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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Accelerating CO2 Storage Site Characterization through a New Understanding of Favorable Formation Properties and the Impact of Core-Scale Heterogeneities

CO2 sequestration in deep geologic formations can permanently reduce atmospheric CO2 emissions and help to abate climate change. Target formations must undergo a time- and resource-intensive site evaluation process, assessing storage capacity, environmental safety, and suitability for CO2 trapping via reactive transport models based on data from a limited number of core samples. As such, simulations are often simplified and omit heterogeneities in formation properties that may be significant but are not well understood. To facilitate more rapid site assessment, this work first defines the aquifer properties of favorable storage formations through the analysis of promising and active storage sites. Data show quartz is the most prevalent formation mineral with carbonate minerals, highly reactive with injected CO2, present in over 75% of formations. Porosity and permeability data are highly clustered at 10–30% and 10–1000 mD. Field-scale reactive transport simulations are then constructed and used to analyze CO2 trapping efficiency. The models consider porosity and carbonate mineral heterogeneity as well as the impacts of typical temperature gradients. Simulated sequestration efficiencies are compared to results from a comparable homogenous model to understand the implications of aquifer non-uniformities. The results show a lower sequestration efficiency in the homogeneous model during the injection phase. During the post-injection phase, the homogenization of porosity and carbonate mineralogy results in a higher sequestration efficiency. Incorporating the temperature gradient also increases the sequestration efficiency. Importantly, the maximum deviation between the homogeneous and heterogeneous simulations at the end of the 50-year study period is only ~10%. Larger impacts may be incurred for properties outside the defined, promising ranges suggested here.

Environmental Sciences & Ecology↗
DOE OSTI2026

Transfer Learning Meets Embedded Correlated Wavefunction Theory for Chemically Accurate Molecular Simulations: Application to Calcium Carbonate Ion Pairing

Achieving chemical accuracy for molecular simulations remains a central challenge in computational chemistry. Here, we present an embedded correlated wavefunction transfer learning (ECW-TL) framework for accurately simulating molecular dynamics in the condensed phase. ECW-TL incorporates high-level electron exchange and correlation effects in ECW theory while preserving the training and computational efficiency of machine-learned interatomic potentials. We demonstrate the framework on Ca 2+ –CO 3 2– ion pairing in aqueous solution, a key process underlying CO 2 mineralization in seawater. As proof of principle, we first show that fine-tuning a DFT-revPBE-D3(BJ) baseline model with embedded-DFT-SCAN data reproduces the DFT-SCAN free-energy surface within 1 kcal/mol across all solvation states. Extending the framework to embedded MP2 and localized natural-orbital CCSD(T) further refines the free-energy profile, revealing the crucial role of exact electron exchange and correlation in determining ion-pair stability and structure. The computed ion-pair association free energy is in quantitative agreement with experimental measurements, further validating the accuracy of the ECW-TL framework. ECW-TL thus provides a general, data-efficient route for transferring CW accuracy to efficient simulations of complex aqueous and interfacial chemical processes.

cluster chemistry↗
DOE OSTI2025

Unsupervised Clustering of Microseismic Events and Focal Mechanism Analysis at the CO 2 Injection Site in Decatur, Illinois

Characterization of induced microseismicity at a carbon dioxide (CO 2 ) storage site is critical for preserving reservoir integrity and mitigating seismic hazards. We apply a multilevel machine learning (ML) approach that combines the nonnegative matrix factorization and hidden Markov model to extract spectral representations of microseismic events and cluster them to identify seismic patterns at the Illinois Basin-Decatur Project. Unlike traditional waveform correlation methods, this approach leverages spectral characteristics of first arrivals to improve event classification and detect previously undetected planes of weakness. By integrating ML-based clustering with focal mechanism analysis, we resolve small-scale fault structures that are below the detection limits of conventional seismic imaging. Our findings reveal temporal bursts of microseismicity associated with brittle failure, providing insights into the spatio-temporal evolution of fault reactivation during CO 2 injection. This approach enhances seismic monitoring capabilities at CO 2 injection sites by improving fault characterization beyond the resolution of standard geophysical surveys.

