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DOE OSTI2025

Vehicle-Cycle Inventory for Type C School Buses & Intra-City Transit Buses

This report documents the new inventory incorporated into the Research and Development version of Greenhouse gases, Regulated Emissions, and Energy use in Technologies (R&D GREET) 2025 model for the vehicle cycle of Type C school buses and intracity transit buses. The transportation sector contributes significantly to the United States’ energy consumption and resultant emissions (EPA, 2025a). However, public transit plays an important role in mitigating these impacts because it consumes a relatively low amount of energy per passenger (Congressional Budget Office, 2022). Public transit is widely used in the United States; more than 500,000 school buses (EPA, 2025b) and ~75,000 service buses (American Public Transportation Association, 2025) operate in the nation. These are primarily internal combustion engine vehicles (ICEVs) powered by diesel. Original equipment manufacturers (OEMs) are making efforts to electrify U.S. bus fleets by using batteries as a propulsion system to replace internal combustion engines. Electrification can reduce tailpipe emissions, such as particulate matter (with a diameter ≤10 µm [PM 10 ] and with a diameter ≤2.5 µm [PM 2.5 ]) and nitrogen oxides (Jonas et al., 2025; Martinez and Samaras, 2024; EPA, 2025b; Wayne et al., 2009). Hence, any energy and emission impact analysis of public transit must consider both conventional ICEVs and upcoming electric vehicle (EV) options for the school and transit buses that dominate this landscape. To understand the detailed environmental impact profiles of ICEV and EV school and transit buses, it is necessary to conduct a thorough analysis covering both vehicle manufacturing and vehicle use stages. The current literature lacks a detailed vehicle-cycle inventory for school and transit buses, which makes this kind of comparison difficult. To overcome this gap, we developed a comprehensive vehicle-cycle model for school and transit buses in Argonne’s R&D GREET 2025 model. The model is flexible in handling user inputs for key assumptions, such as component weights and material compositions, upstream energy sources for material processing, and vehicle operating parameters, to understand their impacts on energy use and emissions for both school and transit buses. This report is organized as follows: Section 2 provides details on the modeling approach and vehicle specifications (weights and composition of different vehicle components, and vehicle operating parameters) for both school and transit buses. Section 3 provides details on vehicle assembly, disposal, and recycling (ADR) approaches for the two buses. Section 4 includes details about their incorporation into the R&D GREET model.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2024

