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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 1,063 records · Page 59
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

TCR Central Shutdown Rod Fine Motion Control

Transformational Challenge Reactor (TCR) is a Helium cooled 3 MWt test reactor that leverages advances in materials and manufacturing, computing, and AI in its design. Classical design of a shutdown rod uses either gravity, pneumatic, or springs to quickly release the Central Shutdown Rod (CSR) containing neutron absorber into the reactor core stopping nuclear reaction. Generally, the motor/actuator resides outside the reactor, but the motion is transmitted through a penetration into the pressure vessel. There are also designs where the control rod drive incorporates magnetic latches with coil residing outside the pressure boundary for precise position control of the rod. We are proposing a magnetic coupling to position the shutdown rod without any penetration into the pressure vessel for the entire drive length of TCR shutdown rod. Electromagnets are currently used in non-power nuclear reactors for shutdown rods, but these electromagnets are resident inside the reactor pressure vessel. This paper will describe the use of an electromagnet outside the pressure vessel to position and release the shutdown rod. A prototype was developed at ORNL to demonstrate the concept, and a design optimization of the ferritic core and material was conducted to maximize the lift force of the electromagnet. An elevated temperature testing was also performed to ensure that the system will perform under the temperature conditions inside an operating reactor.

Fountain, Eliott J.↗
DOE OSTI2015

Systems-based approach to understanding Technetium immobilization in the subsurface - 15326

The purpose of this work is to identify the chemical and biological reactions that occur and potentially influence the mobility of Technetium (Tc-99) in the subsurface. Tc-99 is a by-product of nuclear fission processes and has a relatively long half-life (t{sub 1/2}=212,000 years); additionally, it is highly soluble and mobile in groundwater and is most often remediated through pump and treat systems. The oxidized form of Tc-99 [Pertechnetate, Tc(VII)O{sub 4}-] is highly soluble and very mobile, while the reduced form of Tc-99 [Technetium-oxide, Tc(IV)O{sub 2}·nH{sub 2}O] is insoluble. Historically, complex interactions within the subsurface have made clean-up efforts for Tc-99 challenging. It is thought that environmental bacteria play a role in reducing contaminants to less soluble forms but it is difficult to predict or estimate the interactions and impacts of the complex, mixed microbial communities found in the environment. We have set up controlled batch experiments to examine a selection of organisms (Anaeromyxobacter dehalogenans strain CP-C, Geobacter sulfurreducens strain PAC, Geobacter daltonii strain FRC-32, and Shewanella oneidensis strain MR1) that have known metal reducing capabilities, for their ability to reduce Tc-99 to less soluble forms. An additional organism, Cellulomonas strain ES6 was chosen based on its origin of isolation from the Hanford site. Organisms were evaluated under anaerobic conditions both as isolates and in mixed consortia with and without the presence of iron-bearing mineral substrate. Experiments were monitored using spectroscopy, qPCR, volatile organic acid (VOA) analysis, and inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectrometer techniques (ICP-MS). Initial data collected has shown that the presence and type of substrate may increase the reduction of Tc-99 to less mobile forms. Data collected from these experiments will allow for (a) a better understanding of the mobility of Tc-99 in the subsurface, (b) better predictions of contaminant fate and transport over time, and (c) the development of long term remediation strategies for Tc-99. Additionally, information collected will be used to develop a systems-based metabolic model with predictive capabilities. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Measurements of SNAC2 area dosimeters placed in different configurations around the PROSPERO reactor and comparison with TRIPOLI-4 calculations

