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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The preparation and characterization of chemically deuterium incorporated cotton fibers

Preparation of deuterium incorporated cellulose is a vital tool to investigate cellulose internal structure and to expand the application fields of cellulose materials. In this study, cellulosic cotton fibers with anti-rehydration (exchange-resistant) deuterium incorporated in cellulose were prepared by chemical hydrogen–deuterium exchange treatment. The chemical hydrogen–deuterium exchange process, along with exchange time, were characterized by nuclear magnetic resonance hydrogen spectroscopy (1H-NMR). The anti-rehydration deuterium incorporation was determined by Fourier Transform infrared spectroscopy (FTIR) and Stable Isotope Ratio Mass Spectrometer (IRSM). Here, the effect of the deuterium hydroxyl substitution on cotton fiber’s spectral data, microstructure, crystalline information, degree of polymerization, as well as it’s thermogravimetric analysis (charcoalization and combustion) are explored. Analysis of the chemical exchange process indicated that the hydrogen–deuterium exchange occurred preferentially in the amorphous cellulose component over the first several minutes. Deuterium exchange in the anti-rehydration crystalline phase took several hours. Increasing the treatment time, enhanced exchange-resistant deuterium incorporation to as high as about 60% of the cotton fibers’ cellulose hydroxyl groups was achieved. The characterization of FTIR, Fourier transform Raman (FT-Raman), and near-infrared spectra (NIR) all exhibited the deuterium spectral isotope effect on cellulose hydroxl groups. While, apart from the effect of reaction temperature, deuterium incorporation isotope effect did not affect the cellulose microstructure, crystalline index and the degree of polymerization properties. Furthermore, the thermogravimetric analysis of deuterated cotton fibers under N 2 and air atmosphere were both altered due to the thermodynamic isotope effect. These observations revealed the hydrogen–deuterium exchange treatment process and impacts on cellulose fiber properties, which helped us to better understand the cellulose internal structure and may facilitate the potential utilization of deuterated cellulosic materials.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Computing diffraction patterns of microstructures from phase-field simulations

The diffraction pattern of a material contains information not only on the crystal structures of its constituting phases, but also on its mesoscale spatial distributions of phases, grains, and ferroelastic, ferroelectric, and ferromagnetic domains. While diffraction patterns from experiments such as X-ray diffraction are presented in the reciprocal or Fourier space, mesoscale microstructure models such as the phase-field method naturally produce real-space images of spatial distribution of chemical composition, structural, and ferroic domains. Although one could rather readily compute the Fourier amplitudes of chemical and structural domain distributions generated by mesoscale simulations, they only contain information about the length scale and alignment of the real-space chemical and structure domains. Therefore, a direct comparison between diffraction experiments and mesoscale microstructure simulations is not possible. Here, we develop a theoretical approach to directly compute the crystal diffraction patterns of microstructures predicted by phase-field simulations. In particular, we consider five representative examples of microstructure patterns involving purely compositional domains, a single pair of tetragonal twin structures, multiple twin variants in a hexagonal system, ferroelectric polar vortices, and polycrystalline grains. The results are compared with previous experimental observations as well as X-ray diffraction experiments performed in the present study. Furthermore, the theoretical framework allows one to directly connect material microstructures and diffraction patterns predicted from phase-field simulations and the corresponding diffraction patterns from experiments, and thus providing guidance to experimental diffraction characterization and interpretation of microstructures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Information theory optimization of signals from small-angle scattering measurements