HarDWR - Harmonized Water Rights Records

For a detailed description of the database of which this record is only one part, please see the HarDWR meta-record. Here we present a new dataset of western U.S. water rights records. This dataset provides consistent unique identifiers for each spatial unit of water management across the domain, unique identifiers for each water right record, and a consistent categorization scheme that puts each water right record into one of 7 broad use categories. These data were instrumental in conducting a study of the multi-sector dynamics of intersectoral water allocation changes through water markets (Grogan et al., in review). Specifically, the data were formatted for use as input to a process-based hydrologic model, WBM, with a water rights module (Grogan et al., in review). While this specific study motivated the development of the database presented here, U.S. west water management is a rich area of study (e.g., Anderson and Woosly, 2005; Tidwell, 2014; Null and Prudencio, 2016; Carney et al, 2021) so releasing this database publicly with documentation and usage notes will enable other researchers to do further work on water management in the U.S. west. The raw downloaded data for each state is described in Lisk et al. (in review), as well as here. The dataset is a series of various files organized by state sub-directories. The first two characters of each file name is the abbreviation for the state the in which the file contains data for. After the abbreviation is the text which describes the contents of the file. Here is each file type described in detail: XXFullHarmonizedRights.csv: A file of the combined groundwater and surface water records for each state. Essentially, this file is the merging of XXGroundwaterHarmonizedRights.csv and XXSurfaceWaterHarmonizedRights.csv by state. The column headers for each of this type of file are: state - The name of the state the data comes from. FIPS - The two-digit numeric state ID code. waterRightID - The unique identifying ID of the water right, the same identifier as its state uses. priorityDate - The priority date associated with the right. origWaterUse - The original stated water use(s) from the state. waterUse - The water use category under the unified use categories established here. source - Whether the right is for surface water or groundwater. basinNum - The alpha-numeric identifier of the WMA the record belongs to. CFS - The maximum flow of the allocation in cubic feet per second (ft3s-1). Arizona is unique among the states, as its surface and groundwater resources are managed with two different sets of boundaries. So, for Arizona, the basinNum column is missing and instead there are two columns: surBasinNum - The alpha-numeric identifier of the surface water WMA the record belongs to. grdBasinNum - The alpha-numeric identifier of the groundwater WMA the record belongs to. XXStatePOD.shp: A shapefile which identifies the location of the Points of Diversion for the state's water rights. It should be noted that not all water right records in XXFullHarmonizedRights.csv have coordinates, and therefore may be missing from this file. XXStatePOU.shp: A shapefile which contains the area(s) in which each water right is claimed to be used. Currently, only Idaho and Washington provided valid data to include within this file. XXGroundwaterHarmonizedRights.csv: A file which contains only harmonized groundwater rights collected from each state. See XXFullHarmonizedRights.csv for more details on how the data is formatted. XXSurfaceWaterHarmonizedRights.csv: A file which contains only harmonized surface water rights collected from each state. See XXFullHarmonizedRights.csv for more details on how the data is formatted. Additionally, one file, stateWMALabels.csv, is not stored within a sub-directory. While we have referred to the spatial boundaries that each state uses to manage its water resources as WMAs, this term is not shared across all states. This file lists the proper name for each boundary set, by state. For those whom may be interested in exploring our code more in depth, we are also making available an internal data file for convenience. The file is in .RData format and contains everything described above as well as some minor additional objects used within the code calculating the cumulative curves. For completeness, here is a detailed description of the various objects which can be found within the .RData file: states: A character vector containing the state names for those states in which data was collected for. More importantly, the index of the state name is also the index in which that state's data can be found in the various following list objects. For example, if California is the third index in this object, the data for California will also be in the third index for each accompanying list. rightsByState_ground: A list of data frames with the cleaned ground water rights collected from each state. This object holds the the data that is exported to created the xxGroundwaterHarmonizedRights.csv files. rightsByState_surface: A list of data frames with the cleaned surface water rights collected from each state. This object holds the the data that is exported to created the xxSurfaceWaterHarmonizedRights.csv files. fullRightsRecs: A list of the combined groundwater and surface water records for each state. This object holds the the data that is exported to created the xxFullHarmonizedRights.csv files. projProj: The spatial projection used for map creation in the beginning of the project. Specifically, the World Geodetic System (WGS84) as a coordinate reference system (CRS) string in PROJ.4 format. wmaStateLabel: The name and/or abbreviation for what each state legally calls their WMAs. h2oUseByState: A list of spatial polygon data frames which contain the area(s) in which each water right is claimed to be used. It should be noted that not all water right records have a listed area(s) of use in this object. Currently, only Idaho and Washington provided valid data to be included in this object. h2oDivByState: A list of spatial points data frames which identifies the location of the Point of Diversion for the state's water rights. It should be noted that not all water right records have a listed Point of Diversion in this object. spatialWMAByState: A list of spatial polygon data frames which contain the spatial WMA boundaries for each state. The only data contained within the table are identifiers for each polygon. It is worth reiterating that Arizona is the only state in which the surface and groundwater WMA boundaries are not the same. wmaIDByState: A list which contains the unique ID values of the WMAs for each state. plottingDim: A character vector used to inform mapping functions for internal map making. Each state is classified as either "tall" or "wide", to maximize space on a typical 8x11 page. The code related to the creation of this dataset can be viewed within HarDWR GitHub Repository/dataHarmonization.

