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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 91 records · Page 5

Fast product release requires active-site water dynamics in carbonic anhydrase

Water plays an essential role in enzyme structure, stability, and the substantial rate enhancement of enzyme catalysis. However, direct observations linking enzyme catalysis and active-site water dynamics pose a significant challenge due to experimental difficulties. By integrating an ultraviolet (UV) photolysis technique with temperature-controlled X-ray crystallography, we track the catalytic pathway of carbonic anhydrase II (CAII) at 1.2 Å resolution. This approach enables us to construct molecular movies of CAII catalysis, encompassing substrate (CO 2 ) binding, conversion from substrate to product (bicarbonate), and product release. In the catalytic pathway, we identify an unexpected configuration in product binding and correlate it with sub-nanosecond rearrangement of active-site water. Based on these experimental observations, we propose a comprehensive mechanism of CAII and describe the detailed structure and dynamics of active-site water in CAII. Our findings suggest that CAII has evolved to utilize the structure and fast dynamics of the active-site waters for its diffusion-limited catalytic efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scale-Up of Electrode Coating and Flow-Field for Commercial Hydrogen Peroxide Electrolyzer: Cooperative Research and Development Final Report, CRADA Number CRD-17-00687

Hydrogen peroxide is currently produced at central chemical plants via the anthraquinone oxidation process. This process produces environmental pollutants that are costly to remediate, requires hazardous long distance shipping of highly concentrated peroxide (50% or 70%), and necessitates extra handling costs related to storage and dilution. Peroxygen Systems, Inc. (PSi) is developing breakthrough technology for on-site hydrogen peroxide production. PSi’s on-site on-demand electrolyzer can reduce the cost of producing hydrogen peroxide by 50%, while also completely eliminating the cost and safety issues associated with shipping and handling of high concentration hydrogen peroxide. The challenge for PSi is scaling. To support the next step toward commercialization (customer pilot tests), scaling the prototype into larger single cells and 20-40 cell stacks is required. In addition to internal hardware and flow-field design efforts at PSi, NREL will address three critical problems for this scale-up effort: (1) demonstrating a large scale roll-to-roll (R2R) process to coat uniform electrode materials for 100 cm2 and 500 cm2 stack testing, (2) demonstrating an in-line diagnostic to achieve better electrode quality control, and (3) performing in situ cell/stack testing to better understand and optimize the performance of the flow field design.

28 EE - Advanced Manufacturing Office (EE-5A)↗

The Molecular Path Approaching the Active Site in Catalytic Metal–Organic Frameworks

How molecules approach, bind at, and release from catalytic sites is key to heterogeneous catalysis, including for emerging metal-organic framework (MOF)-based catalysts. Here, we use in situ synchrotron X-ray scattering analysis to evaluate the dominant binding sites for reagent and product molecules in the vicinity of catalytic Ni-oxo clusters in NU-1000 with different surface functionalization under conditions approaching those used in catalysis. The locations of the reagent and product molecules within the pores can be linked to the activity for ethylene hydrogenation. For the most active catalyst, ethylene reagent molecules bind close to the catalytic clusters, but only at temperatures approaching experimentally observed onset of catalysis. The ethane product molecules favor a different binding location suggesting that the product is readily released from the active site. An unusual guest-dependence of the framework negative thermal expansion is documented. We hypothesize that reagent and product binding sites reflect the pathway through the MOF to the active site and can be used to identify key factors that impact the catalytic activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advanced Simulation and Experiments of Strongly Coupled Geomechanics and Flow for Gas Hydrate Deposits: Validation and Field Application. Final Report

