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At least 1,387 records · Page 77

Iridium-Doped Nanosized Zn–Al Layered Double Hydroxides as Efficient Water Oxidation Catalysts

Layered double hydroxides (LDHs) are an ideal platform to host catalytic metal centers for water oxidation (WO) owing to the high accessibility of water to the interlayer region, which makes all centers potentially reachable and activated. In this paper, we report the syntheses of three iridium-doped zinc–aluminum LDHs (Ir-LDHs) nanomaterials (1–3, with about 80 nm of planar size and a thickness of 8 nm as derived by field emission scanning electron microscopy and powder X-ray diffraction studies, respectively), carried out in the confined aqueous environment of reverse micelles, through a very simple and versatile procedure. These materials exhibit excellent catalytic performances in WO driven by NaIO 4 at neutral pH and 25 °C, with an iridium content as low as 0.5 mol % (~0.8 wt %), leading to quantitative oxygen yields (based on utilized NaIO 4 , turnover number up to ~10,000). Nanomaterials 1–3 display the highest ever reported turnover frequency values (up to 402 min –1 ) for any heterogeneous and heterogenized catalyst, comparable only to those of the most efficient molecular iridium catalysts, tested under similar reaction conditions. The boost in activity can be traced to the increased surface area and pore volume (>5 times and 1 order of magnitude, respectively, higher than those of micrometric materials of size 0.3–1 μm) estimated for the nanosized particles, which guarantee higher noble metal accessibility. X-ray absorption spectroscopy (XAS) studies suggest that 1–3 nanomaterials, as-prepared and after catalysis, contain a mixture of isolated, single octahedral Ir(III) sites, with no evidence of Ir–Ir scattering from second-nearest neighbors, excluding the presence of IrO 2 nanoparticles. The combination of the results obtained from XAS, elemental analysis, and ionic chromatography strongly suggests that iridium is embedded in the brucite-like structure of LDHs, having four hydroxyls and two chlorides as first neighbors. These results demonstrate that nanometric LDHs can be successfully exploited to engineer efficient WOCs, minimizing the amount of iridium used, consistent with the principle of the noble-metal atom economy.

36 MATERIALS SCIENCE↗

Industrial Assessment Center for Energy Efficiency, Smart Manufacturing and Cyber Security of Illinois and Northwestern Indiana Small and Medium Sized Manufacturing Companies and Water Facilities (Final Technical Report)

The University of Illinois Chicago (UIC) established and implemented a U.S. Department of Energy (DOE) sponsored Industrial Assessment Center (IAC) from September 1, 2016 through December 31, 2021. The established UIC IAC focused on providing 1) technical assistance to small and medium-sized enterprises (SMEs) and water and wastewater facilities in Illinois and northwestern Indiana and 2) education and training university students developing the future energy workforce. The technical assessments incorporated energy efficiency, increasing productivity via smart manufacturing, energy management systems, enhancing on-site cyber security practices, and the promotion of DOE best practices and tools. The educational training enabled UIC faculty and staff to provide classroom education, exposure to industry research, multiple targeted training sessions, real world experience with industry professionals, and live training to implement professional grade audits and recommendations.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Integration and commissioning plan of Full Flow Purifier at Muon Campus

The Full Flow Purifier for Fermilab’s Muon Campus uses a charcoal bed surrounded by a liquid nitrogen jacket to purify up to 240 g/s of helium gas. Fabrication by Ability Engineering Technology Inc. has been completed and the purifier delivered to Fermilab. It is the largest purifier to be used at Fermilab based on both capacity and size. A previous paper discussed the design of purifier for various operational conditions and horizontal shipping. The purifier is designed to withstand 5g force in vertical and 2g force in lateral and longitudinal directions. Transportation experience from vendor to Fermilab and within site is discussed. Integration of the purifier involved design and fabrication of a liquid nitrogen transfer line, regeneration system, and helium piping to connect it to Muon Campus cryogenic system. It also involved establishing electrical, instrumentation and controls connections to the system. Integration of the purifier is discussed in detail. The purifier is to be commissioned using up to 4 MYCOM helium compressors to supply helium and liquid nitrogen supplied by a 15,000 -gallon tank. Actual effectiveness of the 3-stream heat exchanger is to be estimated based on measured temperatures and flow rate. Impurity levels shall be monitored at inlet and outlet of the purifier. Theoretical adsorption capacity of the purifier is calculated based on the measured temperatures and flowrates and is compared to actual adsorption capacity over time.