Economics↗
DOE OSTI2021

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Dynamic Linking of Upstream Energy and Freight Demands for Bio and Fossil Energy Pathways in the Global Change Analysis Model

Comprehensive study of the environmental impacts associated with demand for an energy resource or carrier in any one sector requires a full consideration of the direct and indirect impacts on the rest of the regional and global energy system. It is important to consider the energy that is consumed in producing primary energy resources and energy consumed in transporting these energy resources internationally and domestically in order to produce a complete picture of these impacts. Biofuels are especially complex since they have feedbacks not just to the energy system but also to regional and global crop markets. Different modeling and analysis strategies have been applied to consider these impacts, which occur “upstream” of final energy consumption, with some success. Traditional life cycle models allow for rich technological detail in linking upstream impacts of energy demand with downstream final consumption; however, they cannot by themselves represent dynamic economic feedbacks across multiple sectors and regions over time. Computable general equilibrium (CGE) modeling does account for economic feedback among all sectors and regions; however, CGE modeling does not lend itself to physical representation of technological detail. Partial equilibrium (PE) modeling is a heterogeneous category describing economic models that focus on a subset of the economy, and they differ in coverage and ease in incorporating more sectors and economic links. In this study, we present a strategy for dynamically including the direct and indirect impacts of energy demand with physical and technology detail by explicitly adding these upstream energy and transportation links to GCAM, a PE model of global energy, land use, and emissions. We incorporate the following inter-sectoral linkages: energy inputs to crop production, energy inputs to fossil resource production, and freight transport requirements of energy and agricultural commodities. We assess the implications of explicitly including these links by measuring the global impacts of increased corn ethanol demand in the United States with and without these links included. Although the net global impact of the upstream links on energy and emissions are relatively modest in the scenarios we studied, the inclusion of these links illustrates interesting trade-offs in energy and transportation demand among fossil fuel and agriculture sectors. These sectoral interactions suggest that this level of modeling detail could be important in evaluating future analytical questions.

Sampedro Martinez de Estivariz, Jon↗
DOE OSTI2024

Reduced-order condensed-phase kinetic models for polyethylene, polypropylene and polystyrene thermochemical recycling

Thermochemical recycling of plastic waste (PW) into chemicals and energy vectors requires coupling particle and reactor-scale simulations to accurate condensed phase pyrolysis mechanisms for each constituent. This work proposes a methodology to derive reduced-order condensed-phase kinetic models from validated semi-detailed kinetic mechanisms. Two types of kinetic models are obtained for polyethylene (PE), polypropylene (PP) and polystyrene (PS): reduced semi-detailed models and multi-step fully lumped ones. These families offer different compromises between accuracy and computational cost. The former employ 50–100 gas + liquid species and describe both the radical degradation and the detailed carbon distribution of the products. Conversely, the latter involves 5–10 species per polymer tracking only the main petroleum cuts. The kinetic mechanisms are complemented by the definition of thermochemical properties of gas, liquid, and solid-phase species, accounting for phase-transitions through pseudo-chemical reactions. Model validations are performed by comparison with experimental data and the original semi-detailed mechanisms in terms of mass loss, heat fluxes and product distribution profiles. The resulting CHEMKIN-like condensed-phase models are attached as Supplementary Material and as a GitHub repository. Extending the proposed approach to other polymers and coupling it with existing subsets in the CRECK kinetic framework (e.g., biomass, PVC, PET) offers a powerful tool to model thermochemical recycling of PW and biomass/PW mixtures.

kinetics↗
DOE OSTI2023

Direct observation of C 3 S particle dissolution using fast nano X-ray computed tomography