The objectives of the proposed research are (1) to investigate geomechanical responses induced by depressurization experimentally and numerically; (2) to enhance the current numerical simulation technology in order to simulate complex physically coupled processes by depressurization and (3) to perform in-depth numerical analyses of two selected potential production test sites: one based on the deposits observed at the Ulleung basin UBGH2-6 site; and the other based on well-characterized accumulations from the westend Prudhoe Bay. To these ends, the recipient will have the following specific objectives: 1). Information obtained from multi-scale experiments previously conducted at the recipient’s research partner (the Korean Institute of Geoscience and Mineral Resources (KIGAM)) that were designed to represent the most promising known Ulleung Basin gas hydrate deposit as drilled at site UBGH2-6 will be evaluated (Task 2). These findings will be further tested by new experimental studies at Lawrence Berkeley National Laboratory (LBNL) and Texas A&M (TAMU) (Task 3) that are designed capture complex coupled physical processes between flow and geomechanics, such as sand production, capillarity, and formation of secondary hydrates. The findings of Tasks 2 and 3 will be used to further improve numerical codes. 2) Develop (in Tasks 4 through 6) an advanced coupled geomechanics and non-isothermal flow simulator (T+MAM) to account for large deformation and strong capillarity. This new code will be validated using data from the literature, from previous work by the project team, and with the results of the proposed experimental studies. The developed simulator will be applied to both Ulleung Basin and Prudhoe Bay sites, effectively addressing complex geomechanical and petrophysical changes induced by depressurization (e.g., frost-heave, strong capillarity, cryo-suction, induced fracturing, and dynamic permeability).

02 PETROLEUM↗

Biorefinery upgrading of herbaceous biomass to renewable hydrocarbon fuels, Part 2: Air pollutant emissions and permitting implications

The development of advanced biofuel production facilities is still at a nascent stage, and the biorefineries could face challenges in obtaining air permits required for their construction and operation because they are novel emission sources. To fill gaps in knowledge regarding potential emissions, we perform a detailed federal regulatory analysis and estimate air pollutant emissions for an advanced biorefinery that produces renewable diesel blendstock (RDB) from lignocellulosic biomass via aerobic respiration documented in Part 1 of the paper. We evaluate 12 design permutations that include two feedstocks, a uniform format blend (UFB) and corn stover; three biorefinery scales, 2,000, 5,200, and 9,100 dry metric tons per day (dmtd) of lignocellulosic biomass feed; and two lignin uses, as either a boiler fuel or for pellet production. We also evaluate 6 additional design permutations by incorporating non-emitting renewable power, which could reduce up to 63% carbon monoxide (CO) and nitrogen oxides (NO x ) each, 21% volatile organic compounds (VOC), and 43% hazardous air pollutants (HAP) as opposed to on-site power production, for biorefineries that produce pellets, using either UFB or corn stover. Our results indicate that all 18 design permutations would be classified as a major source under the Clean Air Act's New Source Review program without additional emission controls. Compared to using lignin as a boiler fuel, diverting lignin for pellet production reduces the emissions of CO up to 88%, NOx up to 73%, sulfur dioxide (SO 2 ) up to 99%, VOCs up to 72%, and HAPs up to 66%. Additionally, we explore control options that could further reduce emissions and assess whether reductions are enough to achieve minor source classification. Insights from our analysis can help biorefinery developers and regulators develop permitting strategies to mitigate investment risks.

09 BIOMASS FUELS↗

Time-resolved momentum imaging of UV photodynamics in structural isomers of iodopropane probed by site-selective XUV ionization

The photodynamics of 1- and 2-iodopropane (1 and 2-IP) were studied in a time-resolved scheme incorporating ultraviolet (UV) excitation and extreme ultraviolet (XUV) probing, which initiates photoionization selectively from the I 4d core orbital. UV absorption in the A-band of both isomers leads to prompt C–I bond fission, with significant disposal of internal energy into the propyl radical product. Site-selective ionization enables a range of charge transfer (CT) processes between the nascent highly charged iodine ions and neutral propyl radicals, dependent on the interfragment distance at the instant of ionization. Subtle differences in the dynamics of these CT processes between the two isomers are observed. In 1-IP, the kinetic energies of iodine ions produced by UV photodissociation and subsequent XUV multiple ionization increased notably over the first few hundred femtoseconds, which could be understood in terms of differing gradients along the photodissociation coordinates of the neutral and polycationic states involved in the pump and probe steps, respectively. Led by a recent report of HI elimination in UV photoexcited 2-IP [Todt et al., Phys. Chem. Chem. Phys., 22(46), 27338 (2020)], we also model the most likely signatures of this process in the present experiment, and can identify signal in the 2-IP data (that is absent or significantly weaker in the data from the unbranched 1-IP isomer) that is consistent with such a process occurring on ultrafast timescales.