In the context of criticality accident alarm system tests, several experiments were carried out in 2013 on the PROSPERO reactor to study the response to neutron and gamma of different devices and dosimeters, particularly on the SNAC2 dosimeter. This article presents the results of this criticality dosimeter in different configurations, and compares the experimental measurements with the results of calculation performed with the TRIPOLI-4 Monte-Carlo Neutral Particles transport code. PROSPERO is a metallic critical assembly managed by the Criticality, Neutron Science and Measurement Department located at the French CEA Research Center of Valduc. The core, surrounded by a reflector of depleted uranium, is composed of 2 horizontal cylindrical blocks made of a highly enriched uranium alloy which can be placed in contact, and of 4 depleted uranium control rods which allow the reactor to be driven. This reactor, placed in a cell 10 m x 8 m x 6 m high, with 1.4-meter-thick concrete walls, is used as a fast neutron spectrum source and is operated at stable power level in delayed critical state, which can vary from 3 mW to 3 kW. PROSPERO is extensively used for electronic hardening or to study the effect of the neutrons on various materials. The SNAC2 criticality dosimeter is a zone dosimeter allowing the off line measurement of criticality accident neutron doses. This dosimeter consists of the pile up of seven activation foils embedded into a 23 mm diameter x 21 mm height cadmium container. The activation measurement of each foil, using a gamma spectroscopy technique, gives information about the neutron reaction rates. The SNAC2 software allows the spectrum unfolding from these values, taking into account the hypothesis of a particular spectrum shape, in three components: a Maxwell spectrum component for the thermal range, a 1/E component for the epithermal range, and a Watt spectrum component for the high energy range. Moreover, from the neutron spectrum, the SNAC software can calculate the neutron fluence integrated by the dosimeter and the neutron dose. During the 3 weeks measurement campaign many radioprotection devices were used. To modify the spectrum seen by these devices, several shields of various thicknesses made of concrete or polyethylene, with or without cadmium covers, were placed in the PROSPERO cell. These devices allow the study of criticality accident spectra in several environments: from metal to pseudo liquid. The fluxes measured by the SNAC2 devices were compared with TRIPOLI-4 calculations. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2026

Liquified SO 2 induced solid/cathode electrolyte interphase for lithium ion batteries

Formation of robust solid/cathode electrolyte interphases (S/CEI) is vital for long-term stability and high-performance operation of lithium-ion batteries (LIBs), particularly under high voltage regimes. However, engineering electrochemically stable S/CEIs that effectively suppress interfacial side reactions remains a key challenge. Herein, we introduce a liquefied sulfur dioxide (SO 2 )– ionic liquid complex as a fluorine-free multifunctional electrolyte additive for the first time that significantly improves the formation of sulfate/sulfite-rich S/CEI layers at both graphite and NMC811 interfaces. The unique SO 2 -N coordination with a 1,2,4-triazolide-based ionic liquid enables homogeneous SO 2 dissolution, resulting in controlled SO 2 decomposition during the initial electrochemical cycle. This decomposition yields sulfur-rich interphase species that stabilize the electrolyte-electrode interface, reduce impedance growth, and lessen electrolyte decomposition. Electrochemical tests show significantly improved cycle life, reduced polarization, and increased Coulombic efficiency for both anodes and cathodes. XPS confirms the presence of SO 2 -derived surface species that contribute to interfacial stability. In conclusion, this approach highlights a new direction for interphase engineering using liquefied gas additives and opens pathways for sulfur-based S/CEI chemistry in advanced battery systems.

Graphite↗
DOE OSTI2025

Alkali Metal Cation Effects for Rapid C–H Activation by Iron(0) Complexes

C–H oxidative addition is a key reaction in organometallic catalysis, motivating efforts to accelerate it. Here, we examine an anionic beta-diketiminate-supported iron(0) species that was previously observed to activate C-H bonds with Na(15-crown-5), but not with K(18-crown-6) or Rb(18-crown-6). Though crown ethers are usually seen as beneficial due to their ability to solubilize alkali metal cations, we observe that removing the crown ether leads to rapid and complete oxidative addition of the C-H bond even by K, Rb, and Cs. The products are iron(II) phenyl hydride complexes that exist as dimers bridged by the alkali metals. Neutron crystallography of the cesium complex verifies the presence and location of the bridging hydrides. It is likely that the crown-free alkali metal cations have greater Lewis acidity that enables them to facilitate oxidative addition of the C-H bond. This system gives insight on how to control the rate and favorability of C-H activation through manipulation of the countercation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

