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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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Tailoring the Structure of Carbon Molecular Sieves Derived from an Aromatic Polyamide

Energy-efficient and selective separation technologies are required to reclaim aqueous waste streams for reuse. Carbon molecular sieves (CMS) are one material capable of separating organic solvent and gaseous mixtures due to the presence of permanent, rigid, and molecular sieving pores and could potentially be used in aqueous separations. Here, a novel CMS material is derived from an aromatic polyamide precursor with tailored fabrication techniques. Structural characteristics of this CMS have been probed with various analyses and are potentially ideal for selective separations as adsorbents. In this work, elemental analyses provide insight about the potential chemical structures of CMS materials that result from degradation mechanisms. Gravimetric sorption data is used to estimate sorption, diffusion, and permeability selectivity with water and N, N-dimethylformamide. While challenges to the development and implementation of such carbonaceous materials remain, highly selective materials are critical starting points for enabling ultra-challenging separation processes of the future.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Abstract Hierarchically porous materials containing sub-nm ultramicropores with molecular sieving abilities and microcavities with high gas diffusivity may realize energy-efficient membranes for gas separations. However, rationally designing and constructing such pores into large-area membranes enabling efficient H 2 separations remains challenging. Here, we report the synthesis and utilization of hybrid carbon molecular sieve membranes with well-controlled nano- and micro-pores and single zinc atoms and clusters well-dispersed inside the nanopores via the carbonization of supramolecular mixed matrix materials containing amorphous and crystalline zeolitic imidazolate frameworks. Carbonization temperature is used to fine-tune pore sizes, achieving ultrahigh selectivity for H 2 /CO 2 (130), H 2 /CH 4 (2900), H 2 /N 2 (880), and H 2 /C 2 H 6 (7900) with stability against water vapor and physical aging during a continuous 120-h test.

42 ENGINEERING↗
DOE OSTI2025

Design strategies for ion-sieving charge mosaic membranes toward sustainable lithium extraction

Membrane-based technologies are essential for realizing sustainable ion-sieving processes such as lithium extraction. Much effort was devoted to designing new membrane materials, whereas the effect of charge distribution has been largely overlooked. Here, we filled this knowledge gap by providing a quantitative transport model for selective ion diffusion through a charge mosaic membrane (CMM). Composed of alternating regions of Li-selective ceramic and anion-selective polymeric materials, CMMs offered the unique advantage of promoting the transport of both Li + and anions while blocking other cations. As a result, the membrane achieved a high Li/Mg selectivity of 62 and a high permeation rate of 59 mmol·m −2 ·h −1 at a low feeding concentration of 30 mM, without any external driving force. Systematical experiments revealed the influence of brine Mg/Li ratio and membrane ceramic/polymer ratio on the overall extraction rate, which was consistent with the prediction of our transport model. In conclusion, the model developed in this work not only presented the design strategies of CMMs for Li extraction but also provided guidance for the development of other ion-sieving processes in general.

25 ENERGY STORAGE↗
DOE OSTI2026

Transformational Molecular Layer Deposition Tailor-Made Size-Sieving Sorbents for Post-Combustion CO 2 Capture

This report summarizes the carbon capture research and development conducted by The State University of New York at Buffalo (UB), University of South Carolina (USC), GTI Energy (GTI), and Rensselaer Polytechnic Institute (RPI) for U.S. Department of Energy (DOE) project DE-FE0031730 titled “Transformational Molecular Layer Deposition Tailor-made Size-Sieving Sorbents for Post-Combustion CO 2 capture.” The objective of this project was to develop a transformational molecular layer deposition (MLD) tailor-made size-sieving sorbent integrated with a pressure swing adsorption (PSA) cycle schedule that can be installed in new or retrofitted into existing pulverized coal (PC) power plants for CO 2 capture with a cost of electricity at least 30% lower than a supercritical PC power with CO 2 capture, or approximately $\$$30 per tonne of CO 2 captured, and with it being ready for demonstration by 2030.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2022

New Insights into Physical Aging-Induced Structure Evolution in Carbon Molecular Sieve Membranes

Carbon molecular sieve (CMS) membranes offer the best available combination of scalable economical processability with excellent separation performance. Physical aging of CMS membranes causes pore structure changes over time that affect CMS membrane performance. To provide fundamental insights into the structure evolution in CMS membranes during physical aging, a combined dual-mode sorption and transport model is used in this study to characterize the diffusion coefficients of gas molecules in fresh and 7-day vacuum aged CMS membranes. Further, the results show physical aging of CMS membrane is primarily “diffusion related” and such aging behavior simultaneously causes ultramicropore changes in the continuous phase and Langmuir phase of CMS membrane. The new insights offered in this study suggest strategies to control the physical aging of CMS membranes and even use it as a valuable tool to tune the separation performance of CMS membranes for demanding gas separations.

