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WIYN Open Cluster Study LXXIX. M48 (NGC 2548) I. Radial Velocities, Rotational Velocities, and Metallicities of Stars in the Open Cluster M48 (NGC 2548)
WIYN/Hydra spectra (R ∼ 13,500, signal-to-noise pixel{sup −1} = 50–1000) of a 400 Å region around Li 6708 Å are used to determine radial and rotational velocities for 287 photometrically selected candidate members of the open cluster M48. The sample ranges from turnoff A stars to late-K dwarfs and eight giants. We combine our V {sub RAD} measurements and power spectrum analysis with parallax and proper motion data from Gaia DR2 to evaluate membership and multiplicity. We classify 152 stars as single cluster members, 11 as binary members, 16 as members of uncertain multiplicity, 56 as single nonmembers, 28 as single “likely” nonmembers, two as single “likely” members, one as a binary “likely” member, five as binary nonmembers, 10 as “likely” members of uncertain multiplicity, three as nonmembers of uncertain multiplicity, and three as “likely” nonmembers of uncertain multiplicity. From a subsample of 95 single members, we derive V {sub RAD} = 8.512 ± 0.087 km s{sup −1} (σ {sub μ}, and σ = 0.848 km s{sup −1}). Using 16 isolated Fe I lines for a subsample of 99 single members (that have σ{sub T{sub e{sub f{sub f}}}}<75 K (from 10 colors from UBVRI), v sin i < 25 km s{sup −1}, and well-behaved Fe I lines), [Fe/H]{sub M48} = −0.063 ± 0.007 dex (σ {sub μ}). [Fe/H] is independent of T {sub eff} over an unprecedentedly large range of 2500 K. The minimum cluster binary fraction is 11%–21%. M48 exhibits a clear but modest broadening of the main-sequence turnoff, and there is no correlation between color and v sin i.
The impact of environmental effects on active galactic nuclei: A decline in the incidence of ionized outflows
Active galactic nuclei (AGNs) have generally been considered to be less frequent in denser environments due to a lower number of galaxy-galaxy interactions and/or the removal of their gas-rich reservoirs by the dense intergalactic medium. However, recent observational and theoretical works suggest that the effect of ram-pressure stripping acting on galaxies in dense environments might reduce the angular momentum of their gas, causing it to infall towards the super massive black hole at their centre, activating the AGN phase. In this work we explore the connection between environment and nuclear activity by evaluating the variation in the incidence of ionized outflows, a common phenomenon associated with nuclear activity, in AGNs across different environments. We select a sample of approximately 3300 optical AGNs from the Sloan Digital Sky Survey Data Release 13, which we match with a group catalogue to identify galaxies in isolation or residing in groups. We further probe their environments through the projected distance to the central galaxy of the group or cluster and the projected surface density to the fifth neighbour (δ 5 ). The presence of ionized outflows is determined through the modelling of the [O III] λ5007 emission line. We find that at lower masses (< 10 10.3 M ⊙ ), the fraction of ionized outflows is significantly lower in satellite AGNs (~7%) than in isolated (~22%) AGNs, probably due to their different AGN luminosity, L [O III] , in this stellar mass range. The fraction of outflows decreases at distances closer to the central galaxy of the group or cluster for all satellite AGNs; however, only the lower-mass ones (10 9 - 10 10.3 M ⊙ ) display a significant decline with δ 5 . Although this study does not include AGNs in the densest regions of galaxy clusters, our findings suggest that AGNs in dense environments accrete less gas than those in the field, potentially due to the removal of the gas reservoirs via stripping or starvation, leading to a negative connection between environment and AGN activity. Based on our results, we propose that the observed change in the incidence of outflows when moving towards denser regions of groups and clusters could contribute to the higher gas metallicities of cluster galaxies compared to field galaxies, especially at lower masses.