CCS2, an Octatricopeptide-Repeat Protein, Is Required for Plastid Cytochrome c Assembly in the Green Alga Chlamydomonas reinhardtii

In bacteria and energy generating organelles, c -type cytochromes are a class of universal electron carriers with a heme cofactor covalently linked via one or two thioether bonds to a heme binding site. The covalent attachment of heme to apocytochromes is a catalyzed process, taking place via three evolutionarily distinct assembly pathways (Systems I, II, III). System II was discovered in the green alga Chlamydomonas reinhardtii through the genetic analysis of the ccs mutants (cytochrome c synthesis), which display a block in the apo- to holo- form conversion of cytochrome f and c6, the thylakoid lumen resident c-type cytochromes functioning in photosynthesis. Here we show that the gene corresponding to the CCS2 locus encodes a 1,719 amino acid polypeptide and identify the molecular lesions in the ccs2-1 to ccs2-5 alleles. The CCS2 protein displays seven degenerate amino acid repeats, which are variations of the octatricopeptide-repeat motif (OPR) recently recognized in several nuclear-encoded proteins controlling the maturation, stability, or translation of chloroplast transcripts. A plastid site of action for CCS2 is inferred from the finding that GFP fused to the first 100 amino acids of the algal protein localizes to chloroplasts in Nicotiana benthamiana . Here, we discuss the possible functions of CCS2 in the heme attachment reaction.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

PageRank as a Collective Variable to Study Complex Chemical Transformations and Their Energy Landscapes

A reduced set of reaction coordinates are often employed in chemistry to describe the collective change between reactants and products within the context of rare event theories and in the exploration of energy landscapes. While incredibly powerful, use of these collective variables becomes increasingly challenging as the systems under study become more complex. Recent advancement of new descriptions of collective molecular coordinates have included PageRank (PR) analysis of the network of interactions about molecules and atoms within a system. Herein, PR is developed as a continuous variable that not only captures chemical transformations but can also be employed as a collective variable for a process that could span a highly dimensional energy surface. The derivatives of PR with respect to atomic coordinates are presented, and subsequently combined with forces during a chemical transformation within biased molecular dynamics sampling simulations to create the potential of mean force (PMF). This technique is demonstrated for two reactions: 1) the transformation of tetrahedral [Al(OH)4]-(aq) to octahedral [Al(OH)4(H2O)2]-(aq), and 2) the formation of contact ion pairs (CIPs) and solvent separated ion pairs (SSIPs) of Na+ and OH- in bulk water. Comparison of the behavior of the PR collective variable in both examples reveals that the ability of the PR to resolve local versus extended configurational attributes is tuned by the size of the network employed. This is a unique feature of PageRank that enables control over the resolution of the PMF that is produced.

chemistry, theories, PageRank↗
DOE OSTI2026

Cation Data for the East River Watershed, Colorado (2014-2025)

