COFS-2 system with the Orbiter on-orbit Flight Control System (FCS) and the gimbal pointing control system has been studied using analysis and simulation. The Orbiter pointing requirements have been assessed for their impact on allowable free drift time for COFS experiments. Three fixed antenna configurations were investigated. Also simulated was Orbiter attitude control behavior with active vernier jets during antenna slewing. The effect of experiment mast dampers was included. Control system stability and performance and loads on various portions of the COFS-2 structure were investigated. The study indicates possible undesirable interaction between the Orbiter FCS and the flexible, articulated COFS-2 mast/antenna system, even when restricted to vernier reaction jets.

Fay, Stanley↗
DOE OSTI2021

Compositions and methods for the modification of imine covalent organic frameworks (COFs)

The present invention provides for a method for modifying a covalent organic framework (COF), the method comprising: contacting a COF comprising an imine group with a phenylacetylene in, or to form, a mixture, in a suitable reaction condition for converting the imine group into a quinoline group, and COF comprising a quinoline group. The present invention also provides for a superhydrophobic surface comprising a solid surface coated with or comprising the covalent organic framework (COF).

Li, Xinle↗
DOE OSTI2024

Gas Permeation and Separation Characteristics of Microporous TpHz COF Membranes Synthesized by Substrate-Assisted Interfacial Polymerization

Microporous two-dimensional covalent organic framework (2D COF) membranes offer promise for gas separation applications, but their gas transport mechanism remains unclear. In this study, a TpHz 2D COF membrane supported on a macroporous nylon substrate is prepared by substrate-assisted interfacial polymerization under mild conditions. The formation of a continuous and dense thin (~300 nm thick) TpHz layer is confirmed by scanning electron microscopy and Fourier transform infrared spectroscopy. Characterization by X-ray diffraction, grazing incidence wide-angle X-ray scattering, and N 2 porosimetry qualitatively reveals the microstructures of the supported TpHz membranes, i.e., they comprise partially oriented 2D COF lamellar crystallites with moderate crystallinity in an eclipsed (AA) stacking geometry, centering the effective membrane pore size distribution at ~1.1 nm. Further, single gas permeation data show that the transport of common molecular gases, including H 2 , He, CH 4 , N 2 , and CO 2 , through the synthesized TpHz membranes follows the Knudsen transport mechanism, where single gas permeance decreases with an increasing molecular weight and permeation temperature. Binary gas separation results show that in the equimolar CO 2 /N 2 mixture, the presence of the CO 2 surface flow slightly hinders the N 2 flow at room temperature due to the reduced membrane channel size by the adsorbed CO 2 gas layer on TpHz’s pore wall. In contrast, permeation of the equimolar CH 4 /N 2 binary mixture does not exhibit a discernible surface flow of both gases due to their much lower gas uptake on TpHz, and their transport mechanism follows Knudsen-like behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Discovery of Stacking Heterogeneity, Layer Buckling, and Residual Water in COF-999-NH 2 and Implications on CO 2 Capture

Covalent organic frameworks (COFs), with their modular architectures and tunable functionalities, provide a versatile platform to design sorbents for the direct capture of CO 2 from air. Here, for this work, we combined density functional theory, molecular dynamics, and grand canonical Monte Carlo simulations with experiment to understand structural factors for furthering COF-999-NH 2 ’s performance as the precursor to COF-999 for direct air CO 2 capture. Small energy differences among laterally shifted stackings suggest intrinsic stacking heterogeneity. The simulations show pronounced layer buckling coupled to extensive amine–nitrile hydrogen bonding and persistent pore water, which initiates undesired polymerization and undermines uptake. The predicted presence of water is confirmed by subsequent experiments. These insights point to a single, actionable design rule: exclude retained water by introducing hydrophobic pore environments to maximize the CO 2 capture efficiency.

adsorption↗
NASA NTRS1985

Control of Flexible Structures (COFS) Flight Experiment Program

The Control of Flexible Structures (COFS) Flight Experiment Program consists of a series of four Shuttle-attached experiments specifically designed to systematically evaluate algorithms and techniques for on-orbit systems identification and flexible body control of large flexible structures, and as such, develops the enabling technologies for future NASA missions such as the evolutionary Space Station and large orbital antennas. These flight experiments are conducted on 1-year centers starting in 1989. This paper presents a description of the test article for the first two flights (COFS-I) and a discussion of the strategy for conducting the various experiments. A guest investigator program provides the opportunity for the research community to participate in the structures/controls research associated with the multi-flight COFS Program.

Fontana, A.↗
NASA NTRS1986

COFS 1: Beam dynamics and control technology overview

The Control of Flexible Structures (COFS) 1 Project provides the invaluable opportunity to test, validate, and measure the effectiveness of theories, structural concepts, control systems, and flight certification processes for future missions through a research program focusing on multiple issues in large flexible structures, dynamics, and controls. The COFS 1 Project consists of a series of ground and flight activities building progressively from modeling and dynamic characterization of large space systems to the more complex issues of flexible-body control. The program objectives are to: determine the degree to which theory and ground testing can predict flight performance of next-generation low-frequency structures; evaluate structural fidelity of representative next-generation large deployable precision structure; assess math modeling requirements for large lightweight complex systems on which ground test results are questionable; determine degree to which scale model analysis and tests can be correlated to full-scale performance; evaluate system identification and state estimation algorithms on complex lightweight structures in the space environment; evaluate and verify controls/structures modeling capability; evaluate control laws and control systems; and evaluate damping effects in micro-g environment.

