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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Dynamic metal-linker bonds in metal–organic frameworks

Metal-linker bonds serve as the “glue” that binds metal ions to multitopic organic ligands in the porous materials known as metal–organic frameworks (MOFs). Despite ample evidence of bond lability in molecular and polymeric coordination compounds, the metal-linker bonds of MOFs were long assumed to be rigid and static. Given the importance of ligand fields in determining the behaviour of metal species, labile bonding in MOFs would help explain outstanding questions about MOF behaviour, while providing a design tool for controlling dynamic and stimuli-responsive optoelectronic, magnetic, catalytic, and mechanical phenomena. Here, in this work, we present emerging evidence that MOF metal-linker bonds exist in dynamic equilibria between weakly and tightly bond conformations, and that these equilibria respond to guest–host chemistry, drive phase change behavior, and exhibit size-dependence in MOF nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Covalent organic frameworks in heterogeneous catalysis: recent advances and future perspective

Catalysis is ubiquitous in ~90% of chemical manufacturing processes and contributes up to 35% of global GDP. Hence, the development of advanced catalytic systems is of utmost importance for academia, industry, and government. Covalent organic frameworks (COFs) are a rapidly emerging class of crystalline porous materials that precisely integrate organic monomer units into extended periodic networks, offering a propitious platform for heterogeneous catalysis due to salient structural merits of ultralow density, high crystallinity, permanent porosity, structural tunability, functional diversity, and synthetic versatility. The past decade has witnessed an upsurge of interest in COFs for heterogeneous catalysis and this trend is expected to continue. In this review, we briefly introduce COF chemistry concerning the design principles, growth mechanism, and cutting-edge advances in structural evolution, linkage chemistry, and facile synthesis. Further, we then scrutinize four leading design strategies for COF catalysts, namely pristine COFs with catalytically active backbones, COFs as hosts for the inclusion of catalytic species, COF-based heterostructures, and COF-derived carbons for thermo-, photo-, and electrocatalysis. Next, we overview the most recent advances (mainly from 2020 to 2023) of COFs in heterogeneous catalysis, along with their fundamentals and advantages. Finally, we outline the current challenges and offer our perspectives on the future directions of COFs for heterogeneous catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Structure prediction of porous organic crystals

In this work, we explore the possibility of applying automated crystal structure prediction to reproduce the experimentally identified metastable porous polymorphs. Using our recently developed High-Throughput Organic Crystal Structure Prediction ( HTOCSP ) framework, we conducted a systematic study on five representative organic crystalline systems including hydrogen-bonded frameworks (HOFs), featured by the presence of significant porosity, in conjunction with different choices of energy models from classical, machine learning force fields, tight binding to density functional theory. Our results suggest that the current structure generation framework, with careful selection of symmetry conditions, is likely to generate rather complex and abundant metastable crystal candidates for porous crystals. In conjunction with the recent advance in universal machine learning force fields, it becomes possible to identify experimental structures as the energetically favorable candidates from a simple energy versus density analysis, thus paving the way for computational design of complex porous materials with the target systems prior to the experimental synthesis and characterization.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tailoring multi-dimensional hierarchical self-assembly of metallacages through balancing non-covalent interactions

Despite advances in non-covalent interactions and complex self-assembly, precise control of multi-dimensional hierarchical self-assembly (HSA) from the molecular level to larger scales remains challenging. Herein, we designed and synthesized two rigid tetratopic ligands with multiple preset driving forces, and assembled them with Zn(II) ions to obtain metallacages SC6 and SC12 . Through balancing multiple non-covalent interactions, including metal–organic coordination, hydrophobic, and π–π interactions, SC6 can hierarchically self-assemble driven by a poor solvent, from one-dimensional nanowires to super-helical nanostructures via non-equilibrium self-assembly, progressing continuously with time and the increasing proportion of the poor solvent. However, for SC12 with enhanced hydrophobic interactions, two-dimensional monolayer nanogrids were formed by hierarchical self-assembly. Notably, these structures can be recycled back to primary metallacages through simple dissolution, highlighting their potential for efficient recycling and reuse. These results demonstrate that multi-dimensional hierarchical structures enable precise construction by balancing non-covalent interactions through a bottom-up self-assembly approach. This study provides deeper insight into the mechanisms of HSA and a promising strategy for the tailored creation of complex structures and sustainable porous materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Relative permeability as a stationary process: Energy fluctuations in immiscible displacement