Small-angle X-ray scattering (SAXS) of particles in solution informs on the conformational states and assemblies of biological macromolecules (bioSAXS) outside of cryo- and solid-state conditions. In bioSAXS, the SAXS measurement under dilute conditions is resolution limited, and through an inverse Fourier transform, the measured SAXS intensities directly relate to the physical space occupied by the particles via the P (r)-distribution. Yet, this inverse transform of SAXS data has been historically cast as an ill-posed, ill-conditioned problem requiring an indirect approach. Here, we show that through the applications of matrix and information theories, the inverse transform of SAXS intensity data is a well-conditioned problem. The so-called ill-conditioning of the inverse problem is directly related to the Shannon number. By exploiting the oversampling enabled by modern detectors, a direct inverse Fourier transform of the SAXS data is possible, provided the recovered information does not exceed the Shannon number. The Shannon limit corresponds to the maximum number of significant singular values that can be recovered in a SAXS experiment, suggesting this relationship is a fundamental property of band-limited inverse integral transform problems. This correspondence reduces the complexity of the inverse problem to the Shannon limit and maximum dimension. We propose a hybrid scoring function using an information theory framework that assesses both the quality of the model-data fit as well as the quality of the recovered P (r)-distribution. The hybrid score utilizes the Akaike information criteria and Durbin-Watson statistic that considers parameter-model complexity, i.e., degrees of freedom, and the randomness of the model-data residuals. The described tests and findings extend the boundaries for bioSAXS by completing the information theory formalism initiated by Peter B. Moore to enable a quantitative measure of resolution in SAXS, robustly determine maximum dimension, and more precisely define the best parameter model appropriately representing the observed scattering data.

Rambo, Robert P. [Science and Technology Facilitie↗
DOE OSTI2022

Spatial resolution of different discretizations over long-time for the Dirac equation with small potentials

In this report we compare the long-time error bounds and spatial resolution of finite difference methods with different spatial discretizations for the Dirac equation with small electromagnetic potentials characterized by $\varepsilon \in (0, 1]$ a dimensionless parameter. We begin with the simple and widely used finite difference time domain (FDTD) methods, and establish rigorous error bounds of them, which are valid up to the time at $O(1/\varepsilon)$. In the error estimates, we pay particular attention to how the errors depend explicitly on the mesh size $h$ and time step $\tau$ as well as the small parameter $\varepsilon$. Based on the results, in order to obtain "correct" numerical solutions up to the time at $O(1/\varepsilon)$, the $\varepsilon$-scalability (or meshing strategy requirement) of the FDTD methods should be taken as $h = O(\varepsilon^{1/2})$ and $\tau = O(\varepsilon^{1/2})$. To improve the spatial resolution capacity, we apply the Fourier spectral method to discretize the Dirac equation in space. Error bounds of the resulting finite difference Fourier pseudospectral (FDFP) methods show that they exhibit uniform spatial errors in the long-time regime, which are optimal in space as suggested by the Shannon's sampling theorem. Extensive numerical results are reported to confirm the error bounds and demonstrate that they are sharp.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2022

Three-dimensional Skyrme Hartree-Fock-Bogoliubov solver in coordinate-space representation

The coordinate-space representation of the Hartree-Fock-Bogoliubov theory is the method of choice to study weakly bound nuclei whose properties are affected by the quasiparticle continuum space. To describe such systems, we developed a three-dimensional Skyrme-Hartree-Fock-Bogoliubov solver HFBFFT based on the existing, highly optimized and parallelized Skyrme-Hartree-Fock code Sky3D. The code does not impose any self-consistent spatial symmetries such as mirror inversions or parity. The underlying equations are solved in HFBFFT directly in the canonical basis using the fast Fourier transform. To remedy the problems with pairing collapse, we implemented the soft energy cutoff and pairing annealing. The convergence of HFB solutions was improved by a sub-iteration method. The Hermiticity violation of differential operators brought by Fourier-transform-based differentiation has also been solved. Furthermore, the accuracy and performance of HFBFFT were tested by benchmarking it against other HFB codes, both spherical and deformed, for a set of nuclei, both well-bound and weakly-bound.

3D coordinate-space representation↗
DOE OSTI2024

A parallel and performance portable implementation of a full-field crystal plasticity model

