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Size-dependent diffusion of supported metal nanoclusters: mean-field-type treatments and beyond for faceted clusters
Size-dependent diffusion of supported faceted nanoclusters is mediated by disassembly & reassembly of outer layers of facets. A mean-field picture (random independent motion of surface atoms) fails to capture behavior.
The Open Cluster Chemical Abundances and Mapping Survey. V. Chemical Abundances of CTIO/Hydra Clusters Using The Cannon
Open clusters are key chemical and age tracers of Milky Way evolution. While open clusters provide significant constraints on galaxy evolution, their use has been limited due to discrepancies in measuring abundances from different studies. We analyze medium-resolution ( R ~ 19,000) Cerro Tololo Inter-American Observatory/Hydra spectra of giant stars in 58 open clusters using The Cannon to determine [Fe/H], [Mg/Fe], [Si/Fe], [Al/Fe], and [O/Fe]. This work adds an additional 55 primarily southern hemisphere open clusters calibrated to the Sloan Digital Sky Survey/Apache Point Observatory Galactic Evolution Experiment DR16 metallicity system. This uniform analysis is compared to previous studies [Fe/H] measurements for 23 clusters and we present spectroscopic metallicities for the first time for 35 open clusters.
Signature of a Massive Rotating Metal-poor Star Imprinted in the Phoenix Stellar Stream
The Phoenix stellar stream has a low intrinsic dispersion in velocity and metallicity that implies the progenitor was probably a low-mass globular cluster. In this work we use Magellan/Magellan Inamori Kyocera Echelle (MIKE) high-dispersion spectroscopy of eight Phoenix stream red giants to confirm this scenario. In particular, we find negligible intrinsic scatter in metallicity ($σ$([FE II/H]) = ${0.04}_{-0.03}^{+0.11}$) and a large peak-to-peak range in [Na/Fe] and [Al/Fe] abundance ratios, consistent with the light element abundance patterns seen in the most metal-poor globular clusters. However, unlike any other globular cluster, we also find an intrinsic spread in [Sr II/Fe] spanning ~1 dex, while [Ba II/Fe] shows nearly no intrinsic spread ($σ$([Ba II/H]) = ${0.03}_{-0.02}^{+0.10}$). This abundance signature is best interpreted as slow-neutron-capture element production from a massive fast-rotating metal-poor star (15–20 $M$ ⊙ , $v$ ini /$v$ crit = 0.4, [Fe/H] = -3.8). The low inferred cluster mass suggests the system would have been unable to retain supernovae ejecta, implying that any massive fast-rotating metal-poor star that enriched the interstellar medium must have formed and evolved before the globular cluster formed. Furthermore, neutron-capture element production from asymptotic giant branch stars or magneto-rotational instabilities in core-collapse supernovae provide poor fits to the observations. We also report one Phoenix stream star to be a lithium-rich giant ($A$(Li) = 3.1 ± 0.1). At [Fe/H ] = -2.93; it is among the most metal-poor lithium-rich giants known.
X-ray nano-imaging of defects in thin film catalysts via cluster analysis
Functional properties of transition-metal oxides strongly depend on crystallographic defects; crystallographic lattice deviations can affect ionic diffusion and adsorbate binding energies. Scanning x-ray nanodiffraction enables imaging of local structural distortions across an extended spatial region of thin samples. Yet, localized lattice distortions remain challenging to detect and localize using nanodiffraction, due to their weak diffuse scattering. Here, in this study, we apply an unsupervised machine learning clustering algorithm to isolate the low-intensity diffuse scattering in as-grown and alkaline-treated thin epitaxially strained SrIrO 3 films. We pinpoint the defect locations, find additional strain variation in the morphology of electrochemically cycled SrIrO 3 , and interpret the defect type by analyzing the diffraction profile through clustering. Our findings demonstrate the use of a machine learning clustering algorithm for identifying and characterizing hard-to-find crystallographic defects in thin films of electrocatalysts and highlight the potential to study electrochemical reactions at defect sites in operando experiments.