This data package contains mean values for cation concentration for water samples taken from the East River Watershed in Colorado. Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentrations of elements of interest simultaneously for the East River Watershed, Colorado groundwater and surface water samples to inform insights on the biogeochemistry processes within the watershed. The East River is part of the Watershed Function Scientific Focus Area (WFSFA) located in the Upper Colorado River Basin, United States. For samples collected prior to 06-16-2021, the instrumentation, Elan DRC II, PerkinElmer SCIEX, automatically switches among the three models necessary to analyze all 37 elements. These 37 elements include: (1) Lithium (Li), Beryllium (Be), Boron (B), Sodium (Na), Magnesium (Mg), Aluminium (Al), Silicon (Si), Phosphorus (P), Titanium (Ti), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Caesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th), Uranium (U) using standard model, argon Ar as reaction gas, (2) Potassium (K), Calcium (Ca), Vanadium (V), Chromium (Cr), Manganese (Mn), Iron (Fe) using dynamic reaction cell (DRC) model, ammonia NH3 as reaction gas, and (3) Phosphorus (P) and Selenium (Se) using DRC model, oxygen O2 as reaction gas. Note for the samples with higher concentrations of chloride (Cl-), asenic (As) concentrations were analysed with DRC model (oxygen O2 as reaction gas) to avoid the interference of chloride. For samples collected on and after 06-16-2021, an advanced Agilent 8900 triple quadrupole inductively coupled plasma mass spectrometry system (Agilent 8900 QQQ ICP-MS, Agilent Technologies) has been used to measure the concentrations of interested 36 elements simultaneously for environmental samples, including (1) Lithium (Li), Beryllium (Be) and Boron (B) using standard no gas mode, (2) Sodium (Na), Magnesium (Mg), Aluminium (Al) Phosphorus (P), Potassium (K), Chromium (Cr), Manganese (Mn), Iron (Fe), Cobalt (Co), Nickel (Ni), Copper (Cu), Zinc (Zn), Germanium (Ge), Arsenic (As), Rubidium (Rb), Strontium (Sr), Zirconium (Zr), Molybdenum (Mo), Silver (Ag), Cadmium (Cd), Tin (Sn), Antimony (Sb), Cesium (Cs), Barium (Ba), Europium (Eu), Lead (Pb), Thorium (Th) and Uranium (U) using standard helium (He) collision mode, (3) Titanium (Ti) and Vanadium (V) using high Energy (HEHe) helium (He) collision mode, and (4) Silicon (Si), Calcium (Ca) and Selenium (Se) using standard H2 reaction mode. All samples were prepared/diluted with 2% (v/v) ultrapure nitric acid in Milli-Q water (18.2 mega ohm-cm), and analyzed under a rigorous quality assurance and quality control (QA/QC) process. This data package contains (1) a zip file (cation_data_2014_2025.zip) containing a total of 5,849 files: 5.848 data files of cation data from across the Lawrence Berkeley National Laboratory (LBNL) Watershed Function Scientific Focus Area (SFA) which is reported in .csv files per location and a locations.csv (1 file) with latitude and longitude for each location; (2) a file-level metadata (v6_20260901_flmd.csv) file that lists each file contained in the dataset with associated metadata; (3) a data dictionary (v6_20260901_dd.csv) file that contains terms/column_headers used throughout the files along with a definition, units, and data type; (4) PDF and docx files for the detemination of Method Detection Limits (MDLs) for ICP-MS PerkinElmer DRC II instrumentation (Detemination_of_Method_Detection_Limits__MDLs__for_ICP_MS__PerkinElmer_Elan_DRC_II__LBL_Bldg74_Lab214D) for samples before November 2021; (5) PDF and docx files for the determination of MDLs for ICP-MS Agilent 8900 QQQ instrumentation (ICP_MS_Analysis_detection_limits_and_QA_QC_WenmingDong_updated_2026-08-06) for samples November 2021 and onward. Missing values within the anion data files are noted as either "-9999" or "0.0" for not detectable (N.D.) data. There are a total of 113 locations containing cation data. Update on 2021-04-11: Added Detemination of Method Detection Limits (MDLs) for ICP-MS document, which can be accessed as a PDF or with Microsoft Word. Update on 2022-06-10: versioned updates to this dataset was made along with these changes: (1) updated cation data for all locations up to 2021-12-31, (2) removal of units from column headers in datafiles, (3) added row underneath headers to contain units of variables, (4) removed suffix and prefix on two variables (“aqberylliumion_asberyllium” and “aqlithiumion_aslithium”), (5) added -9999 for empty numerical cells, and (6) the addition of the file-level metadata (flmd.csv) and data dictionary (dd.csv) were added to comply with the File-Level Metadata Reporting Format. Update on 2022-09-09: Updates were made to reporting format specific files (file-level metadata and data dictionary) to correct swapped file names, add additional details on metadata descriptions on both files, add a header_row column to enable parsing, and add version number and date to file names (v2_20220909_flmd.csv and v2_20220909_dd.csv). Update on 2023-08-08: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-01-05. The file level metadata and data dictionary files were updated to reflect the additional data added. Update on 2024-03-11: Updates were made to both the data files and reporting format specific files. New available anion data was added, up until 2023-10-16. Further, revisions to the data files were made to remove incorrect data points (from 1970 and 2001). The reporting format specific files were updated to reflect the additional data added. Updated versions of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021. Update on 2025-05-15: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2024 (September 30, 2024). International Generic Sample Numbers (IGSNs), when registered, were added to the data files. The reporting format specific files were updated to reflect the additional data added. Update on 2026-09-01: Updates were made to both the data files and reporting format specific files. New available cation data was added, up until the end of WY2025 (September 30, 2025). Updated versions, as of 2026-08-06, of the PDF and docx files for determination of MDLs for ICP-MS data were added to this dataset for samples starting in November 2021.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2013

