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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 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Printed graphene oxide-based membranes for gas separation and carbon capture

Graphene oxide (GO)-based separation membranes have demonstrated the great potential to separate molecules and ions by the interlayer spacing with tunable nano-sized channels. The scalable fabrication of GO-based gas separation membranes, however, remains challenging, although a few preparation approaches have been reported. Here in this work, we present for the first time that the co-solvent ink-jet printing, as a fast and scalable method, can be utilized for scalable GO-based gas separation membrane preparation. Large-area (>100 cm 2 ), ultrathin, and high-quality GO membrane was successfully deposited on commercial polysulfone (PS) support, and characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, et al., Selective hydrogen (H 2 ) and helium (He) transport over carbon dioxide (CO 2 ) and nitrogen (N 2 ) was demonstrated for the printed GO membrane. To further explore the separation potential of the printed GO-based gas membrane, additives for facilitated molecular transport were incorporated during the membrane printing process. By inserting CO 2 -philic agents into the printed GO membrane, highly efficient separation of CO 2 from N 2 was achieved with CO 2 /N 2 selectivity of 70 and CO 2 permeance as high as 2,500 GPU. The strategy proposed here may provide guidance for large-scale GO-based gas separation membrane production and a versatile approach for applying other functional 2-dimensional materials towards the membrane separation application.

42 ENGINEERING↗
DOE OSTI2021

New insights into creep characteristics of calcium silicate hydrates at molecular level

The fundamental mechanisms under concrete creep are far from being fully understood, especially at the molecular level. Hereby, a calcium-silicate-hydrate (C-S-H) molecular model is developed to explain, for the first time, the creep characteristics at various stress states, temperature levels and water contents, which are not accessible experimentally. Rather tensile and compressive loadings, C-S-H only creeps under shear loadings originating from the sliding of the calcium silicate layers over each other as the interlayer component (water and ions) acts as a lubricator. A heterogeneous creep characteristic is observed. Elevated temperature reduces the interlayer lubricator viscosity and weakens the interfacial adhesion between the layers and the interlayer lubricator, which accelerates C-S-H creep. The removal of interlayer water enhances the creep resistance, resulting from the reduced interlayer space and enhanced interfacial adhesion. The atomic-level mechanisms explain the inter-CSH-particle behaviours at the microscale, which bridges the gap between atomistic simulation and microcosmic phenomenon.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Local structure and Ca/Si ratio in C-S-H gels from hydration of blends of tricalcium silicate and silica fume

At the microscale, C-S-H gels from alite, or neat Portland cements, has a Ca/Si ratio close to 1.80. At the nanoscale, C-S-H is described by a defective tobermorite structure which allows a maximum Ca/Si ratio close to 1.40. There is no agreement in the location of the extra 0.40 mol of Ca(OH){sub 2} at the nanoscale. Atomistic modelling studies reported Ca(OH){sub 2} species within the tobermorite interlayer space. Other works point toward a fine intermixing of defective tobermorite and nanoportlandite. Here, we have prepared a series of alite blended with silica fume and studied the pastes by several techniques including synchrotron pair distribution function (PDF). In the employed conditions, the C-S-H gel formed by the pozzolanic reaction has nearly the same local structure than the primary C-S-H gel. Furthermore, differential PDF points toward Ca(OH){sub 2} excess having a local structure compatible with few-layer thick nanoparticles stretched along the c-axis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Specific molecular design of polycarboxylate polymers exhibiting optimal compatibility with clay contaminants in concrete