Directional Bonding in Decaniobate Inorganic Frameworks
Abstract Metal–oxo clusters offer an opportunity to assemble inorganic and metal–organic frameworks (MOFs) by a controlled building‐block approach, which led to the revolutionary discoveries of zeolites and MOFs. Polyoxometalate clusters are soluble in water, but more challenging to link into frameworks; the inert oxo‐caps that provide solubility are resistant to replacement or further connectivity. We demonstrate how the unique directional bonding and varying basicity of the decaniobate ([Nb 10 ]) oxo‐caps can be exploited to build 1D, 2D, and 3D inorganic frameworks. In nine structures, A + (A=Li, Na, K, Rb and Cs), AE 2+ (AE=Ca, Sr, Ba) and Mn 2+ demonstrate that the dimensionality of the obtained material is controlled by cation charge and size. Increased cation charge decreases selectivity for oxo‐site bonding, leading to higher dimensional linking. Larger cation radii also decreases bonding selectivity, yielding higher dimensional materials. Ion‐exchange studies of the A + ‐Nb 10 family shows exclusive selectivity for Cs + over other alkalis, which is important for radioactive Cs removal and sequestration.
Dialing in Catalytic Sites on Metal Organic Framework Nodes: MIL-53(Al) and MIL-68(Al) Probed with Methanol Dehydration Catalysis
Many metal organic frameworks (MOFs) incorporate metal oxide clusters as nodes. Node sites where linkers are missing can be catalytic sites. We now show how to dial in the number and occupancy of such sites in MIL-53 and MIL-68, which incorporate aluminum-oxide-like nodes. Here, the methods involve modulators used in synthesis and postsynthesis reactions to control the modulator-derived groups on these sites. We illustrate the methods using formic acid as a modulator, giving formate ligands on the sites, and these can be removed to leave μ 2 -OH groups and open Lewis acid sites. Methanol dehydration was used as a catalytic reaction to probe these sites, with infrared spectra giving evidence of methoxide ligands as reaction intermediates. Control of node surface chemistry opens the door for placement of a variety of ligands on a wide range of metal oxide cluster nodes for dialing in reactivity and catalytic properties of a potentially immense class of structurally well-defined materials.
Screening of Cu-Based Catalysts for Selective Methane to Methanol Conversion
Developing selective catalysts for methane conversion to added value chemicals has been considered as a promising approach for efficient utilization of abundant natural gas resources. Here, we present a descriptor-based screening for high methane conversion and methanol selectivity at the interfaces between metal oxide clusters and Cu 2 O/Cu(111) support (MO x /Cu 2 O/Cu(111), M = Mg, Fe, Co, Ni, Cu, Zn, Ti, Zr, Sn, Ce) on exposure to the mixture of CH 4 /O 2 /H 2 O. Wherein, the activation energy of direct methane to methanol conversion, *OH + *CH 4 → *CH 3 OH + *H, and the ratio for adsorption energy of oxygen and water, E ads (O 2 )/E ads (H 2 O), are identified as the effective descriptor for methane conversion and methanol selectivity, respectively. Finally, by providing an exceptional oxygen and hydroxyl sites with high-lying O 2p states, the MgO/Cu 2 O/Cu(111) catalyst is found to be the most promising system among the systems studied, being able to provide the highest methane conversion with high methanol selectivity.
Cluster-mining: an approach for determining core structures of metallic nanoparticles from atomic pair distribution function data
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Genesis of Active Pt/CeO 2 Catalyst for Dry Reforming of Methane by Reduction and Aggregation of Isolated Platinum Atoms into Clusters
Atomically dispersed metal catalysts offer the advantages of efficient metal utilization and high selectivities for reactions of technological importance. Such catalysts have been suggested to be strong candidates for dry reforming of methane (DRM), offering prospects of high selectivity for synthesis gas without coke formation, which requires ensembles of metal sites and is a challenge to overcome in DRM catalysis. However, investigations of the structures of isolated metal sites on metal oxide supports under DRM conditions are lacking, and the catalytically active sites remain undetermined. Data characterizing the DRM reaction-driven structural evolution of a cerium oxide- supported catalyst, initially incorporating atomically dispersed platinum, and the corresponding changes in catalyst performance are reported. X-ray absorption and infrared spectra show that the reduction and agglomeration of isolated cationic platinum atoms to form small platinum clusters/nanoparticles are necessary for DRM activity. Density functional theory calculations of the energy barriers for methane dissociation on atomically dispersed platinum and on platinum clusters support these observations. Here the results emphasize the need for in-operando experiments to assess the active sites in such catalysts. The inferences about the catalytically active species are suggested to pertain to a broad class of catalytic conversions involving the rate-limiting dissociation of light alkanes.