Allen, John L.↗
NASA NTRS1986

Distributed control for COFS 1

An overview is given of the work being done at NASA LaRC on developing the Control of Flexible Structures (COFS) 1 Flight Experiment Baseline Control Law. This control law currently evolving to a generic control system software package designed to supply many, but not all, guest investigators. A system simulator is also described. It is currently being developed for COFS-1 and will be used to develop the Baseline Control Law and to evaluate guest investigator control schemes. It will be available for use whether or not control schemes fall into the category of the Baseline Control Law. First, the hardware configuration for control experiments is described. This is followed by a description of the simulation software. Open-loop sinusoid excitation time histories are next presented both with and without a local controller for the Linear DC Motor (LDCM) actuators currently planned for the flight. The generic control law follows and algorithm processing requirements are cited for a nominal case of interest. Finally, a closed-loop simulation study is presented, and the state of the work is summarized in the concluding remarks.

Montgomery, R. C.↗
DOE OSTI2022

Covalent Organic Framework (COF) Derived Ni–N–C Catalysts for Electrochemical CO 2 Reduction: Unraveling Fundamental Kinetic and Structural Parameters of the Active Sites

Electrochemical CO 2 reduction is a potential approach to convert CO 2 into valuable chemicals using electricity as feedstock. Abundant and affordable catalyst materials are needed to upscale this process in a sustainable manner. Nickel-nitrogen-doped carbon (Ni-N-C) is an efficient catalyst for CO 2 reduction to CO, and the single-site Ni-N x motif is believed to be the active site. However, critical metrics for its catalytic activity, such as active site density and intrinsic turnover frequency, so far lack systematic discussion. In this work, we prepared a set of covalent organic framework (COF)-derived Ni-N-C catalysts, for which the Ni-N x content could be adjusted by the pyrolysis temperature. The combination of high-angle annular dark-field scanning transmission electron microscopy and extended X-ray absorption fine structure evidenced the presence of Ni single-sites, and quantitative X-ray photoemission addressed the relation between active site density and turnover frequency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

COFS 1 research overview

The Control of Flexible Structures (COFS) program is divided into three areas of research. These three areas are controls/structures analysis development, ground test experiments, and in-space experiments. The ground test experiments are intended to validate analyses and to confirm through hardware tests our technical readiness to successfully fly the Mast hardware. There is this close relation to the results of ground tests and analytical predictions that must be understood before flight experiments may be attempted. Details relative to each program area are given.

Horner, G. C.↗
NASA NTRS1986

COFS 1 Guest Investigator Program

The process for selecting guest investigators for participation in the Control of Flexible Structures (COFS)-1 program is described. Contracts and grants will be awarded in late CY87. A straw-man list of types of experiments and a distribution of the experiments has been defined to initiate definition of an experiments package which supports development and validation of control structures interaction technology. A schedule of guest investigator participation has been developed.

Fontana, Anthony↗
NASA NTRS1986

COFS 2: 3-D dynamics and controls technology

The Control of Flexible Structures (COFS) 2 project is a complex and ambitious undertaking which will address several critical technology areas. Among them are modeling, structural dynamics, controls, and ground testing issues which are not only germane to this effort, but to other large space structure programs being contemplated. This effort requires the early integration of controls and structural dynamics considerations in order to achieve mission success. Several technology advances must be achieved in the areas of system modelling, control synthesis and methodology, sensor/actuator development, and ground testing techniques for system evaluation and on-orbit performance prediction and verification. This project offers a unique opportunity for the integration of several disciplines to produce technology advances which will benefit many future programs. In addition, the opportunities available to participate in the various levels in the phase of this project, e.g., analytical development and modelling, ground testing, and flight testing, permit for the involvement of a significant number of interested researchers and organizations from government, universities and industry.

Pyle, Jon S.↗
NASA NTRS1986

Analysis and simulation of the MAST (COFS-1 flight hardware)

In-house analysis work in support of the Control of Flexible Structures (COFS) program is being performed at the NASA Langley Research Center. The work involves evaluation of the proposed design configuration, controller design as well as actuator dynamic modeling, and MAST/actuator dynamic simulation of excitation and damping. A complete finite element model of the MAST has been developed. This finite element model has been incorporated into an optimization procedure which minimizes total mass while maintaining modal coupling. Results show an increase in the total mass due to additional constraints (namely, the diagonal frequency constraint) imposed on the baseline design. A valid actuator dynamic model is presented and a complete test sequence of the proposed flight experiment is demonstrated. The actuator dynamic model is successfully used for damping and the stroke limitations for first mode excitation are demonstrated. Plans are to incorporate additional design variables and constraints into the optimization procedure (such as actuator location) and explore alternative formulations of the objective function. A different actuator dynamic model to include hardware limitations will be investigated.

Horta, Lucas G.↗