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At least 433 records · Page 24
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Concept of Operations for Advanced Reactor Spent Nuclear Fuel Management

This presentation presents a preliminary description of a concept of operations to incorporate advanced-reactor spent nuclear fuel (SNF) into an integrated waste-management system (IWMS). The evaluation includes SNF from four advanced-reactor concepts with the following fuel types: (1) small modular reactors using oxide fuels, (2) tristructural-isotropic (TRISO) fuels, (3) metallic fuels, and (4) fuel salts. To provide context for the proposed concept of operations for advanced reactors, a comparison is made with traditional light-water reactors (LWRs) to identify potential gaps in the IWMS. The technical differences between advanced reactors and LWRs are assessed to determine the feasibility of managing advanced-reactor waste streams using existing operations and technology. This presentation emphasizes fuel types from Advanced Reactor Demonstration Program reactors: Xe 100, which uses TRISO fuel and Natrium, with its metallic fuels while also analyzing management options for molten-salt reactors and advanced light-water reactors (ALWRs). Understanding the storage, transportation, and disposal requirements of SNF is dependent on both the quantity and characteristics of the SNF generated by nuclear reactors. This presentation provides a high level overview, comparing the anticipated concept of operations for different SNFs from advanced reactors. The IWMS includes at-reactor storage, transportation, potential off-site storage, potential treatment, and disposition. To assess the potential effect of advanced-reactor concept of operations on the IWMS, estimates were made for fuel characteristics that contribute to storage, transportation, disposal, and possible treatment of advanced-reactor SNF. These include canister heat load, dose rates, and criticality-control limits, which are important for determining the condition and configuration of the advanced reactor SNF. At-reactor storage of LWR SNF traditionally involves a spent-fuel pool (SFP) before transfer to an independent spent-fuel storage installation. However, some advanced-reactor concepts, particularly those using TRISO and salt fuels, do not anticipate the use of an SFP. This difference in at-reactor storage could impact the IWMS. Additionally, transportation of advanced-reactor SNF may include additional processes tied to potential off gassing, and transportation of microreactor SNF may occur within the reactor vessel. Some advanced-reactor SNF could also undergo treatment to meet requirements of an acceptable waste form for disposition, and the treatment location will be a major contributor to efficiently performing IWMS responsibilities. Moreover, the quantity of SNF generated is an important consideration for IWMS because it could affect the size of the transportation fleet and potential off-site storage requirements. Additionally, volume and heat load are the primary drivers for SNF disposition. This presentation compares potential packaging options for advanced reactor SNF with traditional LWR packaging to provide a high-level comparison for the needs of the IWMS for advanced-reactor SNF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

ActiveBAS: A Low-cost, Scalable Control Solution for Grid-Interactive Small and Medium Sized Commercial Buildings

This project aims to develop and enhance a low-cost, highly scalable control solution for Small and Medium-Sized Commercial Buildings (SMCB), assess the business potential at multiple sites, and perform commercialization efforts. The technology can be applied to any buildings served by multiple units, with the benefits being greatest for open-spaced buildings, such as banks, retail stores, restaurants, and factories. This project aims to develop an affordable control solution for: 1) SMCB grid responsiveness, 2) reduction of GHG by changing unit operations, 3) greater reduction in utility costs, and 4) rapid adoption in the marketplace. The proposed technology will be built on a previously developed and demonstrated MPC solution. The minimal sensor requirement and less need of control expertise are the unique feature of the algorithm that leads to low capital and maintenance costs, and short installation and implementation time. These attributes contribute to low capital and maintenance costs, as well as a short installation and implementation time. However, these advantages come with a trade-off: increased difficulties and unreliability when applying traditional modeling and MPC control approaches due to limited information. This final report describes the modeling approaches developed and tested to overcome these challenges. It begins by outlining the modeling challenge posed by minimal sensor requirements, then delves into the proposed modeling approaches, which primarily involve system identification. Finally, preliminary test results for a simulation case study are presented.

