Dramatic Enhancement of Rare-Earth Metal–Organic Framework Stability Via Metal Cluster Fluorination
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Engineering Papers
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.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Development of LpxH Inhibitors Chelating the Active Site Dimanganese Metal Cluster of LpxH
Abstract Despite the widespread emergence of multidrug‐resistant nosocomial Gram‐negative bacterial infections and the major public health threat it brings, no new class of antibiotics for Gram‐negative pathogens has been approved over the past five decades. Therefore, there is an urgent medical need for developing effective novel antibiotics against multidrug‐resistant Gram‐negative pathogens by targeting previously unexploited pathways in these bacteria. To fulfill this crucial need, we have been investigating a series of sulfonyl piperazine compounds targeting LpxH, a dimanganese‐containing UDP‐2,3‐diacylglucosamine hydrolase in the lipid A biosynthetic pathway, as novel antibiotics against clinically important Gram‐negative pathogens. Inspired by a detailed structural analysis of our previous LpxH inhibitors in complex with K. pneumoniae LpxH ( Kp LpxH), here we report the development and structural validation of the first‐in‐class sulfonyl piperazine LpxH inhibitors, JH‐LPH‐45 ( 8 ) and JH‐LPH‐50 ( 13 ), that achieve chelation of the active site dimanganese cluster of Kp LpxH. The chelation of the dimanganese cluster significantly improves the potency of JH‐LPH‐45 ( 8 ) and JH‐LPH‐50 ( 13 ). We expect that further optimization of these proof‐of‐concept dimanganese‐chelating LpxH inhibitors will ultimately lead to the development of more potent LpxH inhibitors for targeting multidrug‐resistant Gram‐negative pathogens.
Pharmacology & Pharmacy↗
Highly selective electrocatalytic CO 2 reduction to ethanol by metallic clusters dynamically formed from atomically dispersed copper
Direct electrochemical conversion of CO 2 to ethanol offers a promising strategy of lowering CO 2 emission while storing energy from renewable electricity. However, current electrocatalysts offer only limited selectivity toward ethanol. Here we report a copper catalyst synthesized by a unique Cu-Li amalgm method over a commercial carbon support that achieved Faradaic efficiency (FE) higher than 91% at -0.7 V (RHE) and the active potential as low as -0.4 V (RHE) during direct electrocatalytic CO 2 -to-ethanol conversion. The catalyst also demonstrated stability over an extended period of operation. A strong correlation between the catalytic selectivity and the initial Cu atoms dispersion was found and Operando X-ray absorption spectroscopy identified a dynamic and reversible transformation from atomically dispersed copper atoms to Cu n (n = 3 and 4) under the electrochemical reaction. Frist-principles calculations further elucidate the possible catalytic mechanism of CO 2 reduction over Cu n .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Non-equilibrium growth of metal clusters on a layered material: Cu on MoS 2
Not Available
36 MATERIALS SCIENCE↗
Stability and structure of metal clusters - Be(13) and Be(55)
Face-centered cubic (fcc) and hexagonally close-packed (hcp) structures are compared for Be(13) and Be(55) clusters. Both Be(13) and Be(55) prefer the fcc structure over the bulk hcp structure, but the energy difference per atom decreases for Be(55) relative to Be(13). The binding energy per atom, 1.3 eV for Be(55) and 0.8-0.9 eV for Be(13), reflects the greater total number of bonds in the larger cluster rather than a difference in bonding. The energies per bond are much more similar, in the range of 0.30-0.34 eV for both clusters. The size of the p-basis set used influences both stability and ionization potentials strongly.
Pettersson, Lars G. M.↗
Candidate Intermediate-mass Black Hole Discovered in an Extremely Young Low-metallicity Cluster in the Tadpole Galaxy KUG 1138+327
Explore the source record for details and available documents.
Q. Daniel Wang↗
Characterization, Structure, and Reactivity of Hydroxyl Groups on Metal‐Oxide Cluster Nodes of Metal–Organic Frameworks: Structural Diversity and Keys to Reactivity and Catalysis
Among the most stable metal–organic frameworks (MOFs) are those incorporating nodes that are metal oxide clusters with frames such as Zr 6 O 8 . This review is a summary of the structure, bonding, and reactivity of MOF node hydroxyl groups, emphasizing those bonded to nodes containing aluminum and zirconium ions. Hydroxyl groups are often present on these nodes, sometimes balancing the charges of the metal ions. They arise during MOF syntheses in aqueous media or in post-synthesis treatments. They are identified with infrared and 1 H nuclear magnetic resonance spectroscopies and characterized by their reactivities with polar compounds such as alcohols. Terminal OH, paired µ 2 -OH, and aqua groups on nodes are catalytic sites in numerous reactions. Relatively unreactive hydroxyl groups (such as isolated µ 2 -OH groups) may replace reactive groups and inhibit catalysis; some node hydroxyl groups (e.g., µ 3 -OH) are mere spectators in catalysis. There are similarities between MOF node hydroxyl groups and those on the surfaces of bulk metal oxides, zeolites, and enzymes, but the comparisons are mostly inexact, and much remains to be understood about MOF node hydroxyl group chemistry. It is posited that understanding and controlling this chemistry will lead to tailored MOFs and improved adsorbents and catalysts.