Tricalcium silicate (C 3 S) occupies 50 % to 70 % of ordinary portland cement (OPC) by mass and it is an important component affecting the hydration of OPC [1], [2], [3], [4], [5], [6], [7]. Generally, the hydration of C 3 S is described by two processes: the dissolution of C 3 S particles and the precipitation of hydration products. While it is understood that the dissolution rates of C 3 S vary with time, more precise measurements are needed to understand this process. Many mechanisms have been proposed to explain the time-evolving dissolution rates of C 3 S [2]. The metastable barrier hypothesis suggests that a thin metastable layer of hydrates forms around the C 3 S particle surface and prohibits the access of grains to the aqueous solution [8], [9], [10], [11], [12]. The slow dissolution step hypothesis suggests that the increased ion concentration from the initial reaction delays the C 3 S dissolution [2], [13], [14], [15], [16], [17]. More recent publications suggest that C 3 S may react differently depending on the existence of crystallographic defects [18], [19], [20]. Etch pits are thought to open on the particle surface during the initial reaction and this contributes to the C 3 S dissolution [21], [22]. As hydrates precipitate and cover these highly reactive surfaces, hydration slows down and the induction period starts [18], [23], [24], [25], [26]. Many experiments have been conducted to test the aforementioned mechanisms. Some hydration studies utilize bulk measurements, such as isothermal calorimetry [27], [28], [29], pore solution analysis [30], quasi-elastic neutron scattering [31], and nuclear magnetic resonance spectroscopy [32], [33]. One limitation of these measurements is that they do not provide direct and detailed information on the individual C 3 S particles. Some other studies utilize imaging techniques, such as scanning electron microscopy (SEM) [34], [35], [36] and transmission electron microscopy (TEM) [37]. However, SEM/TEM cannot track the evolution of individual particles throughout hydration [34], [35], [38], [39], [40] and they do not give insights into the microstructure of materials before hydration [34], [35], [39]. This makes it challenging to draw strong conclusions from only SEM or TEM observations. Synchrotron X-ray tomography techniques have been used more broadly in recent years to study cement hydration. They are not only non-destructive but also able to image a sample in full 3D with resolutions that can reach from micron to nanoscale. Nano computed tomography (nCT) is one technique that has been applied to study cement hydration at the nanoscale [26], [41]. A typical nCT can reach a pixel size from 15 to 65 nm, providing enough detail for observing features <1 μm. However, nCT often takes >0.5 h to finish one scan. This makes the application of this technique on continuous scans for in-situ observations challenging. Fast X-ray computerized tomography (fCT) is another technique that has shown success in studying the time-evolving cement microstructures [20], [42], [43], [44], [45], [46], [47], [48], [49]. Due to the high flux of the X-ray beam from the synchrotron ring, fCT allows a scan to be captured within 1 min at a pixel size of 1 μm. This allows a paste sample to be continuously scanned during the hydration process. However, the micron-sized resolutions limit does not provide detailed insights for particles <5 μm [20], [49]. Fortunately, the combination of nCT and fCT has allowed the development of fast nano X-ray computed tomography (fnCT). fnCT can capture a 3D data set in <2 min at a pixel size of 50 nm. This makes this procedure an exciting method to evaluate hydrating pastes. fnCT collects multiple X-ray radiographs at various rotation angles and generates a 3D model of the scanned sample, which is also referred to as a 3D tomography [50], [51]. In one tomography, the X-ray absorptions of different components (e.g., C 3 S and hydrates) differ as functions of density and chemistry [52], [53]. These X-ray absorption contrasts can be used to extract detailed information about the 3D microstructure [26], [54], [55]. In this paper, fnCT is used to collect time-lapse tomographs of hydrating C 3 S paste from 18 min after mixing to 7 h of hydration. The bulk measurements of anhydrous C 3 S, as well as the microstructural changes of individual C 3 S particles, are directly observed, quantified, and discussed. The dissolution behavior of C 3 S particles at various size scales is systematically analyzed and compared. This work aims to find the relationship between the size of C 3 S particle sizes and their dissolution rates. This provides significant insights into the early-age hydration of C 3 S on length and time scales not previously possible. Because of the magnitude of the data and the substantial amount of observations, this work will solely focus on the change in the anhydrous particles. Changes in the hydration products will be reported in future work.

42 ENGINEERING↗
DOE OSTI2021

The Delplot kinetic method applied to systems with adsorbates: Hydrodeoxygenation of benzofuran on a bimetallic CoPd phosphide catalyst supported on KUSY

The Delplot method provides a means of analyzing conversion and selectivity data to derive a reaction sequence and has been applied so far to gas-phase or liquid-phase species. This study analyses the applicability of the method for catalytic reactions and considers for the first time adsorbed intermediates. The method is applied to a contact time study of the hydrodeoxygenation (HDO) of benzofuran at 0.5 MPa and 350 °C over a catalyst consisting of bimetallic CoPd phosphide supported on a potassium ion-exchanged ultra-stable Y (KUSY) zeolite. Both simple and detailed reaction networks were derived. The simple networks considered only gas-phase species and were modeled by a first-order sequence of steps, whereas the detailed network took into account adsorbed intermediates and was simulated using a rake mechanism. The networks were compared using F-statistics, which accounted for the differences in the number of fitting parameters. The detailed network gave a better fit to the experimental data because it represented a more realistic description of the transformation. A suggested sequence from the Delplot method was consistent with the simple network but not with the detailed network. The lack of applicability of the Delplot analysis to the network with adsorbates was linked to overly large equilibrium constants, a determination supported by Delplot fitting for a model sequence. Further, this study indicated the inapplicability of the Delplot method in determining reaction sequences that involve adsorbed species with large equilibrium constants for formation.