Highlights: • Allyl ether-based PCEs with short side chain length and low side chain density presented superior clay resistance. • PCEs with medium side chain density exhibited best clay robustness when compared at the absolute dosed quantities. • The proportion of PCE being intercalated into the layered structure of clay was quantified. It is widely recognized that the dispersing ability of polycarboxylate superplasticizers (PCEs) could be hindered due to the presence of clay contaminants in concrete. In this study, a series of allyl ether-based polycarboxylate superplasticizers possessing short polyethylene glycol side chains was successfully synthesized and probed for their clay tolerance. The resulting PCE polymers were characterized via Size Exclusion Chromatography (SEC) to obtain their molecular properties. Thereafter, their dispersing ability was probed in the absence and presence of sodium bentonite. Allyl ether-based polycarboxylate (APEG) polymers possessing short side chains were found to exhibit enhanced clay resistance as compared to that of conventional MPEG PCEs holding long pendant chains. The mode of interaction between APEG PCEs and bentonite was investigated via sorption and XRD measurements. The data revealed that APEG PCEs possessing a lower side chain density intercalate less into the interlayer space of bentonite than those exhibiting higher side chain density.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Boron adsorption in clay minerals: Implications for martian groundwater chemistry and boron on Mars

Boron has been detected on Mars in calcium-sulfate veins found within clay mineral rich rocks on Mars by the Mars Science Laboratory (MSL) Curiosity rover using Laser Induced Breakdown Spectroscopy (LIBS) analysis. Borates play a vital role in stabilizing ribose on Earth and has been suggested as a key requirement for life. Borate ions readily adsorb to phyllosilicate clay minerals. The discovery of boron on Mars in proximity to phyllosilicate-bearing bedrock may have strong implications for potential past prebiotic conditions on Mars. In this study we generated a suite of clay minerals with adsorbed borate, including both typical terrestrial clay minerals (montmorillonite) and Mars-analog clay minerals (nontronite, saponite, griffithite), to understand controls on borate adsorption and to analyze with LIBS to compare with MSL data. Clay minerals were subjected to mineralogical and chemical analysis before and after adsorption. Adsorption analysis revealed that the Mars analog clay minerals adsorbed less boron than terrestrial counterparts, but within comparable amounts to those detected on Mars and in meteorites. Post-adsorption analysis by X-ray diffraction (XRD) revealed slight changes in the interlayer spacing of many of the clay minerals. Based on the adsorption analysis of the Mars-analog clay minerals, phyllosilicate-bearing bedrock in Gale crater may contain up to 90-110 ppm B. A series of borate-enriched samples were created for analysis of LIBS spectra from ChemCam on the Curiosity rover and SuperCam on the Perseverance Rover. Finally, the results of this study may provide insight into martian groundwater geochemistry processes and the mobility of a key molecule connected with life.

58 GEOSCIENCES↗
DOE OSTI2023

Synthesis, structure and canted antiferromagnetism of layered cobalt hydroxide sorbate

Layered hybrid organic–inorganic compounds of the transition metal hydroxides, in which part of the hydroxide ions are exchanged for organic ligands that act as spacers of the 2-dimensional inorganic layers, elicit new or enhanced properties. The interlayer ligands enable fine-tuning of the physicochemical properties of the metal hydroxide layers, including their magnetism. Specifically, within the Co(OH) 2 family of transition ion hydroxides, this approach has been leveraged to stabilize antiferromagnetic and ferrimagnetic ground states for pillared and layered complexes, respectively. Here, in this work, we further investigate the effects of changing dimensionality, local Co coordination, and interlayer spacing on the magnetic ground state of brucite-like β-Co(OH) layered complexes. We report the hydrothermal synthesis of a new crystalline material, Co(OH)(sorb), where the inorganic layers are spaced by monotopic, doubly unsaturated sorbate ligands (sorb = [C 6 H 7 O 2 ] – ). The material was structurally characterized using powder X-ray and neutron diffraction measurements and the crystal structure was solved ab initio from powder diffraction data and refined using the Rietveld method. The magnetic susceptibility and magnetization measurements reveal canted antiferromagnetic ordering with T N = 41.7 K. This report augments our understanding of tuning magnetism through dimensionality in layered complexes and represents a step forward in the design of new 2D layered hybrid compounds.