Willis, Rachel Marie [Sandia National Laboratories↗
DOE OSTI2020

CO 2 Hydrogenation to Formate and Formic Acid by Bimetallic Palladium–Copper Hydride Clusters

Mass spectrometric analysis of the anionic products of interaction between bimetallic palladium-copper tetrahydride anions, PdCuH 4 – , and carbon dioxide, CO 2 , in a reaction cell shows an efficient generation of the PdCuCO 2 H 4 – intermediate and formate/formic acid complexes. Multiple structures of PdCuH 4 – and PdCuCO 2 H 4 – are identified by a synergy between anion photoelectron spectroscopy and quantum chemical calculations. The higher energy PdCuH 4 – isomer is shown to drive the catalytic hydrogenation of CO 2 , emphasizing the importance of accounting for higher energy isomers for cluster catalytic activity. In conclusion, this study represents the first example of CO 2 hydrogenation by bimetallic hydride clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Chemistry-mediated Ostwald ripening in carbon-rich C/O systems at extreme conditions

Abstract There is significant interest in establishing a capability for tailored synthesis of next-generation carbon-based nanomaterials due to their broad range of applications and high degree of tunability. High pressure (e.g., shockwave-driven) synthesis holds promise as an effective discovery method, but experimental challenges preclude elucidating the processes governing nanocarbon production from carbon-rich precursors that could otherwise guide efforts through the prohibitively expansive design space. Here we report findings from large scale atomistically-resolved simulations of carbon condensation from C/O mixtures subjected to extreme pressures and temperatures, made possible by machine-learned reactive interatomic potentials. We find that liquid nanocarbon formation follows classical growth kinetics driven by Ostwald ripening (i.e., growth of large clusters at the expense of shrinking small ones) and obeys dynamical scaling in a process mediated by carbon chemistry in the surrounding reactive fluid. The results provide direct insight into carbon condensation in a representative system and pave the way for its exploration in higher complexity organic materials. They also suggest that simulations using machine-learned interatomic potentials could eventually be employed as in-silico design tools for new nanomaterials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Atomistic modeling of tensile deformation and fracture of carbon fibers: Nanoscale stress redistribution, effect of local structural characteristics and nanovoids

The mechanisms of tensile deformation and fracture of carbon fibers are investigated in large-scale molecular dynamics simulations. The simulations performed for computational samples with different structural characteristics enable analysis of the structural sensitivity of the mechanical properties. It is found that the carbon fiber nanostructure can be represented by a fine (nanoscale) mixture of stiff and soft regions. Despite the nanoscale structural heterogeneity of the computational fibers, their fracture strain and tensile strength exceed the experimental values by almost an order of magnitude. Here, this observation is explained by the ability of the carbon fiber nanostructure, largely consisting of curved and folded layers of turbostratic carbon, to exhibit continuous nanoscale load redistribution during the deformation. The transient, fluid nature of a percolating cluster of stress-holding structural elements prevents stress localization at the early stage of the deformation and enables the fiber nanostructure to adapt to the increasing load. Overall, the results of the simulations suggest that the design of advanced carbon fiber manufacturing and post-processing methods focused on the elimination of critical mesoscopic structural defects (internal voids, foreign inclusions, and surface flaws) can yield a substantial increase in the strength and fracture strain of carbon fibers.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Development and application of ReaxFF methodology for understanding the chemical dynamics of metal carbonates in aqueous solutions

A new ReaxFF reactive force field has been developed for metal carbonate systems including Na + , Ca 2+ , and Mg 2+ cations and the CO 3 2– anion. This force field is fully transferable with previous ReaxFF water and water/electrolyte descriptions. The Me–O–C (Me = metal) three-body valence angle parameters and Me–C non-reactive parameters of the force field have been optimized against quantum mechanical calculations including equations of state, heats of formation, heats of reaction, angle distortions and vibrational frequencies. The new metal carbonate force field has been validated using molecular dynamics simulations to study the solvation and reactivity of metal and carbonate ions in water at 300 K and 700 K. The coordination radius and self-diffusion coefficient show good consistency with existing experimental and simulation results. The angular distribution analysis explains the structural preference of carbonate ions to form carbonates and bicarbonates, where Na + predominantly forms carbonates due to weaker angular strain, while Ca 2+ and Mg 2+ prefer to form bicarbonate monodentate in nature. Residence time distribution analyses on different systems reveal the role of ions in accelerating and decelerating the dynamics of water and carbonate ions under different thermodynamic conditions. The formation and dissolution of bicarbonates and carbonates in solution were explored on the basis of the protonation capability in different systems. Here, the nucleation phenomenon of metal carbonates at ambient and supercritical conditions is explained from the perspective of cluster formation over time: Ca 2+ ions can form prenucleation clusters at ambient temperature but show saturation with increasing temperature, whereas Na + and Mg 2+ ions show a rapid increase in cluster size and amount upon increasing time and temperature.

