Thermal Treatment Effect on CO and NO Adsorption on Fe(II) and Fe(III) Species in Fe 3 O-Based MIL-Type Metal–Organic Frameworks: A Density Functional Theory Study
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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Results for “Metal clusters”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Spatiotemporal Studies of Soluble Inorganic Nanostructures with X‐rays and Neutrons
Abstract This Review addresses the use of X‐ray and neutron scattering as well as X‐ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub‐Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal‐organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small‐ and wide‐angle X‐ray or neutron scattering), 2) PDF (pair‐distribution function analysis of X‐ray total scattering), and 3) XANES and EXAFS (X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure, respectively). While the scattering techniques provide structural information, X‐ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.
Yin, Jia‐Fu↗
Effect of Collective Dynamics and Anharmonicity on Entropy in Heterogenous Catalysis: Building the Case for Advanced Molecular Simulations
In this paper, we present a perspective on the computational determination of entropy and its effects and consequences on heterogeneous catalysis. Special attention is paid to the role of anharmonicity and the deviations from the standard harmonic oscillator approximations which can fail to provide a reliable assessment of entropy. To address these challenges, advanced methodologies are needed that can explicitly account for these thermodynamic drivers through the appropriate statistical sampling of reactive free energy surfaces. We discuss where anharmonicity should be expected, where it has been observed from a theoretical perspective, and the methods currently employed to address it. We concentrate on three types of systems where we have observed major, nonnegligible anharmonic effects: (1) supported nanoparticles, where the migration of metal atoms, complexes, and entire clusters exhibit anharmonic behavior in their dynamic motion; (2) porous solids where confinement effects distort potential energy surfaces and hinder molecular motions resulting in large entropic terms; and (3) solid/liquid interfaces, where interactions between solvent molecules and adsorbed species can result in large solvent organization free energy and unique reactivity.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tunable room-temperature ferromagnetism in Co-doped two-dimensional van der Waals ZnO
The recent discovery of ferromagnetism in two-dimensional van der Waals crystals has provoked a surge of interest in the exploration of fundamental spin interaction in reduced dimensions. However, existing material candidates have several limitations, notably lacking intrinsic room-temperature ferromagnetic order and air stability. Here, motivated by the anomalously high Curie temperature observed in bulk diluted magnetic oxides, we demonstrate room-temperature ferromagnetism in Co-doped graphene-like Zinc Oxide, a chemically stable layered material in air, down to single atom thickness. Through the magneto-optic Kerr effect, superconducting quantum interference device and X-ray magnetic circular dichroism measurements, we observe clear evidences of spontaneous magnetization in such exotic material systems at room temperature and above. Transmission electron microscopy and atomic force microscopy results explicitly exclude the existence of metallic Co or cobalt oxides clusters. X-ray characterizations reveal that the substitutional Co atoms form Co 2+ states in the graphitic lattice of ZnO. By varying the Co doping level, we observe transitions between paramagnetic, ferromagnetic and less ordered phases due to the interplay between impurity-band-exchange and super-exchange interactions. Our discovery opens another path to 2D ferromagnetism at room temperature with the advantage of exceptional tunability and robustness.
36 MATERIALS SCIENCE↗
Materials Data on B13N2 by Materials Project
B13N2 crystallizes in the trigonal R-3m space group. The structure is zero-dimensional and consists of eighteen boron, metallic molecules and three B7N2 clusters. In each B7N2 cluster, there are two inequivalent B+0.23+ sites. In the first B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one N+1.50- atom. The B–N bond length is 1.57 Å. In the second B+0.23+ site, B+0.23+ is bonded in a linear geometry to two equivalent N+1.50- atoms. Both B–N bond lengths are 1.43 Å. N+1.50- is bonded to four B+0.23+ atoms to form corner-sharing NB4 tetrahedra.
