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At least 721 records · Page 40

Low-Temperature Direct Oxidation of Propane to Propylene Oxide Using Supported Subnanometer Cu Clusters

Propylene oxide, a key commodity of the chemical industry for a wide range of consumer products, is synthesized through sequential propane dehydrogenation and epoxidation reactions. However, the lack of a direct catalytic route from propane to propylene oxide reduces efficiency and represents a major challenge for catalysis science. Herein, we report the discovery of a highly active and selective catalyst, made of alumina-supported subnanometer copper clusters, which can directly convert propane to propylene oxide at temperatures as low as 150 °C. Moreover, at higher temperatures, on the same catalysts, the selectivity is switched to propylene. Accompanying theoretical calculations indicate that partially oxidized and/or hydroxylated clusters have low activation energies for both propane dehydrogenation and propylene epoxidation pathways, enabling direct conversion with very high selectivity for propylene oxide. The discovery of a low-temperature catalyst that can convert propane directly to propylene oxide provides an important opportunity for the development of energy-efficient and economic catalysts for this industrially critical process. Similarly, when operating at higher temperatures, these catalysts are posed as potent oxidative dehydrogenation catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Framework for assessing land‐management effects on at‐risk species: Example of SE USA wood pellet production and gopher tortoise ( Gopherus polyphemus )

Abstract Land‐management choices made for economic and societal gains intrinsically influence landscapes and species that are dependent upon them. We propose a simple analysis framework to examine critical intersections between land‐management choices and the life‐history conditions of selected species of concern, thereby facilitating the identification of mitigation practices that can reduce negative impacts on species at risk. We test the proposed framework through application to gopher tortoise ( Gopherus polyphemus ), a keystone species that is the focus of conservation efforts across the southeastern region of United States of America, where wood pellets are being produced for bioenergy. Production of these wood pellets for export to Europe and Asia has drastically increased in the past decade, raising concerns about potential harm to biodiversity since many species in the forests sourcing pellet production were already at risk prior to the development of this new commodity. Identifying the mechanisms of potential impacts of wood pellet production on species of concern is essential to establishing meaningful management recommendations that can enhance conservation efforts while supporting sustainable bioenergy. By considering the intersections between life‐history conditions of gopher tortoise and forest‐management practices related to woody biomass extraction for pellet production, we identify several mechanisms by which the wood‐pellet industry might affect this species of concern, both positively and negatively. We then identify mitigation practices that can help offset the potential impacts of logging, thinning, and dead wood removal on gopher tortoise. Our analysis framework may be transferable to other species of concern and land‐management practices across diverse landscapes. This article is categorized under: Bioenergy > Economics and Policy Bioenergy > Climate and Environment

54 ENVIRONMENTAL SCIENCES↗

Design of Hypothetical Processes for the Production of 131 I and 99 Mo from Activation Targets

For over six decades, medical isotope production has been a high-priority focus of many research reactors across the globe. The majority of these isotopes were produced using highly-enriched uranium (HEU) or low enriched uranium (LEU) – delivering millions of doses of diagnostic and therapeutic isotopes. As a consequence of this production, however, six decades of isotope production has resulted in massive quantities of spent uranium material worldwide with no known disposition pathway creating growing proliferation concerns. Supported by the National Nuclear Security Administration’s (NNSA) Material Management and Minimization (M3) program, there has been increased focus in the production of high-priority isotopes without special nuclear materials or without uranium altogether. Isotope production via activation can potentially fulfill regional isotope demands – particularly in under-developed regions without access to isotope supply chains. The benefits of this approach would be a reduction in uranium proliferation risks, less special nuclear material wastes, and reduced risk of supply disruption in the likely event that major isotope producers will again go off-line as has happened in recent years due to a number of factors.

07 ISOTOPE AND RADIATION SOURCES↗

Global Electrification of Vehicles and Intertwined Material Supply Chains of Cobalt, Copper and Nickel

Electric vehicles (EVs) will be an important part of a low-carbon economy. Future EV adoption depends on overcoming multiple barriers, including charging infrastructure, sufficient electricity generation, and the availability of battery raw materials at acceptable costs, including cobalt, copper and nickel – which typically are co-produced. Various EV projections have been made, along with associated requirements for battery raw materials (demand). There have been separate assessments of the availability of raw materials (supply). However, integrated assessments of supply and demand and their interaction over time are lacking to support decision-making. Using a dynamic market model that reflects the co-produced nature of cobalt, copper and nickel production as well as recycling, we estimate global output of these three metals under different EV growth scenarios from 2020 to 2040. In this work, results suggest that starting in 2025, replacement demand for battery raw materials becomes important. Thus, estimates for future material demand that consider only demands from new EVs are incomplete and misleading. EV deployment and associated increased demand for raw materials will have a greater impact on prices for cobalt than nickel and, in turn, for nickel than copper. High EV deployment scenarios will be difficult to achieve without larger supplies of copper, nickel and cobalt than forthcoming under the conditions modeled here, which anticipates a six-year time lag between a demand increase and the expansion of metal-production capacity. Shortening battery lifetimes and improving collection and recycling rates increase secondary supply, but the extent to which these factors support additional EV deployment is mixed.

