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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 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Computer Science Research Needs for Parallel Discrete Event Simulation (PDES)

Historically, scientific computing efforts have demonstrated the clear need for, and effective use of, supercomputing with traditional time-stepped simulations. Nevertheless, there are several areas in the mission spaces of the U.S. Department of Energy and other agencies waiting to tap advanced computing research using a different, discrete event style of modeling, simulation, and analysis. These span a wide spectrum of applications including energy grid resilience, urban planning and policy, transportation science, building technologies, emergency response and planning, environmental impact analysis, computational epidemiology, Internet communications, cyber security, and cyber-physical systems, to name only a few. Even within traditional scientific applications, the role of discrete event modes of execution is increasing in the form of new event-based mathematical solvers such as quantized state integration methods and discrete-continuous hybrid system solvers. Co-design of advanced supercomputing hardware systems is another area that exploits discrete event simulation at its core for effective analyses. Complex systems, entity behaviors and interconnections play a significant role in all these applications, which are mapped to large-scale models with discrete event formulations. To make advancements in all the aforementioned scientific areas, many technical aspects need to be more thoroughly studied and deeply understood in parallel discrete event simulation (PDES). The unique dynamics inherent in a discrete event modeling approach, by their very nature, intersect and influence the entire stack of the computing system, including (a) the unique nature of the instruction sets exercised in PDES workloads without a predominance of high-precision floating point operations, (b) virtual time-constrained multi-threaded execution of many logical processes per processor, (c) extremely variable and difficult to predict network traffic characteristics, (d) interfaces and inter-dependencies with machine learning and artificial intelligence codes at higher software layers, and (e) highly challenging load balancing needs, especially in effectively accounting for accelerated/extremely heterogeneous computing in current and future high-performance computing systems. Efficient and accurate parallel execution of PDES workloads is also dominated by challenges in dealing with their asynchronous concurrency fundamentally present at the model level. Conservative synchronization, optimistic/speculative synchronization, and their hybrid schemes open new questions in fundamental computer science with respect to reversibility of computation and prediction (lookahead) of behaviors inherent within model codes. On the implementation front, there are relatively few scalable, general-purpose parallel discrete event simulators in the world, and even fewer have been studied on emerging hardware platforms. To enable scientific advances using PDES, the research needs in computer science must also be pursued and met in the intersection of the algorithmic and hardware-aware aspects of scalable PDES engines. This report is aimed at capturing a computer science-oriented view of this important area of research in PDES, presenting a sample of important applications with their inherent discrete event technology elements. Needs are outlined in core areas of parallel discrete event research as well as cross-cutting directions in computer science research that positively impact scientific advancements across several important application areas. A selection of priority research opportunities in advanced computing for PDES is identified to serve as reference for key research topics and their order of importance for scientific advancements.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2024

Characterize and control the multi-range structure of solution-phase systems with resonant x-ray scattering

This work aims at demonstrating the feasibility and impact of Anomalous X-ray Scattering (AXS) in characterizing the multi-range structures of solution-state systems. We will show preliminary investigation of long-range correlations in concentrated aqueous electrolytes with a combination of AXS and molecular dynamics (MD) simulations. We will also start exploring the capability of AXS to capture intra- and inter-molecular structure of dilute molecular systems, and specifically its sensitivity to the chemical environment surrounding active metal sites. We anticipate that the development of this method will help us to understand ion solvation and transport, which affect the performances of, for instance, electrocatalytic cells, as well as to identify/control the intrinsic structural factors that lead to selectivity, efficiency, and stability control during catalysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Importance of Site Diversity and Connectivity in Electrochemical CO Reduction on Cu

