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Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS 2 grown on silica
Homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH 3 OH) was partially converted to acetaldehyde (CH 3 CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C 2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS 2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. Here, the formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.
Linking Remotely Sensed Aerosol Types to Their Chemical Composition
Aerosol types measured during the Ship-Aircraft Bio-Optical Research (SABOR) experiment are related to GEOS-Chem model chemical composition. The application for this procedure to link model chemical components to aerosol type is desirable for understanding aerosol evolution over time. The Mahalanobis distance (DM) statistic is used to cluster model groupings of five chemical components (organic carbon, black carbon, sea salt, dust and sulfate) in a way analogous to the methods used by Burton et al. [2012] and Russell et al. [2014]. First, model-to-measurement evaluation is performed by collocating vertically resolved aerosol extinction from SABOR High Spectral Resolution LiDAR (HSRL) to the GEOS-Chem nested high-resolution data. Comparisons of modeled-to-measured aerosol extinction are shown to be within 35% +/- 14%. Second, the model chemical components are calculation into five variables to calculate the DM and cluster means and covariances for each HSRL-retrieved aerosol type. The layer variables from the model are aerosol optical depth (AOD) ratios of (i) sea salt and (ii) dust to total AOD, mass ratios of (iii) total carbon (i.e. sum of organic and black carbon) to the sum of total carbon and sulfate (iv) organic carbon to black carbon, and (v) the natural log of the aerosol-to-molecular extinction ratio. Third, the layer variables and at most five out of twenty SABOR flights are used to form the pre-specified clusters for calculating DM and to assign an aerosol type. After determining the pre-specified clusters, model aerosol types are produced for the entire vertically resolved GEOS-Chem nested domain over the United States and the model chemical component distributions relating to each type are recorded. Resulting aerosol types are Dust/Dusty Mix, Maritime, Smoke, Urban and Fresh Smoke (separated into 'dark' and 'light' by a threshold of the organic to black carbon ratio). Model-calculated DM not belonging to a specific type (i.e. not meeting a threshold probability) is termed an outlier and those DM values that can belong to multiple types (i.e. showing weak probability of belonging to a specific cluster) are termed as Overlap. MODIS active fires are overlaid on the model domain to qualitatively evaluate the model-predicted Smoke aerosol types.
Analysis of Fiber Clustering in Composite Materials Using High-Fidelity Multiscale Micromechanics
A new multiscale micromechanical approach is developed for the prediction of the behavior of fiber reinforced composites in presence of fiber clustering. The developed method is based on a coupled two-scale implementation of the High-Fidelity Generalized Method of Cells theory, wherein both the local and global scales are represented using this micromechanical method. Concentration tensors and effective constitutive equations are established on both scales and linked to establish the required coupling, thus providing the local fields throughout the composite as well as the global properties and effective nonlinear response. Two nondimensional parameters, in conjunction with actual composite micrographs, are used to characterize the clustering of fibers in the composite. Based on the predicted local fields, initial yield and damage envelopes are generated for various clustering parameters for a polymer matrix composite with both carbon and glass fibers. Nonlinear epoxy matrix behavior is also considered, with results in the form of effective nonlinear response curves, with varying fiber clustering and for two sets of nonlinear matrix parameters.