Subedi, Jeewan [Fermilab]↗

Neurophysiological model of the normal and abnormal human pupil

Anatomical, experimental, and computer simulation studies were used to determine the structure of the neurophysiological model of the pupil size control system. The computer simulation of this model demonstrates the role played by each of the elements in the neurological pathways influencing the size of the pupil. Simulations of the effect of drugs and common abnormalities in the system help to illustrate the workings of the pathways and processes involved. The simulation program allows the user to select pupil condition (normal or an abnormality), specific site along the neurological pathway (retina, hypothalamus, etc.) drug class input (barbiturate, narcotic, etc.), stimulus/response mode, display mode, stimulus type and input waveform, stimulus or background intensity and frequency, the input and output conditions, and the response at the neuroanatomical site. The model can be used as a teaching aid or as a tool for testing hypotheses regarding the system.

Krenz, W.↗

Predicting thunderstorm evolution using ground-based lightning detection networks

Lightning measurements acquired principally by a ground-based network of magnetic direction finders are used to diagnose and predict the existence, temporal evolution, and decay of thunderstorms over a wide range of space and time scales extending over four orders of magnitude. The non-linear growth and decay of thunderstorms and their accompanying cloud-to-ground lightning activity is described by the three parameter logistic growth model. The growth rate is shown to be a function of the storm size and duration, and the limiting value of the total lightning activity is related to the available energy in the environment. A new technique is described for removing systematic bearing errors from direction finder data where radar echoes are used to constrain site error correction and optimization (best point estimate) algorithms. A nearest neighbor pattern recognition algorithm is employed to cluster the discrete lightning discharges into storm cells and the advantages and limitations of different clustering strategies for storm identification and tracking are examined.

Goodman, Steven J.↗

Vertically Resolved Aerosol Optical Properties over the ARM SGP Site

In order to meet one of its goals - to relate observations of radiative fluxes and radiances to the atmospheric composition - the Department of Energy's Atmospheric Radiation Measurement (ARM) program has pursued measurements and modeling activities that attempt to determine how aerosols impact atmospheric radiative transfer, both directly and indirectly. However, significant discrepancies between aerosol properties measured in situ or remotely remain. To this end, the ARM program will conduct an Aerosol Intensive Operational Period (IOP) in May 2003 at the ARM Southern Great Plains (SGP) site in north central Oklahoma. The IOP involves airborne measurements from two airplanes over the heavily instrumented SGP site. We will give an overview of early airborne results obtained aboard Center for Interdisciplinary Remotely-Piloted Aircraft Studies (CIRPAS) Twin Otter aircraft. The aircraft will carry instrumentation to perform in-situ measurements of aerosol absorption, scattering, extinction and particle size including such novel techniques as the photoacoustic and cavity ring-down methods. Aerosol optical depth and extinction will be measured with the NASA Ames Airborne Tracking 14-channel sunphotometer. Furthermore up- and downwelling solar (broadband and spectral) and infrared radiation will be measured using three different instruments. The up-looking radiation instruments will be mounted on a newly developed stabilized platform, which will keep the instruments level up to aircraft pitch and roll angles of 10 degrees. Additional effort will be directed toward measurement of cloud condensation nucleus concentration as a function of supersaturation and relating CCN concentration to aerosol composition and size distribution. This relation is central to description of the aerosol indirect effect.