Blanco DECam Bulge Survey (BDBS) II: project performance, data analysis, and early science results
ABSTRACT The Blanco DECam Bulge Survey (BDBS) imaged more than 200 sq deg of the Southern Galactic bulge using the ugrizY filters of the Dark Energy Camera, and produced point spread function photometry of approximately 250 million unique sources. In this paper, we present details regarding the construction and collation of survey catalogues, and also discuss the adopted calibration and dereddening procedures. Early science results are presented with a particular emphasis on the bulge metallicity distribution function and globular clusters. A key result is the strong correlation (σ ∼ 0.2 dex) between (u − i)o and [Fe/H] for bulge red clump giants. We utilized this relation to find that interior bulge fields may be well described by simple closed box enrichment models, but fields exterior to b ∼ −6° seem to require a secondary metal-poor component. Applying scaled versions of the closed box model to the outer bulge fields is shown to significantly reduce the strengths of any additional metal-poor components when compared to Gaussian mixture models. Additional results include: a confirmation that the u band splits the subgiant branch in M22 as a function of metallicity, the detection of possible extratidal stars along the orbits of M 22 and FSR 1758, and additional evidence that NGC 6569 may have a small but discrete He spread, as evidenced by red clump luminosity variations in the reddest bands. We do not confirm previous claims that FSR 1758 is part of a larger extended structure.
Small bimetallic clusters Agn-1M (M = Au, Co, Cu, Ni, Pd, Pt; n = 3, 9, 15): Density functional theory and genetic algorithm
We investigated the effect of size and composition on the properties of bimetallic nanoclusters. The geometric structures, stabilities, and electronic properties of size-selected Ag n-1 M (M = Au, Co, Cu, Ni, Pd, Pt; n = 3, 9, 15) bimetallic nanoclusters are systematically analyzed using spin-polarized density functional theory (DFT) within the generalized gradient approximation (GGA). We determine the most stable geometries for these clusters using a genetic algorithm (GA) in combination with DFT. Our results show that doping pure silver clusters with an M atom (transition metal), referred to as a “guest atom”, increases the stability as compared to pure Ag n (n = 3, 9, 15) clusters. The results for various properties including formation energy per atom, electronic structure, magnetic moments, and vibrational density of states (VDOS) are evaluated as a function of both size and composition of the system. The adsorption of selected bimetallic clusters on hydroxylated alumina substrate shows weak binding and minor changes in geometric properties except for Ag 8 Pt.
Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters
Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.
Dynamic and reversible transformations of subnanometre-sized palladium on ceria for efficient methane removal
Reversibly adjusting the active structures of supported metal catalysts in response to dynamic working conditions has long been pursued. Here we report the reaction-environment-modulated transformations of subnanometre-sized Pd on CeO 2 for efficient methane removal, leveraging the reaction environments at different stages of automotive exhaust aftertreatment. During the cold start of vehicles, inactive Pd 1 single atoms are readily transformed into PdO $x$ subnanometre clusters by CO even at room temperature with excess O 2 , resulting in boosted low-temperature CH 4 oxidation. At elevated temperatures, dispersion of PdO $x$ cluster into Pd 1 against metal sintering renders outstanding hydrothermal stability to the catalyst, to be activated during the next vehicle start. Combined experimental and computational studies elucidate the dynamically evolved Pd speciation on CeO 2 at an atomic level. In conclusion, modulating the reversible nature of supported metals helps overcome the long-existing trade-off between low-temperature activity and high-temperature stability, also providing a new paradigm for designing intelligent catalysts that brings single-atom/cluster catalysts closer to real applications.