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

Scalable synthesis of ultrathin MoS 2 membranes for dye desalination

Molybdenum disulfide (MoS 2 ) has been fabricated into thin-film composite (TFC) membranes for dye desalination due to its excellent underwater stability and tunable interlay spacing. However, it remains challenging to synthesize thin layers of MoS 2 with high water permeance and high dye rejection due to the difficulty in fabricating large crystalline sheets or exfoliation. Herein, we report a scalable method coupling bottom-up hydrothermal synthesis and top-down ultrasonic exfoliation to obtain well-dispersed MoS 2 nanosheets and a vacuum filtration method to prepare ultrathin membranes (thickness: 30 – 60 nm) for dye desalination. The MoS 2 nanosheets and membranes are thoroughly characterized for their chemistries and nanostructures. The membrane with 60-nm MoS 2 exhibits water permeance of 32 LMH/bar, Na 2 SO 4 rejection of 2.3%, and Direct Red-80 rejection of 99.0%. The MoS 2 membranes exhibit dye desalination performance superior to state-of-the-art commercial polyamide membranes and many leading membranes based on two-dimensional materials.

Dye desalination↗
DOE OSTI2024

In situ oxidation of reduced graphene oxide membranes by peracetic acid for dye desalination

Graphene oxide (GO) membranes with tunable interlayer spacings are of interest for dye removal from salty textile wastewater, and the membranes are often reduced to improve their stability, which inevitably lowers water permeance. Herein, we demonstrate that reduced GO (rGO) membranes can be facilely modified using peracetic acid (PAA) in situ to dramatically enhance water permeance while retaining dye rejection. Specifically, PAA-modified membranes (PrGO) are synthesized by vacuum-filtering hydrazine-reduced rGO nanosheets onto Nylon substrate and then exposing them to PAA solutions. The effects of the rGO layer thickness, PAA content, and PAA exposure time on the membrane chemistry, nanostructures, and salt/dye separation properties are thoroughly examined. For example, the PAA oxidation of a 100 nm-thick rGO membrane for 10 min increases water permeance by 180 %, from 35 to 93 Liter m −2 h −1 bar −1 , and decreases Na 2 SO 4 rejection from 10 % to 3.3 % while retaining the rejection of Congo red at ≈99.7 %. The PrGO membranes exhibit stable water permeance and >99 % dye rejection in multi-cycle tests in a crossflow system, surpassing state-of-the-art GO membranes and showcasing their potential for practical applications.

Dye desalination↗
DOE OSTI2021

Exfoliation of surfactant swollen layered MWW zeolites into two-dimensional zeolite nanosheets using telechelic liquid polybutadiene

We report two-dimensional (2D) zeolites have the potential to enhance mass transport by reducing diffusion lengths and thus find applications in catalysis and separation. High aspect ratio 2D zeolite nanosheets are required for fabrication of thin, high-flux zeolite membranes. Preparation of 2D zeolite nanosheets can be achieved by exfoliation of layered zeolite precursors, which usually requires multiple steps including swelling with cationic surfactants, exfoliation by applying a mechanical force such as shearing or sonication, purification and removal of the surfactants. The exfoliation of surfactant swollen layered zeolite precursors has been studied using molten polystyrene and telechelic liquid polybutadiene, but still requires extensive shearing force. Recently, a novel one-step exfoliation method has been developed for nonswollen MWW zeolite precursors using tetrabutylammonium hydroxide (TBAOH) solution. In this work, we study the exfoliation of surfactant swollen MWW layered precursors (with and without aluminum) in commercially available liquid hydroxyl-terminated polybutadiene (HTPB) with the aim to provide fundamental understanding of the interaction between the liquid polybutadiene and the surfactant swollen layered zeolite precursors. It was found that surfactant swollen ITQ-1, (ITQ-1(S)), a pure silica layered precursor with MWW framework after being swollen with a cationic surfactant, can be exfoliated in liquid HTPB at room temperature without applying any additional shearing force. The aluminum containing surfactant swollen MWW precursors can be also exfoliated in HTPB at room temperature, but require additional shearing forces. The exfoliation process was monitored using rheology experiments and studied by tuning the composition of the zeolite precursors. The interaction between the layered zeolite precursor and the hydroxyl group of the liquid polybutadiene allows the polymer to intercalate the precursor and exfoliate it into nanosheets. The presence of framework aluminum and the nature of the organic structure directing agents (OSDAs) are key parameters affecting the exfoliation process. Framework Al is unfavorable for the exfoliation possibly due to the surface charges introduced by the aluminum. Bulky OSDA, trimethyladamantammonium (TMAda + ), in the interlayer spacing may facilitate the exfoliation.