Electrochemical CO 2 reduction on Cu is a promising approach to produce value-added chemicals using renewable feedstocks, yet various Cu preparations have led to differences in activity and selectivity toward single and multicarbon products. Here, we find, surprisingly, that the effective catalytic activity toward ethylene improves when there is a larger fraction of less active sites acting as reservoirs of *CO on the surface of Cu nanoparticle electrocatalysts. In an adaptation of chemical transient kinetics to electrocatalysis, we measure the dynamic response of a gas diffusion electrode (GDE) cell when the feed gas is abruptly switched between Ar (inert) and CO. When switching from Ar to CO, CO reduction (COR) begins promptly, but when switching from CO to Ar, COR can be maintained for several seconds (delay time) despite the absence of the CO reactant in the gas phase. A three-site microkinetic model captures the observed dynamic behavior and shows that Cu catalysts exhibiting delay times have a less active *CO reservoir that exhibits fast diffusion to active sites. The observed delay times and the estimated *CO reservoir sizes are affected by catalyst preparation, applied potential, and microenvironment (electrolyte cation identity, electrolyte pH, and CO partial pressure). Notably, we estimate that the *CO reservoir surface coverage can be as high as 88 ± 7% on oxide-derived Cu (OD-Cu) at high overpotentials (–1.52 V vs SHE) and this increases in reservoir coverage coincide with increased turnover frequencies to ethylene. We also estimate that *CO can travel substantial distances (up to 10s of nm) prior to desorption or reaction. It appears that active C–C coupling sites by themselves do not control selectivity to C 2+ products in electrochemical COR; the supply of CO to those sites is also a crucial factor. More generally, the overall activity of Cu electrocatalysts cannot be approximated from linear combinations of individual site activities. Future designs must consider the diversity of the catalyst network and account for intersite transportation pathways.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2026

Data for Genetic Variation in Zea mays Influences Microbial Nitrification and DeNitrification in Conventional Agroecosystems

Nitrogenous fertilizers provide a short-lived benefit to crops in agroecosystems, but stimulate nitrification and denitrification, processes that result in nitrate pollution, N2O production, and reduced soil fertility. Recent advances in plant microbiome science suggest that genetic variation in plants can modulate the composition and activity of rhizosphere N-cycling microorganisms. Here we attempted to determine whether genetic variation exists in Zea mays for the ability to influence the rhizosphere nitrifier and denitrifier microbiome under “real-world” conventional agricultural conditions. To capture an extensive amount of genetic diversity within maize we grew and sampled the rhizosphere microbiome of a diversity panel of germplasm that included ex-PVP inbreds ( Z. mays ssp. mays ), ex-PVP hybrids ( Z. mays ssp. may s), and teosinte ( Z. mays ssp. mexicana and Z. mays ssp. parviglumis ). From these samples, we characterized the microbiome, a suite of microbial genes involved in nitrification and denitrification and carried out N-cycling potential assays. Here we are showing that populations/genotypes of a single species can vary in their ecological interaction with denitrifers and nitrifers. Some hybrid and teosinte genotypes supported microbial communities with lower potential nitrification and potential denitrification activity in the rhizosphere, while inbred genotypes stimulated/did not inhibit these N-cycling activities. These potential differences translated to functional differences in N2O fluxes, with teosinte plots producing less GHG than maize plots. Taken together, these results suggest that Zea genetic variation can lead to changes in N-cycling processes that result in N leaching and N2O production, and thereby are selectable targets for crop improvement. Understanding the underlying genetic variation contributing to belowground microbiome N-cycling into our conventional agricultural system could be useful for sustainability.

Nitrogen↗
DOE OSTI2020

In Situ Chemical Monitoring and Imaging of Contents within Microfluidic Devices Having a Porous Membrane Wall Using Liquid Microjunction Surface Sampling Probe Mass Spectrometry

The ability to observe dynamic chemical processes (e.g., signaling, transport, etc.) in vivo or in situ using nondestructive chemical imaging opens a new door to understanding the complex dynamics of developing biological systems. With the advent of “biology-on-a-chip” devices has come the ability to monitor dynamic chemical processes in a controlled environment, using these engineered habitats to capture key features of natural systems while allowing visual observation of system development. Having the capability to spatially and temporally map the chemical signals within these devices may yield new insights into the forces that drive biosystem development. Here, a porous membrane sealed microfluidic device was designed to allow normal microfluidic operation while enabling continuous, location specific sampling and chemical characterization by liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS). LMJ-SSP was used to extract fluids with nL-to-μL/min flow rates directly from selected areas of the microfluidic device without negatively impacting the device function. These extracts were subsequently characterized using MS. This technique was used to acquire MS images of the entirety of several multi-input microfluidic devices having different degrees of fluid mixing. LMJ-SSP MS imaging visualized the spatial distribution of chemical components within the microfluidic channels and could visualize chemical reactions occurring in the device. These microfluidic devices with a porous membrane wall are wholly compatible with the construction of biology-on-a-chip devices. This ultimately would enable correlation of biosystem physical structure with an evolving chemical environment