24 POWER TRANSMISSION AND DISTRIBUTION↗
NASA NTRS2007

Focal-Plane Arrays of Quantum-Dot Infrared Photodetectors

Focal-plane arrays of semiconductor quantum-dot infrared photodetectors (QDIPs) are being developed as superior alternatives to prior infrared imagers, including imagers based on HgCdTe devices and, especially, those based on quantum-well infrared photodetectors (QWIPs). HgCdTe devices and arrays thereof are difficult to fabricate and operate, and they exhibit large nonunformities and high 1/f (where f signifies frequency) noise. QWIPs are easier to fabricate and operate, can be made nearly uniform, and exhibit lower 1/f noise, but they exhibit larger dark currents, and their quantization only along the growth direction prevents them from absorbing photons at normal incidence, thereby limiting their quantum efficiencies. Like QWIPs, QDIPs offer the advantages of greater ease of operation, greater uniformity, and lower 1/f noise, but without the disadvantages: QDIPs exhibit lower dark currents, and quantum efficiencies of QDIPs are greater because the three-dimensional quantization of QDIPs is favorable to the absorption of photons at normal or oblique incidence. Moreover, QDIPs can be operated at higher temperatures (around 200 K) than are required for operation of QWIPs. The main problem in the development of QDIP imagers is to fabricate quantum dots with the requisite uniformity of size and spacing. A promising approach to be tested soon involves the use of electron-beam lithography to define the locations and sizes of quantum dots. A photoresist-covered GaAs substrate would be exposed to the beam generated by an advanced, high-precision electron beam apparatus. The exposure pattern would consist of spots typically having a diameter of 4 nm and typically spaced 20 nm apart. The exposed photoresist would be developed by either a high-contrast or a low-contrast method. In the high-contrast method, the spots would be etched in such a way as to form steep-wall holes all the way down to the substrate. The holes would be wider than the electron beam spots perhaps as wide as 15 to 20 nm, but may be sufficient to control the growth of the quantum dots. In the low-contrast method, the resist would be etched in such a way as to form dimples, the shapes of which would mimic the electron-beam density profile. Then by use of a transfer etching process that etches the substrate faster than it etches the resist, either the pattern of holes or a pattern comprising the narrow, lowest portions of the dimples would be imparted to the substrate. Having been thus patterned, the substrate would be cleaned. The resulting holes or dimples in the substrate would serve as nucleation sites for the growth of quantum dots of controlled size in the following steps. The substrate would be cleaned, then placed in a molecular-beam-epitaxy (MBE) chamber, where native oxide would be thermally desorbed and the quantum dots would be grown.

Gunapala, Sarath↗
DOE OSTI2020

Supported and coordinated single metal site electrocatalysts

The ever-increasing global environmental and energy crisis issues necessitates technological innovation, especially in the development of renewable energy-related devices, such as electrochemical energy conversion and storage technologies, including fuel cells, water electrolyzers, and CO 2 electrolyzers. Reliable and sustainable energy conversion devices are highly dependent on engineering of electrocatalysts. Furthermore, state-of-the-art electrocatalysts for these electrochemical conversion systems are usually platinum group metal (PGM)-based nanoparticles with high cost, which has sparked intensive research on atomically dispersed single metal site electrocatalysts for decreasing metal loadings and boosting catalytic efficiencies by taking advantage of their inherent electronic effects, quantum size effects, and metal-support interactions. In this review, we first introduced the intrinsic active site identification and stabilization, followed by addressing the mutual metal-support interactions, and most important, their correlations with catalytic properties. Next, the advances in synthetic strategies and characterization techniques for single metal site electrocatalysts are highlighted. Additionally, recent advances in single metal site electrocatalysts designs for applications in electrochemical conversion reactions are also presented. Finally, remaining challenges and a forward-looking perspective on this field of research are provided.