Relative permeability is commonly used to model immiscible fluid flow through porous materials. In this work, we derive the relative permeability relationship from conservation of energy, assuming that the system to be non-ergodic at large length scales and relying on averaging in both space and time to homogenize the behavior. Explicit criteria are obtained to define stationary conditions: (1) there can be no net change for extensive measures of the system state over the time averaging interval; (2) the net energy inputs into the system are zero, meaning that the net rate of work done on the system must balance with the heat removed; and (3) there is no net work performed due to the contribution of internal energy fluctuations. Results are then evaluated based on direct numerical simulation. Dynamic connectivity is observed during steady-state flow, which is quantitatively assessed based the Euler characteristic. We show that even during steady-state flow at low capillary number ([Formula: see text]), typical flow processes will explore multiple connectivity states. The residence time for each connectivity state is captured based on the time-and-space average. The distribution for energy fluctuations is shown to be multi-modal and non-Gaussian when terms are considered independently. However, we demonstrate that their sum is zero. Given an appropriate choice of the thermodynamic driving force, we show that the conventional relative permeability relationship is sufficient to model the energy dissipation in systems with complex pore-scale dynamics that routinely alter the structure of fluid connected pathways.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Spin echo small-angle neutron scattering using superconducting magnetic Wollaston prisms

Here, we show the implementation of superconducting magnetic Wollaston prisms for spin echo small-angle neutron scattering. Two calibration methods for the spin echo length are presented: one utilizing spin echo modulated small-angle neutron scattering and the other based on the neutron refraction by quartz wedge crystals. Our experimental results with polystyrene nano-particle colloids showcase the system’s efficacy in measuring both dilute and concentrated colloidal systems. Additionally, investigations into the pore diameter and pitch of a nano-porous alumina membrane demonstrate its capability in analyzing nano-porous materials. Furthermore, we discuss potential optimizations to further extend the accessible spin echo length.

47 OTHER INSTRUMENTATION↗
DOE OSTI2026

Initial Assessment of 3D-Printed Molybdenum Lattices as a Substrate for Liquid Metal Plasma-Facing Components

Many liquid metal plasma-facing component concepts for fusion reactors require a capillary porous material to wick the liquid metal to the surface of the component. In this work, samples of 3D-printed molybdenum lattices designed to have pore sizes ranging from 100 to 1000 µm were fabricated by two different suppliers. The dimensions of the lattice structures were characterized using an optical microscope, revealing that the lattice walls were almost systematically thicker than they were designed to be and in turn the pores are all smaller than they were designed to be. In many cases the pores were completely clogged. Several spectroscopic techniques were used to characterize the chemical composition of the materials, collectively indicating the presence of a thick layer of oxygen-rich material extending more than 1 µm below the surface. Compression testing revealed significant asymmetry in the mechanical behavior depending on which direction the force was applied relative to the print direction. Lastly, lithium wetting tests of several lattice samples were performed, and a sample with ~250-µm pores was found to soak up lithium quickly after initial wetting of the surface occurred. The implications of these results for future liquid metal plasma-facing component design are discussed.