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Continuous precipitation‐filtration process for initial capture of a monoclonal antibody product using a four‐stage countercurrent hollow fiber membrane washing step

The significant increase in product titers, coupled with the growing focus on continuous bioprocessing, has renewed interest in using precipitation as a low‐cost alternative to Protein A chromatography for the primary capture of monoclonal antibody (mAb) products. In this work, a commercially relevant mAb was purified from clarified cell culture fluid using a tubular flow precipitation reactor with dewatering and washing provided by tangential flow microfiltration. The particle morphology was evaluated using an inline high‐resolution optical probe, providing quantitative data on the particle size distribution throughout the precipitation process. Data were obtained in both a lab‐built 2‐stage countercurrent washing system and a commercial countercurrent contacting skid that provided 4 stages of continuous washing. The processes were operated continuously for 2 h with overall mAb yield of 92 ± 3% and DNA removal of nearly 3 logs in the 4‐stage system. The high DNA clearance was achieved by selective redissolution of the mAb using a low pH acetate buffer. Host cell protein clearance was 0.59 ± 0.08 logs, comparable to that based on model predictions. The process mass intensity was slightly better than typical Protein A processes and could be significantly improved by preconcentration of the antibody feed material.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Evaluating offshore legacy wells for geologic carbon storage: A case study from the Galveston and Brazos areas in the Gulf of Mexico

In this article, federal offshore waters in the Gulf of Mexico are of interest for large-scale geologic carbon storage (GCS). However, more than 80,000 offshore oil and gas wells exist in the region, which could impact the integrity of sealing intervals. In this study, we propose a screening methodology for ranking offshore legacy wells based on the challenge they may present to GCS. The methodology relies on the review of well regulatory records to 1) identify leakage pathways and assess the potential hazards that wells pose to planned GCS operations, 2) evaluate well features that impact the accessibility of wells to determine the feasibility of potential corrective actions, and 3) rank wells based on the overall challenge they may pose for GCS. We demonstrate our framework by evaluating the construction and abandonment of 156 wells across eight areas of interest (AOIs) in shallow federal waters along the Texas Gulf Coast. The majority (99.3 %) of wells considered were constructed and plugged in a manner that did not isolate prospective GCS targets in the Upper and Lower Miocene formations and may potentially require a challenging or uncertain corrective action prior to GCS. Dataset trends suggest that the observed well construction and plugging designs may be common in shallow offshore federal waters along the Texas Gulf Coast. Consequently, operators pursuing offshore GCS projects in the region may consider selecting areas that avoid challenging wells or performing robust evaluations of legacy well leakage risks to plan corrective action prior to CO 2 injection.

58 GEOSCIENCES↗
DOE OSTI2026

Carbon dioxide pipeline network transportation cost model: evaluating economic and geographic factors for efficient carbon capture, storage, and utilization

This study presents a comprehensive pipeline network modeling framework to estimate the CO 2 delivery cost for CO 2 utilization and geologic CO 2 storage across the United States. We developed a Python-based CO 2 pipeline transportation cost model leveraging Argonne National Laboratory’s pipeline engineering expertise and detailed natural gas transmission pipeline cost data across U.S. regions. Using existing road corridors as practical routing guides, the model designs pipeline networks that aggregate CO 2 from one or multiple sources and deliver it to selected destinations. It then minimizes the total transportation cost by optimizing pipeline diameters and incorporating booster pumps. A key contribution is the incorporation of up-to-date, region-specific cost factors with itemized components for materials, labor, miscellaneous construction expenses, and right-of-way acquisition. Results emphasize that regional variation and economies of scale associated with CO 2 pipeline costs are significant and should be explicitly accounted for in screening and planning studies. By combining realistic routing constraints with regionalized cost inputs, the model provides transparent design methodology and location-specific insights into source–destination delivery costs, including the effects of routing complexity along existing road networks. We demonstrate the model with two illustrative case studies – one for CO 2 storage and one for CO 2 utilization – in which the model designs pipeline networks spanning hundreds of miles across the states, collecting CO 2 from multiple sources and delivering it to designated endpoints while minimizing levelized cost of delivery via diameter and compression optimization. The model offers a practical, scalable approach for alternative design option screening and early-stage CO 2 transportation planning.