25 ENERGY STORAGE↗
DOE OSTI2022

Central-place foraging poses variable constraints year-round in a neotropical migrant

Background: “Central-place foragers” are constrained in their habitat selection and foraging range by the frequency with which they need to return to a central place. For example, chick-rearing songbirds that must feed their offspring hourly might be expected to have smaller foraging ranges compared to non-breeding songbirds that return nightly to a roost. Methods: We used GPS units to compare the foraging behaviour of an aerial insectivorous bird, the purple martin (Progne subis), during the breeding season in three regions across North America, as well as the non-breeding season in South America. Specifically, we tested foraging range size and habitat selection. Results: Foraging range did not vary among regions during breeding (14.0 ± 39.2 km 2 ) and was larger during the nonbreeding period (8840 ± 8150 km 2 ). Purple martins strongly preferred aquatic habitats to other available habitats year-round and in the Amazon commuted from night roosts in low productivity sediment-poor water, where risk of predation was probably low, to daytime foraging sites in productive sediment-rich water sites. Conclusions: We provide the first estimates for foraging range size in purple martins and demonstrate foraging preference for aquatic habitats throughout two stages of the annual cycle. Understanding foraging constraints and habitat of aerial insectivores may help plan conservation actions throughout their annual cycle. Future research should quantify foraging behaviour during the post-breeding period and during migration.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Impacts of Different Operation Conditions and Geological Formation Characteristics on CO2 Sequestration in Citronelle Dome, Alabama

Major concerns of carbon dioxide (CO2) sequestration in subsurface formations are knowledge of the well injectivity and gas storage capacity of the formation, the CO2 pressure and saturation plume extensions during and after injection, and the risks associated with CO2 leakage and fault reactivation. Saline reservoirs are considered as one of the target formations for CO2 sequestration through structural, residual, dissolution, and mineral trapping mechanisms. The boundary condition of the saline reservoir dictates the pressure and saturation plume extension of the injected supercritical CO2 that could expand over large distances. This can lead to sources of risk, e.g., leakage and/or fault reactivation due to presence of wells, thief zones, and geological discontinuities. Therefore, there is a critical need to develop a model that describes how risk-related performance metrics (i.e., the CO2 saturation plume size, the pressure differential plume area, and the pressure differential at specific locations) vary as a function of the size of injection, time following injection, injection operations, and geologic environment. In this study, a systematic reservoir modeling studies of anthropogenic CO2 sequestration in Citronelle dome, Alabama, was performed where all relevant scenarios and conditions to address the questions of the saturation and pressure plume size in the area of review (AoR) and post-injection site care (PISC) are considered. The objective for this study was firstly to systematically simulate CO2 sequestration, i.e., saturation dynamics, and pressure behavior over a range of operational and geological conditions and to derive conclusions about the factors influencing saturation and pressure plume size, post-injection behavior, and the risk associated with them, by developing third-generation reduced order models (ROMs) for reservoir behavior. Finally, to assess the uncertainty associated with our studies, Latin Hypercube Sampling (LHS) together with an experimental design technique, i.e., Plackett–Burman design, was used. Application of Pareto charts and respond surfaces enabled us to determine the most important parameters impacting saturation and pressure plume sizes and to quantify the auto- and cross-correlation among different parameters in both history-matched and upscaled models.