36 MATERIALS SCIENCE↗
What determines the stellar mass functions in globular clusters?
We analyze the dependence of stellar mass function slopes for a sample of 17 globular clusters on a variety of cluster parameters. The principal novelty of our approach is the use of appropriate multivariate statistical methods to disentangle the complex situation which is present in this problem: the slopes depend simultaneously on more than one variable, and many cluster parameters are mutually correlated. We find that the mass function slopes in the range M/M(solar) = 0.5-0.8 are largely determined by the position in the Galaxy and to a lesser extent by the cluster metallicity. Clusters closer to the Galactic center or plane have shallower mass function slopes. At a given distance to the Galactic center, clusters closer to the Galactic plane have shallower mass function slopes. At a given R(GC) and/or Z(GP), more metal-rich clusters have shallower mass function slopes. Thus, the monovariate correlations with the position or metallicity are both correct, but only partial, and in terms of slopes, biased descriptions of the situation. We present trivariate least-squares solutions where the mass function slopes can be predicted within the measurement accuracy. This relation can serve as a powerful observational constraint for theories of globular cluster formation and evolution, and it is one of the tightest correlations between globular cluster properties now known.
Djorgovski, S.↗
Tailoring and Identifying Brønsted Acid Sites on Metal Oxo-Clusters of Metal–Organic Frameworks for Catalytic Transformation
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Metal carbonyl clusters of groups 8–10: synthesis and catalysis
In this review article, we discuss advances in the chemistry of metal carbonyl clusters (MCCs) spanning the last three decades, with an emphasis on the more recent reports and those involving groups 8–10 elements.
Chemistry↗
High-Spin and Reactive Fe 13 Cluster with Exposed Metal Sites
We report atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp* 4 W 4 Fe 13 S 12 , displaying a Fe 13 core with M-M bonds that has precedent only in main group and late metal chemistry. M 13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp* 4 W 4 Fe 13 S 12 displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High‐Spin and Reactive Fe 13 Cluster with Exposed Metal Sites
Abstract Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp* 4 W 4 Fe 13 S 12 , displaying a Fe 13 core with M−M bonds that has precedent only in main group and late metal chemistry. M 13 clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp* 4 W 4 Fe 13 S 12 displays a large spin ground state of S =13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.
Scott, Anna G.↗
Promoting the cleavage of C-O bonds at the interface between a metal oxide cluster and a Co(0001) support
As a first step toward the rational design of Co-based catalysts with a higher activity and selectivity, we determine how one can activate a C-O bond at the interface between a metal oxide cluster and a Co(0001) support. The hypothesis here is that the metal ions in metal oxide clusters on a Co(0001) support enhance the adsorption of CO and weaken the C-O bond strength, which can then facilitate the dissociation of the CO reactant. To test this hypothesis, we developed three computational models of Ti4O8/Co(0001), Zr4O8/Co(0001), and Mn8O8/Co(0001). We quantify the CO adsorption behavior at the interface sites between an oxide cluster and the Co(0001) support as well as the corresponding IR spectra. We correlate the computed CO stretch frequencies with their CO adsorption energies, as well as the CO stretch frequency with the C-O bond length, and related these findings to the changes in the chemical bonding in the bound CO. The interface is the most favorable site for CO adsorption. Adsorption results in an increase of the C-O bond length and a decrease in its vibrational frequency. From a chemical bonding analysis, the bond order in CO at this site drops from 3 (in the gas phase) to 1. This decrease in bond order is a necessary precursor stage for CO dissociation. The experimental measurements of the corresponding FTIR spectra support this point. The favorability of CO adsorption at the interface sites is due to an electron transfer from the metal ion in the metal oxide cluster to the O atom in CO. We establish a linear relationship between C-O bond length and CO frequency and this relationship is found to be independent of the support, type of metal oxide cluster, or the adsorption site.
