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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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

A scintillator attenuation spectrometer for intense gamma-rays

A new type of compact high-resolution high-sensitivity gamma-ray spectrometer for short-pulse intense gamma-rays (250 keV to 50 MeV) has been developed by combining the principles of scintillators and attenuation spectrometers. The first prototype of this scintillator attenuation spectrometer (SAS) was tested successfully in Trident laser experiments at LANL. Later versions have been used extensively in the Texas Petawatt laser experiments in Austin, TX, and more recently in OMEGA-EP laser experiments at LLE, Rochester, NY. The SAS is particularly useful for high-repetition-rate laser applications. Furthermore, we give a concise description of the design principles, capabilities, and sample preliminary results of the SAS.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Search for nonreciprocal magnons in MnPS 3

Recent articles have suggested that the quasi-two-dimensional antiferromagnet MnPS 3 may have nonreciprocal magnons, whereby magnons in a Brillouin zone corner at + q have different energies than those at q . The magnons along the Brillouin zone boundaries were measured using neutron three-axis spectrometry, paying careful attention to the resolution function, to determine whether such nonreciprocity was present. The data show that, within the resolution, there are no significant differences between the magnons in opposite Brillouin zone corners. The findings are combined with a recently published study of MnPS 3 by neutron resonant spin-echo spectroscopy and discussed within the context of the theories for nonreciprocal magnons.

2-dimensional systems↗
NASA NTRS2000

Effects of forearm bier block with bretylium on the hemodynamic and metabolic responses to handgrip

We tested the hypothesis that a reduction in sympathetic tone to exercising forearm muscle would increase blood flow, reduce muscle acidosis, and attenuate reflex responses. Subjects performed a progressive, four-stage rhythmic handgrip protocol before and after forearm bier block with bretylium as forearm blood flow (Doppler) and metabolic (venous effluent metabolite concentration and (31)P-NMR indexes) and autonomic reflex responses (heart rate, blood pressure, and sympathetic nerve traffic) were measured. Bretylium inhibits the release of norepinephrine at the neurovascular junction. Bier block increased blood flow as well as oxygen consumption in the exercising forearm (P < 0.03 and P < 0.02, respectively). However, despite this increase in flow, venous K(+) release and H(+) release were both increased during exercise (P < 0.002 for both indexes). Additionally, minimal muscle pH measured during the first minute of recovery with NMR was lower after bier block (6.41 +/- 0.08 vs. 6.20 +/- 0.06; P < 0.036, simple effects). Meanwhile, reflex effects were unaffected by the bretylium bier block. The results support the conclusion that sympathetic stimulation to muscle during exercise not only limits muscle blood flow but also appears to limit anaerobiosis and H(+) release, presumably through a preferential recruitment of oxidative fibers.

Non-NASA Center↗
DOE OSTI2022

CLEAR: The Ionization and Chemical-enrichment Properties of Galaxies at 1.1 < z < 2.3

We use deep spectroscopy from the Hubble Space Telescope Wide-Field-Camera 3 IR grisms combined with broadband photometry to study the stellar populations, gas ionization and chemical abundances in star-forming galaxies at z ~ 1.1–2.3. The data stem from the CANDELS Lyα Emission At Reionization (CLEAR) survey. At these redshifts, the grism spectroscopy measure the [O II] λλ3727, 3729, [O III]λλ4959, 5008, and Hβ strong emission features, which constrain the ionization parameter and oxygen abundance of the nebular gas. We compare the line-flux measurements to predictions from updated photoionization models (MAPPINGS V; Kewley et al.), which include an updated treatment of nebular gas pressure, $\mathrm{log}P/k={n}_{e}{T}_{e}$. Compared to low-redshift samples (z ~ 0.2) at fixed stellar mass, $\mathrm{log}{M}_{* }/{M}_{\odot }\,=$ 9.4–9.8, the CLEAR galaxies at z = 1.35 (1.90) have lower gas-phase metallicity, ${\rm{\Delta }}(\mathrm{log}Z)$ = 0.25 (0.35) dex, and higher ionization parameters, ${\rm{\Delta }}(\mathrm{log}q)$ = 0.25 (0.35) dex, where U ≡ q/c. We provide updated analytic calibrations between the [O III], [O II], and Hβ emission-line ratios, metallicity, and ionization parameter. The CLEAR galaxies show that at fixed stellar mass, the gas ionization parameter is correlated with the galaxy specific star formation rates, where ${\rm{\Delta }}\mathrm{log}q\simeq 0.4\times {\rm{\Delta }}(\mathrm{log}\,\mathrm{sSFR})$, derived from changes in the strength of galaxy Hβ equivalent width. We interpret this as a consequence of higher gas densities, lower gas covering fractions, combined with a higher escape fraction of H-ionizing photons. We discuss both tests to confirm these assertions and implications this has for future observations of galaxies at higher redshifts.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Thermoelastic properties of zircon: Implications for geothermobarometry