CCS↗
DOE OSTI2025

Optimizing CO 2 -Loaded Aqueous Amine Solutions for Higher Electrocatalytic CO 2 Reduction Activity

The activity of aqueous-based carbon dioxide reduction (CO 2 R) reactions is often limited by the solubility of CO 2 . The addition of amines can increase the total dissolved carbon in water through the formation of bicarbonate and carbamate species, which has been used to a great effect to capture CO 2 from dilute streams. Here, in this study, we explore the effect of 12 primary and secondary amines of varying Brønsted basicity, steric profile, and hydrogen-bonding capabilities on the aqueous CO 2 R to CO activity of a molecular Ni(cyclam)Cl 2 catalyst with a Hg electrode. Addition of some of the amines results in greater activity and selectivity for CO production compared to equivalent aqueous solutions without added amines. Under optimal conditions (0.4 M 3-amino-propionitrile), there is an over sevenfold increase in partial current density and greater selectivity for CO compared to equivalent conditions with no amine. Interestingly, the increase in activity did not correlate to any single property across the 12 amines. To elucidate the effect of the amine additives on catalysis, we used vapor–liquid equilibrium modeling (VLE), 13 C NMR spectroscopy, and computational analysis to determine the carbon speciation of the solutions. These results indicate that for amines without ethylalcohol functionalities, CO 2 R activity correlates with carbamate concentration, which is in turn governed by amine basicity and steric effects. However, this correlation does not persist for amines with ethylalcohol functionalities, which can form more stable carbamates through intramolecular-hydrogen bonding. These studies demonstrate that amine additives can enhance aqueous CO 2 R activity and selectivity and describe amine properties that lead to these higher performance metrics.

Amines↗
DOE OSTI2026

A dual membrane-adsorption evaporator for solar-powered lithium extraction from complex brines

A reliable supply of lithium is required to meet the increased demand for batteries over the coming decades. In this work, we demonstrated the potential to effectively extract lithium from brines by coupling solar-powered evaporation, adsorption, and membrane technologies together. We first synthesized a three-dimensional adsorptive evaporator by coating a lithium manganese oxide material onto a cotton stick using an easily scalable, one-step method. An osmotic membrane was then installed at the root of the evaporator to enhance the lithium to magnesium selectivity, prevent scaling caused by divalent cations, and thus further increase the water evaporation flux. The operation of the dual membrane-adsorption evaporator is entirely driven by osmosis and capillary force, demanding no extra energy input. The integration of the osmotic membrane was found to increase the lithium to magnesium selectivity over 10-fold to higher than 40. The dual process also produced high lithium to calcium selectivity and proved to sustain long-term stability by self-managing its internal osmotic pressure. Last, a test was done in three simulated brine solutions with varied brine chemistry and the evaporation rate stayed high and consistent throughout the long-term test. This illustrates that this technology can be used in varied brine solutions throughout the world providing efficient lithium capture and separation from competing divalent cations.

Eskafi, Aydin F. [University of California, Berkel↗
DOE OSTI2022

Capturing Ultrafast Electron Driven Chemical Reactions in Molecules

The goals of this project are to develop experimental tools to investigate the dynamics of dissociative electron attachment (DEA) reactions in real time. In a DEA reaction, the attachment of a low energy electron to a molecule results in bond breaking and the fragmentation of the molecule. A new instrument has been designed and is under construction to perform time-resolved photoelectron and photo-fragment spectroscopy following electron transfer from an iodide anion to a molecule within a mass-selected molecular dimer. Iodide binds only weakly through the dipole interaction with many polar molecules, and such molecules forming a dimer with iodide undergo only small changes from the equilibrium geometry in isolation. When the electron is transferred from the iodide, the iodine atom is no longer bound, so the electron transfer step can be considered analogous to electron attachment and brings the key advantage of ultrafast timing precision. The experiments proposed here will establish the experimental tools to interrogate the dynamics of dissociative electron attachment on the fundamental timescales of the nuclear motion, by simultaneously probing the valence electronic structure and the fragmentation pathways.