Fischer-Tropsch Synthesis, Heterogeneous Catalysis↗
Fatty acid capped, metal oxo clusters as the smallest conceivable nanocrystal prototypes
Metal oxo clusters of the type M 6 O 4 (OH) 4 (OOCR) 12 (M = Zr or Hf) are valuable building blocks for materials science. Here, we synthesize a series of zirconium and hafnium oxo clusters with ligands that are typically used to stabilize oxide nanocrystals (fatty acids with long and/or branched chains). The fatty acid capped oxo clusters have a high solubility but do not crystallize, precluding traditional purification and single-crystal XRD analysis. We thus develop alternative purification strategies and we use X-ray total scattering and Pair Distribution Function (PDF) analysis as our main method to elucidate the structure of the cluster core. We identify the correct structure from a series of possible clusters (Zr3, Zr4, Zr6, Zr12, Zr10, and Zr26). Excellent refinements are only obtained when the ligands are part of the structure model. Further evidence for the cluster composition is provided by nuclear magnetic resonance (NMR), infrared spectroscopy (FTIR), thermogravimetry analysis (TGA), and mass spectrometry (MS). We find that hydrogen bonded carboxylic acid is an intrinsic part of the oxo cluster. Using our analytical tools, we elucidate the conversion from a Zr6 monomer to a Zr12 dimer (and vice versa), induced by carboxylate ligand exchange. Finally, we compare the catalytic performance of Zr12-oleate clusters with oleate capped, 5.5 nm zirconium oxide nanocrystals in the esterification of oleic acid with ethanol. The oxo clusters present a five times higher reaction rate, due to their higher surface area. Since the oxo clusters are the lower limit of downscaling oxide nanocrystals, we present them as appealing catalytic materials, and as atomically precise model systems. In addition, the lessons learned regarding PDF analysis are applicable to other areas of cluster science as well, from semiconductor and metal clusters, to polyoxometalates.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomically Precise Single Metal Oxide Cluster Catalyst with Oxygen–Controlled Activity
Single cluster catalysts (SCCs) consisting of atomically precise metal nanoclusters dispersed on supports represent a new frontier of heterogeneous catalysis. However, the ability to synthesize SCCs with high loading and to precisely introduce non-metal atoms to further tune their catalytic activity and reaction scope of SCCs have been longstanding challenges. In this work, a new interface confinement strategy is developed for the synthesis of a high density of atomically precise Ru oxide nanoclusters (Ru 3 O 2 ) on reduced graphene oxide (rGO), attributed to the suppression of diffusion-induced metal cluster aggregation. Ru 3 O 2 /rGO exhibits a significantly enhanced activity for oxidative dehydrogenation of 1,2,3,4-tetrahydroquinoline (THQ) to quinoline with a high yield (≈86%) and selectivity (≈99%), superior to Ru and RuO 2 nanoparticles, and homogeneous single/multiple-site Ru catalysts. In addition, Ru 3 O 2 /rGO is also capable of efficiently catalyzing more complex oxidative reactions involving three reactants. The theoretical calculations reveal that the presence of two oxygen atoms in the Ru 3 O 2 motif not only leads to a weak hydrogen bonding interaction between the THQ reactant and the active site, but also dramatically depletes the density of states near the Fermi level, which is attributed to the increased positive valence state of Ru and the enhanced oxidative activity of the Ru 3 O 2 cluster for hydrogen abstraction.
36 MATERIALS SCIENCE↗
Massive dipoles across the metal–semiconductor cluster interface: towards chemically controlled rectification
An interface between a metallic cluster (MgAl 12 ) and a semiconducting cluster (Re 6 Se 8 (PMe 3 ) 5 ) is shown to be marked by a massive dipole reminiscent of a dipolar layer leading to a Schottky barrier at metal–semiconductor interfaces.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Low-metallicity Young Clusters in the Outer Galaxy. III. Sh 2-127
In deep near-infrared imaging of the low-metallicity ([O/H] = −0.7 dex) H ii region Sh 2-127 (S127) with Subaru/MOIRCS, we detected two young clusters with 413 members (S127A) in a slightly extended H ii region and another with 338 members (S127B) in a compact H ii region. The limiting magnitude was K = 21.3 mag (10σ), corresponding to a mass detection limit of ∼0.2 M{sub ⊙}. These clusters are an order of magnitude larger than previously studied young low-metallicity clusters and larger than the majority of solar neighborhood young clusters. Fits to the K-band luminosity functions indicate very young cluster ages of 0.5 Myr for S127A and 0.1–0.5 Myr for S127B, consistent with the large extinction (up to A {sub V} ≃ 20 mag) from thick molecular clouds and the presence of a compact H ii region and class I source candidates, and suggest that the initial mass function (IMF) of the low-metallicity clusters is indistinguishable from typical solar neighborhood IMFs. Disk fractions of 28% ± 3% for S127A and 40% ± 4% for S127B are significantly lower than those of similarly aged solar neighborhood clusters (∼50%–60%). The disk fraction for S127B is higher than those of previously studied low-metallicity clusters (<30%), probably due to S127B’s age. This suggests that a large fraction of very young stars in low-metallicity environments have disks, but the disks are lost on a very short timescale. These results are consistent with our previous studies of low-metallicity star-forming regions, suggesting that a solar neighborhood IMF and low disk fraction are typical characteristics for low-metallicity regions, regardless of cluster scales.
36 MATERIALS SCIENCE↗