Abstract A thermal-pressure equation of state has been determined for zircon (ZrSiO4) that characterizes its thermoelastic behavior at metamorphic conditions. New pressure-volume (P-V) data from a “Mud Tank” zircon have been collected from 1 bar to 8.47(1) GPa using X-ray diffraction, and elastic moduli were measured from room temperature up to 1172 K by resonance ultrasound spectroscopy. These data were fitted simultaneously with temperature-volume (T-V) data from the literature in EosFit7c using a new scaling technique. The parameters of a third-order Birch-Murnaghan EoS with a Mie-Grüneisen-Debye model for thermal pressure have compressional EoS parameters K0T = 224.5(1.2) GPa, K0T' = 4.90(31) with a fixed initial molar volume V0 = 39.26 cm3/mol and thermal parameters γ0 = 0.868(15), q = 2.37(80), and ΘD = 848(38) K. EoS parameters that describe the variation of unit-cell parameters with pressure and temperature were determined using an isothermal-type EoS. This new EoS confirms that zircons are stiffer than garnets and exhibit a much lower thermal expansion. This results in steep isomekes between zircon and garnets, which makes zircon trapped as inclusions in garnets at metamorphic conditions a good piezothermometer.

Geochemistry & Geophysics↗
NASA NTRSDate not supplied

Scalar Atomic Defect-Based Solid-State Self-calibrating Magnetometer (3SM) for Space Plasma Analysis

The Earth’s magnetosphere is a system of multiple, co-located particle populations interacting via plasma waves. Things to understand are driving processes, radiation belt and ring current issues, auroral physics, internal plasma processes, and magnetosphere-ionosphere mapping issues. These plasma-physics processes enable the Earth’s magnetosphere to evolve in response to temporal changes in the solar wind and they underlie the phenomena of space weather, which impacts spacecraft systems, astronauts, radio communications, and ground based electric-power grids. The objective of 3SM is to measure magnetic field strength and to calibrate the Vector Magnetometer (VM) device to maintain absolute accuracy during a mission. The 3SM features make the instrument preferably suited not only for the traditional role of scalar magnetometers as absolute references for the calibration of the on-board vector instruments, but also for extended operational capacities, such as higher frequency scalar measurements (of potential interest for magnetosphere studies for the low frequency part of the spectrum) or autonomous scalar / vector operations. Diamond has been the solid-state platform of choice for quantum device technologies for some time, however, it suffers from difficulties such as scalability, integration, and cost. While the diamond platform is very useful for quantum technologies, further development is needed to make it viable. The material platform of choice for NASA Glenn’s Quantum Sensing And Spin Physics (Q-SASP) is silicon carbide (SiC). This is due to the much higher industry development of the SiC material platform for high-power and high-temperature electronics. It leverages both the decades-long SiC development expertise and infrastructure at NASA Glenn and its growing capabilities in quantum metrology. To make SiC devices usable for quantum technologies such as quantum sources, a much deeper understanding of defects is needed. Q-SASP is developing quantum metrology capabilities to evaluate the energy structure, defect formation energy, band structure augmentation, generation/recombination rates, and limits of dipole-dipole coupling in non-metal implanted SiC devices. This can be achieved by analysis of zero-field splitting, low-field resonance, and singlet-triplet mixing through various forms of Electrically Detectable Magnetic Resonance (EDMR) and Near-Zero Field Magnetic Resonance (NZFMR) spectroscopy. This work will discuss recent system developments, device developments, computational modeling, and spectroscopy results and analysis of defects created by non-metal implantations in SiC devices. The defect formation energies of V Si ,V C , V C V Si , N C V Si , N Si , N C in 4H-SiC are previously reported values in other research [2]-[3]. The defect formation energies of PSi and PC were calculated in GPAW [fig 1A]. The basic underlying mechanism of the zero-field phenomenon is the mixing of singlet and triplet states [4]-[5]. In most spin-dependent transport, two electron spins are involved, and thus one must consider each of their interactions with the field. We investigated the electronic and magnetic properties of 4H-SiC and 6H-SiC. The defect formation energy helps us determine what types of defects we are observing in the SiC EDMR experiment. They have very low formation energy (it is negative). The phosphorus substitution in 4H-SiC is a very stable defect. The band diagrams provide us with vital information about how the electronic properties of SiC (such as band gap) change as we add non-metal defects. The zero-field splitting parameters allow us to study the inflection point in the NZFMR [fig 1B]. We clearly observed zero-field splitting. We also noted that the zero-field splitting remained constant with changing bias. We aspect it zero-field splitting to remain constant while the hyperfine and exchange interaction perturbations shift under the influence of an external magnetic field. This is the essence of quantum magnetometry and self-calibration.