A framework to measure the properties of intergalactic metal systems with two-point flux statistics
ABSTRACT The abundance, temperature, and clustering of metals in the intergalactic medium are important parameters for understanding their cosmic evolution and quantifying their impact on cosmological analysis with the Ly α forest. The properties of these systems are typically measured from individual quasar spectra redward of the quasar’s Ly α emission line, yet that approach may provide biased results due to selection effects. We present an alternative approach to measure these properties in an unbiased manner with the two-point statistics commonly employed to quantify large-scale structure. Our model treats the observed flux of a large sample of quasar spectra as a continuous field and describes the one-dimensional, two-point statistics of this field with three parameters per ion: the abundance (column density distribution), temperature (Doppler parameter), and clustering (cloud–cloud correlation function). We demonstrate this approach on multiple ions (e.g. ${\rm C\, \small {\rm IV}}$ , ${\rm Si\, \small {\rm IV}}$ , and ${\rm Mg\, \small {\rm II}}$ ) with early data from the Dark Energy Spectroscopic Instrument (DESI) and high-resolution spectra from the literature. Our initial results show some evidence that the ${\rm C\, \small {\rm IV}}$ abundance is higher than previous measurements and evidence for abundance evolution over time. The first full year of DESI observations will have over an order of magnitude more quasar spectra than this study. In a future paper, we will use those data to measure the growth of clustering and its impact on the Ly α forest, as well as test other DESI analysis infrastructure such as the pipeline noise estimates and the resolution matrix.
The superatomic state beyond conventional magic numbers: Ligated metal chalcogenide superatoms
The field of cluster science is drawing increasing attention due to the strong size and composition-dependent properties of clusters and the exciting prospect of clusters serving as the building blocks for materials with tailored properties. However, identifying a unifying central paradigm that provides a framework for classifying and understanding the diverse behaviors is an outstanding challenge. One such central paradigm is the superatom concept that was developed for metallic and ligand-protected metallic clusters. The periodic electronic and geometric closed shells in clusters result in their properties being based on the stability they gain when they achieve closed shells. This stabilization results in the clusters having a well-defined valence allowing them to be classified as superatoms – thus, extending the periodic table to a third dimension. This perspective focuses on extending the superatomic concept to ligated metal-chalcogen clusters that have recently been synthesized in solutions and form assemblies with counterions that have wide-ranging applications. Here we illustrate that the periodic patterns emerge in the electronic structure of ligated metal-chalcogenide clusters. The stabilization gained by the closing of their electronic shells allows for the prediction of their redox properties. Further investigations reveal how the selection of ligands may control the redox properties of the superatoms. These ligated clusters may serve as chemical dopants for two-dimensional semiconductors to control their transport characteristics. Superatomic molecules of multiple metal-chalcogen superatoms allow for the formation of nano pn junctions ideal for directed transport and photon harvesting. As a result, the perspective outlines future developments, including the synthesis of magnetic superatoms.