We have developed a parallel implementation of an Elasto-Viscoplastic Fast Fourier Transform-based (EVPFFT) micromechanical solver to enable computationally efficient crystal plasticity modeling for polycrystalline materials. Our primary focus lies in achieving performance portability, allowing a single EVPFFT implementation to run optimally on various homogeneous architectures, including multi-core Central Processing Units (CPUs), as well as on heterogeneous computer architectures comprising multi-core CPUs and Graphics Processing Units (GPUs) from different vendors. To accomplish this goal, we have leveraged MATAR, a C++ software library that simplifies the creation and utilization of multidimensional dense or sparse matrix and array data structures. These data structures are designed to be portable across diverse architectures through the use of Kokkos, a performance-portable library. Additionally, we have employed the Message Passing Interface (MPI) to efficiently distribute the computational workload among processors. The heFFTe (Highly Efficient FFT for Exascale) library is used to facilitate the performance portability of the fast Fourier transforms (FFTs) computation. The computational performance of EVPFFT is evaluated and presented in terms of parallel scalability and simulation runtime on different high-performance computing (HPC) architectures. As a result, the utility of the developed framework to efficiently simulate the micro-mechanical fields in polycrystalline microstructures in engineering applications is discussed.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Neural operators for stochastic modeling of nonlinear structural system response to natural hazards

Traditionally, neural networks have been employed to learn the mapping between finite-dimensional Euclidean spaces. However, recent research has opened up new horizons, focusing on the utilization of deep neural networks to learn operators capable of mapping infinite-dimensional function spaces. Here, in this work, we employ two state-of-the-art neural operators, the deep operator network (DeepONet) and the Fourier neural operator (FNO) for the prediction of the nonlinear time history response of structural systems exposed to natural hazards, such as earthquakes and windstorms. Specifically, we propose two architectures, a self-adaptive FNO and a fast Fourier transform-based DeepONet (DeepFNOnet), where we employ a FNO beyond the DeepONet to learn the discrepancy between the ground truth and the solution predicted by the DeepONet. To demonstrate the efficiency and applicability of the architectures, two problems are considered. In the first, we use the proposed model to predict the seismic nonlinear dynamic response of a six-story shear building subject to stochastic ground motions. In the second problem, we employ the operators to predict the wind-induced nonlinear dynamic response of a high-rise building while explicitly accounting for the stochastic nature of the wind excitation. In both cases, the trained metamodels achieve high accuracy while being orders of magnitude faster than their corresponding high-fidelity models.

DeepONet↗
DOE OSTI2026

Composition and persistence of soil organic matter along eroding and depositional transects in buried vs. modern soil layers: A case of the Brady paleosol at Wauneta, Nebraska

Paleosols form when soils are buried through deposition by aeolian, colluvial, alluvial or other processes. Burial of former topsoil isolates soil organic matter (SOM) from surface conditions, allowing carbon to accumulate and potentially remain stable for millennia. In this study, SOM composition, distribution, and persistence were analyzed in the Brady Soil of Nebraska, USA to compare SOM spatial variability in modern and buried soils, as well as the impact of erosional exposure on SOM stability. The Brady Soil, formed as a surface soil during the Pleistocene-Holocene transition and now a paleosol buried up to 6 m deep (or more) by loess deposition during the Holocene, was sampled along burial (up to 5.8 m depth) and erosional (up to 1.8 m depth) transects to compare SOM dynamics in different geomorphic settings. Fourier Transform Infrared Spectroscopy (FTIR) and Fourier Transform ion cyclotron resonance mass spectrometry (FTICR-MS) were used to analyze SOM composition, while δ 13 C isotope analyses identified SOM sources and radiocarbon values were used to estimate turnover rates. Results confirmed a vegetation shift from C3 to C4 plants after Brady Soil formation, reflecting warming climatic conditions. Increasing SOM age and decreasing δ 13 C and δ 15 N values with depth indicated slowing of decomposition rate in buried soils. Higher pH in the Brady Soil suggested greater base cation content, supporting SOM stabilization through organo-mineral associations and aggregate formation. However, exposure of the Brady Soil due to surface erosion caused faster SOM turnover. This result suggested susceptibility of buried SOM to losses via decomposition upon erosional exposure, possibly accelerated by priming in response to modern SOM inputs. These findings highlight the potential loss of carbon stocks in buried soils under future climate change, as shifts in soil physicochemical properties may destabilize long-preserved SOM.