Catalyst design for small molecule activation of energy consequence
This project targets the conversion of ubiquitous small molecules (e.g. NO, CO, H 2 O) into viable precursors to synthetic fuels. Current state of the art catalyst design has not directly targeted transition metal complexes capable of mediating the multi-electron redox processes necessary to reduce the overpotential (energy loss) required achieve efficient activation of small molecule substrates. In this vein, a new strategy has been developed for the assembly of polynuclear architectures; allowing for the construction of tunable polymetallic centers that assemble easily within a pre-organized template (conferring stability, selectivity and tunability) that can effect multi-electron redox processes for reactions. Catalyst development has commenced with the following target design elements: (1) catalysts featuring multiple transition metal ions in the same reaction space to greatly expand accessible molecular redox capabilities; (2) catalysts are assembled in a polynucleating ligand framework that permits control over the cluster morphology as well as the local steric and electronic environment of the transition metal ions within the cluster. The high-tunability of the catalyst composition (metal content) and geometric flexibility has permitted a rigorous assessment of electronic-structure-to-function relationship to be developed, further guiding synthetic efforts to realize more potent catalysts. The numerous permutations possible showcase the high degree of generality to this approach with many synthetic handles to tune redox and reaction chemistry. Trinuclear complexes have been synthesized featuring homo- and hetero-trinuclear cores featuring a variety of first row transition metal ions (Cr→Ni). The molecular clusters have been shown to successfully mediate multi-electron redox processes in a cooperative fashion without requiring strong chemical reductants or oxidants. The reactive molecular complexes are being utilized to activate and breakdown the robust bonds within typical waste stream small molecules (e.g., greenhouse gases) and convert them into value-added commodity chemicals. Ultimately, the catalysts developed by this approach will be required to convert energy acquired via renewable resources (e.g., solar or wind) into synthetic fuels as an energy storage mechanism.
The Second Data Release of the Survey of the MAgellanic Stellar History (SMASH)
The Large and Small Magellanic Clouds (LMC and SMC) are the largest satellite galaxies of the Milky Way and close enough to allow for a detailed exploration of their structure and formation history. The Survey of the MAgellanic Stellar History (SMASH) is a community Dark Energy Camera (DECam) survey of the Magellanic Clouds using ∼50 nights to sample over ∼2400 deg{sup 2} centered on the Clouds at ∼20% filling factor (but with contiguous coverage in the central regions) and to depths of ∼24th mag in ugriz. The primary goals of SMASH are to map out the extended stellar peripheries of the Clouds and uncover their complicated interaction and accretion history as well as to derive spatially resolved star formation histories of the central regions and create a “movie” of their past star formation. Here we announce the second SMASH public data release (DR2), which contains all 197 fully calibrated DECam fields including the main body fields in the central regions. The DR2 data are available through the Astro Data Lab hosted by the NSF’s National Optical-Infrared Astronomy Research Laboratory. We highlight three science cases that make use of the SMASH DR2 data and will be published in the future: (1) preliminary star formation histories of the LMC, (2) the search for Magellanic star clusters using citizen scientists, and, (3) photometric metallicities of Magellanic Cloud stars using the DECam u-band.
Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters
Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4-vinylpyridine) thin films result in the 3D-nucleation of clusters consistent with a cubane-type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few-atom Cd-based clusters are consistent with electronic and vibrational spectroscopy and grazing-incidence total X-ray scattering measurements of 3D-cluster-arrays synthesized at 80 °C. The direct synthesis of few-atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light-absorbing materials including solar energy harvesting and conversion applications.
Continuous momentum dependence in the dynamical cluster approximation
The dynamical cluster approximation (DCA) is a quantum cluster extension to the single-site dynamical mean-field theory that incorporates spatially nonlocal dynamic correlations systematically and nonperturbatively. The DCA + algorithm addresses the cluster shape dependence of the DCA and improves the convergence with cluster size by introducing a lattice self-energy with continuous momentum dependence. However, we show that the DCA + algorithm is plagued by a fundamental problem when its self-consistency equations are formulated using the bare Green's function of the cluster. This problem is most severe in the strongly correlated regime at low doping, where the DCA + self-energy becomes overly metallic and local, and persists to cluster sizes where the standard DCA has long converged. In view of the failure of the DCA + algorithm, we propose to complement DCA simulations with a post-interpolation procedure for single-particle and two-particle correlation functions to preserve continuous momentum dependence and the associated benefits in the DCA. We demonstrate the effectiveness of this practical approach with results for the half-filled and hole-doped two-dimensional Hubbard model.