space plasma↗
DOE OSTI2025

Real-Time Detection of Hydrogen and Ammonia Isotopologues for Impurity Removal and Recovery of Tritium

To accommodate gas measurements for impurity removal and recovery of tritium, a silver-coated optical or waveguide is employed for collecting Raman scattered signals to determine relative hydrogen and ammonia isotopologue populations in real time. The data and results presented here demonstrate an analytical methodology for the analysis of four ammonia and three hydrogen isotopologues in a hydrogen–deuterium exchange reaction by gas phase Raman spectroscopy. Standard chemometric modeling techniques effectively unravel the signatures of the isotopologues involved observed here; however, a sophisticated quantum chemical approach supports the spectral assignments. An interpretation of the data presented here can emphasize the practicality and reliability of the gaseous monitoring system in complex chemical environments for the hydrogen fuel economy as well as the more distant energy source from a facility that handles tritium. There are still considerable concerns about the measurement of tritium in isotope separation and radiological impurities from gas processing. A common impurity in gas processing is ammonia, which can form readily in the presence of nitrogen and tritium. Substituted ammonia (NQ 3 ), where Q = H, D, or T, is traditionally removed through getters or diffusers along with other non-hydrogen contaminants. A preferable analytical approach is noninvasive and can be deployed for real-time process evaluation in radiological environments.

Ammonia↗
DOE OSTI2021

Identifying Order and Disorder in Double Four-Membered Rings via Raman Spectroscopy during Crystallization of LTA Zeolite

Fluoride (F – ) has been essential for the synthesis of low-defect siliceous zeolites. It has been hypothesized that F – balances the positive charges from organic structure-directing agents (OSDAs) and stabilizes key building units during zeolite crystallization such as the double four-membered ring (D4R). However, due to the lack of characterization techniques for investigating medium-range structures, including rings and cages formed during zeolite crystallization, the roles of F – in stabilizing building units and maintaining local charge balance during zeolite assembly are not yet fully understood. Here, the crystallization of siliceous Linde type A (LTA) zeolite in the presence of F – was investigated using Raman spectroscopy and periodic density functional theory (DFT) calculations. We have discovered that the F – -filled double four-membered ring (F – /D4R) and the empty D4R exhibit rather distinct Raman features. Both the F – /D4R and empty D4R are formed in the LTA zeolite synthesized in the presence of F – using 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the OSDA. Observed Raman bands of the F – /D4R and empty D4R, along with predictive DFT calculations on LTA supercells, reveal an ordered distribution of these two D4R units in the final as-made LTA zeolite. The discovery of these distinct Raman signatures of F – /D4R and empty D4R units opens an interesting new window for studying defects in the D4R during zeolite formation. In particular, we have observed variation in Raman intensities of F – /D4R and empty D4R bands during LTA crystallization; periodic DFT calculations indicate that the observed Raman behavior is consistent with empty D4R units containing one or two Si vacancies surrounded by Q 3 Si—consistent also with solid-state nuclear magnetic resonance measurement. These defects appear to heal during further crystallization, leading to the formation of defect-free LTA zeolite crystals. Altogether, our results provide deeper understanding on the roles of F – in charge balancing and stabilizing intact D4R units during zeolite formation.