Testing of Alternative Abrasives for Water-Jet Cutting at C Tank Farm

Legacy waste from defense-related activities at the Hanford Site has predominantly been stored in underground tanks, some of which have leaked; others may be at risk to do so. The U.S. Department of Energy’s goal is to empty the tanks and transform their contents into more stable waste forms. To do so requires breaking up, and creating a slurry from, solid wastes in the bottoms of the tanks. A technology developed for this purpose is the Mobile Arm Retrieval System. This system is being used at some of the older single shell tanks at C tank farm. As originally planned, access ports for the Mobile Arm Retrieval System were to be cut using a high- pressure water-jet cutter. However, water alone was found to be insufficient to allow effective cutting of the steel-reinforced tank lids, especially when cutting the steel reinforcing bar (“rebar”). The abrasive added in cutting the hole in Tank C-107 was garnet, a complex natural aluminosilicate. The hardness of garnet (Mohs hardness ranging from H 6.5 to 7.5) exceeds that of solids currently in the tanks, and was regarded to be a threat to Hanford Waste Treatment and Immobilization Plant systems. Olivine, an iron-magnesium silicate that is nearly as hard as garnet (H 6.5 to 7), has been proposed as an alternative to garnet. Pacific Northwest National Laboratory proposed to test pyrite (FeS 2 ), whose hardness is slightly less (H 6 to 6.5) for 1) cutting effectiveness, and 2) propensity to dissolve (or disintegrate by chemical reaction) in chemical conditions similar to those of tank waste solutions. Cutting experiments were conducted using an air abrader system and a National Institute of Standards and Technology Standard Reference Material (SRM 1767 Low Alloy Steel), which was used as a surrogate for rebar. The cutting efficacy of pyrite was compared with that of garnet and olivine in identical size fractions. Garnet was found to be most effective in removing steel from the target; olivine and pyrite were less effective, but about equal to each other. The reactivity of pyrite, compared to olivine and garnet, was studied in high-pH, simulated tank waste solutions in a series of bench-top experiments. Variations in temperature, degree of agitation, grain size, exposure to air, and presence of nitrate and nitrite were also studied. Olivine and garnet showed no sign of dissolution or other reaction. Pyrite was shown to react with the fluids in even its coarsest variation (150-1000 μm). Projected times to total dissolution for most experiments range from months to ca. 12 years, and the strongest control on reaction rate is the grain size.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Control blade degradation test under temperature gradient in steam atmosphere