36 MATERIALS SCIENCE↗
EFRC Materials Science of Actinides (Final Report)
The Energy Frontier Research Center Materials Science of Actinides (MSA) conducted basic research from 2009-2019. The scientific personnel and participating institutes changed several times during the evolution of the Center, and in total included 24 senior investigators, four national laboratories, and ten universities. Workforce development was a motivating goal of the university-led Center, which included many undergraduate, graduate, and post-doctoral researchers. The center focused on the actinide elements, which arise from the sequential filling of the 5f electron orbitals. Although the specific themes evolved during the Center’s history, the final research themes were: (1) Nanoscale Cage Clusters, (2) Complex Ceramic and Metallic Materials, and (3) Materials Under Extreme Environments. To date, the Center has produced 254 peer-reviewed journal publications and book chapters that acknowledged only the EFRC funding, and an additional 161 journal publications and book chapters that acknowledged funding from the EFRC and additional sources (a few manuscripts are still in preparation). Broad highlights include: (1) Development of an extensive family of actinide nanomaterials that self-assemble in aqueous solution, an understanding of their formation mechanisms and stabilities, and possible uses in nuclear fuel cycles; (2) Establishment of facilities and methodologies to conduct high-temperature calorimetry on transuranium materials, and extensive thermodynamic-based studies of uranium and thorium compounds important to the nuclear fuel cycle; (3) A vastly improved understanding of the behavior of actinide materials in extreme conditions, including high radiation fields, temperatures, and pressures, as well coupled effects of two or more of these; (4) Development of resonance ultrasound spectroscopy and direct measurement of aging of plutonium alloys.
36 MATERIALS SCIENCE↗
Nonprecious Single Atom Catalyst for Methane Pyrolysis
The development of a suitable catalytic system for methane pyrolysis reactions requires a detailed investigation of the activation energy of C-H bonds on catalysts, as well as their stability against sintering and coke formation. In this work, both single-metal Ni atoms and small clusters of Ni atoms deposited on titanium nitride (TiN) plasmonic nanoparticles were characterized for the C-H bond activation of a methane pyrolysis reaction using ab initio spin-polarized density functional theory (DFT) calculations. The present work shows the complete reaction pathway, including energy barriers for C-H bond activation and dehydrogenated fragments, during the methane pyrolysis reaction on catalytic systems. Interestingly, the C-H bond activation barriers were low for both Ni single-atom and Ni-clusters, showing the energy barriers of ~1.10 eV and ~0.88 eV, respectively. Additionally, single-atom Ni-TiN showed weaker binding to adsorbates, and a net endothermic reaction pathway indicated that the single-atom Ni-TiN was expected to resist coke formation on its surface. However, these Ni single-atom catalysts can sinter, aggregate into a small cluster, and form a coke layer from the highly exothermic reaction pathway that the cluster takes despite the facile reaction pathway.
08 HYDROGEN↗
The Binary INformation from Open Clusters Using SEDs (BINOCS) Project: Reliable Photometric Mass Determinations of Binary Star Systems in Clusters
We introduce a new binary detection technique, Binary INformation from Open Clusters using SEDs (binocs), which we show is able to determine reliable stellar multiplicity and masses over a much larger mass range than current approaches. This new technique determines accurate component masses of binary and single systems of the open clusters’ main sequence by comparing observed magnitudes from multiple photometric filters to synthetic star spectral energy distributions (SEDs), allowing us to systematically probe the binary population for low-mass stars in clusters for eight well-studied open clusters. We provide new deep, infrared photometric catalogs (1.2–8.0 μm) for the key open clusters NGC 1960 (M36), NGC 2099 (M37), NGC 2420, and NGC 2682 (M67), using observations from NOAO/NEWFIRM and Spitzer/IRAC. Using these deep multiwavelength catalogs, the binocs method is applied to these clusters to determine accurate component masses for unresolved cluster binaries. We explore binary fractions as a function of cluster age, Galactic location, and metallicity.
47 OTHER INSTRUMENTATION↗
Positive ion composition in the polar D and E regions measured during moderate ionospheric absorption
During the MAC/Epsilon campaign a mass spectrometer probe was flown on a rocket launched from Andoya (Norway) on 12 November 1987 at 0021 UT providing partial ion density profiles in the altitude range between less than 50 to 125 km. Due to the short sampling period of 0.17 seconds structural features could be observed at approx. 150 m height resolution in the regimes where metal ions occur and where cluster ions are dominant. The observations were made during stable ionospheric absorption of 1 to 1.5 dB. Preliminary results are presented and discussed.
Laemmerzahl, P.↗
Nitrogen Isotopic Signatures: Tracers of Relationships Among Meteorite Groups
We report N data of H- and L-chondritic metal separates, which show tight clustering and overlap the signatures of the IIE(Y) and IVA(-6) subgroups of iron meteorites.