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

Formation of active sites on transition metals through reaction-driven migration of surface atoms

Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. Here we used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH 3 ) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Microhardness studies on thin carbon films grown on P-type, (100) silicon

A program to grow thin carbon films and investigate their physical and electrical properties is described. Characteristics of films grown by rf sputtering and vacuum arc deposition on p type, (100) silicon wafers are presented. Microhardness data were obtained from both the films and the silicon via the Vickers diamond indentation technique. These data show that the films are always harder than the silicon, even when the films are thin (of the order of 1000 A). Vacuum arc films were found to contain black carbon inclusions of the order of a few microns in size, and clusters of inclusions of the order of tens of microns. Transmission electron diffraction showed that the films being studied were amorphous in structure.

Kolecki, J. C.↗
NASA NTRS1985

A search for mini-clusters in Japan-USSR Joint Experiment at Pamir

A search for mini-clusters, very collimated shower clusters of hadrons and electromagnetic particles, is made for the hadron and gamma families observed by Japan-USSR joint carbon chamber at Pamir. The existence of anomalous correlation between hadrons and electromagnetic particles is found. The decascading method is applied to the families and it is found that 11 clusters which include hadrons as members have smaller spread, Er 3.5 GeV.m and larger lateral spread, E'R' 100 GeV.m, from the family center. In the simulated events, such clusters were found to be very rare.

Source record↗
NASA NTRS1995

Grain formation around carbon stars. 1: Stationary outflow models

Asymptotic giant branch (AGB) stars are known to be sites of dust formation and undergo significant mass loss. The outflow is believed to be driven by radiation pressure on grains and momentum coupling between the grains and gas. While the physics of shell dynamics and grain formation are closely coupled, most previous models of circumstellar shells have treated the problem separately. Studies of shell dynamics typically assume the existence of grains needed to drive the outflow, while most grain formation models assume a constant veolcity wind in which grains form. Furthermore, models of grain formation have relied primarily on classical nucleation theory instead of using a more realistic approach based on chemical kinetics. To model grain formation in carbon-rich AGB stars, we have coupled the kinetic equations governing small cluster growth to moment equations which determine the growth of large particles. Phenomenological models assuming stationary outflow are presented to demonstrate the differences between the classical nucleation approach and the kinetic equation method. It is found that classical nucleation theory predicts nucleation at a lower supersaturation ratio than is predicted by the kinetic equations, resulting in significant differences in grain properties. Coagulation of clusters larger than monomers is unimportant for grain formation in high mass-loss models but becomes more important to grain growth in low mass-loss situations. The properties of the dust grains are altered considerably if differential drift velocities are ignored in modeling grain formation. The effect of stellar temperature, stellar luminosity, and different outflow velocities are investigated. The models indicate that changing the stellar temperature while keeping the stellar luminosity constant has little effect on the physical parameters of the dust shell formed. Increasing the stellar luminosity while keeping the stellar temperature constant results in large differences in grain properties. For small outflow velocities, grains form at lower supersaturation ratios and close to the stellar photosphere, resulting in larger but fewer grains. The reverse is true when grains form under high outflow velocities, i.e., they form at higher supersaturation ratios, farther from the star, and are much smaller but at larger quantities.