Parsons, Matthew S. [Princeton Plasma Physics Labo↗
DOE OSTI2026

Phase-field model of freeze casting

Directional solidification of water-based solutions has emerged as a versatile technique for templating hierarchical porous materials. However, the underlying mechanisms of pattern formation remain incompletely understood. In this work, we present a detailed derivation and analysis of a quantitative phase-field model for simulating this nonequilibrium process. The phase-field model extends the thin-interface formulation of dilute binary alloy solidification with antitrapping to incorporate the highly anisotropic energetic and kinetic properties of the partially faceted ice-water interface. This interface is faceted in the basal plane normal to the ⟨0001⟩ directions and atomically rough in other directions within the basal plane. On the basal plane, the model reproduces a linear or nonlinear relationship between the interface growth rate and the kinetic undercooling that can be linked to experimental measurements. In both cases, spontaneous parity breaking of the solidification front is observed when the preferred growth direction is aligned with the temperature gradient. This phenomenon leads to the formation of partially faceted ice lamellae that drift laterally in one of the ⟨0001⟩ directions. Here, we demonstrate that the drifting velocity of the ice lamellae is controlled by the kinetics on the basal plane and converges as the thickness of the diffuse solid-liquid interface decreases. Furthermore, we examine the effect of the form of the kinetic anisotropy, which is chosen here such that the inverse of the kinetic coefficient varies linearly from a finite value in the ⟨0001⟩ directions to zero in all other directions within the basal plane, consistent with the assumption that the interface grows in local thermodynamic equilibrium in this plane. Our results indicate that the drifting velocity of ice lamellae is not affected by the slope of this linear relation, and the radius and undercooling at the tip of an ice lamella converge at relatively small slope values. Consequently, the phase-field simulations remain quantitative with computationally tractable choices of both the interface thickness and the slope assumed in the form of the kinetic anisotropy.

Materials science↗
DOE OSTI2026

Parity breaking at faceted crystal growth fronts during ice templating

Directional solidification of water-based solutions has emerged as a versatile technique to template hierarchical porous materials, but this nonequilibrium process remains incompletely understood. Here, in this study, we use phase-field simulations to shed light on the mechanism that selects the growth direction of the lamellar ice structure that templates those materials. Our results show that this selection can be understood within the general framework of spontaneous parity breaking, yielding quantitative predictions for the tilt angle of lamellae with respect to the thermal axis. The results provide a theoretical basis to interpret a wide range of experimental observations.

Materials science↗
DOE OSTI2021

Evolution of water structures in metal-organic frameworks for improved atmospheric water harvesting

Designing water uptake Although the locations of water molecules in some porous materials have been determined with diffraction techniques, determining the filling sequence of water sites has been challenging. Hanikel et al . used single-crystal x-ray diffraction to locate all of the water molecules in pores of the metal-organic framework MOF-303 at different water loadings (see the Perspective by Öhrström and Amombo Noa). They used this information on the water molecule adsorption sequence to modify the linkers of this MOF and control the water-harvesting properties from humid air for different temperature regimes. —PDS

Science & Technology - Other Topics↗
DOE OSTI2024

Machine Learned Force Field Modeling of Metal Organic Frameworks for CO2 Direct Air Capture

Metal organic frameworks (MOFs) are a large class of porous materials and have garnered significant interest due to their large surface areas and their tunable physical and chemical properties. Numerous prior studies have been performed to screen large databases of this material class for promising DAC sorbent materials. These studies have often relied on classical model potentials. While density functional theory (DFT) calculations have been shown to be very accurate for modeling the interaction of CO2 with MOFs, such calculations are too computationally demanding for statistically significant adsorption predictions. To overcome this barrier, we developed methods for training models to achieve DFT-level accuracy for the forces and energies associated with MOF flexibility and CO2 adsorption using machine learned force fields (MLFFs). These methods were parametrized based on DFT calculations of CO2 in a flexible MOF and used to predict MOF structural properties as well as CO2 adsorption in several MOFs.

Findley, John↗
DOE OSTI2024

Nanoconfined Interfaces for Highly Selective Separation of Critical Rare Earth Elements

Industrial demand for rare earth elements (REEs) has surged over the past three decades due to their unique properties that support sustainable energy and new technologies. Separating individual REEs is challenging and hazardous, typically done through liquid-liquid extraction. There is an urgent need for environmentally friendly and efficient separation technologies for REEs. Porous materials offer promising advances for sustainable REE separation via ion-selective capture. We hypothesize that REE separation can be efficiently achieved in reactive nanopores, such as Zr(IV) and Cr(III) metal-organic frameworks (MOFs), through surface functionalization. By integrating material synthesis, interfacial chemistry experiments, theory, computation, and machine learning, we gained insights into the chemical factors controlling REE speciation and their competitive adsorption on MOFs. Our findings show that these materials’ selectivity can be tuned by surface functionalization. The machine learning component addressed ion-specific diffusion based on MOF topology and chemistry.