Environmental sciences↗
DOE OSTI2022

Integrating a ponderomotive guiding center algorithm into a quasi-static particle-in-cell code based on azimuthal mode decomposition

High fidelity modeling of plasma based acceleration (PBA) requires the use of three dimensional, fully nonlinear, and kinetic descriptions based on the particle-in-cell (PIC) method. In PBA an intense particle beam or laser (driver) propagates through a tenuous plasma whereby it excites a plasma wave wake. Three-dimensional PIC algorithms based on the quasi-static approximation (QSA) have been successfully applied to efficiently model the interaction between relativistic charged particle beams and plasma. In a QSA PIC algorithm, the plasma response to a charged particle beam or laser driver is calculated based on forces from the driver and self-consistent forces from the QSA form of Maxwell's equations. These fields are then used to advance the charged particle beam or laser forward by a large time step. Since the time step is not limited by the regular Courant-Friedrichs-Lewy (CFL) condition that constrains a standard 3D fully electromagnetic PIC code, a 3D QSA PIC code can achieve orders of magnitude speedup in performance. Recently, a new hybrid QSA PIC algorithm that combines another speedup technique known as an azimuthal Fourier decomposition has been proposed and implemented. This hybrid algorithm decomposes the electromagnetic fields, charge and current density into azimuthal harmonics and only the Fourier coefficients need to be updated, which can reduce the algorithmic complexity of a 3D code to that of a 2D code. Modeling the laser-plasma interaction in a full 3D electromagnetic PIC algorithm is very computationally expensive due the enormous disparity of physical scales to be resolved. In the QSA the laser is modeled using the ponderomotive guiding center (PGC) approach. We describe how to implement a PGC algorithm compatible for the QSA PIC algorithms based on the azimuthal mode expansion. Here this algorithm permits time steps orders of magnitude larger than the cell size and it can be asynchronously parallelized. Details on how this is implemented into the QSA PIC code that utilizes an azimuthal mode expansion, QPAD, are also described. Benchmarks and comparisons between a fully 3D explicit PIC code (OSIRIS), as well as a few examples related to laser wakefield acceleration, are presented.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2021

Two-phase accurate multiplexed structured image capture (2pAc-MUSIC)

Multiplexed Structural Image Capture (MUSIC) technique uses modulation of light from a scene prior to imaging to encode the temporal evolution of target into spatial frequency shifts, with each shift corresponding to a unique time and resulting in individual distinct snapshots. Computational-processing of the multiplexed single-shot image can recover the nanosecond-resolution scene evolution. One of the limitations is the loss of spatial resolution of the recovered image due to limitations of the low-pass spatial frequency filtering depth. Here we demonstrated that two images with complementary spatial phases can be used to enhance the spatial resolutions. For this application, 2 Phase Accurate (2pAc)-MUSIC is implemented that a scene is encoded with two complementary phases. The increased spatial information captured reduces the lower frequency noise in the Fourier domain found in single-phase MUSIC. A recovery algorithm combines the 180-degree spatial frequency shifted images into a single scene and applies a spatial filter in the Fourier domain that has a larger depth than previously possible to achieve a scene with increased spatial resolution. The 2pAc-MUSIC can effectively enhance the spatial resolution by removing the overlapping zero-order spatial frequencies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Organic amendments change soil organic C structure and microbial community but not total organic matter on sub-decadal scales

Organic C has many benefits for soil, but it is depleted by tillage and crop harvest, and especially so for biofuel crops. Accordingly, strategies such as partially retaining stover or planting a cover crop can help ameliorate the negative effect of C removal. We used a long-term field experiment to study the impacts of stover retention and planting cover crop on soil organic matter (SOM), its extractable components and the soil microbial community. SOM chemical composition characterization was determined by electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in sequential water, methanol (MeOH), and chloroform (CHCl3) extracts. The characteristics of the soil bacterial community were measured by phospholipid fatty acid (PLFA), real-time quantitative PCR, and 16S rRNA gene sequence. The variations in total SOM content, total microbial biomass, and bacterial population were slight among treatments, but SOM chemical compounds, arbuscular mycorrhizal fungi (AMF) biomass, and bacterial structure changed significantly, and especially so in the coupled application of stover retention and cover crop. Specifically, stover retention enriched more lignin-like compounds in soil, whereas cover crop enriched more condensed hydrocarbons, and had more compounds with an aromaticity index (AI) >0.5. The bacterial community was not altered by the cover crop, but the corn stover retention increased the relative abundances of Myxococcales (Deltaproteobacteria) and decreased that of Actinobacteria. Redundancy analysis (RDA) further unveiled that the bacterial community in the stover treatments had significantly positive association with CHCl3-extracted chemical classes, i.e. unsaturated hydrocarbon and lipid with the coupled application (stover and cover crop), and lignin and protein with the single corn stover treatment. Taken together, our study shows how different C addition practices influence the molecular composition of SOM and the structure of soil microbial communities.