Identifying geological structures through microseismic cluster and burst analyses complementing active seismic interpretation
At the Decatur carbon capture and storage site (IL, USA) CO 2 has been injected from 2011–2014 and from 2017 to present near the base of the Lower Mt. Simon Sandstone saline reservoir, resulting in microseismicity. Microseismicity is mainly located in the basement and distributed in distinct spatial clusters. The lack of significant impedance contrasts within the basement makes the interpretation of active-source seismic reflection data challenging, however, recent reprocessing allowed to resolve faults above and at the top of the basement. These faults generally do not coincide with the location of microseismic events and their continuation to the general depth of the seismic events cannot be assumed. This paper shows how the interpretation of the microseismicity can complement structural interpretations of active-source seismic reflection data. In particular, we analyze clusters and bursts (abrupt increases) of microseismicity, identify unresolved, smaller-scale weaknesses and extract statistical parameters. These parameters allow comparisons with the interpreted faults, and with fracture sets intercepted by boreholes. During injection at the Decatur site, the injection pressure was kept far below fracture pressure, nevertheless, seismic events were induced and spread far beyond the expected extent of the CO 2 plume. We argue that local stress transfers related to the CO 2 injection reactivated pre-existing fractures within the critically stressed basement. Finally, we conducted a slip tendency analysis for faults interpreted from active seismic, selected cluster, bursts and nodal planes from focal mechanisms to determine if the interpreted structures are optimally oriented with respect to the stress regime. Our results suggest that the orientation of fractures close to the injection well, generally shows slight deviations from the optimal orientation for slip. This might indicate either slight local deviations of the maximum horizontal stress azimuth from the average direction used in the analysis, or the lack of optimally oriented fractures at this location.
Linear-Scaling Local Natural Orbital-Based Full Triples Treatment in Coupled-Cluster Theory
We present an efficient, asymptotically linear-scaling implementation of the canonically O(N 8 ) coupled-cluster method with singles, doubles, and full triples excitations (CCSDT) method. We apply the domain-based local pair natural orbital (DLPNO) approach for computing CCSDT amplitudes. Our method, called DLPNO–CCSDT, uses the converged coupled-cluster amplitudes from a preceding DLPNO–CCSD(T) computation as a starting point for the solution of the CCSDT equations in the local natural orbital basis. To simplify the working equations, we t1-dress our two-electron integrals and Fock matrices, allowing our equations to take on the form of CCDT. With appropriate parameters, our method can recover more than 99.99% of the total canonical CCSDT correlation energy. In addition, we demonstrate that our method consistently yields sub-kJ mol –1 errors in relative energies when compared to canonical CCSDT, and, likewise, when computing the difference between CCSDT and CCSD(T). Finally, to highlight the low scaling of our algorithm, we present timings on linear alkanes (up to 30 carbons and 730 basis functions) and water clusters (up to 131 water molecules and 3144 basis functions).
Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon
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Spectroscopic Analysis of the Bulge Globular Cluster ESO 456-SC38
It has been suggested that the oldest stellar populations in the Milky Way are tightly bound and confined to the central regions of the Galaxy. This is one of the reasons why a handful of globular clusters located in the bulge region are thought to be remnants of the primeval formation stages of the Milky Way. The globular cluster, ESO 456-SC38 (Djorgovski 2), is one such cluster; it has a blue horizontal branch, is projected very close to the center of the Galaxy, and has an orbit confining it to the bulge/bar region. The first α abundances of seven stars in this heavily reddened cluster are presented using Apache Point Observatory Galaxy Evolution Experiment Data Release 16. A significant spread in the abundances of N, C, Na, and Al indicates the presence of multiple stellar populations in this cluster. Using Gaia DR2 proper motions and radial velocities from the Bulge Radial Velocity Assay for RR Lyrae stars, we confirm that RR Lyrae stars belong to this globular cluster.
The nature of the metal-CO interaction and bonding
The adsorption of CO on metal surfaces is represented by molecular orbital cluster models of CO at an on top site and adsorbed normal to the surface carbon end down. Ab initio SCF and MCSCF calculations are performed for several clusters. The new constrained space orbital variation CSOV approach is used to analyze the bonding and to compare CO adsorption on Al, representative of sp metals, with that on Cu, representative of transition metals. There is a large repulsion between the superposed free CO and metal charge distributions which is considerably smaller for Cu than for Al because there are fewer valence sigma electrons for Cu than for Al. The CSOV analysis shows that the metal to CO pi donation is much more important than the CO to metal sigma donation. It is also shown that for Cu, the d pi contribution to the metal pi donation is larger than the valence 4p pi contribution. The d pi donation is compared between Fe, Ni, and Cu and this donation and the metal-CO interaction are found to be different in the order Fe greater than Ni greater than Cu.