54 ENVIRONMENTAL SCIENCES↗

HydroGEN STCH node support: FY25 Q1 quarterly report – LLNL's input

For reducing the cost of H 2 production by enhancing the efficiency and cyclability of water splitting reactions, we aim to understand the relationship between microstructure and surface reaction performance on perovskite oxides. In this quarter, mesoscale simulations were carried with various 3D porous microstructures to characterize the microstructure-dependent H 2 production. During the water splitting process, incoming gas including steam (H 2 O) passes through porous regions, which can induce local pressure variations according to the Bernoulli’s principle. Accordingly, we developed the mesoscale simulation method to characterize the reaction kinetics with inhomogeneous local pressures within porous microstructures.

08 HYDROGEN↗

Irradiation And Post-Irradiation Examination Plan For A709

The Advanced Materials and Manufacturing Technologies program is proposing a neutron irradiation campaign for alloy 709 (A709) plate product developed by the Advanced Reactor Technologies program. This irradiation campaign will support the deployment of A709 (included welded components) by providing data of engineering importance, such as data that can be used for establishing end-of-life design parameters and knockdown factors for irradiated materials properties versus properties for non-irradiated material. It will also advance the scientific understanding of A709 irradiation behaviors and material property evolution, which is vital for deploying A709 components into reactors with different neutron spectra, neutron fluxes, and irradiation temperatures as well as accelerating the deployment of new product forms and weld procedures. This document presents the plan for the neutron irradiation and post-irradiation examination for A709 and the scientific and technical basis for the plan.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Survey of emerging nuclear data needs for nonproliferation applications with advanced reactors

Nuclear science plays a key role in non-proliferation activities supporting advanced reactor technologies. Nuclear data underpin predictions and interpretations of nuclear material behavior and signatures in reactor fuel production, use, transport, and storage. Advanced reactors provide new challenges compared to the current fleet of thermal fission reactors. This report consolidates reported nuclear data needs from representative workshops, conferences, and publications, identifying six themes for recommended future investments supporting non-proliferation and safeguards applications. While also identified as data needs, major fission product evaluations and (α,n) reactions were omitted as there are ongoing activities producing new data under NA22/Objective O. Each theme is summarized below with example data and association with the nonproliferation mission for advanced fuels and reactors.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Status memorandum on ORNL support of vendor irradiation capsule design and ASME irradiation code development and new ASTM test standard development activities

This report is in submission of completion of the Level 4 milestone number M4TG-24OR0501111 within the larger Advanced Reactor Technologies Gas Cooled Reactor program at Oak Ridge National Laboratory (ORNL). The focus of this year’s efforts is to continue support of industry needs related to the development of future industry-funded irradiation programs. At ORNL these efforts included the development of a generalized three-dimensional CAD model of an irradiation creep capsules for graphite, cost estimates of the expansion of the Materials Irradiation Facility (MIF), involvement with ASTM D02.F0 “Manufactured Carbon and Graphite Products” and the ASME Boiler and Pressure Vessel Code, and publication of papers supporting these efforts. This report will document the status of these activities.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

NP-MRD: the Natural Products Magnetic Resonance Database

The Natural Products Magnetic Resonance Database (NP-MRD) is a comprehensive, freely available electronic resource for the deposition, distribution, searching and retrieval of nuclear magnetic resonance (NMR) data on natural products, metabolites and other biologically derived chemicals. NMR spectroscopy has long been viewed as the ‘gold standard’ for the structure determination of novel natural products and novel metabolites. NMR is also widely used in natural product dereplication and the characterization of biofluid mixtures (metabolomics). All of these NMR applications require large collections of high quality, well-annotated, referential NMR spectra of pure compounds. Unfortunately, referential NMR spectral collections for natural products are quite limited. It is because of the critical need for dedicated, open access natural product NMR resources that the NP-MRD was funded by the National Institute of Health (NIH). Since its launch in 2020, the NP-MRD has grown quickly to become the world's largest repository for NMR data on natural products and other biological substances. It currently contains both structural and NMR data for nearly 41,000 natural product compounds from >7400 different living species. All structural, spectroscopic and descriptive data in the NP-MRD is interactively viewable, searchable and fully downloadable in multiple formats. Extensive hyperlinks to other databases of relevance are also provided. The NP-MRD also supports community deposition of NMR assignments and NMR spectra (1D and 2D) of natural products and related meta-data. The deposition system performs extensive data enrichment, automated data format conversion and spectral/assignment evaluation.