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

Reactive Carbon Capture: Cooperative and Bifunctional Adsorbent-Catalyst Materials and Process Integration for a New Carbon Economy

To say the least, releasing CO 2 into the atmosphere is reaping undue environmental consequences given the ever-present increase in severe global weather events over the past five years. However, it can be argued that–at least in the confines of current technological capabilities–the atmospheric release of CO 2 is somewhat unavoidable given that even shifting toward clean energy sources–such as solar, nuclear, wind, battery, or H 2 power–incurs an initial carbon requirement by way of manufacturing the very production abilities through which “clean” energy is generated. Even years from now, experts agree that energy production will be diversified and–as the global population continues to drive the growth of global energy consumption–thermal power derived from carbon combustion is likely to remain one intrinsic energetic source, of which CO 2 will always be a byproduct. In this context, it is the responsibility of the scientific community to devise improved pathways of carbon management such that (i) the consequences of combustion on the global environment are reduced and (ii) carbon fuels can be leveraged in a sustainable fashion. In this Account, we discuss a pivotal perspective shift on CO 2 emissions derived from a considerable breakthrough in material science from our work on shape engineering of nanoporous adsorbents and catalysts. This account details the development of materials which no longer vilify CO 2 emissions as a valueless combustion byproduct, instead providing a path for them to become a potential feedstock. In more specific terms, this work details the development of structured, cooperative “bifunctional” materials (BFMs) comprised of (i) a high-temperature adsorbent and (ii) a heterogeneous catalyst that enable single-bed CO 2 capture and utilization in oxidative ethane dehydrogenation (ODHE), oxidative propane dehydrogenation (ODHP), and dry methane reforming (DMR) processes. This Account begins with the conceptual development of the BFMs in the powdered state, followed by detailing the first-ever reports of structuring the materials into facile honeycomb contactors by 3D printing. The Account then summarizes the impressive performance of the 3D-printed BFMs, specifically focusing on how their catalysts (metal oxides and perovskites) influence their reactive CO 2 capture performances in ODHE, ODHP, and DMR processes. Such promise of CO 2 -as-fuel offers a glimpse into the future of a diversified energy economy, in which CO 2 /fuel looping can play an important role. A major factor in achieving this future is, of course, developing an appropriately active catalyst; an account of whose first breakthroughs in material science are detailed herein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2021

A Minimal Information Set To Enable Verifiable Theoretical Battery Research

Batteries are an enabling technology for addressing sustainability through the electrification of various forms of transportation (1) and grid storage. (2) Batteries are truly multi-scale, multi-physics devices, and accordingly various theoretical descriptions exist to understand their behavior (3-5) ranging from atomistic details to techno-economic trends. As we explore advanced battery chemistries (6,7) or previously inaccessible aspects of existing ones, (8-10) new theories are required to drive decisions. (11-13) The decisions are influenced by the limitations of the underlying theory. Advanced theories used to understand battery phenomena are complicated and require substantial effort to reproduce. However, such constraints should not limit the insights from these theories. We can strive to make the theoretical research verifiable such that any battery stakeholder can assess the veracity of new theories, sophisticated simulations or elaborate analyses. We distinguish verifiability, which amounts to “Can I trust the results, conclusions and insights and identify the context where they are relevant?”, from reproducibility, which ensures “Would I get the same results if I followed the same steps?” With this motivation, we propose a checklist to guide future reports of theoretical battery research in Table 1. We hereafter discuss our thoughts leading to this and how it helps to consistently document necessary details while allowing complete freedom for creativity of individual researchers. Given the differences between experimental and theoretical studies, the proposed checklist differs from its experimental counterparts. (14,15) This checklist covers all flavors of theoretical battery research, ranging from atomic/molecular calculations (16-19) to mesoscale (20,21) and continuum-scale interactions, (9,22) and techno-economic analysis. (23,24) Finally, as more and more experimental studies analyze raw data, (25) we feel this checklist would be broadly relevant.