Drivers of Decadal Carbon Fluxes Across Temperate Ecosystems
Long-running eddy covariance flux towers provide insights into how the terrestrial carbon cycle operates over multiple timescales. Here, we evaluated variation in net ecosystem exchange (NEE) of carbon dioxide (CO 2 ) across the Chequamegon Ecosystem-Atmosphere Study AmeriFlux core site cluster in the upper Great Lakes region of the USA from 1997 to 2020. The tower network included two mature hardwood forests with differing management regimes (US-WCr and US-Syv), two fen wetlands with varying levels of canopy sheltering and vegetation (US-Los and US-ALQ), and a very tall (400 m) landscape-level tower (US-PFa). Together, they provided over 70 site-years of observations. The 19-tower Chequamegon Heterogenous Ecosystem Energy-balance Study Enabled by a High-density Extensive Array of Detectors 2019 campaign centered around US-PFa provided additional information on the spatial variation of NEE. Decadal variability was present in all long-term sites, but cross-site coherence in interannual NEE in the earlier part of the record became weaker with time as non-climatic factors such as local disturbances likely dominated flux time series. Average decadal NEE at the tall tower transitioned from carbon source to sink to near neutral over 24 years. Respiration had a greater effect than photosynthesis on driving variations in NEE at all sites. Declining snowfall offset potential increases in assimilation from warmer springs, as less-insulated soils delayed start of spring green-up. Higher CO 2 increased maximum net assimilation parameters but not total gross primary productivity. Stand-scale sites were larger net sinks than the landscape tower. Clustered, long-term carbon flux observations provide value for understanding the diverse links between carbon and climate and the challenges of upscaling these responses across space.
Neutron irradiation induced defects and clustering in NF616 and T91
NF616 is a third-generation ferritic martensitic steel, developed to have better creep resistance than the prior generation T91. Unlike relatively numerous studies of T91, there is a lack of understanding of the irradiation effect on the microstructural evolution and mechanical response of NF616. This work evaluated the microstructures and radiation hardening of NF616 irradiated up to 8.2 displacement per atom (dpa) at 292 °C – 431 °C, compared with T91 from two heats. Dislocation loops were observed in all investigated samples. NF616 exhibited comparable loop size but slightly lower loop density than those in the general T91 heat at 430 °C. Cavities were only observed in NF616 at 431 °C but absent at lower irradiation temperatures (292 °C and 359 °C). Ni-rich clusters were also observed in NF616 at 431 °C, while only weak Ni-clustering were observed at lower irradiation temperatures. Compared to the general T91 heat, NF616 demonstrated better swelling resistance (e.g., one third of swelling in the general T91 heat at 430 °C), a slightly higher number density of Ni-rich clusters, and slightly lower radiation hardening. The low-carbon T91 showed the greatest hardening with the largest swelling and loop sizes, despite its lowest irradiation temperature and intermediate dose. The calculated hardening from loops, cavities and Ni-rich clusters using the classic dispersed barrier-hardening model had reasonable agreement with the experiment-derived results, with the primary hardening contribution attributed to dislocation loops.
Accelerating the density-functional tight-binding method using graphical processing units
Acceleration of the density-functional tight-binding (DFTB) method on single and multiple graphical processing units (GPUs) was accomplished using the MAGMA linear algebra library. Herein two major computational bottlenecks of DFTB ground-state calculations were addressed in our implementation: the Hamiltonian matrix diagonalization and the density matrix construction. The code was implemented and benchmarked on two different computer systems: (1) the SUMMIT IBM Power9 supercomputer at the Oak Ridge National Laboratory Leadership Computing Facility with 1–6 NVIDIA Volta V100 GPUs per computer node and (2) an in-house Intel Xeon computer with 1–2 NVIDIA Tesla P100 GPUs. The performance and parallel scalability were measured for three molecular models of 1-, 2-, and 3-dimensional chemical systems, represented by carbon nanotubes, covalent organic frameworks, and water clusters.