Ultra-fast Proton Conduction and Photocatalytic Water Splitting in a Pillared Metal–Organic Framework
Proton-exchange membrane fuel cells enable the portable utilization of hydrogen (H 2 ) as an energy resource. Current electrolytic materials have limitation, and there is an urgent need to develop new materials showing especially high proton conductivity. Here, we report the ultra-fast proton conduction in a novel metal–organic framework, MFM-808, which adopts an unprecedented topology and a unique structure consisting of two-dimensional layers of {Zr 6 }-clusters. By replacing the bridging formate with sulfate ligands within {Zr 6 }-layers, the modified MFM-808-SO 4 exhibits an exceptional proton conductivity of 0.21 S·cm –1 at 85 °C and 99% relative humidity. Modeling by molecular dynamics confirms that proton transfer is promoted by an efficient two-dimensional conducting network assembled by sulfate–{Zr 6 }-layers. MFM-808-SO 4 also possesses excellent photocatalytic activity for water splitting to produce H 2 , paving a new pathway to achieve a renewable hydrogen-energy cycle.
Electrochemically Determined and Structurally Justified Thermochemistry of H atom Transfer on Ti-Oxo Nodes of the Colloidal Metal–Organic Framework Ti-MIL-125
Titanium dioxide (TiO 2 ) has long been employed as (photo)electrodes for reactions relevant to energy storage and renewable energy synthesis. Proton-coupled electron transfer (PCET) reactions with equimolar amounts of protons and electrons at the TiO 2 surface or within the bulk structure lie at the center of these reactions. Because a proton and an electron are thermochemically equivalent to an H-atom, these reactions are essentially H-atom transfer reactions. Thermodynamics of H-atom transfer has a complex dependence on the synthetic protocol and chemical history of the electrode, the reaction medium, and many others; together, these complications preclude the understanding of the H-atom transfer thermochemistry with atomic-level structural knowledge. Herein, we report our success in employing open-circuit potential (E OCP ) measurements to quantitatively determine the H-atom transfer thermochemistry at structurally well-defined Ti-oxo clusters within a colloidally stabilized metal–organic framework (MOFs), Ti-MIL-125. The free energy to transfer H-atom, Ti 3+ O–H bond dissociation free energy (BDFE), was measured to be 68(2) kcal mol -1 . To the best of our understanding, this is the first report on using E OCP measurements to quantify thermochemistry on any MOFs. The proton topology, the structural change upon the redox reaction, and BDFE values were further quantitatively corroborated using computational simulations. Furthermore, comparisons of the E OCP -derived BDFEs of Ti-MIL-125 to similar parameters in the literature suggest that E OCP should be the preferred method for quantitatively accurate BDFE calculations. Here, the reported success in employing E OCP for nanosized Ti- MIL-125 should lay the ground for thermochemical measurements of other colloidal systems, which are otherwise challenging. Implications of these measurements on Ti-MIL-125 as an H-atom acceptor in chemical reactions and comparisons with other MOFs/metal oxides are discussed.
Metal?Metal Bonding as an Electrode Design Principle in the Low-Strain Cluster Compound LiScMo[subsc
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Unraveling the Effects of Cobalt on Crystal Growth and Solution Behavior of Nb 6 P 2 W 12 -based Dimeric Clusters
We report the synthesis, characterization, and solution self-assembly of plenary Nb 6 P 2 W 12 -based transition-metal substituted polyoxometalate, which is obtained by simply adding transition metals (Co 2+ ) into aqueous solution containing cluster [(NbO 2 ) 6 P 2 W 12 O 56 ] 12- , which is obtained by an in situ synthetic method. The incorporation of Co 2+ ions significantly affects the crystal structure, resulting in the formation of a 1D chain-like crystal and the first example of a niobotungstate-based cobalt derivative cluster. The behavior and stability of this cluster in solution are confirmed by time-resolved static light scattering, dynamic light scattering, small-angle X-ray scattering, and electrospray mass spectrometry studies.