58 GEOSCIENCES↗
DOE OSTI2024

A Data-Driven Approach to Real-World Degradation of Backsheets

The objectives of this project are as follows: • The population behavior of fielded modules in various conditions of use • Predictions of materials in specific climatic zones • Understanding of a module’s local environment in the field on its degradation It aims to understand how and what backsheet materials of photovoltaic modules degrade in the real world field. • Field Survey Protocol This project is started from the protocol, because all the data, information, domain knowledge are from experience of the real world field surveys, which is based on the protocol. The Protocol is explored from the experience of the field survey observations. With the increasing of the field surveys, it is refined for three versions, which are Task 1.0 (Section 3.1), Task 6.0 (Section 3.6), Task 10.0 (Section 3.10) respectively. It includes a document and a training video, which is able to direct other teams to follow the same procedure with the sites surveyed during this project. The documents include the detailed information but is not limited to the terminology definition, instruments SOP, preparation items for the surveys, form for the data collections, the order of the information collection. The final version of the protocol can be found at Appendix A, see Section 5. Additional, It can also be found at Open Science Framework (OSF), see Section 3.18 for detail. • Written Waiver Request Before staring the field surveys, the request of the waiver for international surveys is completed, because the limitation of climate zone in the United States, see Appendix B in Section 6 for the request documents. Unfortunately, only 1 international site from Taiwan, China can be finished, due to the COVID-19. • Field Survey According to the protocol we built in Section 3.1, 3.6 and 3.10, 41 sites have been surveyed across seven different climate zones (Cfa, Csa, Csb, BSk, Dfa, Dfb, Am). A variety of materials, including Polyethylene Naphthalate (PEN), Polyethylene Terephthalate (PET), Polyvinyl Fluoride (PVF), Polyvinylidene Fluoride (PVDF), Acrylic PVDF, Fluoroethylene Vinyl Ether (FEVE), and Glass, were identified. These sites are located in various states including California, South Carolina, New Mexico, Maryland, Ohio, Tennessee, Florida, Massachusetts, Illinois, Minnesota, Oregon, Colorado, and Taiwan, Republic of China. The ages of the sites ranged from 2 - 38 years in service and the field size varied from 1 MW - 25 MW. All requirements for the modeling have been satisfied. Some observations like ’Edge Effect’ for the rows and Junction box heating will also be a useful knowledge to build the model. Section 3.7 provides detailed information on the sites visited during this reporting period.

14 SOLAR ENERGY↗
NASA NTRS2005

Thermal Characterization of Fe3O4 Nanoparticles Formed from Poorly Crystalline Siderite

Increasing interest in environmental geochemistry has led to the recognition that crystals with sizes in the nanometer range (e.g., colloids and nanoscale precipitates) and poorly crystalline compounds (e.g., ferrihydrites) may comprise the majority of reactive mineral surface area near the Earth s surface. When the diameters of individual particles are in the range of 100 nm or less, the surface energy contribution to the free energy modifies phase stability. This results in stabilization of polymorphs not normally encountered in the macrocrystal domain. These phases potentially have very different surface-site geometries, adsorptive properties, and growth mechanisms, and exhibit size-dependent kinetic behavior. Thus nanophases dramatically modify the physical and chemical properties of soils and sediments. In a more general sense, the characteristics of nanocrystals are of intense technological interest because small particle size confers novel chemical, optical, and electronic properties. Thus, nanocrystalline materials are finding applications as catalytic substrates, gas phase separation materials, and even more importantly in the field of medicine. This is an opportune time for mineral physicists working on nanocrystalline materials to develop collaborative efforts with materials scientists, chemists, and others working on nanophase materials of technological interest (e.g., for magnetic memories). Our objective in this study was to synthesize submicron (<200 nm) magnetite and to study their thermal and particle size properties.

Lauer, H. V., Jr.↗
DOE OSTI2022

Spatial Study 2021: Sensor-Based Time Series of Surface Water Temperature, Specific Conductance, Total Dissolved Solids, pH, and Dissolved Oxygen from across Multiple Watersheds in the Yakima River Basin, Washington, USA (v3)