59 BASIC BIOLOGICAL SCIENCES↗

Alkali-induced catalytic tuning at metal and metal oxide interfaces

Alkali metals have been recognized as effective promoters in heterogeneous catalysis, capable of enhancing catalytic activity and tuning product distributions. Over the past few decades, significant efforts have been made aiming to reveal the mechanisms underlying the promoting effect of alkalis. However, the roles that alkali metals play in the catalytic process remain elusive due to challenges in capturing their catalytic behaviours upon exposure to reactive environments. This review summarizes recent surface science and theoretical studies of alkali (potassium, cesium)-decorated metal and metal oxide model catalysts, revealing the crucial tuning by alkalis of activity and selectivity for CO 2 hydrogenation. The analysis of electronic structures identifies the selective binding mechanism of the positively charged alkali ions on the surface, being able to reduce the surface work function and lead to strong electron polarization on the surfaces. Depending on the alkali–support interaction, the deposition of alkalis can selectively modify the bindings of reaction intermediates involved in CO 2 hydrogenation via the interplay among the ionic, covalent and electrostatic tunings. As a result, CO 2 can be effectively activated and converted into diverse products at the alkali–support interface, ranging from formic acid to methanol and ethanol. The identified selective bond-tuning advances the application of alkalis in promoting catalytic activity and controlling catalytic selectivity at alkali–support interfaces.

03 NATURAL GAS↗

Deciphering the Mechanistic Role of Individual Oxide Phases and Their Combinations in Supported Mn–Na 2 WO 4 Catalysts for Oxidative Coupling of Methane

Oxidative coupling of methane (OCM) is an attractive direct route for upgrading methane to valuable chemicals. In this study, Temporal Analysis of Products (TAP) and steady state experiments are conducted to understand the role of individual oxide phases and their combinations in supported Mn-Na 2 WO 4 /SiO 2 catalysts for OCM. The results from TAP transient kinetic studies indicate that Mn plays an important role in promoting gas phase oxygen activation, while NaO x /SiO 2 and WO x /SiO 2 are relatively inert towards gas phase oxygen and methane activation. However, the supported catalyst combining Na and W in the form Na 2 WO 4 show enhanced gas phase oxygen activation exhibiting a much lower oxygen activation energy (148 kJ/mol) and enhanced activity toward methane activation as compared to the individual supported oxide catalysts. Addition of Mn to Na 2 WO 4 /SiO 2 further decreases the oxygen activation energy by 40 kJ/mol. Moreover, methane activation is also enhanced with CH 3 as the main intermediate but, with increasing Mn content, more CH 2 intermediates are observed. Different forms of oxygen (both dioxygen and atomic) are detected on the catalyst surface using isotopic pump/probe pulsing and their distribution is found to depend on the catalyst composition. An optimal Mn content in the Na 2 WO 4 /SiO 2 catalyst system is needed to enhance the amount of dioxide surface species (e.g., superoxide 16 O 2 - or peroxide 16 O 2 2- ) associated with the Na 2 WO 4 leading to high C 2 selectivity for OCM. When the Mn content is too high, the larger MnOx domains are shown to contribute to the formation of higher concertation of monoxide surface species that lead to nonselective OCM pathways. This insight from transient kinetic characterization using TAP combined with conventional steady state studies, provides a deeper understanding of the role of individual oxide phases and their combination on supported catalysts toward the formation of intermediate surface species and their impact on the OCM reaction mechanism. This knowledge is critical toward designing superior catalyst formulations for OCM.