The core of a boiling water reactor (BWR) consists of an array of fuel assemblies with cross-shaped control blades located between these assemblies. The typical control blade consists of a control blade sheath made of 316L-type S.S., a center pole made of 316L-type S.S., and control rods. In order to understand the degradation process of the control blade channel, control blade degradation tests were performed under various atmospheres with a temperature increase condition and in the presence of a temperature gradient. A test device was built. Four carbon heaters are set on both sides at the upper and the middle parts of the test device. The bottom ceramic part of the test device is cooled by water. Heating in the upper region and cooling at the bottom of the test piece give rise to the temperature gradient in the test piece. Temperatures of the test piece are measured by five W-Re type thermocouples placed close to the test piece. Steam carried by the argon gas is supplied from the bottom of the device and flows to the top inside a square carbon muffle in which the test piece is set. Three windows for visual observations are installed, with one located above the furnace and the others located at the back of the furnace. In the steam atmosphere with a steam flow rate of 0.0125 g/s/rod, the control blade, channel box, and fuel rods were degraded, especially at the upper part of the test piece. This result was similar to that observed in the argon atmosphere test. However, the observed degradation was rather different at a higher steam flow rate of 0.0417 g/s/rod. At the upper part of the test piece, only the control blade was degraded preferentially and did not react with the channel box wall. In contrast, the eutectic reaction of the stainless steel/boron carbide melt and zircaloy occurred at the lower part by coexisting with the relocated melt from the top part. These observations suggested the existence of a threshold condition for the control rod degradation between 0.0125 and 0.0417 g/s/rod which is significantly affected by the thickness of the oxide layer on zircaloy.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2016

Studies in High Energy Heavy Ion Nuclear Physics

This close-out report covers the period 1994 - 2015 for DOE grant DE-FG02-94ER40845 with the University of Texas at Austin. The research was concerned with studies of the strong nuclear force and properties of nuclear matter under extreme conditions of temperature and density which far exceed that in atomic nuclei. Such extreme conditions are briefly created (for about 10 trillionths of a trillionth of a second) during head-on collisions of large atomic nuclei (e.g. gold) colliding at speeds very close to the speed-of-light. The collisions produce thousands of subatomic particles, many of which are detected in our experiment called STAR at the Relativistic Heavy-Ion Collider at the Brookhaven National Lab in New York. The goal of our research is to learn how the strong nuclear force and its fundamental particles (quarks and gluons) behave in extreme conditions similar to that of the early Universe when it was about 1 micro-second old, and in the cores of very dense neutron stars. To learn anything new about the matter which exists for such a very short amount of time requires carefully designed probes. In our research we focused on two such probes, one being short-lived resonance particles and the other using correlations between pairs of the detected particles. Resonances are short-lived particles created in the collision, which interact with the surrounding matter, and which break apart, or "decay" into more stable particles which survive long enough to be seen in our detectors. The dependence of resonance properties on the conditions in the collision system permit tests of theoretical models and improve our understanding. Dynamical interactions in the matter also leave imprints on the final, outgoing particle distributions measured in the experiment. In particular, angular correlations between pairs of particles can be related to the fundamental strong force as it behaves in the hot, dense matter. Studying correlations as a function of experimentally controlled conditions of the collisions provides another test of theory. Our results provide unambiguous evidence that the briefly existing hot, dense matter has strong effects on the measurements and indicate that the matter is best described in terms of the fundamental quarks and gluons, that its internal interactions are surprisingly strong, and that new and never before seen strong interaction processes are occurring which remain to be explained theoretically. To enable these studies our group has also made substantial contributions to the detection capabilities of the STAR experiment. These contributions were to the electronics required to "read out" the weak electrical signals from the detectors and transfer the raw data to offline computers for processing. Although this experimental program is now concluded, the resonance and correlation results we have extracted from the raw collision data will continue to challenge and perhaps guide theoretical developments of the strong nuclear force for many years to come.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2026

Transformation of CeO 2 Nanoparticles into Atomically Dispersed Ce Cations Leads to Enhanced Reactivity for Automotive Emissions Control