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

Collective modes of excitation in 64 Cu

Medium and high-spin level sequences in 64 Cu were investigated using the complex 26 Mg( 48 Ca, αp5nγ ) multinucleon transfer reaction. The experiment was performed at the ATLAS accelerator facility at the Argonne National Laboratory using the Gammasphere array and the fragment mass analyzer (FMA). Two high-spin, quasirotational bands consisting of stretched-E2 transitions were observed in coincidence with the known low-spin structure for the first time. These bands share remarkable similarities with highly deformed and/or superdeformed bands observed in the A ≈ 60–70 mass region. In addition, a regular dipole sequence with weak E2 crossover transitions was observed. A general discussion of the observed structures, complemented by theoretical calculations carried out within the framework of the adiabatic and configuration-fixed constrained covariant density functional theory and the quantum particle-rotor model, are presented. Furthermore, the results are interpreted in the context of shell-structure evolution and the collectivity in the mass region.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2025

The structure of high-Mg alkali-bearing aluminosilicate glasses investigated in situ at ambient and high pressure by multi-angle energy dispersive X-ray diffraction and infrared microspectroscopy

The structural properties of synthetic high-Mg alkali-bearing aluminosilicate glasses analogues of natural picritic-to-komatiitic magmas were investigated in situ by multiangle energy dispersive X-ray diffraction at 2.1 GPa and ambient pressure and by Fourier Transform infrared spectroscopy up to 5.4 GPa in a cycle of compression and decompression experiments. Our results show that the intermediate range ordering of the glass structure at 2.1 GPa is 3.14 Å, increasing to 3.19 Å when decompressed. The local structure shows T-O lengths of 1.66 Å (2.1 GPa) and 1.65 Å (ambient pressure), T-T distances of 3.19 Å at high pressure, which lengthen to 3.21 Å at ambient pressure, causing the T-O-T angle of 147° determined at 2.1 GPa to widen to 154° upon decompression. The deconvoluted infrared spectra result in the presence of Q 1 , Q 2 , Q 3 populations in the aluminosilicate spectral region, whose proportions remain relatively unchanged up to 5.4 GPa. The structural response of the investigated glasses to cold-compression does not involve changes in polymerization, but rather a shrinking and compaction of the structure as evidenced by the Qn species shifting to higher wavenumbers as a function of pressure. The structural properties determined from X-ray diffraction for this glass composition are discussed together with those of glasses emerging from previous studies to highlight a compositional dependence mainly dictated by the amount of SiO 2 and Al 2 O 3 .

glass structure↗
NASA NTRS1986

High resolutions spectroscopy of P/Halley

High resolution spectra of the coma of P/Halley were obtained on 25 April, 2 May, and 3 May 1986. The self-scanned Digicon detector of the 2.7 m telescope coude spectrograph was used to obtain spectra at a resolution of 0.6A. Results of the observation of the NH (A 3 Pi i yields X 3 Sigma (-)) band near 3360 A are presented. The summed NH spectrum represents the results of 190 min of integration centered on the nucleus of the comet. Eight rotational lines from the P and R branches of the band are detected. The lines from the Q branch are especially weak, and are not obviously resolved in the spectrum. The data are compared with the theoretical emission spectrum of Litvak and Kuiper (1982) and substantial discrepancies are found. These discrepancies are explained through a consideration of the relative timescales for collisions, resonance fluorescence, and radiative decays of the NH molecules in the coma.

Cochran, W. D.↗
DOE OSTI2022

Star-forming S0 Galaxies in SDSS-MaNGA: fading spirals or rejuvenated S0s?

ABSTRACT We investigate the origin of rare star formation in an otherwise red-and-dead population of S0 galaxies, using spatially resolved spectroscopy. Our sample consists of 120 low redshift (z < 0.1) star-forming S0 (SF-S0) galaxies from the SDSS-IV MaNGA DR15. We have selected this sample after a visual inspection of deep images from the DESI Legacy Imaging Surveys DR9 and the Subaru/HSC-SSP survey PDR3 to remove contamination from spiral galaxies. We also construct two control samples of star-forming spirals (SF-Sps) and quenched S0s (Q-S0s) to explore their evolutionary link with the star-forming S0s. To study star formation at resolved scales, we use dust-corrected H α luminosity and stellar density (Σ⋆) maps to construct radial profiles of star formation rate (SFR) surface density (ΣSFR) and specific SFR (sSFR). Examining these radial profiles, we find that star formation in SF-S0s is centrally dominated as opposed to disc-dominated star formation in spirals. We also compared various global (size–mass relation, bulge-to-total luminosity ratio) and local (central stellar velocity dispersion) properties of SF-S0s to those of the control sample galaxies. We find that SF-S0s are structurally similar to the quenched S0s and are different from star-forming spirals. We infer that SF-S0s are unlikely to be fading spirals. Inspecting stellar and gas velocity maps, we find that more than $50{{\ \rm per\ cent}}$ of the SF-S0 sample shows signs of recent galaxy interactions such as kinematic misalignment, counter-rotation, and unsettled kinematics. Based on these results, we conclude that in our sample of SF-S0s, star formation has been rejuvenated, with minor mergers likely to be a major driver.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS2016