10 SYNTHETIC FUELS↗

HFIR High Power HEU Neutronics Analyses

Department of Energy National Nuclear Security Administration Office of Material Management and Minimization’s mission includes the conversion of civilian research reactors from highly enriched uranium (HEU) to low-enriched uranium (LEU) fuel. Analyses have shown that the Oak Ridge National Laboratory High Flux Isotope Reactor (HFIR) will need to operate at 95 MW for the LEU silicide dispersion fuel designs to match key performance metrics obtained with HEU fuel at 85 MW. To prove safe operation of HFIR after installation of plant modifications to increase power, a high power HEU test cycle was proposed. Neutronics model updates and reactor physics analyses are performed to support the development of safety design reports for the high power (HP) HEU test cycle. Reactor physics metrics evaluated herein include fuel depletion, actinide production, cycle length, fission rate density distributions, axial power peaking factors, and reactor kinetic parameters. These reactor physics analyses support the development of future LEU safety design reports by providing key input for future HP HEU HFIR thermal hydraulics and reactor transient safety analyses.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Deliver Signal Phase and Timing (SPAT) for Energy Optimization of Vehicle Cohort Via Cloud-Computing and LTE Communications

Predictive Signal Phase and Timing (SPAT) message set is one fundamental building block for vehicle-to-infrastructure (V2I) applications such as Eco-Approach and Departure (EAD) at traffic signal controlled urban intersections. Among the two complementary communication methods namely short-range sidelink (PC5) and long-range cellular radio link (Uu), this paper documents the work with long-range link: the complete data chain includes connecting to the traffic signals via existing backhaul communication network, collecting the raw signal phase state data, predicting the signal state changes and delivering the SPAT data via a geofenced service to requests over HTTP protocols. An Application Programming Interface (API) library is developed to support various cellular data transmission reduction and latency improvement techniques. An emulation-based algorithm is applied to predict the traffic signal state changes to provide adequate prediction horizon (e.g., at minimum 2 minutes) for the cohort energy optimization. In fact, the same connectivity and SPAT delivery methodology has been applied to traffic signalized intersections nationwide in the United States upon public agency approvals for access to their firewalled traffic control network and signal control systems or directly to individual controllers. This methodology proves its effectiveness and potential for rapid growth of such SPAT deliveries at mass production scale without needing infrastructure hardware retrofit or excessive communication means. To support the energy optimization of light and heavy-duty vehicle cohorts of mixed automation and propulsion systems (EV, ICE and hybrid), the connection and SPAT deliveries at two sites were completed, including public roads in Washtenaw County, Michigan and closed track test sites at American Center for Mobility (ACM) in Ypsilanti, Michigan. However, only closed test track results at ACM will be presented in this paper. A neuroevolution based optimizer is developed and implemented to control the speed of a vehicle cohort with different propulsion systems and automation levels. Closed track tests showed significant energy savings of the cohort operation.

99 GENERAL AND MISCELLANEOUS↗

Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization

The current scale of plastics production and the accompanying waste disposal problems represent a largely untapped opportunity for chemical upcycling. Tandem catalytic conversion by platinum supported on γ-alumina converts various polyethylene grades in high yields (up to 80 weight percent) to low-molecular-weight liquid/wax products, in the absence of added solvent or molecular hydrogen, with little production of light gases. The major components are valuable long-chain alkylaromatics and alkylnaphthenes (average ~C 30 , dispersity Ð = 1.1). Coupling exothermic hydrogenolysis with endothermic aromatization renders the overall transformation thermodynamically accessible despite the moderate reaction temperature of 280°C. This approach demonstrates how waste polyolefins can be a viable feedstock for the generation of molecular hydrocarbon products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth and biochemical composition of the carrageenophyte Eucheumatopsis isiformis (Solieriaceae, Rhodophyta) under cultivation at different irradiance levels

Long-term production of a few species of Eucheuma and Kappaphycus from the Indo-Pacific Ocean supports the global carrageenan industry. The widespread use of vegetative propagation has resulted in low genetic diversity among farmed populations, making these crops increasingly vulnerable to diseases and environmental stressors, and resulting in declining yields and reduced biomass production over time. Insufficient efforts to develop and select new native cultivars, combined with the ecological risks posed by introducing nonindigenous species, underscore the urgent need to enhance cultivar diversification in eucheumatoid farming. Eucheumatopsis isiformis , a native carrageenophyte to the Atlantic Ocean, has potential for its cultivation in the Yucatán peninsula, Mexico. This study evaluated the growth and biochemical composition (pigments, elemental C and N, kappa/iota carrageenan ratio) of E. isiformis under different irradiance conditions in an indoor cultivation system. Specimens were collected in a subtidal population in Yucatán, Mexico, characterized, acclimatized to laboratory conditions, and exposed to five irradiance levels (71 ± 10.59 –1014 ± 65.85 µmol quanta m −2 s −1 ; 23.4 °C, salinity 33–34). Growth was measured weekly for six weeks, and elemental C and N content, pigment composition, and the kappa/iota-carrageenan ratio were evaluated. Growth and chromatic photoacclimation to light conditions were observed in all treatments. Highest growth rates (3.1–3.2% day −1 ) were registered between 238 ± 28.3 – 518 ± 44.3 µmol quanta m −2 s −1 , with a predominant iota-type carrageenan (0.97 ± 0.02) observed in all treatments. This study aims to provide guidelines for the successful development of the aquaculture of this carrageenophyte.