Allum, Felix [Deutsches Elektronen-Synchrotron (DE↗

MetaFlux: Meta-learning global carbon fluxes from sparse spatiotemporal observations

We provide a global, long-term carbon flux dataset of gross primary production and ecosystem respiration generated using meta-learning, called MetaFlux. The idea behind meta-learning stems from the need to learn efficiently given sparse data by learning how to learn broad features across tasks to better infer other poorly sampled ones. Using meta-trained ensemble of deep models, we generate global carbon products on daily and monthly timescales at a 0.25-degree spatial resolution from 2001 to 2021, through a combination of reanalysis and remote-sensing products. Site-level validation finds that MetaFlux ensembles have lower validation error by 5–7% compared to their non-meta-trained counterparts. In addition, they are more robust to extreme observations, with 4–24% lower errors. We also checked for seasonality, interannual variability, and correlation to solar-induced fluorescence of the upscaled product and found that MetaFlux outperformed other machine-learning based carbon product, especially in the tropics and semi-arids by 10–40%. Overall, MetaFlux can be used to study a wide range of biogeochemical processes.

54 ENVIRONMENTAL SCIENCES↗

The Modeling of Synfuel Production Process: ASPEN Model of FT production with electricity demand provided at LWR scale

Synfuels, or electro-fuels (e-fuels) have the unique potential to significantly reduce greenhouse gas (GHG) emissions across the transportation sector. This is especially true for applications with substantial payloads and daily miles traveled, such as long-haul heavy-duty vehicles, rail locomotives, marine vessels and aviation aircrafts that are challenging to directly electrify via battery or fuel cell powertrain technologies. Synfuels, or electro-diesel/electro-jet fuels, have similar properties with the incumbent petroleum fuels, compatible with current infrastructure but have much lower GHG emissions relative to the petroleum counterpart, because they utilize waste carbon dioxide (CO2) streams and green hydrogen (H2) sourced from electrolysis. To achieve substantial reductions in GHG emissions, electricity sources must be zero carbon or near-zero carbon, which is the case with solar, wind, hydro and nuclear power. Compared to the intermittency of solar, wind and hydro, nuclear energy provides a steady energy source. In addition, it’s advantageous for nuclear power to produce synfuels because it provides not only near-zero carbon electricity to displace grid electricity, but also near-zero carbon steam to displace carbon-intensive natural gas combustion for steam generation. The availability of electricity and steam also enables more efficient green hydrogen production by using high-temperature electrolysis. In this work, Argonne National Laboratory (ANL) models a synfuel production process via the Fischer- Tropsch (FT) reaction by using nuclear power to provide electricity and steam. In 2021, using ASPEN Plus software, ANL established a detailed process model of a stand-alone FT production facility, assuming feedstocks of pure CO2 and H2. This stand-alone model can be expanded to integrate H2 production from nuclear power via low-temperature and high-temperature electrolysis at light-water reactor (LWR) scale. This report summarizes the stand-alone ASPEN Plus model results with a detailed mass and energy analysis. Our modeled facility produces 351 MT/day (130,000 gal/day) of FT fuel (a mixture of naphtha, jet fuel, and diesel) by converting 223 MT/day of H2 and 2,387 MT/day of CO2. The FT fuel production energy efficiency is 58% and the carbon conversion efficiency (from CO2 to FT fuel) is 46%. The production of green hydrogen requires 390–470 MWe of electricity, which is compared with the capacity of an LWR plant. For the stand-alone FT process, the detailed energy demand (electricity and heat) is summarized in the table below. Based on the energy supply source and the required temperature, potential insertion points of nuclear energy are identified. Based on the potential nuclear energy utilization, this report discusses potential modification options for expanding the system boundary to integrate nuclear power use, for example on-site hydrogen production via water electrolysis. Modeling of the integrated system is conducted by closely working with ANL and Idaho National Laboratory (INL) collaborators to harmonize design parameters of nuclear plants and the FT production process.