Mathew, K. J.↗
Chemical Compositions of Red Giant Stars from Habitable Zone Planet Finder Spectroscopy
We have used the Habitable Zone Planet Finder (HPF) to gather high-resolution, high signal-to-noise near-infrared spectra of 13 field red horizontal branch (RHB) stars, one open cluster giant, and one very metal-poor halo red giant. The HPF spectra cover the 0.81–1.28 μm wavelength range of the zyJ bands, partially filling the gap between the optical (0.4–1.0 μm) and infrared (1.5–2.4 μm) spectra already available for the program stars. We derive abundances of 17 species from LTE-based computations involving equivalent widths and spectrum syntheses, and estimate abundance corrections for the species that are most affected by departures from LTE in RHB stars. Generally good agreement is found between HPF-based metallicities and abundance ratios and those from the optical and infrared spectral regions. Light element transitions dominate the HPF spectra of these red giants, and HPF data can be used to derive abundances from species with poor or no representation in optical spectra (e.g., C i, P i, S i, K i). Attention is drawn to the HPF abundances in two field solar-metallicity RHB stars of special interest: one with an extreme carbon isotope ratio, and one with a rare, very large lithium content. The latter star is unique in our sample in exhibiting very strong He i 10830 Å absorption. The abundances of the open cluster giant concur with those derived from other wavelength regions. Detections of C i and S i in HD 122563 are reported, yielding the lowest metallicity determination of [S/Fe] from more than one multiplet.
47 OTHER INSTRUMENTATION↗
X-ray absorption spectroscopy insights on the structure anisotropy and charge transfer in Chevrel Phase chalcogenides
Here, the electronic structure and local coordination of binary (Mo 6 T 8 ) and ternary Chevrel Phases (M x Mo 6 T 8 ) are investigated for a range of metal intercalant and chalcogen compositions. We evaluate differences in the Mo L 3 -edge and K-edge X-ray absorption near edge structure across the suite of chalcogenides M x Mo 6 T 8 (M = Cu, Ni, x = 1–2, T = S, Se, Te), quantifying the effect of compositional and structural modification on electronic structure. Furthermore, we highlight the expansion, contraction, and anisotropy of Mo 6 clusters within these Chevrel Phase frameworks through extended X-ray absorption fine structure analysis. Our results show that metal-to-cluster charge transfer upon intercalation is dominated by the chalcogen acceptors, evidenced by significant changes in their respective X-ray absorption spectra in comparison to relatively unaffected Mo cations. These results explain the effects of metal intercalation on the electronic and local structure of Chevrel Phases across various chalcogen compositions, and aid in rationalizing electron distribution within the structure.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tracing the Energetics of the Universe with Constellation-X: Example Scientific Investigations
Constellation-X will enable us to trace the energetics of a broad range of astrophysical phenomena owing to its capabilities for high spectral resolution X-ray spectroscopy. The dominant baryonic component of galaxy clusters and groups resides in the X-ray bandpass, and the hot phase of the ISM in galaxies harbors the heavy metal production from previous generation of stars. This talk will focus on a few example science questions that are expected to be important during the Constellation-X era. These include the nature of the missing baryons expected to reside in the hot portion of the Warm Hot Intergalactic Medium, which Constellation-X will address via absorption spectroscopy studies of background AGN. We will also discuss spatially resolved spectroscopy of metal enrichment and the effects of turbulence in clusters & groups and of starburst galaxy winds which deposit energy & metals into the Intergalactic Medium.
Hornschemeier, Ann↗
Discovery of an Ultra-faint Stellar System near the Magellanic Clouds with the DECam Local Volume Exploration Survey
We report the discovery of a new ultra-faint stellar system found near the Magellanic Clouds in the DECam Local Volume Exploration Survey. This new system, DELVE J0155−6815 (DELVE 2), is located at a heliocentric distance of D ⊙ = 71 ± 4 kpc, which places it at a 3D physical separation of 12 ± 3 kpc from the center of the Small Magellanic Cloud and from the center of the Large Magellanic Cloud (LMC). DELVE 2 is identified as a resolved overdensity of old (τ > 13.3 Gyr) and metal-poor ( dex) stars with a projected half-light radius of and an absolute magnitude of . The size and luminosity of DELVE 2 are consistent with both the population of recently discovered ultra-faint globular clusters and the smallest ultra-faint dwarf galaxies. However, its photometrically derived age and metallicity would place it among the oldest and most metal-poor globular clusters in the Magellanic system. In the absence of spectroscopic measurements of the system’s metallicity dispersion and internal kinematics, we are unable to conclusively classify this system at this time. DELVE 2 is detected in Gaia DR2 with a clear proper-motion signal, with multiple blue horizontal-branch stars near the centroid of the system with proper motions consistent with the systemic mean. We measure the system proper motion to be = mas yr−1. We compare the spatial position and proper motion of DELVE 2 with simulations of the accreted satellite population of the LMC and find that it is very likely to be associated with the LMC.