Schmid, B.↗

In-Situ and Remotely-Sensed Observations of Biomass Burning Aerosols at Doi Ang Khang, Thailand During 7-SEAS BASELInE 2015

The spring 2015 deployment of a suite of instrumentation at Doi Ang Khang (DAK) in northwestern Thailand enabled the characterization of air masses containing smoke aerosols from burning predominantly in Myanmar. Aerosol Robotic Network (AERONET) Sun photometer data were used to validate Moderate Resolution Imaging Spectroradiometer (MODIS) Collection 6 "Deep Blue" aerosol optical depth (AOD) retrievals; MODIS Terra and Aqua provided results of similar quality, with correlation coefficients of 0.93-0.94 and similar agreement within expected uncertainties to global-average performance. Scattering and absorption measurements were used to compare surface and total column aerosol single scatter albedo (SSA); while the two were well-correlated, and showed consistent positive relationships with moisture (increasing SSA through the season as surface relative humidity and total columnar water vapor increased), in situ surface-level SSA was nevertheless significantly lower by 0.12-0.17. This could be related to vertical heterogeneity and/or instrumental issues. DAK is at approximately 1,500 meters above sea level in heterogeneous terrain, and the resulting strong diurnal variability in planetary boundary layer depth above the site leads to high temporal variability in both surface and column measurements, and acts as a controlling factor to the ratio between surface particulate matter (PM) levels and column AOD. In contrast, while some hygroscopic effects were observed relating to aerosol particle size and Angstrom exponent, relative humidity variations appear to be less important for this ratio here. As part of the Seven South-East Asian Studies (7-SEAS) project, the Biomass-burning Aerosols & Stratocumulus Environment: Lifecycles and Interactions Experiment (BASELInE) was intended to probe physicochemical processes, interactions, and feedbacks related to biomass burning aerosols and clouds during the spring burning season (February-April) in southeast Asia (SEA).

biomass burning↗

Magnetic Flux Cancelation as the Buildup and Trigger Mechanism for CME-Producing Eruptions in Two Small Active Regions

We follow two small, magnetically isolated CME-producing solar active regions (ARs) from the time of their emergence until several days later, when their core regions erupt to produce the CMEs. In both cases, magnetograms show: (a) following an initial period where the poles of the emerging regions separate from each other, the poles then reverse direction and start to retract inward; (b) during the retraction period, flux cancelation occurs along the main neutral line of the regions, (c) this cancelation builds the sheared core field/flux rope that eventually erupts to make the CME. In the two cases, respectively 30% and 50% of the maximum flux of the region cancels prior to the eruption. Recent studies indicate that solar coronal jets frequently result from small-scale filaments eruptions, with those "minifilament" eruptions also being built up and triggered by cancelation of magnetic flux. Together, the small-AR eruptions here and the coronal jet results suggest that isolated bipolar regions tend to erupt when some threshold fraction, perhaps in the range of 50%, of the region's maximum flux has canceled. Our observed erupting filaments/flux ropes form at sites of flux cancelation, in agreement with previous observations. Thus, the recent finding that minifilaments that erupt to form jets also form via flux cancelation is further evidence that minifilaments are small-scale versions of the long-studied full-sized filaments.

Sterling, Alphonse C.↗

Magnetic Flux Cancelation as the Buildup and Trigger Mechanism for CME-Producing Eruptions in two Small Active Regions

We follow two small, magnetically isolated CME-producing solar active regions (ARs) from the time of their emergence until the time that their core regions erupt to produce the CMEs several days later. In both cases, magnetograms show: (a) following an initial period where the poles of the emerging regions separate from each other, the poles then reverse direction and start to retract inward; (b) during the retraction period, flux cancelation occurs along the main neutral line of the regions, (c) this cancelation builds the sheared core field/flux rope that eventually erupts to make the CME. In the two cases, respectively 30% and 50% of the maximum flux of the region cancels prior to the eruption. Recent studies indicate that solar coronal jets frequently result from small-scale filaments eruptions, with those “minifilament” eruptions also being built up and triggered by cancelation of magnetic flux. Together, the small-AR eruptions here and the coronal jet results suggest that isolated bipolar regions tend to erupt before or when a threshold of roughly 50% of the region’s maximum flux has canceled. Our observed erupting filaments/flux ropes form at sites of flux cancelation, in agreement with previous observations. Thus, the recent finding that minifilaments that erupt to form jets also form via flux cancelation is further evidence that minifilaments are small-scale versions of the long-studied full-sized filaments.