25 ENERGY STORAGE↗
DOE OSTI2024

How Precisely Can Individual Molecules Be Analyzed? A Case Study on Locally Quantifying Forces and Energies Using Scanning Probe Microscopy

Recent advances in scanning probe microscopy methodology have enabled the measurement of tip-sample interactions with picometer accuracy in all three spatial dimensions, thereby providing a detailed site-specific and distance-dependent picture of the related properties. This paper explores the degree of detail and accuracy that can be achieved in locally quantifying probe-molecule interaction forces and energies for adsorbed molecules. Toward this end, cobalt phthalocyanine (CoPc), a promising CO 2 reduction catalyst, was studied on Ag(111) as a model system using low-temperature, ultrahigh vacuum noncontact atomic force microscopy. Data were recorded as a function of distance from the surface, from which detailed three-dimensional maps of the molecule's interaction with the tip for normal and lateral forces as well as the tip-molecule interaction potential were constructed. The data were collected with a CO molecule at the tip apex, which enabled a detailed visualization of the atomic structure. Determination of the tip-substrate interaction as a function of distance allowed isolation of the molecule-tip interactions; when analyzing these in terms of a Lennard-Jones-type potential, the atomically resolved equilibrium interaction energies between the CO tethered to the tip and the CoPc molecule could be recovered. Interaction energies peaked at less than 160 meV, indicating a physisorption interaction. As expected, the interaction was weakest at the aromatic hydrogens around the periphery of the molecule and strongest surrounding the metal center. In conclusion, the interaction, however, did not peak directly above the Co atom but rather in pockets surrounding it.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High-Field One-Dimensional and Two-Dimensional 27Al Magic-Angle Spinning Nuclear Magnetic Resonance Study of ?-, d-, and ?-Al2O3 Dominated Aluminum Oxides: Toward Understanding the Al Sites in ?-Al2O3

Herein, a detailed analysis was carried out using high-field (19.9 T) 27Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) on three specially prepared aluminum oxide samples where the ?-, d-, and ?-Al2O3 phases are dominantly expressed through careful control of the synthesis conditions. Specifically, two-dimensional (2D) multiquantum (MQ) MAS 27Al was used to obtain high spectral resolution, which provided a guide for analyzing quantitative 1D 27Al NMR spectra. Six aluminum sites were resolved in the 2D MQ MAS NMR spectra, and seven aluminum sites were required to fit the 1D spectra. A set of octahedral and tetrahedral peaks with well-defined quadrupolar line shapes was observed in the ?-phase dominant sample and was unambiguously assigned to the ?-Al2O3 phase. The distinct line shapes related to the ?-Al2O3 phase provided an opportunity for effectively deconvoluting the more complex spectrum obtained from the d-Al2O3 dominant sample, allowing the peaks/quadrupolar parameters related to the d-Al2O3 phase to be extracted. The results show that the d-Al2O3 phase contains three distinct AlO sites and three distinct AlT sites. This detailed Al site structural information offers a powerful way of analyzing the most complex ?-Al2O3 spectrum. It is found that the ?-Al2O3 phase consists of Al sites with local structures similar to those found in the d-Al2O3 and ?-Al2O3 phases albeit with less ordering. Spin–lattice relaxation time measurement further confirms the disordering of the lattice. Collectively, this study uniquely assigns 27Al features in transition aluminas, offering a simplified method to quantify complex mixtures of aluminum sites in transition alumina samples.