Zang, Guiyan↗

Supported Organochromium Ethylene Oligomerization Enabled by Surface Lithiation

Here, in this work, supported organochromium ethylene polymerization catalysts have been tuned to mediate ethylene oligomerization via surface lithiation, which provides a generalizable protocol to control stereoelectronics and redox states of surface organometallic active sites. The homoleptic chromium(IV) alkyl complex Cr(CH 2 SiMe 3 ) 4 was grafted on high-surface-area anatase titania (TiO 2 ) nanoparticles as well as on silica to produce Cr/TiO 2 and Cr/SiO 2 , respectively. Treatment of these materials with excess n-butyllithium led to the reduced chromium complexes Cr/Li x TiO 2 and Cr/Li/SiO 2 , each of which still retains one hydrocarbyl ligand on chromium. A set of heterogeneous complexes were studied by electron paramagnetic resonance and X-ray absorption spectroscopy, which indicate a reduction in the oxidation state of the major chromium species to Cr II upon lithiation. Cr/Li x TiO 2 converts ethylene to hexenes with a high selectivity (>80%), which was persistent over 10 days at 80 °C, achieving >950 turnovers. The exclusive formation of C 4 and C 6 olefins, preferring the trimerization product, without a statistical (Flory–Schulz) distribution is characteristic of the oxidative cyclization oligomerization mechanism rather than the traditional Cossee–Arlman mechanism, whereas Cr/Li/SiO 2 produced a mixture of trimerization and polymerization products, suggesting site heterogeneity in the silica-based material. On the other hand, the unreduced chromium(IV) materials as well as low lithium-containing Cr/Li x TiO 2 (x < 0.16) exclusively produced ultrahigh molecular weight polyethylene, determined by differential scanning calorimetry and gel permeation chromatography analysis, likely formed via a linear-insertion mechanism, with a crossover from the polymerization to oligomerization regime observed at ~16% Li intercalation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrogen Refueling Reference Station Lot Size Analysis for Urban Sites

Hydrogen Fueling Infrastructure Research and Station Technology (H2FIRST) is a project initiated by the DOE in 2015 and executed by Sandia National Laboratories and the National Renewable Energy Laboratory to address R&D barriers to the deployment of hydrogen fueling infrastructure. One key barrier to the deployment of fueling stations is the land area they require (i.e. "footprint"). Space is particularly a constraint in dense urban areas where hydrogen demand is high but space for fueling stations is limited. This work presents current fire code requirements that inform station footprint, then identifies and quantifies opportunities to reduce footprint without altering the safety profile of fueling stations. Opportunities analyzed include potential new methods of hydrogen delivery, as well as alternative placements of station technologies (i.e. rooftop/underground fuel storage). As interest in heavy-duty fueling stations and other markets for hydrogen grows, this study can inform techniques to reduce the footprint of heavy-duty stations as well. This work characterizes generic designs for stations with a capacity of 600 kg/day hydrogen dispensed and 4 dispenser hoses. Three base case designs (delivered gas, delivered liquid, and on-site electrolysis production) have been modified in 5 different ways to study the impacts of recently released fire code changes, colocation with gasoline refueling, alternate delivery assumptions, underground storage of hydrogen, and rooftop storage of hydrogen, resulting in a total of 32 different station designs. The footprints of the base case stations range from 13,000 to 21,000 ft 2 . A significant focus of this study is the NFPA 2 requirements, especially the prescribed setback distances for bulk gaseous or liquid hydrogen storage. While the prescribed distances are large in some cases, these setback distances are found to have a nuanced impact on station lot size; considerations of the delivery truck path, traffic flow, parking, and convenience store location are also important. Station designs that utilize underground and rooftop storage can reduce footprint but may not be practical or economical. For example, burying hydrogen storage tanks underground can reduce footprint, but the cost savings they enable depend on the cost of burial and the cost land. Siting and economic analysis of station lot sizes illustrate the benefit of smaller station footprints in the flexibility and cost savings they can provide. This study can be used as a reference that provides examples of the key design differences that fueling stations can incorporate, the approximate sizes of generic station lots, and considerations that might be unique to particular designs.