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

Hydrogen Leak Modeling for Development of Smart Distributed Monitoring Under Unintended Releases

Hydrogen is a versatile and clean energy carrier that can be produced from various renewable sources such as wind, solar, and hydropower. Hydrogen has the potential to play a crucial role in decarbonizing industrial processes that are currently reliant on fossil fuels and provide long-duration and/or seasonal energy storage to enable electricity decarbonization. Hydrogen can also be used as a fuel for fuel cell vehicles, providing a zero-emission alternative to traditional internal combustion engines. DOE launched the Hydrogen Energy Earthshot (Hydrogen Shot) in June 2021 to reduce the cost of clean hydrogen by 80% to $1 per 1 kilogram in 1 decade ("1 1 1"). While promising, Hydrogen is highly-flammable, and in the presence of oxygen, it can form explosive mixtures. . Therefore, understanding leak scenarios is essential to evaluate and mitigate the safety risks associated with potential hydrogen leaks. An increased understanding of leak behavior, and having tools to model leaks, can help assess how hydrogen would disperse in different environments, influencing emergency response plans and safety measures, and identify potential issues with materials and design systems that can withstand the challenges posed by hydrogen. Recently, researchers have attempted to study hydrogen leaks for development of risk management strategies. However, the focus has been on closed or semi-closed spaces like storage rooms, vehicles, garages, and fueling stations - all promising locations for future hydrogen infrastructure. In this presentation, the modeling environment extends the span of research further by modeling hydrogen leak in an outdoor, open space. We will present the key challenges with modeling hydrogen leaks in an uncontrollable environment, how they were handled, and how modeling results informed sensor selection and placement. A Hydrogen research facility at the National Renewable Energy Laboratory (NREL) was used as a case study to model hydrogen leaks. In the future, Hydrogen wide area detection methodologies will be developed and tested at this site to monitor for unintended and operational hydrogen releases. The data generated from modeling will be used to develop a predictive model to detect hydrogen leak location based on concentration measured by sensors in this open space. Furthermore, the facility was also chosen because controlled hydrogen releases can be performed. A computational fluid dynamics (CFD) based modeling approach was taken to model hydrogen leak. The full-scale hydrogen facility was modeled with a large ambient domain. The electrolyzer at the facility can produce a controlled release rate of 27 kg-H2/hr. Site-specific atmospheric and weather condition data such as wind direction, wind speed at various altitudes, and temperature were used as inputs to the model. To capture the variability of weather conditions, a subset of the weather conditions experienced during daytime hours without precipitation over the course of three months was generated; using established data clustering techniques, a total of 100 condition sets were chosen. The results show statistical distributions and ranges of hydrogen concentrations at locations throughout the domain. These distributions are compared to experimental data from a constant mass flow, controlled hydrogen release at the facility. The stochastic wind conditions of the release make direct validation difficult, therefore, statistical comparison approaches were used. Wind conditions are found to significantly impact the release behavior, including direction and concentration. Sensor selection and placement is proposed for the facility and is now based on release behavior predicted for the facility given its weather patterns; this is much more informed than without the modeling results. The methodology and analysis procedure can be translated to other facilities using modified geometries and site-specific weather conditions. Hydrogen holds great promise as a renewable energy fuel, but ensuring safety in its production, storage, and use is paramount. Studying potential leak scenarios in an open space will help develop sensors to detect hydrogen on a large spectrum of concentration and eventually build a smart distributed monitoring system.

CFD↗
DOE OSTI2025

Multiplicity-dependent jet modification from di-hadron correlations in pp collisions at $ \sqrt{s} $ = 13 TeV

Short-range correlations between charged particles are studied via two-particle angular correlations in pp collisions at $\sqrt{s}$ = 13 TeV. The correlation functions are measured as a function of the relative azimuthal angle ∆φ and the pseudorapidity separation ∆η for pairs of primary charged particles within the pseudorapidity interval |η| < 0.9 and the transverse-momentum range 1 < p T < 8 GeV/c. Near-side (|∆φ| < 1.3) peak widths are extracted from a generalised Gaussian fitted over the correlations in full pseudorapidity separation (|∆η| < 1.8), while the per-trigger associated near-side yields are extracted for the short-range correlations (|∆η| < 1.3). Both are evaluated as a function of charged-particle multiplicity obtained by two different event activity estimators. The width of the near-side peak decreases with increasing multiplicity, and this trend is reproduced qualitatively by the Monte Carlo event generators PYTHIA 8, AMPT, and EPOS. However, the models overestimate the width in the low transverse-momentum region (p T < 3 GeV/c). The per-trigger associated near-side yield increases with increasing multiplicity. Although this trend is also captured qualitatively by the considered event generators, the yield is mostly overestimated by the models in the considered kinematic range. The measurement of the shape and yield of the short-range correlation peak can help us understand the interplay between jet fragmentation and event activity, quantify the narrowing trend of the near-side peak as a function of transverse momentum and multiplicity selections in pp collisions, and search for final-state jet modification in small collision systems.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Electrochemical chlor-iron process for iron production from iron oxide and salt water

