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At least 973 records · Page 54

Size‐Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity

Abstract Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al 2 O 3 using in situ/operando spectroscopy and ex situ aberration‐corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

Albrahim, Malik A.↗

Size‐Dependent Dispersion of Rhodium Clusters into Isolated Single Atoms at Low Temperature and the Consequences for CO Oxidation Activity

Abstract Understanding the dynamic structural evolution of supported metal clusters under reaction conditions is crucial to develop structure reactivity relations. Here, we followed the structure of different size Rh clusters supported on Al 2 O 3 using in situ/operando spectroscopy and ex situ aberration‐corrected electron microscopy. We report a dynamic evolution of rhodium clusters into thermally stable isolated single atoms upon exposure to oxygen and during CO oxidation. Rh clusters partially disperse into single atoms at room temperature and the extent of dispersion increases as the Rh size decreases and as the reaction temperature increases. A strong correlation is found between the extent of dispersion and the CO oxidation kinetics. More importantly, dispersing Rh clusters into single atoms increases the activity at room temperature by more than two orders of magnitude due to the much lower activation energy on single atoms (40 vs. 130 kJ/mol). This work demonstrates that the structure and reactivity of small Rh clusters are very sensitive to the reaction environment.

Albrahim, Malik A.↗

Searching for Milky Way twins: Radial abundance distribution as a strict criterion

We search for Milky Way-like galaxies among a sample of approximately 500 galaxies. The characteristics we considered of the candidate galaxies are the following: stellar mass M $\star$ , optical radius R 25 , rotation velocity V rot , central oxygen abundance (O/H) 0 , and abundance at the optical radius (O/H) R 25 . If the values of R 25 and M $\star$ of the galaxy were close to that of the Milky Way, then the galaxy was referred to as a structural Milky Way analogue (sMWA). The oxygen abundance at a given radius of a galaxy is defined by the evolution of that region (astration level, that is, the fraction of gas converted into stars, as well as gas exchange with the surroundings), and we then assumed that the similarity of (O/H) 0 and (O/H) R 25 in two galaxies suggests a similarity in their (chemical) evolution. If the values of (O/H) 0 and (O/H) R 25 in the galaxy were close to that of the Milky Way, then the galaxy was referred to as an evolutionary Milky Way analogue (eMWA). If the galaxy was simultaneously an eMWA and sMWA, then the galaxy was considered a Milky Way twin. We find that the position of the Milky Way on the (O/H) 0 –(O/H) R 25 diagram shows a large deviation from the general trend in the sense that the (O/H) R 25 in the Milky Way is appreciably lower than in other galaxies of similar (O/H) 0 . This feature of the Milky Way evidences that its (chemical) evolution is not typical. We identify four galaxies (NGC 3521, NGC 4651, NGC 2903, and MaNGA galaxy M-8341-09101) that are simultaneously sMWA and eMWA and can therefore be considered as Milky Way twins. In previous studies, Milky Way-like galaxies were selected using structural and morphological characteristics, that is, sMWAs were selected. We find that the abundances at the centre and at the optical radius (evolutionary characteristics) provide a stricter criterion for selecting real Milky Way twins.

79 ASTRONOMY AND ASTROPHYSICS↗

Record of fluid-rock interactions on Mars from the meteorite ALH84001

Allan Hills (ALH) 84001 is the most recently recognized member of a suite of meteorites--the SNCs--that almost certainly originated on Mars. Several factors distinguish ALH84001 from the other SNC meteorites. Preliminary studies suggest that it may be older than other martian meteorites. Moreover, it contains abundant, zoned domains of calcium-iron-magnesium carbonate that are indigenous to the sample and thus may hold important clues regarding near-surface processes on Mars and the evolution of the martian atmosphere. We report here analyses of the carbon and oxygen stable-isotope compositions of the carbonates that place constraints on their formation conditions. Our results imply the presence of at least two chemically distinct carbonates--one Ca,Fe-rich, the other Mg-rich--that are enriched in 13C relative to terrestrial carbonates (delta 13C approximately +41/1000), consistent with martian atmospheric CO2 as the carbon source. The oxygen isotope compositions of the carbonates indicate that they precipitated from a low-temperature fluid in the martian crust. Combined with textural and bulk geochemical considerations, the isotope data suggest that carbonate deposition took place in an open-system environment in which the ambient temperature fluctuated.

Carbonates/analysis↗

Can Lightning Produce Significant Levels of Mass-Independent Oxygen Isotopic Fractionation in Nebular Dust?