Sterling, Alphonse C.↗

Magnetic Flux Cancelation as the Buildup and Trigger Mechanism for CME-Producing Eruptions in Two Small Active Regions

We follow two small, magnetically isolated CME (Coronal Mass Ejection)-producing solar active regions (ARs) from the time of their emergence until several days later, when their core regions erupt to produce the CMEs. In both cases, magnetograms show: (a) following an initial period where the poles of the emerging regions separate from each other, the poles then reverse direction and start to retract inward; (b) during the retraction period, flux cancelation occurs along the main neutral line of the regions, (c) this cancelation builds the sheared core field/flux rope that eventually erupts to make the CME. In the two cases, respectively 30 percent and 50 percent of the maximum flux of the region cancels prior to the eruption. Recent studies indicate that solar coronal jets frequently result from small-scale filaments eruptions (Sterling et al. 2015), with those “minifilament” eruptions also being built up and triggered by cancelation of magnetic flux (Panesar et al. 2016). Together, the small-AR eruptions here and the coronal jet results suggest that isolated bipolar regions tend to erupt when some threshold fraction, perhaps in the range of 50 percent, of the region’s maximum flux has canceled. Our observed erupting filaments/flux ropes form at sites of flux cancelation, in agreement with previous observations. Thus, the recent finding that minifilaments that erupt to form jets also form via flux cancelation is further evidence that minifilaments are small-scale versions of the long-studied full-sized filaments. (Details are in Sterling et al. 2018, ApJ, 864, 68.) Supported by NASA's Heliophysics Guest Investigators (HGI) Program and the MSFC (Marshall Space Flight Center)/Hinode project.

Sterling, Alphonse C.↗

Integration and commissioning plan of Full Flow Purifier at Muon Campus

The Full Flow Purifier for Fermilab's Muon Campus uses a charcoal bed surrounded by a liquid nitrogen jacket to purify up to 240 g/s of helium gas. Fabrication by Ability Engineering Technology Inc. has been completed and the purifier delivered to Fermilab. It is the largest purifier to be used at Fermilab based on both capacity and size. A previous paper discussed the design of purifier for various operational conditions and horizontal shipping. The purifier is designed to withstand 5g force in vertical and 2g force in lateral and longitudinal directions. Transportation experience from vendor to Fermilab and within site is discussed. Integration of the purifier involved design and fabrication of a liquid nitrogen transfer line, regeneration system, and helium piping to connect it to Muon Campus cryogenic system. It also involved establishing electrical, instrumentation and controls connections to the system. Integration of the purifier is discussed in detail. The purifier is to be commissioned using up to 4 MYCOM helium compressors to supply helium and liquid nitrogen supplied by a 60,000-liter tank. Actual effectiveness of the 3-stream heat exchanger is to be estimated based on measured temperatures and flow rate. Impurity levels will be monitored at inlet and outlet of the purifier. Theoretical adsorption capacity of the purifier is calculated based on the measured temperatures and flowrates and is compared to actual adsorption capacity over time.