Xu, Suochang↗
DOE OSTI2025

Reweighting configurations generated by transferable, machine learned models for protein sidechain backmapping

Multiscale modeling requires the linking of models at different levels of detail, with the goal of gaining accelerations from lower fidelity models while recovering fine details from higher resolution models. Communication across resolutions is particularly important in modeling soft matter, where tight couplings exist between molecular-level details and mesoscale structures. While multiscale modeling of biomolecules has become a critical component in exploring their structure and self-assembly, backmapping from coarse-grained to fine-grained, or atomistic, representations presents a challenge, despite recent advances through machine learning. A major hurdle, especially for strategies utilizing machine learning, is that backmappings can only approximately recover the atomistic ensemble of interest. We demonstrate conditions for which backmapped configurations may be reweighted to exactly recover the desired atomistic ensemble. By training separate decoding models for each sidechain type, we develop an algorithm based on normalizing flows and geometric algebra attention to autoregressively propose backmapped configurations for any protein sequence. Critical for reweighting with modern protein force fields, our trained models include all hydrogen atoms in the backmapping and make probabilities associated with atomistic configurations directly accessible. We also demonstrate, however, that reweighting is extremely challenging despite state-of-the-art performance on recently developed metrics and generation of configurations with low energies in atomistic protein force fields. Through detailed analysis of configurational weights, we show that machine-learned backmappings must not only generate configurations with reasonable energies, but also correctly assign relative probabilities under the generative model. These are broadly important considerations in generative modeling of atomistic molecular configurations.

Monroe, Jacob I. [Univ. of Arkansas, Fayetteville,↗
DOE OSTI2020

Spectral solar irradiance on inclined surfaces: A fast Monte Carlo approach

Estimating spectral plane-of-array (POA) solar irradiance on inclined surfaces is an important step in the design and performance evaluation of both photovoltaic and concentrated solar plants. This work introduces a fast, line-by-line spectral, Monte Carlo (MC) radiative transfer model approach to simulate anisotropic distributions of shortwave radiation through the atmosphere as photon bundles impinge on inclined surfaces. This fast Monte Carlo approach reproduces the angular distribution of solar irradiance without the undesirable effects of spatial discretization and thus computes detailed POA irradiance values on surfaces at any orientation and also when surfaces are subjected to the anisotropic ground and atmospheric scattering. Polarization effects are also easily incorporated into this approach that can be considered as direct numerical simulation of the physics involved. Here, we compare our Monte Carlo radiative transfer model with the most widely used empirical transposition model, Perez4, under various conditions. The results show that the Perez4 model reproduces the more detailed Monte Carlo simulations with less than 10% deviation under clear skies for all relevant surface tilt and azimuth angles. When optically thin clouds are present, observed deviations are larger, especially when the receiving surface is strongly tilted. Deviations are also observed for large azimuth angle differences between the receiving surface and the solar position. When optically thick clouds are present, the two models agree within 15% deviation for nearly all surface orientation and tilt angles. The overall deviations are smaller when compared with cases for optically thin clouds. The Perez4 model performs very well (6.0% deviation) in comparison with the detailed MC simulations for all cases, thus validating its widespread use for practical solar applications. When detailed atmospheric profiles and cloud optical properties are available, the proposed fast Monte Carlo radiative model reproduces accurate spectral and angular POA irradiance levels for various atmospheric and cloud cover conditions, surface orientations, and different surface and ground properties.

42 ENGINEERING↗
DOE OSTI2022

Toward a machine-guided approach to energetic material discovery

In this article, we trained a machine learning (ML) model to connect microstructural details of an energetic material formulation to its performance for the purpose of guiding the discovery of new explosive formulations. Our hypothesis was that the algorithm would robustly learn the training data and produce an accurate surrogate model. Specifically, the algorithm learned the relationship between details of the void size distribution (VSD), initiating shock pressure, and the energetic material performance. We used realistic constraints on the VSD and a range of cases were ingested by a physically informed reactive flow model working within a hydrodynamic solver running on high-performance computing resources. The ML algorithm produced a surrogate model that accurately predicted known test points around the parameter space. In addition to the utility of the model and the process used for its development, we noted interesting comparisons between what we, the authors—subject matter experts, would heuristically conclude from the training data and the surrogate model predictions. We detected nuanced details that were missed by the surrogate model; however, these details are not important to an energetic material formulator. We concluded that the algorithm did indeed robustly learn the training data and produce an accurate surrogate model. We further concluded that the surrogate model is a powerful tool to guide the formulator in the absence of subject matter experts and limited-access computing resources.