Based on recent evidence that oxide grains condensed from a plasma will contain oxygen that is mass independently fractionated compared to the initial composition of the vapor, we present a first attempt to evaluate the potential magnitude of this effect on dust in the primitive solar nebula. This assessment relies on previous studies of nebular lightning to provide reasonable ranges of physical parameters to form a very simple model to evaluate the plausibility that lightning could affect a significant fraction of nebular dust and that such effects could cause a significant change in the oxygen isotopic composition of solids in the solar nebula over time. If only a small fraction of the accretion energy is dissipated as lightning over the volume of the inner solar nebula, then a large fraction of nebular dust will be exposed to lightning. If the temperature of such bolts is a few percent of the temperatures measured in terrestrial discharges, then dust will vaporize and recondense in an ionized environment. Finally, if only a small average decrease is assumed in the O-16 content of freshly condensed dust, then over the last 5 million years of nebular accretion the average delta O-17 of the dust could increase by more than 30 per mil. We conclude that it is possible that the measured " slope 1" oxygen isotope line measured in meteorites and their components represents a time-evolution sequence of nebular dust over the last several million years of nebular evolution O-16-rich materials formed first, then escaped further processing as the average isotopic composition of the dust graduaUy became increasingly depleted in O-16 .

Nuth, Joseph A.↗

Mesoproterozoic Archaeoellipsoides: akinetes of heterocystous cyanobacteria

The genus Archaeoellipsoides Horodyski & Donaldson comprises large (up to 135 micrometers long) ellipsoidal and rod-shaped microfossils commonly found in silicified peritidal carbonates of Mesoproterozoic age. Based on morphometric and sedimentary comparisons with the akinetes of modern bloom-forming Anabaena species, Archaeoellipsoides is interpreted as the fossilized remains of akinetes produced by planktic heterocystous cyanobacteria. These fossils set a minimum date for the evolution of derived cyanobacteria capable of marked cell differentiation, and they corroborate geochemical evidence indicating that atmospheric oxygen levels were well above 1% of present day levels 1,500 million years ago.

NASA Discipline Exobiology↗

Factors Influencing Gas Evolution from High‐Nickel Layered Oxide Cathodes in Lithium‐Based Batteries

Abstract Gas evolution from high‐nickel layered oxide cathodes (>90% Ni) remains a major issue for their practical application. Gaseous species, such as CO 2 , O 2 , and CO, that are evolved at high states of charge (SOC) worsen the overall safety of batteries, as pressure build‐up within the cell may lead to cell rupture. Since these gasses are produced during cathode degradation, tracking the formation of gasses is also important in diagnosing cathode failure. Online electrochemical mass spectrometry (OEMS) is a powerful in situ technique to study gas evolution from the cathode during high‐voltage charge. However, the differences in the OEMS experimental setups between different groups make it challenging to compare results between groups. In this perspective, the various factors that influence gas evolution based on the OEMS results collected in this group are presented. The focus is on the conditions that lead to gas release, with a particular emphasis on reactive oxygen formation and subsequent chemical reactions with the electrolyte. Promising strategies, such as electrolytes, compositional tuning, and surface coatings that are effective at suppressing gas evolution from the cathode are highlighted. Critical insights into mitigating cathode degradation and gas evolution are provided to guide the development of safer, high‐energy batteries.

Chemistry↗

Microstructural Evolution and ORR Activity of Nanocolumnar Platinum Thin Films with Different Mass Loadings Grown by High Pressure Sputtering

Nanocolumnar platinum thin films (Pt-TFs) with different Pt mass loadings were grown by high pressure sputtering (HIPS) and investigated as oxygen reduction reaction (ORR) electrocatalysts for polymer electrolyte membrane fuel cell applications. Mass loading was controlled by changing the sputter deposition time. A cauliflower-like columnar microstructure was achieved by depositing the Pt-TFs onto a microporous layer (MPL)-like surface composed of carbon particles in order to mimic catalyst-coated gas diffusion electrodes. Microstructural evolution of HIPS Pt-TFs and their ORR activity were investigated. Electrochemical characterization of the nanocolumnar Pt-TFs was performed by cyclic voltammetry and rotating disk electrode measurements on Pt-TF/MPL-like-layer/glassy-carbon samples in an aqueous perchloric acid electrolyte. The electrochemically active surface area increased from 18 to 39 m 2 g –1 as the Pt mass loading was decreased. Specific activity of the films was similar (~600 μA cm –2 ) for all Pt mass loadings, due to the similar nanoparticle sizes of ~5 nm as observed by transmission electron microscopy and X-ray diffraction. Furthermore, mass activity of the films increased from 0.11 to 0.26 A mg –1 as the Pt mass loading was decreased, which is an indication of the effective Pt utilization and better access through the catalyst layer at lower Pt mass loadings.