This dataset supports a broader study examining the drivers of spatial variability in sediment respiration rates in the Yakima River Basin. The dataset provides two-hour time series hydrological and water chemistry sensor data, manual chamber open channel respiration data, handheld sensor water chemistry data, river substrate grain size photos, general environmental context photos, and field metadata (including qualitative information on instream and river corridor characteristics) collected during the same two-week period at 47 sites within multiple rivers throughout the Yakima River Basin in Washington, USA. Grain size photos can be used to improve estimates of channel substrate D50 data. Related sample-based water chemistry data are published separately at https://data.ess-dive.lbl.gov/datasets/doi:10.15485/1898914.This dataset is comprised of four main folders, one containing three sensor-specific subfolders and the others containing photographs. The SFA_SpatialStudy_2021_SensorData main data folder includes file-level metadata (FLMD), data dictionary (dd), installation methods, field metadata, Ultrameter water chemistry data, field data collection protocols, international generic sample number (IGSN) mapping file, and a readme file. The “Sensor_Manual_Specifications” subfolder contains pdf files from the manufacturer of each sensor with details on the sensor specifications. Each sensor subfolder (BarotrollAtm, MantaRiver, and MinidotManualChamber) contains a sensor data subfolder for timeseries data and a subfolder for plots and summary statistics. The BarotrollAtm Data subfolder contains In Situ Rugged BaroTROLL pressure and temperature data. The MantaRiver Data subfolder contains Eureka Manta+ 35B multisonde temperature, specific conductance, and pH data. The MinidotManualChamber Data subfolder contains PME MiniDOT Logger dissolved oxygen (mg/L and percent saturation) and temperature data. The folder SFA_SpatialStudy_2021_EnvironmentalContextPhotos contains environmental context photographs and videos. The folders SFA_SpatialStudy_2021_SedimentQuadratPhotos_Part1 and SFA_SpatialStudy_2021_SedimentQuadratPhotos_Part2 contain sediment quadrat photographs. All files are .csv, .pdf, .R, .jpg, .jpeg, .mp4, or .mov. This data package was originally published September 2022. It was updated January 2023 (modified files) and June 2024 (new and modified files). See the change history in data package readme for more details.We acknowledge the Yakama Nation as owners and caretakers of the lands where we collected these data. We thank the Confederated Tribes and Bands of the Yakama Nation Tribal Council and Yakama Nation Fisheries for working with us to facilitate sample collection and optimization of data usage according to their values and worldview.

54 ENVIRONMENTAL SCIENCES↗
NASA NTRS2006

Application of Aerosol Hygroscopicity Measured at the Atmospheric Radiation Measurement Program's Southern Great Plains Site to Examine Composition and Evolution

A Differential Mobility Analyzer/Tandem Differential Mobility Analyzer (DMA/TDMA) was used to measure submicron aerosol size distributions, hygroscopicity, and occasionally volatility during the May 2003 Aerosol Intensive Operational Period (IOP) at the Central Facility of the Atmospheric Radiation Measurement Program's Southern Great Plains (ARM SGP) site. Hygroscopic growth factor distributions for particles at eight dry diameters ranging from 0.012 micrometers to 0.600 micrometers were measured throughout the study. For a subset of particle sizes, more detailed measurements were occasionally made in which the relative humidity or temperature to which the aerosol was exposed was varied over a wide range. These measurements, in conjunction with backtrajectory clustering, were used to infer aerosol composition and to gain insight into the processes responsible for evolution. The hygroscopic growth of both the smallest and largest particles analyzed was typically less than that of particles with dry diameters of about 0.100 micrometers. It is speculated that condensation of secondary organic aerosol on nucleation mode particles is largely responsible for the minimal hygroscopic growth observed at the smallest sizes considered. Growth factor distributions of the largest particles characterized typically contained a nonhygroscopic mode believed to be composed primarily of dust. A model was developed to characterize the hygroscopic properties of particles within a size distribution mode through analysis of the fixed size hygroscopic growth measurements. The performance of this model was quantified through comparison of the measured fixed size hygroscopic growth factor distributions with those simulated through convolution of the size-resolved concentration contributed by each of the size modes and the mode-resolved hygroscopicity. This transformation from sizeresolved hygroscopicity to mode-resolved hygroscopicity facilitated examination of changes in the hygroscopic properties of particles within a size distribution mode that accompanied changes in the sizes of those particles. This model was used to examine three specific cases in which the sampled aerosol evolved slowly over a period of hours or days.