2D nanosheets↗
DOE OSTI2023

Chlorination of Hydrogenated Silicon Nanosheets Revealed by Solid-State Nuclear Magnetic Resonance Spectroscopy

We report two-dimensional silicon nanosheets (Si-NS) synthesized by topotactic deintercalation of CaSi 2 are hypothesized to consist of buckled layers of sp 3 -hybridized silicon atoms that are bonded to three other framework Si atoms and a terminal atom or functional group such as H, Cl, or OH. Here, we apply 1 H{ 35 Cl} and 29 Si{ 35 Cl} Resonance-Echo Saturation-Pulse DOuble-Resonance (RESPDOR) solid-state NMR experiments to directly confirm the presence of chlorinated Si atoms within Si-NS. Plotting the 1 H{ 35 Cl} RESPDOR dephasing as a function of the 35 Cl saturation pulse offset reveals that the 35 Cl quadrupolar coupling constant (C Q ) is 38 MHz, consistent with Cl atoms that are covalently bonded to silicon. Modeling the 1 H{ 35 Cl} RESPDOR dephasing curve shows that the Si–Si interlayer spacing is approximately 6 Å. Plane-wave density functional theory (DFT) calculations show that the direct band gap transition of the Si-NS decreases with increasing chlorination and hydroxylation, suggesting that the band gap of Si-NS can be tuned by modifying the terminal atoms or functional groups.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Intercalation-Induced Amorphization Boosts Aqueous Magnesium-Ion Storage

The design of aqueous battery cathode materials that can store divalent ions with high capacity and satisfactory reversibility is of great technical importance and challenge. Here, we report that divalent Mg 2+ storage is facilitated by an intercalation-induced amorphization of vanadate electrode materials. Electrokinetic analyses and in situ synchrotron X-ray diffraction and absorption spectroscopy collectively demonstrate that vanadate layered materials (Li–V 3 O 8 ) undergo a structural transformation to amorphization induced by Mg 2+ intercalation, and a reversible restoration of crystalline structure upon Mg 2+ deintercalation. Debye scattering simulations suggest that intercalation-induced turbostratic disorder, especially random rotations, translational shifts, oscillatory motions, or varied interlayer spacing of adjacent V–O molecular layers, could be responsible for the observed amorphization. The highly distorted local structure, in turn, facilitates Mg 2+ intercalation across the vanadate electrode materials, responsible for nearly 3/7 of the total Mg 2+ ions intercalated. The study presented reveals an intriguing relationship between ion transport and the reversible amorphization-to-crystallization dynamics it induces, opening a paradigm for designing advanced aqueous battery electrodes.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Li x (C 5 H 5 N) y Fe 2– z Se 2 : A Defect-Resilient Expanded-Lattice High-Temperature Superconductor