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

Appealing sheath-core spun high-performance composite carbon molecular sieve membranes

Carbon molecular sieve (CMS) membranes are attractive candidates to meet requirements for challenging gas separations. The added ability to maintain such intrinsic properties in an asymmetric morphology with a structure that we term a “Pseudo Wheel+Hub & Spoke” asymmetric form offers new opportunities. For CMS membrane, specifically, the structure provides both selective layer support and low flow resistance even for high feed pressures and fluxes in CO 2 removal from natural gas. Further, this capability is unavailable to even rigid glassy polymers due to the much higher modulus of CMS materials. Combining precursor asymmetric hollow fiber formation and optimized pyrolysis creates a defect free CMS proof-of-concept membrane for this application. Facile formation of the sheath-core spun precursor with a 6FDA-DAM sheath and Matrimid® core also avoids the need to seal defects before or after the carbonization of the precursors. The composite CMS membrane shows CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 64.3 and CO 2 permeance of 232 GPU at 35 °C. A key additional benefit of the approach is reduction in use of the more costly high performance 6FDA-DAM in a composite sheath-core CMS membrane with the “Pseudo Wheel+Hub & Spoke” structure.

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

Above‐T g Annealing Benefits in Nanoparticle‐Stabilized Carbon Molecular Sieve Membrane Pyrolysis for Improved Gas Separation

Nanoparticles can suppress asymmetric precursor support collapse during pyrolysis to create carbon molecular sieve (CMS) membranes. This advance allows elimination of standard sol-gel support stabilization steps. Here we report a simple but surprisingly important thermal soaking step at 400 °C in the pyrolysis process to obtain high performance CMS membranes. The composite CMS membranes show CO 2 /CH 4 (50 : 50) mixed gas feed with an attractive CO 2 /CH 4 selectivity of 134.2 and CO 2 permeance of 71 GPU at 35 °C. Furthermore, a H 2 /CH 4 selectivity of 663 with H 2 permeance of 240 GPU was achieved for promising green energy resource-H 2 separation processes.

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

Influence of Water, Vacuum, and Temperature on Surface Conditions of a Zeolite‐based Molecular Sieve

Molecular sieves such as zeolite-based materials are ubiquitous in industrial separation processes. However, there is a significant gap in understanding the surface properties and adsorption mechanisms for commercial zeolites, as most research focuses on pure zeolite powders rather than industrially relevant forms. Here, this work addresses this gap in understanding by employing advanced characterization techniques, including positron annihilation spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, liquid nitrogen sorption, and Fourier-transform infrared spectroscopy, to investigate the adsorption and desorption behavior of water in commercial zeolite 13X. Our research reveals insights into the pore-filling mechanisms, the impact of material binders on adsorption properties, and the dynamics of hydration and drying processes for zeolites. Monitoring changes on a minute scale allowed the distinction between fast and slow processes leading to sample drying. The identification of positronium bound to Na + ions indicated that water molecules remain in the vicinity of Na + ions after air-drying zeolite 13X. These findings highlight the importance of various environmental conditions in restoring zeolite properties to baseline after hydration, with significant implications for optimizing industrial processes. This work sets the direction for further research aimed at developing more efficient and robust separation techniques.

Beads Binder↗
DOE OSTI2020

Material erosion measurements and expected operational lifetime of a deployable photon sieve payload