Gasparini, Roberto↗
NASA NTRS2000

Clustered DNA damages induced in isolated DNA and in human cells by low doses of ionizing radiation

Clustered DNA damages-two or more closely spaced damages (strand breaks, abasic sites, or oxidized bases) on opposing strands-are suspects as critical lesions producing lethal and mutagenic effects of ionizing radiation. However, as a result of the lack of methods for measuring damage clusters induced by ionizing radiation in genomic DNA, neither the frequencies of their production by physiological doses of radiation, nor their repairability, nor their biological effects are known. On the basis of methods that we developed for quantitating damages in large DNAs, we have devised and validated a way of measuring ionizing radiation-induced clustered lesions in genomic DNA, including DNA from human cells. DNA is treated with an endonuclease that induces a single-strand cleavage at an oxidized base or abasic site. If there are two closely spaced damages on opposing strands, such cleavage will reduce the size of the DNA on a nondenaturing gel. We show that ionizing radiation does induce clustered DNA damages containing abasic sites, oxidized purines, or oxidized pyrimidines. Further, the frequency of each of these cluster classes is comparable to that of frank double-strand breaks; among all complex damages induced by ionizing radiation, double-strand breaks are only about 20%, with other clustered damage constituting some 80%. We also show that even low doses (0.1-1 Gy) of high linear energy transfer ionizing radiation induce clustered damages in human cells.

NASA Discipline Radiation Health↗
DOE OSTI2020

In-situ IR Spectroscopy Study of Reactions of C3 Oxygenates on Heteroatom (Sn, Mo, and W) doped BEA Zeolites and the Effect of Co-adsorbed Water

The reactions of acetone and hydroxyacetone over heteroatom doped BEA zeolites (Sn, Mo, and W) in the presence and absence of H 2 O vapor are investigated using infrared spectroscopy. Acetone is converted to mesityl oxide over Sn-BEA exclusively. At higher temperatures, larger oxygenates such as phorones, aromatics, and coke form. The presence of co-adsorbed water in Sn-BEA suppresses tautomerization. H 2 O vapor is also beneficial for minimizing coke formation at high temperatures. Hydroxyacetone is converted into 2-hydroxypropanal over Sn-BEA, exhibiting high affinity to Sn sites up to 400 °C. Sn-BEA catalyzes conversion of hydroxyacetone into the enol in the absence of H 2 O, but exposure to H 2 O induces the formation of 2-hydroxypropanal and subsequent conversion to acrolein. Furthermore, the Lewis acid descriptors are used to rationalize the reaction pathways. For the isomerization of hydroxyacetone into 2-hydroxypropanal, the hardness of acid sites influences the reaction and correlates with the overall Lewis acidity of the catalysts, respectively. However, the size of the exchanged metal significantly affects aldol condensation, where keto and enol forms of acetone adsorb to active sites simultaneously.

36 MATERIALS SCIENCE↗
DOE OSTI2024

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

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

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Tailoring the Angular Mismatch in MoS 2 Homobilayers through Deformation Fields

Ultrathin MoS 2 has shown remarkable characteristics at the atomic scale with an immutable disorder to weak external stimuli. Ion beam modification unlocks the potential to selectively tune the size, concentration, and morphology of defects produced at the site of impact in 2D materials. Combining experiments, first-principles calculations, atomistic simulations, and transfer learning, it is shown that irradiation-induced defects can induce a rotation-dependent moiré pattern in vertically stacked homobilayers of MoS 2 by deforming the atomically thin material and exciting surface acoustic waves (SAWs). Furthermore, the direct correlation between stress and lattice disorder by probing the intrinsic defects and atomic environments are demonstrated. The method introduced in this paper sheds light on how engineering defects in the lattice can be used to tailor the angular mismatch in van der Waals (vdW) solids.