FTIR↗

Comparison of metagenomes from fermentation of various agroindustrial residues suggests a common model of community organization

The liquid residue resulting from various agroindustrial processes is both rich in organic material and an attractive source to produce a variety of chemicals. Using microbial communities to produce chemicals from these liquid residues is an active area of research, but it is unclear how to deploy microbial communities to produce specific products from the different agroindustrial residues. To address this, we fed anaerobic bioreactors one of several agroindustrial residues (carbohydrate-rich lignocellulosic fermentation conversion residue, xylose, dairy manure hydrolysate, ultra-filtered milk permeate, and thin stillage from a starch bioethanol plant) and inoculated them with a microbial community from an acid-phase digester operated at the wastewater treatment plant in Madison, WI, United States. The bioreactors were monitored over a period of months and sampled to assess microbial community composition and extracellular fermentation products. We obtained metagenome assembled genomes (MAGs) from the microbial communities in each bioreactor and performed comparative genomic analyses to identify common microorganisms, as well as any community members that were unique to each reactor. Collectively, we obtained a dataset of 217 non-redundant MAGs from these bioreactors. This metagenome assembled genome dataset was used to evaluate whether a specific microbial ecology model in which medium chain fatty acids (MCFAs) are simultaneously produced from intermediate products (e.g., lactic acid) and carbohydrates could be applicable to all fermentation systems, regardless of the feedstock. MAGs were classified using a multiclass classification machine learning algorithm into three groups, organisms fermenting the carbohydrates to intermediate products, organisms utilizing the intermediate products to produce MCFAs, and organisms producing MCFAs directly from carbohydrates. This analysis revealed common biological functions among the microbial communities in different bioreactors, and although different microorganisms were enriched depending on the agroindustrial residue tested, the results supported the conclusion that the microbial ecology model tested was appropriate to explain the MCFA production potential from all agricultural residues.

60 APPLIED LIFE SCIENCES↗

Integrated in situ spectroscopic studies on syngas production from partial oxidation of methane catalyzed by atomically dispersed rhodium cations on ceria

Catalytic reforming of methane to produce syngas is an important strategy for producing value-added chemicals. The conventional reforming catalyst relies on supported nickel nanoparticles. Here, in this work, we investigated singly dispersed Rh cations anchored on a CeO 2 catalyst (Rh 1 /CeO 2 ) for high activity and selectivity towards the production of syngas via partial oxidation of methane (POM) in the temperature range of 600–700 °C. The yields of H 2 and CO at 700 °C are 83% and 91%, respectively. The anchored Rh 1 atoms on CeO 2 of Rh 1 /CeO 2 are in the cationic state, and on an average each Rh 1 atom coordinates with 4–5 surface lattice oxygen atoms of CeO 2 . Compared to inert CeO 2 for POM, via the incorporation of single-atom sites, Rh 1 modifies the electronic state of oxygen atoms proximal to the Rh 1 atoms and thus triggers the catalytic activity of CeO 2 . The high activity of single-atom catalyst Rh 1 /CeO 2 suggests that the incorporation of single atoms of transition metals to the surface of a reducible oxide can modulate the electronic state of proximal anions of the oxide support toward forming an electronic state favorable for the selective formation of ideal products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Milestone 1.2.13: Preliminary Measurements of Radiolytic Nitric Acid Formation to Support Predictive Model Validation

Predictive computational models have been developed to support the technical basis for extended dry storage of aluminum-clad spent nuclear fuel (ASNF) in helium-backfilled cannisters. To date, these models have been optimized on a variety of irradiation experiments designed to elucidate the radiation-induced formation of molecular hydrogen gas, a radiolysis product that is potentially problematic for the safe storage of ASNF. However, the yield of nitric acid (HNO3) has not been determined, despite conservative predictions of its formation (300–4000 ppm) in 1% residual air environments irradiated in contact with ASNF. HNO3, another problematic radiolysis product, can lead to enhanced corrosion and potentially compromise storage canister integrity. Thus, to support the validation of predictive computer models, we report the measurement and quantification of HNO3 from the gamma irradiation of aluminum alloy coupons in humid air.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