Xu, Jiangbin↗
DOE OSTI2021

Quasi-periodic travelling gravity–capillary waves

We present a numerical study of spatially quasi-periodic travelling waves on the surface of an ideal fluid of infinite depth. This is a generalization of the classic Wilton ripple problem to the case when the ratio of wavenumbers satisfying the dispersion relation is irrational. We propose a conformal mapping formulation of the water wave equations that employs a quasi-periodic variant of the Hilbert transform to compute the normal velocity of the fluid from its velocity potential on the free surface. We develop a Fourier pseudo-spectral discretization of the travelling water wave equations in which one-dimensional quasi-periodic functions are represented by two-dimensional periodic functions on the torus. This leads to an overdetermined nonlinear least-squares problem that we solve using a variant of the Levenberg–Marquardt method. We investigate various properties of quasi-periodic travelling waves, including Fourier resonances, time evolution in conformal space on the torus, asymmetric wave crests, capillary wave patterns that change from one gravity wave trough to the next without repeating and the dependence of wave speed and surface tension on the amplitude parameters that describe a two-parameter family of waves.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2025

Multi-modal effects on indirect noise induced by turbulent entropy fields

Planar entropy waves are commonly assumed for predicting indirect combustion noise. However, the non-planar and turbulent nature of flows found in most practical combustors challenges this assumption. In the present paper, we examine the indirect noise generated by non-planar and turbulent entropy fields through subsonic nozzles. Firstly, we introduce a new transfer function framework that accounts for the contribution of non-planar Fourier modes of the entropy field to the indirect noise spectra. When applied to a turbulent flow field, this method demonstrates a significant improvement in spectral predictions compared with a conventional approach that only considers the planar mode. Secondly, simulations show that non-planar Fourier modes become significant above a threshold frequency ƒ thresh , found in the mid- to high-frequency range. This contribution of non-planar modes is explained by two-dimensional shear effects that distort the entropy waves. A scaling relation that uses residence times along streamlines is developed for ƒ thresh , showing good agreement with simulation results. Finally, we show that the indirect noise from non-planar entropy modes found in aviation combustors can be significant at frequencies below 1 kHz, which might be relevant in situations of thermo-acoustic instabilities coupled to indirect noise.

42 ENGINEERING↗
DOE OSTI2023

Natural Abundance Isotope Ratio Measurements of Organic Molecules Using 21 T FTICR MS

Subtle variations in stable isotope ratios at natural abundance are challenging to measure but can yield critical insights into biological, physical, and geochemical processes. Well established methods, particularly multi-collector, gas-source or plasma isotope ratio mass spectrometry (IRMS) are the gold standard for stable isotope measurement but inherent limitations in these approaches make them ill-suited to determining site-specific and multiply substituted isotopic abundances of all but a few compounds, or to characterizing mixtures or larger intact molecules. Additionally, Fourier transform mass spectrometry (FTMS), namely Orbitrap mass spectrometry, has recently demonstrated the ability to measure natural abundance isotope ratios with chemically informative accuracy and precision. Here, we report the first use of Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) for the accurate (<1‰) and precise (<1‰ standard error) simultaneous determination of $δ$ 13 C and $δ$ 15 N in caffeine isotopologues and provide a discussion of the critical instrumental parameters necessary to make such measurements. Finally, we report the ability to make these measurements with online liquid chromatography, expanding the ability of this technique to explore mixtures in the future.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Comparison of the Chemical Composition of Liquids from the Pyrolysis and Hydrothermal Liquefaction of Lignocellulosic Materials