A Raman Study of Carbonates and Organic Contents in Five CM Chondrites

Carbonates comprise the second most abundant class of carbon-bearing phases in carbonaceous chondrites after organic matter (approximately 2 wt.%), followed by other C-bearing phases such as diamond, silicon carbide, and graphite. Therefore, understanding the abundances of carbonates and the associated organic matter provide critical insight into the genesis of major carbonaceous components in chondritic materials. Carbonates in CM chondrites mostly occur as calcite (of varying composition) and dolomite. Properly performed, Raman spectroscopy provides a non-destructive technique for characterizing meteorite mineralogy and organic chemistry. It is sensitive to many carbonaceous phases, allows the differentiation of organic from inorganic materials, and the interpretation of their spatial distribution. Here, with the use of Raman spectroscopy, we determine the structure of the insoluble organic matter (IOM) in the matrix and carbonate phases in five CM chondrites: Jbilet Winselwan, Murchison, Nogoya, Santa Cruz, and Wisconsin Range (WIS) 91600, and interpret the relative timing of carbonate precipitation and the extent of the associated alteration events.

Chan, Q. H. S.↗
NASA NTRS2014

Physical Characterization of Warm Spitzer-observed Near-Earth Objects

Near-infrared spectroscopy of Near-Earth Objects (NEOs) connects diagnostic spectral features to specific surface mineralogies. The combination of spectroscopy with albedos and diameters derived from thermal infrared observations can increase the scientific return beyond that of the individual datasets. For instance, some taxonomic classes can be separated into distinct compositional groupings with albedo and different mineralogies with similar albedos can be distinguished with spectroscopy. To that end, we have completed a spectroscopic observing campaign to complement the ExploreNEOs Warm Spitzer program that obtained albedos and diameters of nearly 600 NEOs (Trilling et al., 2010). The spectroscopy campaign included visible and near-infrared observations of ExploreNEOs targets from various observatories. Here we present the results of observations using the low-resolution prism mode (approx. 0.7-2.5 microns) of the SpeX instrument on the NASA Infrared Telescope Facility (IRTF). We also include near-infrared observations of Explore-NEOs targets from the MIT-UH-IRTF Joint Campaign for Spectral Reconnaissance. Our dataset includes near-infrared spectra of 187 ExploreNEOs targets (125 observations of 92 objects from our survey and 213 observations of 154 objects from the MIT survey). We identify a taxonomic class for each spectrum and use band parameter analysis to investigate the mineralogies for the S-, Q-, and V-complex objects. Our analysis suggests that for spectra that contain near-infrared data but lack the visible wavelength region, the Bus-DeMeo system misidentifies some S-types as Q-types. We find no correlation between spectral band parameters and ExploreNEOs albedos and diameters. We investigate the correlations of phase angle with band area ratio and near-infrared spectral slope. We find slightly negative Band Area Ratio (BAR) correlations with phase angle for Eros and Ivar, but a positive BAR correlation with phase angle for Ganymed.The results of our phase angle study are consistent with those of (Sanchez et al., 2012). We find evidence for spectral phase reddening for Eros, Ganymed, and Ivar. We identify the likely ordinary chondrite type analog for an appropriate subset of our sample. Our resulting proportions of H, L, and LL ordinary chondrites differ from those calculated for meteorite falls and in previous studies of ordinary chondrite-like NEOs.

composition↗
DOE OSTI2025

Chemistry and Interfacial Structure Promoting Quasi-van der Waals Epitaxial Growth of WS 2 Nanosheets on Sapphire for Prospective Application in Field-Effect Transistors