Egan, Michael P.↗
NASA NTRS2018

Fire Induced Rock Spalls as Long-Term Traps for Ash

Severe fires accelerate rock weathering by spalling and exfoliation, creating abundant peels, flakes or spalls. In the following years, these spalls serve as physical traps which accommodate fine particles of dust, ash, organic matter, etc. We searched for traces of ash trapped under the spalls, after four major fires: 1989, 2005, 2010 and 2015 in Israel. Samples were collected beneath the spalls that formed on the rock outcrops, and in the immediate vicinity above and below them. Three laboratory analyses were performed: pH, EC and color. Five mineral/organic compounds were measured across the Mid-Infrared (MIR) spectral region at diffuse reflectance infrared Fourier transform mode: Hydroxylapatite (HAp), charcoal, organic carbon, montmorillonite and kaolinite. Several statistical analyses were performed: MANOVA, PCA and silhouette analysis on K-means clustering. The results show evidence of ash trapped under the spalls formed during the 2005 and 2010 fires, 6 to 11 years after the fires. Charcoal presence is evident, as well as increased amounts of HAp and organic carbon. In the exposed soil above or below the burned rock outcrop, these values are lower. Negligible amounts of ash were measured 27 years after the fire. In the 2015 burned outcrop, large amounts of charcoal were found above and below the outcrop, but not under the spalls. It seems that on the carbonate slopes of Israel and under Mediterranean climate, the time required for spalls to begin functioning as traps is longer than one rainy season, while ash traces are preserved in these traps for a period of two-three decades.

ash↗
NASA NTRS2002

Louisiana NASA EPSCoR Project

In 1994, the National Aeronautics and Space Administration issued a Cooperative Agreement (CA) to the State of Louisiana, through the Louisiana Board of Regents (BOB), for the performance of scientific research under the Experimental Program to Stimulate Competitive Research (EPSCoR) Project. Originally constructed as a three-year program with an optional two-year follow on, this federal-state partnership culminated on 31 October 2001, including two CA extensions. The total value of the project reached $3.3M in NASA funding, matched by $2.75M in BOB funds, and supplemented by several million dollars in institutional contributions. Three Research Clusters comprised the state-wide research effort coupled with scientific/technical management and a teacher involvement component. The three research clusters addressed the Enterprises of Space Science, Earth Science and Aerospace Technology with research in High Energy Astrophysics, the Global Carbon Cycle, and Propulsion. Ten universities, over two dozen faculty, over 150 students and numerous support personnel were involved. All of the scientific and technical objectives were met or exceeded. In aggregate, the clusters generated about $18M in outside support, better than a 2:1 return on investment (better than 5:1 considering only the NASA investment). Moreover, two of the clusters have advanced to the level of applying for major NSF research center designation. This project was a trial of the model of building research infrastructure through mentoring. While not completely successful, the results at the smaller institutions were, none the less, positive. Faculty were engaged in major research and involved their students. Administrations improved their capabilities to handle grants and contracts. Faculty release time was granted, research space was provided and, in some cases, equipment was made available for the research. Some of the faculty at these schools have remained involved in research and/or formed collaborations for new endeavors, demonstrating that the mentoring model can be successful.

Wefel, John P.↗
DOE OSTI2023

Impact of Disorder and Defects on Bond Energies in Highly Fluorinated Graphene

Fluorinated graphite materials are of interest for an assortment of applications and can be synthesized under a variety of synthetic conditions from many different types of carbon. Due to such variations, structural disorders in the form of defects and polymorphism are often present. Here, we investigate the impact of local structural variations on the C–F bond dissociation energies (BDEs) in carbon-based fluoride materials using density functional theory (DFT) computational methods. Employing fluorographene (FG) cluster models, we determine the impact of different C–F bonding configurations in the core of each platelet on the equilibrium BDEs for each C–F bond. The introduction of structural disorder decreases the first C–F BDE by approximately 1 eV compared to the canonical arrangement of axial C–F bonds ordered as in a network of cyclohexane “chairs”. Variability of calculated BDEs among the different polymorphs decreases upon subsequent F removal. Common structural tendencies of the adiabatic defluorination pathways for each polymorph are identified. In conclusion, our analysis suggests that at F/C ratios near 1.0, disorder in the local structure can play a significant role in the energetics of the initial carbon fluoride defluorination and that the influence of this configurational disorder diminishes with decreasing F/C ratios.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

The C9 cluster - Structure and infrared frequencies

A structural characterization is presented for C9, the largest cluster predicted to have a linear ground state. IR laser diode absorption spectroscopy of a supersonic carbon jet is used to measure 51 lines of the nu6 (sigma u) antisymmetric stretch fundamental transition within the linear 1Sigma(g)+ ground electronic state of C9. The measured ground state rotational constant suggests an effective C-C bond length which is in good agreement with ab initio theory and consistent with cumulenic bonding in this cluster.