The infrared emission bands. II - A spatial and spectral study of the Orion bar
The 3-13 micron emission of the Orion Bar is spectroscopically and spatially studied. There are three emission components, one from 'classical' dust that accounts for the bulk of the emission longward of 20 microns, a second one from large amorphous carbon grains or polycyclic aromatic hydrocarbon (PAH) clusters accounting for the broad features, and a third from PAH molecules that accounts for the sharp bands. The 3.3 and 11.3 micron features, which are due to C-H modes, are well correlated spatially, while the 7.7 micron band, due to C=C modes, has a different distribution than the 3.3 and 11.1 micron bands. It is concluded that the sharp emission bands arise in the photodissociation transition region between the H II region and the molecular cloud and are not present in the H II region. The broad continuum feature from 11-13 microns is strong in both regions.
Synergism of Saturn, Enceladus and Titan and Formation of HCNO Prebiotic Molecules
Saturn as a system has two very exotic moons Titan and Enceladus. Titan, taking in energy from Saturn's magnetosphere, solar UV irradiation, and cosmic rays, can make HCN based molecules as discussed in earlier paper by Raulin and Owen. Space radiation effects at both moons, and as coupled by the Saturn magnetosphere, could cause an unexpected series of events potentially leading to prebiotic chemical evolution at Titan with HCNO from magnetospheric oxygen as the new ingredient. The "Old Faithful" model suggests that Enceladus, highly irradiated by Saturn magnetospheric electrons and thus having a source of chemical energy from radiolytic gas production, has episodic ejections of water vapor, carbon dioxide, and various hydrocarbons into Saturn's magnetosphere. The hydrocarbons do not survive transport through the plasma environment, but oxygen ions from Enceladus water molecules become the dominant ion species in the outer magnetosphere. At Titan, Cassini discovered that 1) keV oxygen ions, evidently from Enceladus, are bombarding Titan's upper atmosphere and 2) heavy positive and negative ions exist in significant abundances within Titan's upper atmosphere. Initial models of heavy ion formation in Titan's upper atmosphere invoked polymerization of aromatics such as benzenes and their radicals to make polycyclic aromatic hydrocarbons (PAH) , while a more recent model by Sittler et al., has raised the possibility of carbon chains forming from the polymerization of acetylene and its radicals to make fullerenes. Laboratory measurements indicate that fullerenes, which are hollow carbon shells, can trap keV oxygen ions. Clustering of the fullerenes with aerosol mixtures from PAHs and the dominant nitrogen molecules could form larger aerosols enriched in trapped oxygen. Aerosol precipitation could then convey these chemically complex structures deeper into the atmosphere and to the moon surface. Ionizing solar UV, magnetospheric electron, and galactic cosmic ray irradiation would provide further energy for processing into more complex organic forms. Further ionizing irradiation from cosmic rays deep in the atmosphere "tho lin" molecules are produced with all the molecular components present from which prebiotic organic molecules can form. This synergy of Saturn system, exogenic irradiation, and molecular processes provides a potential pathway for accumulation of prebiotic chemistry on the surface of Titan. Since fullerenes are also thought to exist in interstellar space, similar processes may also occur there to seed molecular clouds with prebiotic chemical species. We will also discuss possible future laboratory experiments that could be done to investigate fullerene formation at Titan and the trapping of oxygen in fullerenes.