How do chemical and structural modifications to the supporting crystal surface affect the subsequent van der Waals (vdW) or quasi(Q)-vdW epitaxial growth of 2D nanocrystals? Developing an atomic-scale picture of such an interfacial system is crucial for understanding its impact on the physical and chemical properties of the supported 2D materials. The elucidation of the interfacial structure and chemistry needed to promote the Q-vdW epitaxial growth of 2D tungsten disulfide (WS 2 ) nanocrystals contributes to the growth mechanism understanding, thus pushing forward the integration of such atomically thin semiconductors toward real field-effect transistor applications. In addition to an atomic-force microscopy top view, we showcase a combination of X-ray techniques for a top-to-bottom investigation of the complexities of the buried interface structures. Furthermore, this approach uses X-ray photoelectron spectroscopy, X-ray standing wave excited X-ray fluorescence, and crystal truncation rod scattering to produce a highly resolved chemical-state-specific 3D atomic map for the extended interface structure of WS 2 /α-Al 2 O 3 (001). Employing these detailed analysis methods, along with density functional theory to further refine the picoscale structure, we demonstrate how two different types of interface engineering during the pregrowth stage lead to significant differences in the chemical and structural modifications to the terminal surface of c-face sapphire, which in turn leads to substantial differences in the submonolayer growth of supported WS 2 2D nanocrystals in terms of lateral domain sizes, epitaxial registry, vdW gaps, and stability.

36 MATERIALS SCIENCE↗
NASA NTRS2006

XRD, TEM, IR, Raman and NMR Spectroscopy of In Situ Crystallization of Lithium Disilicate Glass

The structure of a Li2O-2SiO2 (LS2) glass was investigated as a function of pressure and temperature up to 6 GPa and 750 C respectively, using XRD, TEM, IR, Raman and NMR spectroscopy. Glass densified at 6 GPa has an average Si-O-Si bond angle approx.7deg lower than that found in glass processed at 4.5 GPa. At 4.5 GPa, lithium disilicate crystallizes from the glass, while at 6 GPa a new high pressure form of lithium metasilicate crystallizes. The new phase, while having lithium metasilicate crystal symmetry, contains at least 4 different Si sites. NMR results for 6 GPa sample indicate the presence of Q4 species with (Q(sup 4))Si-O-Si(Q(sup 4)) bond angles of approx.157deg. This is the first reported occurrence of Q(sup 4) species with such large bond angles in alumina free alkali silicate glass. No five- or six- coordinated Si are found.

Fuss, T.↗
DOE OSTI2026

In Situ Insights into Enhanced Cooperative Ligand Exchange Kinetics via Solvent-Induced Restacking in a 2D Metal–Organic Framework

Understanding the reaction kinetics at catalytically active sites is crucial for integrating catalytic two-dimensional (2D) materials into industrial processes. This study focuses on in situ observation of ligand exchange kinetics and solvent-assisted structural restacking transition in the 2D paddle wheel-based MOF [Cu 2 (dttc) 2 ] n (DUT-134(Cu), dttc = dithieno[3,2-b:2′,3′- d]thiophene-2,6-dicarboxylate). The ligand exchange process, involving the replacement of dimethylformamide (DMF) with nitriles such as acetonitrile (ACN), pentanenitrile, and heptanenitrile, was investigated using advanced in situ characterization techniques with high temporal resolution, including powder X-ray diffraction and Raman spectroscopy. The larger analytes exhibited reduced exchange rates, consistent with enhanced steric hindrance and greater diffusion constraints. Interestingly, the study revealed that the exchange of DMF with ACN induces a structural transition to higher symmetry within few seconds, a transition from AB to AA stacking mode of the layers, and a widening of the interlayer distance. Crucially, this structural transition dramatically accelerates the solvent exchange process through cooperative effects, offering critical advantages for catalytic applications. Notably, the reverse exchange from ACN to DMF proceeds more slowly and does not reverse the structural changes, but a new phase is formed with preserved AA stacking. By isotope labeling of linker molecules in combination with two complementary theoretical vibrational simulation methods, the precise assignment of Raman bands and the vibrational modes associated with the ligand exchange process could be achieved. These pioneering insights into the dynamic behavior of 2D MOFs, coupled with ligand exchange, establish a highly promising and transformative approach to achieving enhanced tunability and responsiveness in future catalytic applications.

Layers↗