Synthetic Access to a Framework-Stabilized and Fully Sulfided Analogue of an Anderson Polyoxometalate that is Catalytically Competent for Reduction Reactions
Polyoxometalates (POMs) featuring 7, 12, 18, or more redox-accessible transition metal ions are ubiquitous as selective catalysts, especially for oxidation reactions. The corresponding synthetic and catalytic chemistry of stable, discrete, capping-ligand-free polythiometalates (PTMs), which could be especially attractive for reduction reactions, is much less well developed. Among the challenges are the propensity of PTMs to agglomerate and the tendency for agglomeration to block reactant access of catalyst active sites. Nevertheless, the pervasive presence of transition metal sulfur clusters metalloenzymes or cofactors that catalyze reduction reactions and the justifiable proliferation of studies of two-dimensional (2D) metal-chalcogenides as reduction catalysts point to the promise of well-defined and controllable PTMs as reduction catalysts. Here, we report the fabrication of agglomeration-immune, reactant-accessible, capping-ligand-free Co II Mo 6 IV S 24 n– clusters as periodic arrays in a water-stable, hierarchically porous Zr-metal–organic framework (MOF; NU1K) by first installing a disk-like Anderson polyoxometalate, Co III Mo 6 VI O 24 m– , in size-matched micropores where the siting is established via difference electron density (DED) X-ray diffraction (XRD) experiments. Flowing H 2 S, while heating, reduces molybdenum(VI) ions to Mo(IV) and quantitatively replaces oxygen anions with sulfur anions (S 2– , HS – , S 2 2– ). DED maps show that MOF-templated POM-to-PTM conversion leaves clusters individually isolated in open-channel-connected micropores. Importantly, the structure of the immobilized cluster as determined, in part, by X-ray photoelectron spectroscopy (XPS), X-ray absorption fine structure (XAFS) analysis, and pair distribution function (PDF) analysis of total X-ray scattering agrees well with the theoretically simulated structure. PTM@MOF displays both electrocatalytic and photocatalytic competency for hydrogen evolution. Nevertheless, the initially installed PTM appears to be a precatalyst, gaining competency only after the loss of ~3 to 6 sulfurs and exposure to hydride-forming metal ions.
Distribution Tendencies of Noble Metals on Fe(100) Using Lattice Gas Cluster Expansions
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Electronic Structure and Anion Photoelectron Spectroscopy of Uranium–Gold Clusters UAu n – , n = 3–7
A collaborative effort between experiment and theory towards elucidating the electronic and molecular structures of uranium-gold clusters is presented. Anion photoelectron spectra of UAu n – (n=3-7) were taken at third (355 nm) and fourth (266 nm) harmonics of a Nd:YAG laser, as well as excimer (ArF 193nm) photon energies, where the experimental adiabatic electron affinities (AEA) and vertical detachment energies (VDE) values were measured. Complementary first principles calculations were subsequently carried out to corroborate experimentally determined electron detachment energies and to determine the geometry and electronic structure for each cluster. Except for the ring-like neutral isomer of UAu 6 where one unpaired electron is spread over the Au atoms, all other neutral and anionic UAu n clusters (n = 3 - 7) were calculated to possess open-shell electrons with the unpaired electrons localized on the central U atom. The smaller clusters closely resemble the analogous UF n species, but significant deviations are seen starting with UAu 5 where a competition between U-Au and Au-Au bonding begins to become apparent. The UAu 6 system appears to mark a transition where Au-Au interactions begin to dominate, where both a ring-like and two heavily distorted octahedral structures around the central U atom are to be nearly isoenergetic. With UAu 7 , only ring-like structures are calculated. Altogether, the calculated electron detachment energies are in good agreement with the experimental values
Assessing the Activity of Ni Clusters Supported on TiC(001) toward CO 2 and H 2 Dissociation
Small Ni particles supported on TiC(001) were shown to display a very high activity for the catalytic hydrogenation of CO 2 but the underlying chemistry is, to a large extent, unknown. Here, by means of periodic density functional theory (DFT) calculations with the BEEF–vdW functional, we explore the adsorption and subsequent dissociation of CO 2 and H 2 on several Ni n clusters ( n = 4, 9, 13, and 16) supported on TiC(001) and compare the results to those obtained for the bare Ni(111) and TiC(001) surfaces using exactly the same computational approach. The calculations reveal that the Ni n /TiC system exhibits stronger adsorption energies and lower dissociation energy barriers for CO 2 and H 2 than the bare Ni(111) and TiC(001) surfaces. Furthermore, this is in line with the experimental finding evidencing that the Ni/TiC system has a catalytic activity higher than that of the separated Ni and TiC constituents. In addition, the calculated results show that two-dimensional (2D) supported clusters adsorb CO 2 and H 2 stronger than the three-dimensional (3D) supported clusters and also the 2D clusters exhibit lower energy barriers for CO 2 dissociation. Within the 2D supported clusters, larger particles feature slightly stronger adsorption energies and lower CO 2 dissociation energy barriers. Finally, H 2 dissociation proceeds with a very low energy barrier on all of the studied models, which makes these novel systems potential good candidates for hydrogenation reactions.