42 ENGINEERING↗
DOE OSTI2022

Manufacturing Cost Analysis of Advanced Parabolic Trough Collector

The research team performed a detailed bottom-up manufacturing cost estimate for an advanced parabolic trough design - the Solar Dynamics Sunbeam-MT (Sunbeam Mid-Term). This includes all components for manufacturing and assembly in a manufacturing facility (e.g. space frame and arms), and the purchased parts (e.g. mirrors and receiver tubes). Estimates of the construction and assembly activities have been made to then determine an estimated installed cost. Prior analysis has already undertaken detailed bottom-up manufacturing, assembly, and construction analysis for the Ultimate Trough from schlaich bergermann partner (sbp), and this work updates the solar field cost estimates based on a similar aperture area as the SunBeam-MT. For this analysis, the Ultimate Trough is considered the commercial parabolic trough and the Sunbeam-MT as the advanced parabolic trough. For similarity, both the Sunbeam-MT and the Ultimate Trough have been modelled with a solar field with approximately 800,000 square meters (m2) in aperture area - the equivalent of a large CSP plant. The analysis has found a potential installed cost estimate of the Sunbeam-MT could be $120/m2 but must be built at scale to confirm this estimate. Compared to prior analysis, the commercial Ultimate Trough using U.S. conditions, has reduced in installed cost from $178/m2 to $152/m2. Both designs could be even cheaper with Chinese steel.

cost analysis↗
DOE OSTI2021

Dynamics and chemical mode analysis of plasma thermal-chemical instability

The stability of the weakly ionized plasma and the transition from a stable homogeneous discharge to unstable filaments play an important role in gas laser physics, plasma-assisted combustion, chemical reforming, and material synthesis. Here, theoretical stability analysis and thermal-chemical mode analysis were performed to understand the mechanism of plasma thermal-chemical instability by using a zero-dimensional plasma system with both simplified and detailed chemical kinetics of H 2 /O 2 /N 2 mixtures. The plasma dynamic and kinetic models accounted for multiple physical mechanisms in the chemically-reactive weakly ionized plasma, including ionization, attachment/detachment, recombination, vibrational and electronic energy relaxation, convective and diffusive species/heat removal, Joule heating, and detailed chemical kinetics. An analytical criterion and the explosive mode species/temperature pointers were formulated while the representative active species were identified for different thermal-chemical modes. The results showed that in addition to the classical thermal-ionization mechanism, various chemical modes from chemical heat imbalance and elementary kinetics significantly modified the time dynamics and the stability of the weakly ionized plasma. The present analysis provides insights and guidance to control plasma instability using chemical kinetics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2020

Volume I. Introduction to DUNE

The preponderance of matter over antimatter in the early universe, the dynamics of the supernovae that produced the heavy elements necessary for life, and whether protons eventually decay -- these mysteries at the forefront of particle physics and astrophysics are key to understanding the early evolution of our universe, its current state, and its eventual fate. The Deep Underground Neutrino Experiment (DUNE) is an international world-class experiment dedicated to addressing these questions as it searches for leptonic charge-parity symmetry violation, stands ready to capture supernova neutrino bursts, and seeks to observe nucleon decay as a signature of a grand unified theory underlying the standard model. The DUNE far detector technical design report (TDR) describes the DUNE physics program and the technical designs of the single- and dual-phase DUNE liquid argon TPC far detector modules. This TDR is intended to justify the technical choices for the far detector that flow down from the high-level physics goals through requirements at all levels of the Project. Volume I contains an executive summary that introduces the DUNE science program, the far detector and the strategy for its modular designs, and the organization and management of the Project. The remainder of Volume I provides more detail on the science program that drives the choice of detector technologies and on the technologies themselves. It also introduces the designs for the DUNE near detector and the DUNE computing model, for which DUNE is planning design reports. Volume II of this TDR describes DUNE's physics program in detail. Volume III describes the technical coordination required for the far detector design, construction, installation, and integration, and its organizational structure. Volume IV describes the single-phase far detector technology. A planned Volume V will describe the dual-phase technology.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