The iron and steel industry accounts for ~8% of global greenhouse gas emissions. Electrochemical reduction of iron ore to metal for electric arc furnaces can enable sustainable steel production, but existing electrochemical processes require expensive capital or electrolytes. Here we report a low-temperature, electrochemical cell that consumes low-cost and abundant iron oxide and aqueous sodium chloride, while co-producing sodium hydroxide and chlorine. Industrially relevant current densities and Faradaic efficiencies for iron production were demonstrated, with 94% selectivity to iron metal at an applied current density of 200 mA cm –2 . Freestanding films of phase-pure iron were formed after 4h of continuous, stable electrolysis. The process can lead to levelized costs of iron that are competitive with iron produced in fossil-fuel-powered blast furnaces, and the co-produced sodium hydroxide can be used for CO 2 capture from the air or ocean, creating a net-negative-emission process.

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

Coherent anti-Stokes Raman scattering with squeezed light: CARS for quantum-enhanced spectroscopy and imaging

We theoretically investigate quantum-enhanced coherent anti-Stokes Raman scattering (CARS) using squeezed light to amplify vibrational transition rates at low photon flux. Quantum sensing approaches are needed for nondestructive nanometrology such as in bioimaging where reduced photodamage is desired while retaining resolution and sensitivity. We analyze both single-mode squeezing applied to the pump field and two-mode squeezing between the pump and Stokes fields. We also show that the ordering of displacement and squeezing operations—whether displacement precedes squeezing or squeezing precedes displacement—has an impact on the resulting CARS transition amplitudes due to a difference in the photon number and the quantum-enhancement coefficients, with the latter offering a stronger enhancement in the case of two modes squeezing of the pump and Stokes under experimentally accessible conditions. Furthermore, our calculations capture these quantum enhancements through the intrinsic photon-number correlations of squeezed light, eliminating the need for interferometric detection or higher pump powers that are otherwise required to reach comparable sensitivities in classical CARS. Finally, we outline a quantum plasmonic extension of our model in which local field enhancements caused by surface plasmon excitation in metallic nanoparticles can be incorporated via mode-selective field amplification factors, offering a pathway toward combining squeezed-light quantum optics with surface-enhanced nanoscale spectroscopy and imaging.