79 ASTRONOMY AND ASTROPHYSICS↗
Heterobinuclear Molecular Precursors Direct the Formation of Supported Subnanometer Cu–M Clusters with Tunable Catalytic Behavior
Subnanometer bimetallic clusters hold great promise for catalytic applications due to their unique electronic properties and high surface-to-volume ratios. However, precise control over their composition and size remains a major challenge, particularly for immiscible metal pairs. Here, we report a surface-anchored molecular approach for synthesizing ∼0.7–0.8 nm Cu–M (M = Ru, Mo, W, Fe) bimetallic clusters on mesoporous silica supports, using heterobinuclear N-heterocyclic carbene (NHC)-based complexes as precursors. The NHC ligand functionalized with an alkoxysilane anchor enables robust grafting to the silica interface. Controlled calcination and reduction lead to subnanometer clusters with tunable composition, dictated by the metal–metal bond stability in the precursor. In situ transmission electron microscopy reveals cluster growth proceeds via sintering of adjacent surface-bound units, while elevated temperatures above 300 °C triggering diffusion and phase separation. Catalytic testing in ethylene hydrogenation demonstrates composition-dependent activity and kinetics, with CuRu and CuW clusters exhibiting lower apparent activation energy barriers compared with monometallic Cu nanoparticles. This study establishes a generalizable strategy for the interfacial synthesis of alloyed clusters from molecular precursors and provides mechanistic insight into how precursor design governs nanostructure formation and catalytic behavior.
N-heterocyclic carbene↗
Stepwise Assembly of Quinary Multivariate Metal–Organic Frameworks via Diversified Linker Exchange and Installation
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Bond clusters control rupture force limit in shear loaded histidine-Ni 2+ metal-coordinated proteins
Dynamic noncovalent interactions are pivotal to the structure and function of biological proteins and have been used in bioinspired materials for similar roles. Metal-coordination bonds, in particular, are especially tunable and enable control over static and dynamic properties when incorporated into synthetic materials. Despite growing efforts to engineer metal-coordination bonds to produce strong, tough, and self-healing materials, the systematic characterization of the exact contribution of these bonds towards mechanical strength and the effect of geometric arrangements is missing, limiting the full design potential of these bonds. In this work, we engineer the cooperative rupture of metal-coordination bonds to increase the rupture strength of metal-coordinated peptide dimers. Utilizing all-atom steered molecular dynamics simulations on idealized bidentate histidine-Ni 2+ coordinated peptides, we show that histidine-Ni 2+ bonds can rupture cooperatively in groups of two to three bonds. We find that there is a strength limit, where adding additional coordination bonds does not contribute to the additional increase in the protein rupture strength, likely due to the highly heterogeneous rupture behavior exhibited by the coordination bonds. Further, we show that this coordination bond limit is also found natural metal-coordinated biological proteins. Using these insights, we quantitatively suggest how other proteins can be rationally designed with dynamic noncovalent interactions to exhibit cooperative bond breaking behavior. Altogether, this work provides a quantitative analysis of the cooperativity and intrinsic strength limit for metal-coordination bonds with the aim of advancing clear guiding molecular principles for the mechanical design of metal-coordinated materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Images in the rocket ultraviolet - The initial helium abundance and distance modulus of the globular cluster M5 from photometry of horizontal-branch stars
A natural laboratory for the study of postmain-sequence evolution of low-mass (less than one solar mass) metal-poor stars is provided by globular clusters. These clusters are, therefore, a critical aid for developing an understanding of advanced stages of stellar evolution and of the chemical evolution of the Galaxy. Bohlin et al. (1983) have described a study of the postasymptotic branch star near the center of M5. The present investigation is concerned with the fainter horizontal-branch stars. The observations were made with the aid of a rocket-borne 38 cm f/9.0 Ritchey-Chretien telescope. Attention is given to payload and flight data, preflight bandpass calibration, the reduction of flight data, star selection, position measurement, photometry, the minimum observed horizontal-branch mass and inferences on mass loss, and individual UV-bright stars.
Bohlin, R. C.↗