Major differences in thermal stability and hydrotreatment behavior of HTL and pyrolysis oils have been reported in the literature. However, little is known about the variations in the chemical composition of these oils that could explain such differences. Two commercial wood pyrolysis oils (Pyrovac and BTG), and their water-soluble (WS) and water-insoluble fractions (WIS) were analyzed and compared with the aqueous (WS WD-57 ) and oily (WIS WS-57 ) fractions obtained from hydrothermal liquefaction (HTL) of Douglas-fir. The samples were characterized by GC/MS, Karl Fischer titration, carbonyl content, total acid number, elemental composition, calorific value, proximate analysis, Fourier Transform Infrared Spectroscopy (FTIR), Folin-Ciocalteu (FC), and UV fluorescence. All the fractions were also analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectroscopy (FT-ICR-MS) and by Electrospray Ionization (EI). The most prevalent class of compounds in the water insoluble phases were phenols derived from lignin. Water-soluble phases contain mostly the oxygenated compounds derived from cellulose and hemicellulose and were richer in carbonyl functional groups. The water content of the resulting aqueous phases were between: 65 (WS BTG ) and 96 (WS Pyrovac ) wt. %. The bio-oil from BTG has higher water content and lower HHV, compared to Pyrovac oil. The GC/MS results of BTG oil show the presence of a more prominent acetic acid peak and higher TAN number than the Pyrovac oil. The GC/MS of Pyrovac oil showed more obvious mono-phenol peaks. The quantification of this family by Folin-Ciocalteu method confirmed higher content of monophenolic compounds compared with the BTG oil. The lower thermal stability of pyrolysis oils compared with HTL biocrudes can be partially explained by the fact that pyrolysis oils (BTG and Pyrovac) contain carbohydrates while HTL biocrude (WIS WD-57 ) doesn’t. Thus, we decided to further investigate the chemical differences between the phenolic rich fractions insoluble in water and the holocellulose derived compounds soluble in water. Even after water extraction, the acid content of the water insoluble fraction from BTG (WISBTG) was higher than the acid content of the water insoluble fraction obtained by HTL (WISWSD-57). Likewise, the acid content of the aqueous phases derived from pyrolysis oils (WS Pyrovac , WS BTG ) was also higher than for the aqueous phase obtained by HTL (WSWSD-57). This result is in part due to the use of bases in the HTL process that neutralizes the acid formed in that process. Moreover, the starting feedstock may also influence the differences between the oils. Although, the UV-Fluorescence spectra, ICR-MS and the EI analyses showed some minor differences in the molecular weight and chemical make-up of the oligomers soluble and insoluble in water from pyrolysis and HTL; the differences observed were not large enough to justify the differences in behavior between these oils reported in the literature. Our results suggest that the differences observed between HTL biocrudes and pyrolysis oils are likely partially due to the presence of holocellulose derived products in the pyrolysis oils and higher acid contents.

09 BIOMASS FUELS↗
DOE OSTI2024

Detailed Characterization of Vitrinite-Rich Subbituminous and Bituminous Coals for Utilization in Carbon Fiber Precursor Production

Chemical structures of candidate coals (one subbituminous coal from the Powder River Basin and three bituminous Eastern US coals) were examined for potential low-cost carbon fiber precursor production. Here, the structural evaluation examined the carbon skeleton ( 13 C nuclear magnetic resonance (NMR) and high-resolution transmission electron microscopy (HRTEM)), the heteroatom functionality (X-ray photoelectron spectroscopy (XPS) Fourier transform infrared spectroscopy (FTIR) and NMR), the structural ordering and distribution of PAH sizes (HRTEM), and an estimation of the molecular weight distribution (laser desorption ionization mass spectrometry, LDIMS). The molecular compositional distributions were also evaluated for a mixed solvent extract (atmospheric pressure photoionization, 21 T Fourier transform ion cyclotron resonance mass spectrometry, FT-ICR MS). Significant structural differences existed between the subbituminous and bituminous coals, as expected with coalification (with the bituminous coals having a higher carbon content, lower oxygen content, higher aromaticity values, larger cluster sizes, and so forth). While the bituminous coals were similar in structure (close in rank with Blue Gem being hvAb and the rest being hvBb), structural differences were still evident. Specifically, structural similarities were evident for the average properties of Herrin and Springfield coals: same rank, similar moisture, and volatile matter yields, along with similar aromaticity and carbon and hydrogen content. However, significant structural differences were observed at the molecular level by 21 T FT-ICR MS, which showed that the Springfield coal was structurally more complex. Specifically, 21740, 16931, 30190, and 12982 unique elemental compositions were identified for the Monarch, Herrin, Springfield, and Blue Gem coals, further illustrating the complexity of the coal.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2020