Atomic & molecular structure↗
DOE OSTI2024

NORTH DAKOTA CARBONSAFE PHASE III: SITE CHARACTERIZATION AND PERMITTING OF GEOLOGIC STORAGE OF CARBON DIOXIDE

The Energy & Environmental Research Center (EERC), in partnership with Minnkota Power Cooperative Inc. (Minnkota), SLB, and Computer Modelling Group Ltd. (CMG), supported wide-scale deployment of carbon capture and storage (CCS) as part of the U.S. Department of Energy (DOE) National Energy Technology Laboratory Carbon Storage Assurance Facility Enterprise (CarbonSAFE) Initiative Phase III. This phase included the acquisition, analysis, and development of information to fully characterize two storage complexes to demonstrate viable storage resources for commercial volumes of CO2 (defined by DOE as a minimum of 50 million tonnes [MMt] of CO2 within a 30-year period) (National Energy Technology Laboratory, 2024). Phase III also involved the preparation, submission, and approval of North Dakota underground injection control (UIC) Class VI storage facility permits (SFPs)—required precursors to applications for Class VI injection well permits. The presumed viability of commercial-scale CCS, situated adjacent to Minnkota’s Milton R. Young Station (MRYS), is validated by Minnkota’s continued pursuit of Project Tundra—an initiative to build the world’s largest lignite-based CCS project in central North Dakota (www.projecttundrand.com). Project Tundra comprises two scopes of work, Tundra Capture (installation of postcombustion CO2 capture at MRYS) and Tundra SGS (secure geologic storage). The efforts of North Dakota CarbonSAFE Phase III, Site Characterization and Permitting, supported Tundra SGS. Extensive site-specific characterization activities included a successful multimeasurement geophysical approach and drilling a stratigraphic test well (J-ROC 1, subsequently renamed Liberty-1) adjacent to MRYS. Core collection and analyses, downhole testing and fluid sampling, and geophysical logging were performed on J-ROC 1 and on a nearby stratigraphic test well (known as J-LOC 1), which was drilled, cored, and tested under a complementary project funded by the North Dakota Lignite Research Program. The injection tests performed on J-LOC 1 positively impacted the CarbonSAFE project, resulting in fewer proposed injection wells and significant construction, operations, and monitoring cost savings. The characterization data collected and analyses performed were integrated into geologic models, and successive numerical simulations were run to determine CO2 plume extent and subsurface pressure buildup associated with the planned CO2 injection rate of nearly 4 MMt per year. The latter doubles the CarbonSAFE Initiative goal with an estimated 100 MMt of CO2 stored in 20 years. Application of the U.S. Environmental Protection Agency’s (EPA’s) method for estimating the Class VI Rule area of review (AOR) to the overpressurized Broom Creek Formation inspired an alternative method of calculation, called risk-based AOR delineation. This peer-reviewed method was applied for the first time during the storage facility-permitting process. The two SFP applications submitted in 2021 successfully resulted in North Dakota Industrial Commission (NDIC) orders in 2022 authorizing the creation of the storage facility areas and amalgamation of pore space as well as establishing financial responsibility requirements. After approval of the SFPs, Minnkota filed in 2022 applications for permits to reenter the J-ROC 1 well and to drill two new wells—all with the intended purpose to become Class VI injection wells. To establish eligibility under the Internal Revenue Code for Section 45Q tax incentives, a monitoring, reporting, and verification (MRV) plan was prepared and submitted by Minnkota to EPA in 2022, resulting in the first such plan approved in North Dakota. Also in 2022, under the National Environmental Policy Act (NEPA), Minnkota prepared and submitted an environmental information volume (EIV) describing the proposed CCS project and associated potential environmental impacts. Based on the EIV, DOE determined that the proposed construction project required an environmental assessment, and Minnkota submitted the first draft in 2023 and a revised draft in 2024. Both submissions were followed by a public comment period. Subsequently, DOE issued a finding of no significant impact (FONSI) on September 13, 2024. A successful outreach program, strongly based in the production, presentation, and dissemination of informational material, fostered an environment to aid stakeholders in making informed decisions regarding the planned project. Opportunities for public input were provided at various steps along the way, including at county planning and zoning meetings, before and during the SFP administrative hearing, and during environmental assessment public comment periods. In addition, land/pore space owners and mineral owners had various points of contact, including granting access rights, securing pore space leasing, and mineral owner notifications. Based upon the successful storage facility permitting issued by NDIC, approval of the MRV plan by EPA, and receipt of a FONSI under the NEPA, Minnkota is continuing its pursuit of Project Tundra. In December 2023, the Office of Clean Energy Demonstrations under its Carbon Capture Demonstrations Projects Program announced funding for the capture system (Office of Clean Energy Demonstrations, 2023) and a proposal for CarbonSAFE Phase IV: Construction funding was submitted in March 2024 for the storage project. A go/no-go decision to proceed with construction and operations in the Broom Creek Formation is anticipated in 2024. References National Energy Technology Laboratory, CarbonSafe Initiative, https://netl.doe.gov/carbon-management/carbon-storage/carbonsafe (accessed August 2024). Office of Clean Energy Demonstrations, 2023, OCED selects three projects in CA, ND, and TX to reduce harmful carbon pollution, create new economic opportunities, and advance carbon reducing technologies, December, www.energy.gov/oced/articles/oced-selects-three-projects-ca-nd-and-tx-reduce-harmful-carbon-pollution-create-new (accessed August 2024).

Peck, Wesley↗
DOE OSTI2023

Assessing the Role of Interfacial and Metal Sites in Pt/TiO2-Catalyzed Acetic Acid Hydrodeoxygenation