Oxidation Dynamics of Supported Catalytic Cu Clusters: Coupling to Fluxionality
Copper oxide nanoclusters have a wide range of catalytic applications, such as the selective oxidation of hydrocarbons. O 2 binding to the catalyst, activation, and release upon reagent oxidation are key events in these catalytic chemistries. Furthermore, these events are expected to be accompanied by significant structural changes of the Cu clusters, because O atoms integrate into the cluster, rather than bind to its surface. Topping the complexity of the problem, partially oxidized Cu clusters are known to exhibit strong fluxionality and feature diverse and interconverting structures and oxygen contents in conditions of oxidative dehydrogenation (ODH). Hence, a significant dynamic coupling between the “hot” O 2 molecule impacting the cluster at reaction temperatures and the cluster fluxionality can be expected. In this work, we focus on the dynamics of dioxygen integration into a partially oxidized Cu cluster supported on hydroxylated amorphous alumina–a system recently reported to be an exceptionally selective catalyst for cyclohexane ODH with very little CO produced, whose mechanistic underpinnings are of utmost interest. The statistics over a swarm of adsorption and scattering trajectories where O 2 hits various sites on the cluster at reaction temperature shows that the O 2 binding does not only follow the minimal energy paths. O 2 also rarely integrates into the cluster in a single step and instead first binds to a single Cu atom via either an η 1 -O 2 or an η 2 -O 2 mode. Surprisingly, this step often has a higher barrier than the subsequent O 2 integration and dissociation, which in turn take multiple steps and complete the oxidation process. Dynamic trajectories starting from the key transition state of integration of the adsorbed O 2 can also lead to different intermediate structures during or right after the dissociation, due to the energy released from the transition state and the thermal intracluster effects. From these activated O 2 chemisorbed structures, O 2 dissociation occurs with moderate barriers (~0.5 eV), producing multiple final oxidized Cu 4 O 4 states. Hence, a diversity of reaction profiles for the attack of supported Cu cluster by O 2 emerges due to the dynamic effects, with implications for mechanisms, kinetic models, and catalyst design principles.
Understanding the interaction between carboxylates and coinage metals from first principles
Carboxylate groups have recently been explored as a new type of ligand to protect superatomic copper and silver nanoclusters, but little is known of the interfacial structure and bonding. Here, we employ density functional theory to investigate the interfaces of a model carboxylate group, CH3COO, on the coinage metal surfaces and clusters. We found that μ2-CH3COO is the most preferred binding mode on the three M(111) surfaces (M = Cu, Ag, and Au), while μ3-CH3COO is also stable on Cu(111) and Ag(111). The saturation coverage was found to be about seven CH3COO groups per nm2 for all surfaces. CH3COO has the strongest binding on Cu and weakest on Au. Moving from the flat surfaces to the icosahedral M13 clusters, we found that the eight-electron superatomic [M13(CH3COO)6]− nanoclusters also prefer the μ2-CH3COO mode on the surface. The icosahedral kernel in [Cu13(CH3COO)6]− and [Ag13(CH3COO)6]− was well maintained after geometry optimization, but a larger deformation was found in [Au13(CH3COO)6]−. Given the broad availability and variety of carboxylic acids including amino acids, our work suggests that carboxylate groups could be the next-generation ligands to further expand the universe of atomically precise metal clusters, especially for Cu and Ag.