Assessing the Health and Performance Risks of Reduced Carbon Dioxide Exposures and Resource Utilization
There have been a cluster of anecdotal reports that ISS crews are experiencing adverse health effects from on orbit exposure to CO2 levels well below the current Spacecraft Maximum Allowable Concentration (SMAC), which is 5.3 mmHg for 180 days of exposure. Developing evidence that this standard should be reduced to protect crew health is not a simple process. Dr. John James' team looked at the reports of headaches by the crew during private medical conferences and matched these with CO2 levels around the time of these reports. They then compared these to CO2 levels when there were no reports of headache. Using benchmark dose modeling, they found that the risk of headache could be predicted in concentration ranges from 2 to 5 mmHg. However, the data are incomplete because there were insufficient data when crews were exposed to concentrations below 2 mmHg. James' team also asked whether neuro-cognitive effects could be identified with CO2 exposure levels and found that these could not be associated with CO2 levels. Finally, they addressed the question of resource use to meet various levels of CO2 control if the SMACs were lowered. They estimated that CO2 restrictions approaching 2 mmHg would require substantial increases in power use and up-mass resources. They are refining their data on CO2 and headaches, and are looking at potential interactions of intracranial pressure and CO2 levels in eliciting ocular effects.
Anaerobic Expression and Purification of Holo-CCIS, an Artificial Iron-sulfur Protein
Iron-sulfur proteins are ubiquitous among all living organisms and are indispensable for almost all metabolic pathways ranging from photosynthesis, respiration, nitrogen, and carbon dioxide cycles. The iron-sulfur clusters primarily serve as electron acceptors and donors and transfer electrons to active sites of various enzymes, thus driving the energy metabolism. Prokaryotes like E. coli have ISC and SUF pathways that help in the assembly and maturation of iron-sulfur proteins. These ironsulfur proteins, especially with [4Fe-4S] clusters, are highly sensitive to molecular oxygen, and it would be advantageous if the de novo proteins and native proteins having iron-sulfur binding sites are expressed and isolated under anaerobic conditions. Bacterially assembled iron-sulfur proteins, when isolated and purified anaerobically, exhibit improved biochemical and biophysical stabilities in comparison to the counterparts expressed and purified aerobically and reconstituted under anaerobic conditions. This protocol outlines the expression and purification of the artificial protein, Coiled-Coil IronSulfur (CCIS). It may be deployed to both natural and artificial [4Fe-4S] proteins when heterologously expressed in E. coli.
Optimization of anionic conductivity through the coexistence of ionomer cluster and backbone-backbone morphologies in anion exchange membranes
Random copolymers of poly(4-vinylpyridine) and polyisoprene were synthesized, and subsequently quaternized with 1-alkylbromides. The number of carbons on the pendant side-chain of the resultant comb-shaped polymer, n, ranged from 2-8. The comb-shaped polymers were crosslinked employing thiol-ene chemistry to give mechanically robust ion conducting membranes. Analysis by wide and medium-angle X-ray scattering show three morphology regimes that are dependent on the number of carbons on the pendant side-chains. When n = 2, ionomer cluster morphology was dominant, when n = 8 backbone-backbone morphology was dominant, and when n = 3-6, the membrane showed a coexistence of both ionomer cluster and backbone-backbone morphologies. Evaluation of the water uptake of the membranes showed a maximum water uptake per cation of 9.5 when n = 5 at 95% relative humidity (RH) and 60 degrees C. Finally, conductivity of the samples characterized by electrochemical impedance spectroscopy showed bromide conductivity as high as 110 mS/cm when n = 3 at 95% RH and 90 degrees C.
α -cluster microscopic study of C 12 + C 12 fusion toward the zero energy limit
The carbon burning process is a fundamental step of stellar evolution and governs the synthesis of chemical elements important for the formation of life. In this work, we utilize the microscopic hybrid α cluster (HαC) model and an analytical approach, both in the framework of the Imaginary Time Method (ITM), to study the carbon fusion reaction towards zero energy. We obtain the values of the cross sections, astrophysical factors and correlate our results to collective motion. We also include a calculation for the 2 + carbon fusion and discuss a possible experimental investigation. Our results confirm direct experimental and theoretical results close to the barrier, while suggest possible 2 + mixtures in the indirect experimental data. Furthermore, our study offers an accurate view of the burning process in the somewhat unexplored low energy region.