Mechanistic understanding of catalytic conversion of ethanol to 1-butene over 2D-pillared MFI zeolite

Ethanol is an important C2 platform molecule for producing value-added chemicals and distillate hydrocarbon fuels (e.g., jet and diesel). Among these, catalytic upgrading of ethanol to butenes can generate valuable commodity chemicals (e.g., 1-butene) and provide C4 olefin intermediates that can be further upgraded to jet/diesel fuels. 2D zeolites offer hierarchical mesoporous structures, leading to improved mass transport and reduced diffusion length, which can help to address the coking challenges faced by ethanol conversion to hydrocarbons over 3D zeolites. In this study, we investigate the acid-catalyzed conversion of ethanol to 1-butene over the Brønsted acid sites (BAS) in 2D-pillared MFI zeolite (2D-PMFI) using ab initio molecular dynamics (AIMD) simulations, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and calorimetric measurements. A detailed thermodynamic analysis, using quasi-harmonic approximation (QHA), on the Gibbs free energy pathway of ethanol conversion shows that the consideration of entropy is critical to accurately capture the detailed thermodynamic profiles. The formation of bulky ethoxy-ethene complex is found to be a potential rate-determining step (RDS), proceeding via stepwise mechanism. The reactivity of 2D-PMFI can be further tuned by manipulating RDS through a careful control of number of BAS and operating temperatures. The accuracy of computational model is confirmed through the comparison of calculated vibrational density of states (VDOS) against the experimental DRIFTS measurements. Overall, our study provides mechanistic insights into ethanol upgrading over the 2D-PMFI and shows the importance of evaluating entropic effects in such confined system.

Ethanol conversion, 2D-pillared zeolite, MFI, Anha↗
DOE OSTI2020

Capture and Decomposition of the Nerve Agent Simulant, DMCP, Using the Zeolitic Imidazolate Framework (ZIF-8)

Understanding mechanisms of decontamination of chemical warfare agents (CWA) is an area of intense research aimed at developing new filtration materials to protect soldiers and civilians in case of state-sponsored or terrorist attack. In this study, we employed complementary structural, chemical, and dynamic probes and in situ data collection, to elucidate the complex chemistry, capture, and decomposition of the CWA simulant, dimethyl chlorophosphonate (DMCP). Our work reveals key details of the reactive adsorption of DMCP and demonstrates the versatility of zeolitic imidazolate framework (ZIF-8) as a plausible material for CWA capture and decomposition. Here, the in situ synchrotron-based powder X-ray diffraction (PXRD) and pair distribution function (PDF) studies, combined with Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), zinc K-edge X-ray absorption near edge structure (XANES), and Raman spectroscopies, showed that the unique structure, chemical state, and topology of ZIF-8 enable accessibility, adsorption, and hydrolysis of DMCP into the pores and revealed the importance of linker chemistry and Zn 2+ sites for nerve agent decomposition. DMCP decontamination and decomposition product(s) formation were observed by thermogravimetric analysis, FT-IR spectroscopy, and phosphorus (P) K-edge XANES studies. Differential PDF analysis indicated that the average structure of ZIF-8 (at the 30 Å scale) remains unchanged after DMCP dosing and provided information on the dynamics of interactions of DMCP with the ZIF-8 framework. Using in situ PXRD and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), we showed that nearly 90% regeneration of the ZIF-8 structure and complete liberation of DMCP and decomposition products occur upon heating.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