Two-dimensional iron chalcogenide intercalates display a remarkable correlation of the interlayer spacing with enhancement of the superconducting critical temperature (T c ). In this work, synchrotron X-ray absorption (XAS; at the Fe and Se K-edges) and emission (XES; at the Fe Κβ) spectroscopies allow one to discuss how the important rise of T c (~44 K) in the molecule-intercalated Li x (C 5 H 5 N) y Fe 2-z Se 2 relates to the electronic and local structural changes felt by the inorganic host upon doping (x). XES shows that widely separated layers of edge-sharing FeSe 4 tetrahedra carry low-spin moieties, with a local Fe magnetic moment slightly reduced compared to the parent β-Fe 2-z Se 2 . Pre-edge XAS expresses the progressively reduced mixing of metal 3d-4p states upon lithiation. Doping-mediated local lattice modifications, probed by conventional T c optimization measures (cf. the anion height and FeSe 4 tetrahedra regularity), become less relevant when layers are spaced far away. On the basis of extended X-ray absorption fine structure, such distortions are compensated by a softer Fe network that relates to Fe-site vacancies, alleviating electron-lattice correlations and superconductivity. Density functional theory (DFT) guided modification of the isolated Fe 2-z Se 2 (z, vacant sites) planes, resembling the host layers, identify that Fe-site deficiency occurs at low energy cost, giving rise to stretched Fe sheets, in accordance with experiments. Here, the robust high-T c in Li x (C 5 H 5 N) y Fe 2-z Se 2 , arises from the interplay of electron-donating spacers and the iron selenide layer's tolerance to defect chemistry, a tool to favorably tune its Fermi surface properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Importance of Nuclear Quantum Effects on Aqueous Electrolyte Transport under Confinement in Ti 3 C 2 MXenes

Protons display a high chemical activity and strongly affect the charge storage capability in confined interlayer spaces of two-dimensional (2D) materials. As such, an accurate representation of proton dynamics under confinement is important for understanding and predicting charge storage dynamics in these materials. While often ignored in atomistic-scale simulations, nuclear quantum effects (NQEs), e.g., tunneling, can be significant under confinement even at room temperature. Here, using the thermostatted ring polymer molecular dynamics implementation of path integral molecular dynamics (PIMD) in conjunction with the ReaxFF force field, density functional tight binding (DFTB), and NequIP neural network potential simulations, we investigate the role of NQEs on proton and water transport in bulk water and aqueous electrolytes under confinement in Ti 3 C 2 MXenes. Although overall NQEs are relatively small, especially in bulk, we find that they can alter both quantitative values and qualitative trends on both proton transport and water self-diffusion under confinement relative to classical MD predictions. Therefore, our results suggest the need for NQEs to be considered to simulate aqueous systems under confinement for both qualitative and quantitative accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Graphite Lithiation under Fast Charging Conditions: Atomistic Modeling Insights

The charging of lithium ion batteries in a fast and safe manner is critical for promoting the mass adoption of electric vehicles. Li intercalation in graphite electrodes is known to be one of the bottlenecks during the fast charging process. The mechanism of Li diffusion in highly polarized graphite anode at high current rates remains, however, not well understood. In this work, Density Functional Theory (DFT) calculations are used to gain insights into the Li diffusion process in graphite when it is far from equilibrium under fast charging conditions. The effect of uncompensated charges on Li mobility is determined in the highly polarized regions of the anode close to the interfaces. The extra charge was found to increase the interlayer spacing in the diffusion layer and adjacent channels, increasing the diffusivity and promoting the formation of Li clusters. A concerted diffusion mechanism at the edge of high-concentration Li domains is proposed to enhance the diffusion of Li.

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

Manipulating Photoconduction in Cu–Pyrene 1-D Coordination Nanosheets by Modulating Interlayer π–π Stacking

2D conductive metal organic frameworks (MOFs) have become promising candidates for applications in electronic and photoelectronic devices. However, the lack of a fundamental understanding of the charge transport mechanism and synthetic design to alter their conductivity limits their potential applications. In this work, we report the design and synthesis of two 1D Cu–pyrene coordination nanosheets, Cu–pyrene-4,5,9,10 tetrathiol (Cu-PTT) and Cu–2,7-di-tert-butylpyrene-4,5,9,10-tetrathiol (Cu– tBu PTT), as models of 2D conductive MOFs, where the introduction of two different functional groups (H and tert-butyl groups) at the 2 and 7 positions of the PTT ligands is used to tune the interlayer distance and π–π stacking of MOFs. Using optical pump terahertz probe spectroscopy, we show that both nanosheets exhibit appreciable photoconduction, but the photoconduction in Cu– tBu PTT is reduced with respect to that in Cu–PTT, which can be attributed to the larger interlayer distance in the former leading to the decoupling of the interlayer charge transport pathway. Furthermore, these results demonstrate a unique strategy to investigate the impact of out-of-plane extended conjugation on photoconduction in conductive conjugated polymers, MOFs, or coordination nanosheets through adjusting their interlayer spacing.