Spacecraft operating in low-Earth orbit are subjected to a number of hazardous environmental constituents that can lead to decreased system performance and reduced operational lifetimes. Due to their thermal, optical, and mechanical properties, polymers are used extensively in space systems; however they are particularly susceptible to material erosion and degradation as a result of exposure to the LEO environment. The focus of this research is to examine the material erosion and mass loss experienced by a custom Kaptonlike polyimide due to exposure in a simulated low-earth orbit environment. The deployable membrane telescope design discussed in this research is named Peregrine and is the scientific payload for FalconSat-7, a 3U cubesat designed and developed at the United States Air Force Academy (USAFA) for the purpose of demonstrating the capability of deployable membrane telescope technology on a nanosatellite platform. In addition to the polymer samples, chrome, silver and gold specimens will be examined to measure the oxidation rate and act as a control specimen, respectively. A magnetically filtered atomic oxygen plasma source has previously been developed and characterized for the purpose of simulating the low-Earth orbit environment. The plasma source can be operated at a variety of discharge currents and gas flow rates, of which the plasma parameters downstream of the source are dependent. The characteristics of the generated plasma were examined as a function of these operating parameters to optimize the production of O + ions with energy relevant to LEO applications. The erosion yield of the Kapton-like polyimide was experimentally determined to be 2.84 x 10 -24 cm 3 per atom which is in close agreement when compared to the on-orbit measurement for reaction efficiency of Kapton HN. We report the experimentally determined reaction rate for the Kapton-like polyimide was used to estimate the operational lifetime of the photon sieve during the solar conditions expected beginning in May 2019. The effective lifetime is estimated between 126 and 153 days.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Subtle penetrant size effects on separation of carbon molecular sieve membranes derived from $\mathrm{6FDA:BPDA}$-$\mathrm{DAM}$ polyimide

Economically scalable carbon molecular sieve (CMS) hollow fiber membranes rely upon a tunable bimodal pore morphology to separate gas pairs using angstrom-level size discrimination. Freshly formed CMS membranes experience self-retarding physical aging, reflected by permeance losses and selectivity gains that stabilize over short times compared to the lifetime of the membrane. Self-retarding morphology rearrangements are of special interest here due to tightening of the largest size range of ultramicropores, thereby causing aging for polyimide-derived CMS. We report effects of such aging for two A/B penetrant pairs, C 3 H 6 /C 3 H 8 and CO 2 /CH 4 . These two pairs not only have different average sizes, $\overline{d}_{A/B}$, but also different size differences,Δd A/B , between the members in each pair. We focus primarily on the C 3 H 6 /C 3 H 8 pair, which is the most difficult of the two pairs to separate, and use some CO 2 /CH 4 results as a comparison case. We study CMS derived from 6FDA:BPDA-DAM (1:1) polyimide by pyrolysis at 550 °C, 600 °C and 650 °C. Here we suggest conditions and physical causes that expedite, retard or even suppress the aging process within CMS membranes. Finally, we suggest how analysis of CMS derived from other precursors and other penetrant pairs can be generalized by understanding the results for the 6FDA:BPDA-DAM (1:1) polyimide derived CMS.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Polybenzimidazole-derived carbon molecular sieve hollow fiber membranes with tailored oxygen selective transport

Polymer membrane carbonization is a promising strategy to obtain carbon molecular sieve (CMS) membrane materials with tailorable cavity size distributions for high gas selectivities beyond that attained from traditional polymer membrane materials. Despite their already demonstrated exceptional separation performance characteristics for several gas separation applications (e.g. CO 2 /CH 4 and H 2 /CO 2 ), further development of CMS membranes having high O 2 /N 2 perm-selectivity for energy-efficient high-purity O 2 production has proven challenging. Herein, we explore CMS hollow fiber membranes (HFMs) derived from highly rigid and tightly-packed polybenzimidazole (PBI) materials. Nearly defect-free PBI-derived CMS HFMs were fabricated and evaluated for O 2 /N 2 separation performance for the first time. The micro-structural and O 2 selective gas separation characteristics of PBI-CMS HFMs pyrolyzed at different pyrolysis conditions were intensively studied. With rigorous carbonization protocol optimization, we obtained highly O 2 permselective PBI-CMS HFMs having O 2 /N 2 selectivities approaching 14, enabling high purity O 2 production. The PBI-CMS HFM O 2 /N 2 separation performance dependence on operating conditions (e.g. temperature and feed pressure) are reported.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A carbon molecular sieve membrane-based reactive separation process for pre-combustion CO 2 capture

In this study, we discuss a hybrid system combining a membrane reactor (MR) and an adsorptive reactor (AR), with the MR's reject stream serving as the AR's feed. We apply this system for the water gas shift (WGS) reaction for H 2 generation and simultaneous CO 2 capture in the context of the Integrated Gas Combined Cycle (IGCC) process for power generation from coal and biomass. This MR-AR system attains a high conversion exceeding equilibrium, produces a pure H 2 product for power generation, and delivers a high-pressure CO 2 stream ready for sequestration. Specifically, in our study we use carbon molecular sieve membranes (CMSMs) and a commercial sour-shift WGS catalyst. Lab experiments were carried-out to determine the membrane characteristics, and the MR performance under IGCC-relevant conditions, i.e., for temperatures up to 250 °C and pressures up to 25 bar, employing a model coal gasifier syngas. The CMSM and the catalyst have displayed robust and stable performance during a long-term run (~750 h of syngas exposure). We evaluated the MR-AR system in multi-cycle runs and it has demonstrated superior performance to that of a conventional packed-bed reactor, producing a high-purity H 2 product directly useable in a turbine for power generation. We conclude from the study, that the CMSM-based MR-AR system is a good candidate technology for environmentally-benign power generation. We are currently constructing a pilot-scale system for field demonstration of the technology.