Subedi, J. [Fermilab] (ORCID:0009000185837576)↗

World-Wide Web Tools for Locating Planetary Images

The explosive growth of the World-Wide Web (WWW) in the past year has made it feasible to provide interactive graphical tools to assist scientists in locating planetary images. The highest available resolution images of any site of interest can be quickly found on a map or plot, and, if online, displayed immediately on nearly any computer equipped with a color screen, an Internet connection, and any of the free WWW browsers. The same tools may also be of interest to educators, students, and the general public. Image finding tools have been implemented covering most of the solar system: Earth, Mars, and the moons and planets imaged by Voyager. The Mars image-finder, which plots the footprints of all the high-resolution Viking Orbiter images and can be used to display any that are available online, also contains a complete scrollable atlas and hypertext gazetteer to help locating areas. The Earth image-finder is linked to thousands of Shuttle images stored at NASA/JSC, and displays them as red dots on a globe. The Voyager image-finder plots images as dots, by longitude and apparent target size, linked to online images. The locator (URL) for the top-level page is http: //ic-www.arc.nasa.gov/ic/projects/bayes-group/Atlas/. Through the efforts of the Planetary Data System and other organizations, hundreds of thousands of planetary images are now available on CD-ROM, and many of these have been made available on the WWW. However, locating images of a desired site is still problematic, in practice. For example, many scientists studying Mars use digital image maps, which are one third the resolution of Viking Orbiter survey images. When they douse Viking Orbiter images, they often work with photographically printed hardcopies, which lack the flexibility of digital images: magnification, contrast stretching, and other basic image-processing techniques offered by off-the-shelf software. From the perspective of someone working on an experimental image processing technique for super-resolution, the discovery that potential users are often not using the highest resolution already available, nor using conventional image processing techniques, was surprising. This motivated the present work.

Kanefsky, Bob↗

Climatology of Aerosol Optical Properties in Southern Africa

A thorough regionally dependent understanding of optical properties of aerosols and their spatial and temporal distribution is required before we can accurately evaluate aerosol effects in the climate system. Long term measurements of aerosol optical depth, Angstrom exponent and retrieved single scattering albedo and size distribution, were analyzed and compiled into an aerosol optical properties climatology for southern Africa. Monitoring of aerosol parameters have been made by the AERONET program since the middle of the last decade in southern Africa. This valuable information provided an opportunity for understanding how aerosols of different types influence the regional radiation budget. Two long term sites, Mongu in Zambia and Skukuza in South Africa formed the core sources of data in this study. Results show that seasonal variation of aerosol optical thicknesses at 500 nm in southern Africa are characterized by low seasonal multi-month mean values (0.11 to 0.17) from December to May, medium values (0.20 to 0.27) between June and August, and high to very high values (0.30 to 0.46) during September to November. The spatial distribution of aerosol loadings shows that the north has high magnitudes than the south in the biomass burning season and the opposite in none biomass burning season. From the present aerosol data, no long term discernable trends are observable in aerosol concentrations in this region. This study also reveals that biomass burning aerosols contribute the bulk of the aerosol loading in August-October. Therefore if biomass burning could be controlled, southern Africa will experience a significant reduction in total atmospheric aerosol loading. In addition to that, aerosol volume size distribution is characterized by low concentrations in the non biomass burning period and well balanced particle size contributions of both coarse and fine modes. In contrast high concentrations are characteristic of biomass burning period, combined with significant dominance of fine mode particles.

Queface, Antonio J.↗

Size-resolved Eddy-Covariance Particle Flux Measurement during the TRACER Campaign (Final Report)

The main goal of the TRacking Aerosol Convection interactions ExpeRiment (TRACER) campaign was to study aerosol–cloud interactions during deep convection over the Houston area. This project deployed a suite of instrumentation with the aim to (1) quantify turbulent vertical particle fluxes during at DOE-ARM sites, including TRACER, (2) assess hygroscopic growth factors and hygroscopicity parameters of the material driving modal aerosol growth during new particle formation and growth events, (3) derive turbulent aerosol mass fluxes using co-located Doppler LIDAR measurements, and (4) create quality-controlled PI data products to support future research utilizing data collected during the TRACER campaign. This report summarized the main findings from the deployments at two DOE-ARM sites. Briefly, we found that new particle formation may occur aloft, in a residual layer, near the top of the boundary layer. Small grown particles appear later due to downward mixing with daytime turbulence. The species that are responsible for aerosol modal growth had hygroscopicity parameters varying between 0.05 and 0.34. These values systematically depended on the wind sector, suggesting that the chemical composition of the precursors differed. This work demonstrated that lidar retrievals of the elastic backscatter and Doppler velocity can be used to obtain surface number emissions of particles with a diameter greater than 0.53 µm. During TRACER, emission particle number fluxes peaked near ∼ 100 cm−2 s−1. Multiple quality-controlled PI data products that will support future TRACER related science were generated and made publically available.