Nanosized cerium oxide (CeO 2 ) has been extensively used as the oxygen storage component in automotive emission control systems. However, the possible influence of atomically dispersed Ce in these catalysts has not been recognized. Here, in this study, we demonstrate the controllable transformation of ceria nanoparticles into isolated cerium cations on γ-Al 2 O 3 via reductive atom trapping in 10% H 2 at 800 °C, achieving over half-monolayer coverage. Dispersed Ce 1 ions anchored by surface penta- and octa-coordinated Al sites exhibit outstanding thermal stability in air up to 500 °C, enabling further loading of active metals with well-defined catalyst structures. With this strategy, supported single-atom Rh 1 surrounded by dispersed Ce 1 is confirmed to exhibit much superior performance to Rh 1 on bare Al 2 O 3 or nanocrystalline CeO 2 in catalyzing NO reduction by CO, exhibiting a striking one-order-of-magnitude increase in activity. Dispersed Ce 1 exhibits greatly enhanced oxygen transfer capability compared to ceria nanoparticles and introduces a modified reaction mechanism that involves an adjacent Rh 1 –Ce 1 motif, resulting in a greatly decreased activation barrier (from 192 to 96 kJ/mol). The reactivity enhancements are also seen with Ce 1 -promoted Pt nanoparticles for oxidation of CO and hydrocarbons.

Jiang, Dong [Washington State Univ., Pullman, WA (↗
DOE OSTI2020

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

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

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Density functional theory-based surrogate kinetic models for heterogeneous reactions of hydrocarbon intermediates on silicon carbide

The increasing demand for high-performance materials in advanced technologies highlights the importance of achieving a fundamental understanding and potential control of silicon carbide (SiC) deposition processes. However, existing models often lack sufficient theoretical detail, relying heavily on empirical data and offering limited predictive capability. In particular, the complex surface chemistry governing SiC growth remains poorly understood. This study addresses these challenges by employing density functional theory (DFT) to investigate key heterogeneous reactions involving hydrocarbon intermediates on SiC surfaces, including dehydrogenation, hydrogenation, and carbon deposition. Transition state searches were conducted to identify reaction pathways and energy barriers. While first-principles calculations offer high accuracy, they are computationally intensive. To extend the utility of these first-principles results, vibrational analyses were performed using phonon-based statistical thermochemistry to compute temperature-dependent reaction rates which were used to develop Arrhenius-type surrogate kinetic models. Furthermore, the resulting framework provides a more rigorous, physically grounded basis for integrating atomistic insights into continuum-scale modeling, ultimately enabling improved prediction and optimization of SiC film growth in high-performance material systems.

Density Functional Theory↗
DOE OSTI2019

Influence of Particle Size on the Spin Pinning Effect in the fcc-FePt Nanoparticles

In this work, the Fe{sub 60}Pt{sub 40} nanoparticles were synthesized through the chemical reduction method by using the Fe(CO){sub 5} and the Pt(acac){sub 2} as the metallic precursor. The particle size of the synthesized FePt nanoparticles was controlled by adjusting the reaction conditions involving of the Fe(CO){sub 5}-injecting temperature and the soak time of reaction. The structure, morphology, and magnetic properties of the synthesized FePt nanoparticles were characterized by XRD, TEM, and vibrating sample magnetometer (VSM), respectively. The synthesized nanoparticles exhibit uniform size and good dispersity. The magnetization behaviors indicate that the nanoparticles present the core-shell magnetic structure including the ferromagnetic core part and the spin-disorder shell part. There exists a spin pinning effect of the shell part on the core part. The increase of particle size weakens the spin pinning effect.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2014

CaCO 3 Precipitation, Transport and Sensing in Porous Media with In Situ Generation of Reactants

Ureolytically driven calcite precipitation is a promising approach for inducing subsurface mineral precipitation, but engineered application requires the ability to control and predict precipitate distribution. To study the coupling between reactant transport and precipitate distribution, columns with defined zones of immobilized urease were used to examine the distribution of calcium carbonate precipitation along the flow path, at two different initial flow rates. As expected, with slower flow precipitate was concentrated toward the upstream end of the enzyme zone and with higher flow the solid was more uniformly distributed over the enzyme zone. Under constant hydraulic head conditions the flow rate decreased as precipitates decreased porosity and permeability. The hydrolysis/precipitation zone was expected to become compressed in the upstream direction. However, apparent reductions in the urea hydrolysis rate and changes in the distribution of enzyme activity, possibly due to CaCO 3 precipitate hindering urea transport to the enzyme, or enzyme mobilization, mitigated reaction zone compression. Co-injected strontium was expected to be sequestered by coprecipitation with CaCO 3 , but the results suggested that coprecipitation was not an effective sequestration mechanism in this system. In addition, spectral induced polarization (SIP) was used to monitor the spatial and temporal evolution of the reaction zone.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Final Technical Report - Consolidating Biomass Pretreatment with Saccharification by Resolving the Spatial Control Mechanisms of Fungi