36 MATERIALS SCIENCE↗
DOE OSTI2024

High performance heat exchangers for next generation hybrid cooler (CRADA NFE-19-07891 Final Report)

The evaporative cooling process has been successfully deployed in multiple energy conversion processes such as power generation, process cooling, heating, ventilation & cooling (HVAC), and commercial and industrial refrigeration. The heat exchanger is a very common yet extremely critical component of such systems. The device is important since the performance of the overall cooling system heavily relies on the thermal-hydraulic efficiency of the heat exchanger. The possible wet operation as evaporative cooling heat exchanger complicates the issue. Indeed, based on the hybrid nature of operation (fully dry, partially wet, fully wet) the efficiency can vary significantly and can cause performance variation for the whole system. Understanding the importance of the issue, Oak Ridge National Laboratory (Contractor) and Baltimore Aircoil Company (Participant) propose an activity focused on the analysis of the existing heat exchanger technology used in air and evaporative cooling processes and design, development and demonstration of a novel heat exchanger design based on porous materials. The potential candidates include metallic wire meshes and metal foams carefully designed for the proposed application. Prior research has indicated that these materials have great potential for deployment in thermal systems, particularly heat sinks and heat exchangers. It is expected that the successful completion of the project will lead to novel heat exchanger technology for hybrid systems (capable of dry and wet operation) by exploring newly emerging materials and their potential for heat transfer application. The overall goal is to develop a next generation heat exchanger technology which can be deployed in evaporative cooling systems. The impact of the such development is significant since, it will not only make the overall system highly efficient but will also, reduce the total refrigerant charge in the heat exchanger, a critical aspect for the deployment of refrigerants with lower Global Warming Potential (GWP).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

High performance heat exchangers for next generation hybrid cooler (CRADA Final Report)

The evaporative cooling process has been successfully deployed in multiple energy conversion processes such as power generation, process cooling, heating, ventilation & cooling (HVAC), and commercial and industrial refrigeration. The heat exchanger is a very common yet extremely critical component of such systems. The device is important since the performance of the overall cooling system heavily relies on the thermal-hydraulic efficiency of the heat exchanger. The possible wet operation as evaporative cooling heat exchanger complicates the issue. Indeed, based on the hybrid nature of operation (fully dry, partially wet, fully wet) the efficiency can vary significantly and can cause performance variation for the whole system. Understanding the importance of the issue, Oak Ridge National Laboratory (Contractor) and Baltimore Aircoil Company (Participant) propose an activity focused on the analysis of the existing heat exchanger technology used in air and evaporative cooling processes and design, development and demonstration of a novel heat exchanger design based on porous materials. The potential candidates include metallic wire meshes and metal foams carefully designed for the proposed application. Prior research has indicated that these materials have great potential for deployment in thermal systems, particularly heat sinks and heat exchangers. It is expected that the successful completion of the project will lead to novel heat exchanger technology for hybrid systems (capable of dry and wet operation) by exploring newly emerging materials and their potential for heat transfer application. The overall goal is to develop a next generation heat exchanger technology which can be deployed in evaporative cooling systems. The impact of the such development is significant since, it will not only make the overall system highly efficient but will also, reduce the total refrigerant charge in the heat exchanger, a critical aspect for the deployment of refrigerants with lower Global Warming Potential (GWP).

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2026

Uniting Theory and Experiment to Deliver Flexible MOFS for Superior Methane (NG) Storage