08 HYDROGEN↗

Multisublattice cluster expansion study of short-range ordering in iron-substituted strontium titanate

Owing to the challenges in obtaining realistic atomic configurations in large chemical phase spaces, it is not straightforward to describe structure–property relations in materials exhibiting configurational disorder. One example is iron-substituted strontium titanate (SrTi 1–x Fe x O 3–d , STF), a promising perovskite-derivative cathode material in solid oxide fuel cells that exhibits full solid solubility 0 ≤ x ≤ 1 and a tendency to exhibit short-range order. Here we demonstrate a multisublattice cluster expansion (CE) framework and apply it to STF across the full composition range. The CE approach is distinct from more traditional CE formulations in that clusters are defined explicitly by the chemical species distributed among multiple sublattices, rather than via cluster functions of occupation variables with decoration. The modified CE approach makes it easy to distinguish meaningful chemical interactions that are harder to extract from conventional CE, since for the latter chemical identity in a cluster is expressed as a product of site occupations. The least absolute shrinkage and selection operator (LASSO) is implemented as a regression analysis tool to select key clusters and avoid overfitting. We demonstrate this formulation on STF, and show that it can accurately predict configurational energies in comparison to conventional CE. From the key clusters, we identify that short-range ordering between substitutional Fe and oxygen vacancies (V O ) results in the formation of Fe–VO strings. In addition, we consider the stability of STF through CE-based Monte Carlo (MC) simulations and confirm the presence of superstructures that were previously observed in transmission electron microscopy. In this work, analysis of atomic configurations from MC samples reveals variations in the oxidation state of Fe atoms, which can be explained by the ordering tendency of Fe and V O . The cluster description and selection formalism described here may be applied to other disordered multisublattice systems for accurate and efficient material modeling.

36 MATERIALS SCIENCE↗

Establishing structure-sensitivity of ceria reducibility: real-time observations of surface-hydrogen interactions

The first layer of atoms on an oxide catalyst provides the first sites for adsorption of reactants and the last sites before products or oxygen are desorbed. We employ a unique combination of morphological, structural, and chemical analyses of a model ceria catalyst with different surface terminations under an H 2 environment to unequivocally establish the effect of the last layer of atoms on surface reduction. (111) and (100) terminated epitaxial islands of ceria are simultaneously studied in situ allowing for a direct investigation of the structure–reducibility relationship under identical conditions. Kinetic rate constants of Ce 4+ to Ce 3+ transformation and equilibrium concentrations are extracted for both surface terminations. Unlike the kinetic rate constants, which are practically the same for both types of islands, more pronounced oxygen release, and overall higher reducibility were observed for (100) islands compared to (111) ones. The findings are in agreement with coordination-limited oxygen vacancy formation energies calculated by density functional theory. The results point out the important aspect of surface terminations in redox processes, with particular impact on the catalytic reactions of a variety of catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Accelerating science: The usage of commercial clouds in ATLAS Distributed Computing

The ATLAS experiment at CERN is one of the largest scientific machines built to date and will have ever growing computing needs as the Large Hadron Collider collects an increasingly larger volume of data over the next 20 years. ATLAS is conducting R&D projects on Amazon Web Services and Google Cloud as complementary resources for distributed computing, focusing on some of the key features of commercial clouds: lightweight operation, elasticity and availability of multiple chip architectures. The proof of concept phases have concluded with the cloud-native, vendoragnostic integration with the experiment’s data and workload management frameworks. Google Cloud has been used to evaluate elastic batch computing, ramping up ephemeral clusters of up to O(100k) cores to process tasks requiring quick turnaround. Amazon Web Services has been exploited for the successful physics validation of the Athena simulation software on ARM processors. We have also set up an interactive facility for physics analysis allowing endusers to spin up private, on-demand clusters for parallel computing with up to 4 000 cores, or run GPU enabled notebooks and jobs for machine learning applications. The success of the proof of concept phases has led to the extension of the Google Cloud project, where ATLAS will study the total cost of ownership of a production cloud site during 15 months with 10k cores on average, fully integrated with distributed grid computing resources and continue the R&D projects.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Enhanced Attenuation of Uranium in the Subsurface