08 HYDROGEN↗

Astrobiology: The Search for Life in the Universe

Each of the 11 lead members of NASA's Astrobiology Institute has a specific mission. According to Hiroshi Ohmoto, director of Penn State s Astrobiology Research Center, Here we are mainly concerned with the origin of life and the evolution and extinction of important organisms. These include bacteria that live on methane, cyanobacteria (the inventors of photosynthesis), eukaryotes (a big category, covering anything with a nucleus, from single-celled organisms to humans), land-dwelling organisms, and early animals. Penn State astrobiologists are studying the environment before there was life on Earth, the origin of oxygen in the atmosphere, the chemical and thermal structures of oceans, and the role of metals in the evolution of life. Overall, they want to understand the connection between changes in environment and changes in life forms in the early Earth. PSARC offers research assistantships for graduate and undergraduate students, fellowships for graduate students and post-doctoral fellows, and an undergraduate minor in astrobiology. The minor covers 18 credits in earth sciences, geochemistry, geophysics, astronomy, biology, biochemistry, meteorology, and microbiology. The goal, says Ohmoto, is to teach students to critically evaluate claims related to this field that they encounter well after their college education has ended. Under a scanning electron microscope, Martian meteorite ALH84001 yields tube-like structures that look a lot like remnants of Earthly bacteria except smaller by a factor of ten.

Pacchioli, David↗

Oxygen Isotope Evidence for the Relationship between CM and CO Chondrites: Could they Both Coexist on a Single Asteroid

Water played a critical role in the early evolution of asteroids and planets, as well as being an essential ingredient for life on Earth. However, despite its importance, the source of water in the inner solar system remains controversial. Delivery of water to Earth via comets is inconsistent with their relatively elevated D/H ratios, whereas carbonaceous chondrites (CCs) have more terrestrial-like D/H ratios [1]. Of the eight groups into which the CCs are divided, only three (CI, CM, CR) show evidence of extensive aqueous alteration. Of these, the CMs form the single most important group, representing 34% of all CC falls and a similar percentage of finds (Met. Bull. Database). CM material also dominates the population of CC clasts in extraterrestrial samples [2, 3]. The Antarctic micrometeorites population is also dominated by CM and CI-like material and similar particles may have transported water and volatiles to the early Earth [4]. CCs, and CMs in particular, offer the best opportunity for investigating the evolution of water reservoirs in the early solar system. An important aspect of this problem involves identifying the anhydrous silicate component which co-accreted with ice in the CM parent body. A genetic relationship between the essentially anhydrous CO group and the CMs was proposed on the basis of oxygen isotope evidence [5]. However, previous CM whole-rock oxygen isotope data scattered about a line of approximately 0.5 that did not intersect the field of CO chondrites [5]. Here we discuss new oxygen isotope data which provides additional constraints on the relationship between CO and CM chondrites.

Greenwood, R. C.↗

On the origin of Titan's atmosphere

The present atmosphere of Titan exhibits evidence of extensive evolution, in the form of rapid photochemical destruction of methane and a large fractionation of the nitrogen and oxygen isotopes. Attempts to recover the initial inventory of volatiles lead toward a model in which nitrogen was originally supplied as NH3, essentially unmodified from its relative abundance in the outer solar nebula. Titan's atmospheric methane, in contrast, appears to have been formed from carbon and other carbon compounds, either by gas phase reactions in the subnebula or by accretional heating during the formation of Titan. These conclusions can be tested by further studies of abundances and isotope ratios in Titan's atmosphere, augmented by studies of comets. The possible similarity of carbon and nitrogen inventories on Titan to those on the inner planets makes this investigation particularly intriguing.