The objective of the project was to use previous insights developed through synthesis and quantitative modeling of rigid metal–organic frameworks (MOFs) in an established synergistic theoretical/experimental team to create, modify, and evaluate flexible MOFs (FlexMOFs) for natural gas (NG) storage and release at practically useful pressures and transform the NG storage economy. The goal was reduced pressure absorbed natural gas (ANG) FlexMOF storage at operating pressures less than 100 bar with physisorption exploiting the favorable thermodynamics and kinetics of flexible porous material opening in response to adsorption. Hydrogen behavior in this context was also considered. The specific aim of the project was to design and develop a standard computational modeling methodology for, first, detailed atomistic retrodiction of FlexMOF gating behavior and ultimately prediction of the effects of functionalization and/or substitution on structural transitioning. The project was also geared towards the establishment of the interaction of methane with the framework and binding sites using modeling and the FlexMOF will be both internally and external validated as a SMART metric. This has value to the scientific community both from the obvious standpoint of providing a better understanding of the promising test case systems (CdIF-13 and the MIL-53(Al) series of MOFs), but also in providing an avenue of obtaining insight into these FlexMOF systems in general, which is of particular interest given the tendency of structure-function correlation to lag behind synthesis methodology (making the latter a hit or miss proposition for applications). This gap remains significant for FlexMOF systems whose gate opening behaviors complicate computational examination. The computational methodologies are relatively inexpensive in terms of both money and computational resources enhancing the general viability of these methodologies. The ultimate gain to the public will be in the application of these techniques to design systems for natural gas storage and use to cut down on green-house emissions.

03 NATURAL GAS↗
DOE OSTI2026

Ultra-High Operation Temperature SiC-matrix Solar Thermal Air Receiver (HOTSSTAR) enabled by additive manufacturing: Test Facility & Performance Evaluations

Solar Heat for Industrial Processes (SHIP) cavity receivers are capable of generating electricity or industrial process heat by absorbing thermal energy from solar radiation, focused on a small area. The concentration of solar radiation on the small area of the receiver enables the achievement of high temperatures (ranging from 400°C to 1,100°C) of a working fluid, thus making the SHIP technology thermodynamically comparable with conventional power plants. A volumetric receiver consists of a porous structure-generally made of silicon carbide or metal, which absorbs solar radiation and converts it into heat energy. Heat energy from the porous materials is then transferred to the fluid following through them. A volumetric receiver acts as a convective heat exchanger, transferring heat to the fluid through convection. Open-loop volumetric receivers work with air at atmospheric pressure and are suitable for single-cycle or multi-cycle energy plants. A Model Based Systems Engineering (MBSE) approach was used to develop a test bed at Sandia national Laboratories (SNL) capable of demonstrating an open-loop volumetric air receiver developed by General Electric Aerospace (GE Aerospace). This paper presents the development of the various MBSE methods, test bed, and testing operations for the GE air receiver, which was experimentally demonstrated to achieve 1,350°C for over 3 hours of operation and an approximate 70% receiver efficiency. By being able to achieve such high temperatures >1,000°C, this work provides the potential to support many SHIP industrial use cases.

14 SOLAR ENERGY↗
DOE OSTI2024

Covalent integration of polymers and porous organic frameworks

Covalent integration of polymers and porous organic frameworks (POFs), including metal-organic frameworks (MOFs), covalent organic frameworks (COFs) and hydrogen-bonded organic frameworks (HOFs), represent a promising strategy for overcoming the existing limitations of traditional porous materials. This integration allows for the combination of the advantages of polymers, i.e., flexibility, processability and chemical versatility etc., and the superiority of POFs, like the structural integrity, tunable porosity and the high surface area, creating a type of hybrid materials. These resulting polymer-POF hybrid materials exhibit enhanced mechanical strength, chemical stability and functional diversity, thus opening up new opportunities for applications across a large variety of fields, such as gas separation, catalysis, biomedical applications, environmental remediation and energy storage. In this review, an overview of synthetic routes and strategies on how to covalently integrate different polymers with various POFs is discussed, especially with a particular focus on methods like polymerization within, on and among POF structures. To investigate the unique properties and functions of these resultant hybrid materials, the characterization techniques, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), transmission electron microscopy (TEM) and scanning electron microscopy (SEM), gas adsorption analysis (BET) and computational modeling and machine learning, are also presented. The ability of polymer-POFs to manipulate the pore environments at the molecular level affords these materials a wide range of applications, providing a versatile platform for future advancements in material science. Looking forward, to fully realize the potential of these hybrid materials, the authors highlight the scalability, green synthesis methods, and potential for stimuli-responsive polymer-POF materials as critical areas for future research.

Hossain, Md Amjad↗