Consolidated bioprocessing (CBP) of lignocellulose combines enzymatic sugar release (saccharification) with fermentation, but pretreatments remain separate and costly. In nature, lignocellulose-degrading brown rot fungi consolidate pretreatment and saccharification, likely using spatial gradients to partition these incompatible reactions. With the field of biocatalysis maturing, reaction partitioning is increasingly reproducible for commercial use. Therefore, my goal was to resolve the reaction partitioning mechanisms of brown rot fungi so that they can be applied to bioconversion of lignocellulosic feedstocks. Brown rot fungi consolidate oxidative pretreatments with saccharification and are a focus for biomass refining because 1) they attain >99% sugar yield without destroying lignin, 2) they use a simplified cellulase suite that lacks exoglucanase, and 3) their non-enzymatic pretreatment is facilitative and may be accelerated. Specifically, I hypothesized that during brown rot, oxidative pretreatments occur ahead of enzymatic saccharification, spatially, and the fungus partitions these reactions using gradients in pH, lignin reactivity, and plant cell wall porosity. In fact, we found three key results during these experiments for this work: 1) Brown rot fungi have an inducible cellulase system, unlike previous descriptions of a constitutive mechanism. 2) The induction of cellulases is delayed until there is repression of oxidatively-linked genes, allowing the brown rot fungi to coordinate two incompatible reactions (oxidative pretreatment with enzymatic saccharification, to release wood sugars) in the same pieces of wood. 3) This transition is mediated by the same wood sugar, cellobiose, released by the oxidative pretreatment step. Collectively, these findings have been published in excellent journal outlets and have been presented at conferences around the United States, and they offer clear targets for gene discovery en route to making biofuels and biochemicals affordable, commercially.

09 BIOMASS FUELS↗
DOE OSTI2025

Debonding-on-demand reversible adhesives via heat or light with competitive adhesion strength to conventional epoxy adhesives

Stimuli responsive debonding-on-demand (DoD) reversible adhesives are of great interest for the circular economy. However, the reversible adhesives developed so far often lack competitive adhesion strength in a bonding state. In this work, reversible epoxy adhesives based on Diels–Alder (DA) chemistry were developed and exhibited a competitive adhesion strength (e.g., 12 – 16 MPa of a lap shear strength) to commercial non-reversible epoxy adhesives. The reversible epoxy formulation showed superior thermal stability up to 110°C, and transition to a debonding state in the order of 0.1 MPa at 140°C, consequently, an on/off-type debonding behavior. The transition to a debonding state was attributed to crosslinking density control (e.g., decrease by 33% – 49%) through the reversible DA chemistry and the proximity to the glass transition. Next, for debonding by light stimulus, photothermal refractory plasmonic titanium nitride (TiN) nanoparticles were incorporated in the reversible epoxy, which can generate the required heat for debonding upon exposure to visible light. Photothermal debonding allows for precise debonding at target areas and tunable adhesion strength by controlling the exposure area and light intensity. The DA adhesive formulations containing 0.5 wt.% TiN nanoparticles presented a debonding state with zero adhesion under light exposure with intensity of 1670 mW/cm 2 (inducing 140°C). Even after three cycles of reattachment, the DA adhesive formulations retained 96% of the pristine sample’s adhesion strength measured at 110°C. Therefore, the DA adhesives are attractive candidates as reversible DoD systems applicable in higher temperatures.

42 ENGINEERING↗