Non-NASA Center↗

Evolution of Radicals from the Photolysis of High Ionic Strength Alkaline Nitrite Solutions

Reactive nitrogen species (RNS), along with reactive oxygen species (ROS), are significant products from radiolysis in solution. While much research has been focused on biological systems, these species are also important products in the autoradiolysis that occurs in nuclear waste. In this work, we determine the correlation between solution constituents, particularly nitrite, and radical products in highly alkaline solutions relevant to liquid waste. Because these radicals tend to be very short-lived, we employ spin trapping in conjunction with electron paramagnetic resonance (EPR) to detect them and quantify their production. Most spin traps do not function in these conditions (>1 M NaOH); however, nitroalkanes such as nitromethane will act as spin traps in their aci form, which is dominant at high pH. To restrict the products to those originating from nitrite, we use 280–480 nm UV light to generate radicals, avoiding products from the photolysis of water. Under these circumstances, nitric oxide, nitrite radicals, and hydroxyl radicals are detected, and the trends with the concentration of the constituents of the solutions are tracked. These include nitrite, nitrate, hydroxide, and carbonate. We find that, while the equilibrium shifts with increasing pH from hydroxyl radicals to the more slowly reacting oxide radicals, the production of nitrite radicals does not decrease.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic CO 2 reduction on earth abundant 2D Mo 2 C and Ti 3 C 2 MXenes

Mo 2 C and Ti 3 C 2 MXenes were investigated as earth-abundant electrocatalyts for the CO 2 reduction reaction (CO 2 RR). Mo 2 C and Ti 3 C 2 exhibited faradaic efficiencies of 90% (250 mV overpotential) and 65% (650 mV overpotential), respectively, for the reduction of CO 2 to CO in acetonitrile using an ionic liquid electrolyte. The use of ionic liquid 1-ethyl-2-methylimidazolium tetrafluoroborate as an electrolyte in organic solvent suppressed the competing hydrogen evolution reaction. Density functional theory (DFT) calculations suggested that the catalytic active sites are oxygen vacancy sites on both MXene surfaces. Also, a spontaneous dissociation of adsorbed COOH species to a water molecule and adsorbed CO on Mo 2 C promote the CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

MESA Isochrones and Stellar Tracks (MIST). III. The White Dwarf Cooling Sequence

We present a substantial update to the MESA Isochrones and Stellar Tracks (MIST) library, extending the MIST model grids and isochrones down the white dwarf (WD) cooling sequence with realistic physics for WD cooling timescales. This work provides a large grid of MESA models for carbon–oxygen core WDs with hydrogen atmospheres (spectral type DA/DC), descended from full prior stellar evolution calculations. The model tracks, isochrones, and WD cooling timescale contours are available on the MIST project website and at doi:10.5281/zenodo.15242047. Our WD models provide a very large, publicly available grid with detailed physics for WD cooling timescales: realistic interior and envelope compositions, with element diffusion and heavy-element sedimentation, nuclear burning at the base of the WD hydrogen envelope, core crystallization, and C/O phase separation. As a large grid of open-source stellar evolution models, these WD models provide both out-of-the-box model tracks for comparison with observations and a framework for building further WD models to investigate variations in WD physics.

Astronomy and AstroPhysics↗

Evolution of the atmosphere

Theories on the origin of the Earth atmosphere and chemical composition are presented. The role of oxygenic photosynthesis on the determination of the Earth's origin is discussed. The research suggests that further analysis of the geologic record is needed to more accurately estimate the history of atmospheric oxygen.

Kasting, J. F.↗

Ultraviolet Radiation-induced Alteration of Martian Surface Materials

The nature and origin of martian surface materials cannot be fully characterized without addressing the unusual reactivity of the soil and the effects of exposure to the unique martian environment. Our laboratory experiments show that ultraviolet radiation at the martian surface can result in the oxidation of metal atoms and the creation of reactive oxygen species on grain surfaces. This process is important in understanding the nature and evolution of martian soils. It can explain the reactivity discovered by the Viking Landers and possibly the origin of the ferric component of the soil.

Yen, A. S.↗

Past, present, and future life on Mars

Although the Viking results indicated that the surface of Mars is dry and lifeless, there is direct geomorphological evidence that Mars had large amounts of liquid water on its surface in the past. From a biological perspective the existence of liquid water, by itself, motivates the question of the origin of life on Mars. One of the martian meteorites dates back to this early period and may contain evidence consistent with life. The Mars environment 3.5 to 4.0 Gyr ago was comparable to that on the Earth at this time in that both contained liquid water. Life had originated on Earth and reached a fair degree of biological sophistication by 3.5 Gyr ago. To determine if life similarly arose on Mars may require extensive robotic exploration and ultimately human exploration. Intensive exploration of Mars will require a continued presence on the Martian surface and the development of a self sustaining community in which humans can live and work for very long periods of time. A permanent Mars research station can obtain its life support requirements directly from the martian environment enabling a high degree of self-sufficiency. In the longer term, it is possible that in the future we might restore a habitable climate on Mars, returning it to the life-bearing state it may have enjoyed early in its history.

NASA Center ARC↗