14 SOLAR ENERGY↗
DOE OSTI2026

Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification

Surface groups are central to the properties of MXenes, yet their role in optical anisotropy remains largely unexplored. Here, we use a topochemical route to synthesize single crystals of stacked Ti 3 C 2 Cl 2 and hybrid organic–inorganic MXenes (h-MXenes) with lateral sizes of 38–75 μm, rotational registry, and tunable interlayer spacing. Solid-state NMR spectroscopy shows that topochemical substitution generates mixed amido, imido, and hydride surface motifs, which modify the electronic structure of the Ti 3 C 2 inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti 3 C 2 Cl 2 exhibits a type-II hyperbolicity above 930 nm, whereas h-MXenes do not display hyperbolicity within the measured 300–1700 nm window, instead showing reduced in-plane conductivity, suppressed out-of-plane light absorption, and a chain-length-dependent blue shift of a near-infrared absorption feature. These results demonstrate topochemical surface modification as a direct handle for engineering MXenes as surface-programmable optical media.

Hybrid materials↗
DOE OSTI2021

Long-Term Structural and Chemical Stability of Carbon Electrodes in Vanadium Redox Flow Battery

Predicting the performance decay in carbon electrodes is critical to maximizing the longevity of redox flow battery (RFB) systems. This study investigates the effect of long-term cycling (over 8000 cycles) on the structural and chemical evolution of carbon electrodes. We find that the microstructural aspects such as graphitic stacking order and interlayer spacing along with overall morphological construct remains largely unchanged even after the prolonged cycling process. Conversely, significant changes in surface chemistry such as evolution of functional groups and point defects are evident from our combined multimodal spectroscopic and computational analysis. The XPS and FTIR analysis reveals chemical absorption of chloride counter anions at point defects within graphitic surface. Additionally, our results suggest that vanadium cation plays an important role in counter anion-carbon surface interaction and subsequently the surface chemistry evolutions. Our findings provide insights about surface chemical evolution that is critical for predicting electrode performance and longevity of RFB.

Modachur Sivakumar, Bhuvaneswari↗
DOE OSTI2021

Low-Cost Transformation of Biomass-Derived Carbon to High-Performing Nano-graphite via Low-Temperature Electrochemical Graphitization

Graphite, an essential component of energy storage devices, is traditionally synthesized via an energy-intensive thermal process (Acheson process) at ~3300 K. However, the battery performance of such graphite is abysmal under fast-charging conditions, which is deemed essential for the propulsion of electric vehicles to the next level. Herein, a low-temperature electrochemical transformation approach has been demonstrated to afford a highly crystalline nano-graphite with the capability of tuning interlayer spacing to enhance the lithium diffusion kinetics in molten salts at 850 °C. The essence of our strategy lies in the effective electrocatalytic transformation of carbon to graphite at a lower temperature that could significantly increase the energy savings, reduce the cost, shorten the synthesis time, and replace the traditional graphite synthesis. The resulting graphite exhibits high purity, crystallinity, a high degree of graphitization, and a nanoflake architecture that all ensure fast lithium diffusion kinetics (~2.0 × 10 –8 cm2 s –1 ) through its nanosheet. Such unique features enable outstanding electrochemical performance (~200 mA h g –1 at 5C for 1000 cycles, 1C = 372 mA g –1 ) as a fast-charging anode for lithium-ion batteries. Overall, this finding paves the way to make high energy-density fast-charging batteries that could boost electromobility.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