2D materials↗
DOE OSTI2025

Scanning tunneling microscope tip-induced formation of Bi bilayers on Bi 2 Te 3

We report the formation of Bi(111) bilayer islands and crater structures on Bi 2 Te 3 (111) surfaces induced by voltage pulses from a scanning tunneling microscope tip. Pulses above a threshold voltage (+3 V) produce craters ∼0.5μm in diameter, similar to the size of the tip. Redeposited material self-assembles into a network of atomically ordered islands with a lattice constant identical to the underlying Bi2Te3 surface. The island size monotonically decreases over several micrometers from the pulse site, until the pristine Bi 2 Te 3 surface is recovered. We assign these islands to Bi bilayer based on atomic resolution images, analysis of step heights, and tunneling spectroscopy. Here, the dependence of bilayer formation on bias polarity and the evidence for defect diffusion together suggest a mechanism driven by the interplay of field evaporation and tunneling-current-induced Joule heating.

Bi bilayer↗
DOE OSTI2021

Characterization of aromatic acid/proton symporters in Pseudomonas putida KT2440 toward efficient microbial conversion of lignin-related aromatics

Pseudomonas putida KT2440 (hereafter KT2440) is a well-studied platform bacterium for the production of industrially valuable chemicals from heterogeneous mixtures of aromatic compounds obtained from lignin depolymerization. KT2440 can grow on lignin-related monomers, such as ferulate (FA), 4-coumarate (4CA), vanillate (VA), 4-hydroxybenzoate (4HBA), and protocatechuate (PCA). Genes associated with their catabolism are known, but knowledge about the uptake systems remains limited. In this work, we studied the KT2440 transporters of lignin-related monomers and their substrate selectivity. Based on the inhibition by protonophores, we focused on five genes encoding aromatic acid/H+ symporter family transporters categorized into major facilitator superfamily that uses the proton motive force. Furthermore, the mutants of PP_1376 (pcaK) and PP_3349 (hcnK) exhibited significantly reduced growth on PCA/4HBA and FA/4CA, respectively, while no change was observed on VA for any of the five gene mutants. At pH 9.0, the conversion of these compounds by hcnK mutant (FA/4CA) and vanK mutant (VA) was dramatically reduced, revealing that these transporters are crucial for the uptake of the anionic substrates at high pH. Uptake assays using 14 C-labeled substrates in Escherichia coli and biosensor-based assays confirmed that PcaK, HcnK, and VanK have ability to take up PCA, FA/4CA, and VA/PCA, respectively. Additionally, analyses of the predicted protein structures suggest that the size and hydropathic properties of the substrate-binding sites of these transporters determine their substrate preferences. Overall, this study reveals that at physiological pH, PcaK and HcnK have a major role in the uptake of PCA/4HBA and FA/4CA, respectively, and VanK is a VA/PCA transporter. This information can contribute to the engineering of strains for the efficient conversion of lignin-related monomers to value-added chemicals.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2021

In situ spectroscopic insights into the redox and acid-base properties of ceria catalysts

Cerium oxide (ceria) plays an important and fascinating role in heterogeneous catalysis as illustrated by its versatile use as a catalyst, a catalyst support, or a promotor in various oxidation and reduction reactions. Central to these reactions is the rich defect chemistry, facile redox capability, and unusual acid-base properties of ceria. Understanding the unique redox and acid-base properties of ceria is essential to build the structure-catalysis relationship so that improved catalytic functions can be achieved for ceria-based materials. Among the characterization toolbox, spectroscopic approach indisputably stands out for its unparalleled power in offering chemical insights into the surface properties of ceria at atomic and molecular level. In this review, we summarize advances in revealing the redox and acid-base properties of ceria via a variety of spectroscopic methods including optical, X-ray, neutron, electronic and nuclear spectroscopy. Both direct spectroscopy characterization and its coupling with probe molecules are analyzed to illustrate how the nature, strength and density of different surface sites are influenced by the pretreatment, the morphology and size of ceria nanoparticles. Further directions in taking advantage of in situ/operando spectroscopy for better understanding the catalysis of ceria-based materials are detailed in the summary and outlook section.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