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

Surprising olefin/paraffin separation performance recovery of highly aged carbon molecular sieve hollow fiber membranes by a super-hyperaging treatment

Carbon molecular sieve (CMS) hollow fibers derived from 6FDA 1 :BPDA 1 /DAM 2 , a well-studied polyimide precursor with attractive propylene/propane separation performance, were purposely treated to simulate long time aging under storage conditions. A simple, efficient post-aging thermal-treatment regeneration termed “super-hyperaging” is shown here to recover C 3 H 6 permeance with satisfactory C 3 H 6 /C 3 H 8 selectivity. A super-hyperaging temperature around 280 °C in air is shown to provide an optimum tradeoff in permeance and selectivity for highly aged samples. The regenerated CMS membrane displays performance well beyond the polymer permeance-selectivity tradeoff upper bound, and a hypothetical mechanism for the super-hyperaging recovery of aged CMS fibers is discussed in this work.

Recovery↗
DOE OSTI2022

Co-transport of water and p-xylene through carbon molecular sieve membranes

Carbon molecular sieve (CMS) materials are a potential candidate for scalable and high-performance reverse osmosis membranes due to their impressive chemical and thermal stabilities. Moreover, they have the potential to enable impressive rejections of small neutral solutes from water based on their known ability to separate small organic molecules. CMS has been extensively examined for gas and organic solvent separations, but the transport of organic and aqueous mixtures through CMS microstructures is poorly understood. In this work, we investigated the sorption, diffusion, and permeation behavior of organic compounds and water in poly(vinylidene fluoride)(PVDF)-derived CMS (PVDF-CMS). Experimental observations of diffusion, sorption, and permeation shows how the properties of penetrants such as polarity and molecular size affect the transport rates and selectivity. These basic transport and sorption parameters are utilized in sorption-diffusion models to permeation rates of water-organic mixtures in CMS membranes. The transport of water and p-xylene in CMS was experimentally confirmed to follow the sorption-diffusion mechanism. The sorption-diffusion model ideal permselectivity indicates that the CMS is p-xylene selective over water. Water/p-xylene mixture permeation experiments revealed an increased selectivity of p-xylene over water, thus providing tentative evidence for a competitive sorption-selective separation mechanism. Furthermore, this work suggests that CMS membranes exhibit organic-permeable separation properties in water/organic separations. The results presented here highlight the potential for the removal of dilute organics in water via CMS pervaporation membranes.

02 PETROLEUM↗
DOE OSTI2023

Isotope Exchange of ND 3 on Pt Catalyst–Loaded 5A Molecular Sieve

Recollecting and purifying unburned tritium is a preferred process for D-T fusion operations. However, tritium containing byproducts act as a potential holdup for the material, requiring additional processing to liberate the tritium. Furthermore, using deuterium as a surrogate for tritium, this work demonstrates the capture and isotope exchange of deuterated ammonia using a Pt catalyst–loaded 5A molecular sieve, performed at ambient temperatures, verified by the analysis of the effluent gas streams and desorbed ammonia isotopologues post exchange.

5A↗
DOE OSTI2026

Catalytic Membrane Reactors Based on Carbon Molecular Sieve Hollow Fiber Membranes for Sustainable and Modular H 2 Production

We aimed to develop a catalytic membrane reactor (CMR) that couples water–gas shift (WGS) reaction with in-situ H 2 separation to produce blue H 2 and a CO 2 -rich stream from coal- and biomass-derived syngas. Our core approach employs high-permeance carbon molecular sieve (CMS) hollow-fiber membranes (HFMs) with strong gas separation ability, which we further integrate into catalytic membrane reactors to intensify H 2 production and CO 2 capture in a single unit. Three organizations with complementary skills collaborated to achieve the goal, including the University at Buffalo (UB), Los Alamos National Laboratory (LANL), and Trimeric Corporation (Trimeric).

08 HYDROGEN↗