Over time, the focus for the Hanford Site has moved from production to decommissioning and site remediation. Several hundred metric tons of near-surface vadose zone sediment have been excavated from the 300 Area in an effort to remove the source of the uranium contamination (DOE/RL, 2011). Despite remediation efforts, uranium continues to be problematic with concentrations greater than the maximum contaminant level (MCL, which is 30 µg/L) for drinking water. Due to the close proximity of the Columbia River, the uranium continues to be a focus of investigation and remediation. After finding that the uranium concentrations were not decreasing as quickly as expected (based on the 1996 ROD) the Tri-Parties set new milestones, including an update of the conceptual model for the 300 Area uranium plume (Williams et al., 2007). In order to more accurately complete a feasibility study and identify how to remediate the uranium in the groundwater, the DOE authorized a remedial investigation/feasibility study (RI/FS). RI/FSs are designed to screen technologies to determine effectiveness, implementability, and cost (see Chapter 2b). These studies are designed to be conducted concurrently as part of the CERCLA process, so the data collected during site characterization (part of the RI) can inform the treatability studies and field tests conducted under the FS (EPA 1988). For the 300 Area, this study included laboratory, field, and modeling components as well as additional sediment and groundwater characterization to determine a suitable remediation strategy to reduce the uranium concentration in the groundwater plume within the expected time frame and cost.

300 area, uranium, polyphosphate, Hanford book pro↗

Techno-Economic Assessment of CHP Systems in Wastewater Treatment Plants

Wastewater treatment plant (WWTP) utilization of combined heat and power (CHP) systems allows for the efficient use of on-site biogas production, as well as increased annual savings in utility costs. In this paper, a review of biogas energy recovery options, CHP prime mover technologies, and the costs associated with biogas cleaning give a broad summary of the current state of CHP technology in WWTPs. Even though there are six different prime mover technologies, the main ones currently being implemented in WWTPs are micro turbines, fuel cells and reciprocating engines. Different prime movers offer varying efficiencies, installation costs, and biogas impurity (H2S, siloxanes, HCl) tolerances. To evaluate the long-term savings capabilities, a techno-economic assessment of a CHP installation at a case study WWTP shows the payback, annual savings, and initial costs associated with the installation of a CHP system. In this case, a study a payback of 5.7 years and a net present value of USD 709,000 can be achieved when the WWTP generates over 2,000,000 m3 of biogas per year and utilizes over 36,000 GJ of natural gas per year.

54 ENVIRONMENTAL SCIENCES↗

Modeling Systems’ Disruption and Social Acceptance—A Proof-of-Concept Leveraging Reinforcement Learning

As the need for a just and equitable energy transition accelerates, disruptive clean energy technologies are becoming more visible to the public. Clean energy technologies, such as solar photovoltaics and wind power, can substantially contribute to a more sustainable world and have been around for decades. However, the fast pace at which they are projected to be deployed in the United States (US) and the world poses numerous technical and nontechnical challenges, such as in terms of their integration into the electricity grid, public opposition and competition for land use. For instance, as more land-based wind turbines are built across the US, contention risks may become more acute. This article presents a methodology based on reinforcement learning (RL) that minimizes contention risks and maximizes renewable energy production during siting decisions. As a proof-of-concept, the methodology is tested on a case study of wind turbine siting in Illinois during the 2022–2035 period. Results show that using RL halves potential delays due to contention compared to a random decision process. This approach could be further developed to study the acceptance of offshore wind projects or other clean energy technologies.

17 WIND ENERGY↗

2021 Component Innovation Awardee: Siva Powers America

Siva Powers America earned a Competitiveness Improvement Project (CIP) Component Innovation award that will enable the company to evolve its 250/50 wind turbine design, discontinue its existing 13.4-meter wind turbine blades, and develop new 14.4-meter blades. These longer blades, which have additional extenders at the hub, will increase the rotor diameter to 35 meters, allowing for improved energy production at sites with lower wind resources. A collaboration with the National Renewable Energy Laboratory (NREL) includes a redesign, build, and on-site structural test for the new prototype blades. This will ultimately allow Siva Powers America to pursue recertification of the SIVA 250/50 to meet international standards.

CIP↗