Heath, J. R.↗
DOE OSTI2020

Molecular growth upon ionization of van der Waals clusters containing HCCH and HCN is a pathway to prebiotic molecules

The growth mechanisms of organic molecules in an ionizing environment such as the interstellar medium are not completely understood. Here we examine by means of ab initio molecular dynamics (AIMD) simulations and density functional theory (DFT) computations the possibility of bond formation and molecular growth upon ionization of van der Waals clusters of pure HCN clusters, and mixed clusters of HCN and HCCH, both of which are widespread in the interstellar medium. Ionization of van der Waals clusters can potentially lead to growth in low temperature and low-density environments. Our results show, that upon ionization of the pure HCN clusters, strongly bound stable structures are formed that contain N∙∙∙H bonds, and growth beyond pairwise HCN molecules is seen only in a small percentage of cases. In contrast, mixed clusters, where HCCH is preferentially ionized over HCN, can grow up to 3 or 4 units long with new carbon–carbon and carbon–nitrogen covalent bonds. Moreover, cyclic molecules formed, such as the radical cation of pyridine, which is a prebiotic molecule. The results presented here are significant as they provide a feasible pathway for molecular growth of small organic molecules containing both carbon and nitrogen in cold and relatively denser environments such as in dense molecular clouds but closer to the photo-dissociation regions, and protoplanetary disks. In the mechanism we propose, first, a neutral van der Waals cluster is formed. Once the cluster is formed it can undergo photoionization which leads to chemical reactivity without any reaction barrier.

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

CO 2 hydrogenation over rhodium cluster catalyst nucleated within a manganese oxide framework

Rhodium-based manganese oxide frameworks were explored as a prototype for carbon dioxide reactive capture and conversion. Three-dimensional frameworks of MnOx were utilized as support structures to isolate Rh metal centers. V, Na, and Zn were introduced as counterions to stabilize the structure and for their beneficial effect as promoters. Here, with this multicomponent catalyst, Rh active centers with MnOxs and varied counterions, we were able to selectively tune the catalytic performance of the material via the choice of counterion and structure of the host material. With cryptomelane-type tunnel manganese oxides octahedral molecular sieve (OMS2), we found that Rh-V-OMS2 was highly stable even after 48 hours on stream with a reaction rate of around 1.5x10 -4 mol CO 2 /g Rh /s, surpassing the net reactivity of other initially more active combinations. Furthermore, during CO 2 hydrogenation, in situ XAFS showed that single Rh atoms nucleated into nanoparticles/ sub-nanometer clusters with a coordination number of 5.5 or less. Our finding of the correlation between the reaction rate and particle size offers the potential for enhanced control over the reaction rate by tuning particle size. Our activity study with control experiments demonstrates that the activities of the catalysts are proved due to the unique metal support interaction offered by the Rh-X-MnO.

10 SYNTHETIC FUELS↗
DOE OSTI2026

Isolated and H 2 -reduced Anderson clusters catalyse low-temperature hydrogenation of CO 2 to methanol

CO 2 hydrogenation, especially to methanol, is crucial to establishing sustainable closed-loop systems for carbon utilization. However, the difficulties of CO 2 activation at low temperatures and the ambiguity of structure–activity correlations are obstacles to reducing the energy consumption of the hydrogenation process. Here we report that molecularly defined Anderson PtMo 6 O 24 clusters, sited within a robust metal–organic framework, are catalytic for low-temperature CO 2 hydrogenation. The performance of the cluster showed no signs of decay in either its activity or methanol selectivity over 3,600 h at 180 °C. It also achieves a per-pass yield exceeding that of state-of-the-art heterogeneous catalysts under similar conditions. Combined in situ spectroscopy and density functional theory calculations demonstrated that CH 3 OH formation is dominated by the reverse water–gas shift and subsequent CO* hydrogenation pathway, while the HCOO* pathway may serve as a supplementary route. The well-defined cluster structure offers an ideal model for elucidating structure–activity correlations and opens exciting avenues for the rational design of high-activity, low-temperature catalysts for CO 2 hydrogenation.

heterogeneous catalysis↗