Thermochemical conversion of biomass to produce drop-in quality biofuels typically involves hydrodeoxygenation (HDO) steps following catalytic fast pyrolysis (CFP) to remove excess oxygen and create a more-stable bio-oil product. HDO reactions are performed by co-feeding the CFP vapor-phase product and H2 gas over a bi-functional catalyst. Noble-metal catalysts supported on reducible metal oxides (e.g., Pt/TiO2) are active and selective toward these HDO reactions. Griffin and co-workers showed that Pt/TiO2 catalysts promote the desired deoxygenation steps for m-cresol HDO while mitigating undesired C-C bond-breaking steps that reduce the overall value/energy density of the biofuel. Such model-compound studies to inform the design of improved catalysts for HDO chemistry are necessary to improve the overall process economics/efficiencies for biofuels production. One important class of bio-derived compounds that has not been studied extensively with respect to HDO chemistry, particularly at the atomic level, is carboxylic acids. Past experimental work indicates that Pt/C and Pt/TiO2 catalysts are selective toward C-C and C-O bond-dissociation products for acetic acid HDO, respectively. To understand the role of Pt/TiO2 active sites in this observed change in selectivity and guide catalyst development, the work in this presentation focuses on modeling the role of Pt-metal and Pt-TiO2-interfacial sites in promoting key C-C bond-breaking, C-O bond-breaking, and (de)hydrogenation steps in acetic acid HDO. Density functional theory (DFT) calculations were performed using the Vienna Ab initio Simulation Package (VASP). The exchange-correlation functional was approximated by the Perdew-Burke-Ernzerhof functional. Dispersion interactions were captured using the D3 method. Projector augmented-wave potentials described electron-ion interactions, and electron wavefunctions were expanded via a planewave basis with an energy cutoff of 500 eV. Activation barriers were calculated using the climbing image nudged elastic band method. Results and Discussion: To discern the role of Pt-metal and Pt-TiO2 interface sites in promoting acetic acid HDO chemistry, Pt(111) slab and anatase TiO2(101)-supported Pt-nanowire (PtNW/OH-TiO2) surface models were constructed, respectively. Because H2 is co-fed in HDO reactions, the anatase support was terminated with OH groups. Interfacial vacancies have been shown to facilitate Ru/TiO2-catalyzed phenol HDO; thus, an interfacial model with an OH vacancy was also considered (PtNW/OHv-TiO2). Pt-TiO2-interface sites stabilize adsorption of all studied acetic acid HDO surface intermediates relative to terrace Pt-metal sites, particularly when an interfacial-OH vacancy is present. Oxygenated species prefer to bind at the OH vacancy through the O atom, suggesting a preference for C-O over C-C bond cleavage at these sites. This hypothesis is supported by net-negative and net-positive average shifts in the reaction energy and activation energy barriers for C-O and C-C bond-breaking steps, respectively, at Pt-TiO2-interface sites relative to Pt-metal sites. Using the calculated energetics, the predicted minimum-energy pathway was determined for each surface. Pt(111) is predicted to follow decarboxylation, producing undesired methane and carbon dioxide. Conversely, PtNW/OH-TiO2 and PtNW/OHv-TiO2 are both predicted to produce desired acetaldehyde and ethane. The interfacial vacancy may also play a key role in facilitating the first C-O bond-breaking step in acetic acid HDO, lowering the barrier by 0.6 eV relative to the defect-free interface model. These results demonstrate the critical role of the Pt-TiO2 interface in the shift in acetic acid HDO selectivity experimentally observed on Pt/C and Pt/TiO2 catalysts. The results herein demonstrate the important role of the Pt-TiO2 interface and interfacial oxygen vacancies in improving the carbon efficiency for HDO reactions in CFP upgrading.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2025

Atomically Fine-Tuning Organic–Inorganic Carbon Molecular Sieve Membranes for Hydrogen Production

Polymeric membranes with great processability are attractive for the H 2 /CO 2 separation required for hydrogen production from renewable biomass with carbon capture for utilization and sequestration. However, it remains elusive to engineer polymer architectures to obtain desired sub-3.3 Å ultramicropores to efficiently sieve H 2 from CO 2 . Herein, we demonstrate a scalable way of carbonizing polybenzimidazole (PBI) at low temperatures, followed by vapor phase infiltration (VPI) to atomically narrow ultramicropores throughout the films, forming hybrid organic–inorganic carbon molecular sieves (CMSs). One VPI cycle (100 s) for the PBI carbonized at 500 °C remarkably increases H 2 /CO 2 selectivity from 9.6 to 83 at 100 °C, surpassing Robeson’s upper bound. The CMS demonstrates a stable H 2 /CO 2 separation performance when challenged with simulated syngas streams and can be fabricated into thin-film composite membranes, outperforming state-of-the-art membranes. Finally, the scalable approach can be ubiquitous to molecularly fine-tune ultramicropores of leading polymeric membranes to further improve their size-sieving ability and thus separation efficiency.

36 MATERIALS SCIENCE↗