54 ENVIRONMENTAL SCIENCES↗

Role of social structure in establishment of an invasive large mammal after translocation

Abstract Background Data on the movement behavior of translocated wild pigs is needed to develop appropriate response strategies for containing and eliminating new source populations following translocation events. We conducted experimental trials to compare the home range establishment and space‐use metrics, including the number of days and distance traveled before becoming range residents, for wild pigs translocated with their social group and individually. Results We found wild pigs translocated with their social group made less extensive movements away from the release location and established a stable home range ~5 days faster than those translocated individually. We also examined how habitat quality impacted the home range sizes of translocated wild pigs and found wild pigs maintained larger ranges in areas with higher proportion of low‐quality habitat. Conclusion Collectively, our findings suggest translocations of invasive wild pigs have a greater probability of establishing a viable population near the release site when habitat quality is high and when released with members of their social unit compared to individuals moved independent of their social group or to low‐quality habitat. However, all wild pigs translocated in our study made extensive movements from their release location, highlighting the potential for single translocation events of either individuals or groups to have far‐reaching consequences within a much broader landscape beyond the location where they are released. These results highlight the challenges associated with containing populations in areas where illegal introduction of wild pigs occurs, and the need for rapid response once releases are identified. © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Clontz, Lindsay M.↗

Molecular Dynamics Simulation of Pore-Size Effects on Gas Adsorption Kinetics in Zeolites

Strong gas-mineral interactions or slow adsorption kinetics require a molecular-level understanding of both adsorption and diffusion for these interactions to be properly described in transport models. In this combined molecular simulation and experimental study, noble gas adsorption and mobility is investigated in two naturally abundant zeolites whose pores are similar in size (clinoptilolite) and greater than (mordenite) the gas diameters. Simulated adsorption isotherms obtained from grand canonical Monte Carlo simulations indicate that both zeolites can accommodate even the largest gas (Rn). However, gas mobility in clinoptilolite is significantly hindered at pore-limiting window sites, as seen from molecular dynamics simulations in both bulk and slab zeolite models. Further, experimental gas adsorption isotherms for clinoptilolite confirm the presence of a kinetic barrier to Xe uptake, resulting in the unusual property of reverse Kr/Xe selectivity. Finally, a kinetic model is used to fit the simulated gas loading profiles, allowing a comparison of trends in gas diffusivity in the zeolite pores.

74 ATOMIC AND MOLECULAR PHYSICS↗

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores—referred to as “microporous water”—enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components—including catalysts, proteins, and cells—while retaining as much of their internal pore volume as possible. Here, in this work, we establish design principles for the noncovalent surface functionalization of hydrophobic metal–organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O 2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal–organic framework particles in aqueous environments to augment the properties of microporous water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Eliminating dissolution of platinum-based electrocatalysts at the atomic scale

Deployment of proton-exchange membrane fuel cells is limited by the durability of Pt-nanoscale catalysts during cathodic oxygen reduction reactions. Dissolution processes on single crystalline and thin film surfaces are now correlated leading to the design of PtAu catalysts with suppressed dissolution. A remaining challenge for the deployment of proton-exchange membrane fuel cells is the limited durability of platinum (Pt) nanoscale materials that operate at high voltages during the cathodic oxygen reduction reaction. In this work, atomic-scale insight into well-defined single-crystalline, thin-film and nanoscale surfaces exposed Pt dissolution trends that governed the design and synthesis of durable materials. A newly defined metric, intrinsic dissolution, is essential to understanding the correlation between the measured Pt loss, surface structure, size and ratio of Pt nanoparticles in a carbon (C) support. It was found that the utilization of a gold (Au) underlayer promotes ordering of Pt surface atoms towards a (111) structure, whereas Au on the surface selectively protects low-coordinated Pt sites. Finally, this mitigation strategy was applied towards 3 nm Pt 3 Au/C nanoparticles and resulted in the elimination of Pt dissolution in the liquid electrolyte, which included a 30-fold durability improvement versus 3 nm Pt/C over an extended potential range up to 1.2 V.

36 MATERIALS SCIENCE↗