Morphology and size of Pt on Al2O3: The role of specific metal-support interactions between Pt and Al2O3
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Lee, Jaekyoung↗
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Step-by-step assembly of 4d-4f-3d complex based on heptamolybdate anion
Four new complexes, (NH{sub 4}){sub 11.9}[Ln{sub 4.7}(MoO{sub 4})(H{sub 2}O){sub 23}(Mo{sub 7}O{sub 24}){sub 4}]{center_dot}xH{sub 2}O (Ln=Pr, x=34 (1); Ln=Nd, x=19 (2)), [NH{sub 4}]{sub 28}[Ce{sub 8}(MoO{sub 4}){sub 2}(H{sub 2}O){sub 31}(Mo{sub 7}O{sub 24}){sub 8}]{center_dot}74H{sub 2}O (3), and (NH{sub 4}){sub 26}[CoPr{sub 8}(MoO{sub 4}){sub 2}(H{sub 2}O){sub 33}(Mo{sub 7}O{sub 24}){sub 8}]{center_dot}54H{sub 2}O (4) have been synthesized and characterized by single-crystal and powder X-ray diffraction, CHN elemental analyses TGA analyses, IR and UV-Vis spectroscopy. Complex 1-3 are 0D compounds constructed by the connection between Ln{sup III} ions and [Mo{sub 7}O{sub 24}]{sup 6-} unit. In complex 4, the existence of Co{sup II} connects the polyanion clusters into 1D chain. The introduction of 3d metal (cobalt cation) and 4f metal (Ln=Pr{sup III}, Nd{sup III}, Ce{sup III}) encourages the coordination capability for [Mo{sub 7}O{sub 24}]{sup 6-} unit, which shows interesting coordination modes. The [Mo{sub 7}O{sub 24}]{sup 6-} unit in 1-4 shows three new coordination modes, connecting up to four metal cations. Complexes 1-4 show antiferromagnetic behavior via variable temperature magnetic study. The photoluminescence spectrum indicates the photoluminescence property for 4. - Graphical abstract: Heptamolybdate anion shows extraordinary coordination geometry in the presence of both lanthanide cation (Pr{sup III}) and transitional metal cation (Co{sup II}), which give rise to a new 4d-4f-3d complex. Black-Small-Square Highlights: Black-Right-Pointing-Pointer A new 4d-4f-3d complex that containing 1D chain was obtained and discussed. Black-Right-Pointing-Pointer New coordination geometry with higher coordination number of heptamolybdate. Black-Right-Pointing-Pointer Series of heptamolybdate contained complexes were synthesized and characterized. Black-Right-Pointing-Pointer Complexes mentioned above show antiferromagnetic behavior.
36 MATERIALS SCIENCE↗
Structures of Class Id Ribonucleotide Reductase Catalytic Subunits Reveal a Minimal Architecture for Deoxynucleotide Biosynthesis
Class I ribonucleotide reductases (RNRs) share a common mechanism of nucleotide reduction in a catalytic α subunit. All RNRs initiate catalysis with a thiyl radical, generated in class I enzymes by a metallocofactor in a separate β subunit. Class Id RNRs use a simple mechanism of cofactor activation involving oxidation of a Mn II 2 cluster by free superoxide to yield a metal-based Mn III Mn IV oxidant. This simple cofactor assembly pathway suggests that class Id RNRs may be representative of the evolutionary precursors to more complex class Ia–c enzymes. X-ray crystal structures of two class Id α proteins from Flavobacterium johnsoniae (Fj) and Actinobacillus ureae (Au) reveal that this subunit is distinctly small. The enzyme completely lacks common N-terminal ATP-cone allosteric motifs that regulate overall activity, a process that normally occurs by dATP-induced formation of inhibitory quaternary structures to prevent productive β subunit association. Class Id RNR activity is insensitive to dATP in the Fj and Au enzymes evaluated here, as expected. However, the class Id α protein from Fj adopts higher-order structures, detected crystallographically and in solution. The Au enzyme does not exhibit these quaternary forms. Our study reveals structural similarity between bacterial class Id and eukaryotic class Ia α subunits in conservation of an internal auxiliary domain. Overall, our findings with the Fj enzyme illustrate that nucleotide-independent higher-order quaternary structures can form in simple RNRs with truncated or missing allosteric motifs.
59 BASIC BIOLOGICAL SCIENCES↗
Toward Ultracold Organic Chemistry: Prospects of Laser Cooling Large Organic Molecules
Ultracold organic chemistry enables studies of reaction dynamics and mechanisms in quantum regime. Access to ultracold molecules hinges on the ability to efficiently scatter multiple photons via quasi-closed cycling transitions. Optical cycling in polyatomic molecules is challenging due to their complex electronic structure. Using equation-of-motion coupled-cluster calculations, we demonstrate that an alkaline earth metal attached to various aromatic ligands (such as benzene, phenol, cyclopentadienyl, and pyrrolide) offer nearly closed cycling transitions with only a few additional repump lasers. Here, we also show that aromatic ligands such as benzene can accommodate multiple cycling centers in various geometrical arrangements, opening new avenues in quantum information science, precision measurements, and ultracold chemistry.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Reaction Mechanism for Direct Propylene Epoxidation by Alumina-Supported Silver Aggregates. The Role of the Particle / Support Interface
Sub-nanometer Ag aggregates on alumina supports have been found to be active toward direct propylene epoxidation to propylene oxide by molecular oxygen at low temperatures, with a negligible amount of carbon dioxide formation (Science 328, p. 224, 2010). In this work, we computationally and experimentally investigate the origin of the high reactivity of the sub-nanometer Ag aggregates. Computationally, we study O 2 dissociation and propylene epoxidation on unsupported Ag 19 and Ag 20 clusters, as well as alumina-supported Ag 19 . The O 2 dissociation and propylene epoxidation apparent barriers at the interface between the Ag aggregate and the alumina support are calculated to be 0.2 and 0.2~0.4 eV, respectively. These barriers are somewhat lower than those on sites away from the interface. The mechanism at the interface is similar to what was previously found for the silver trimer on alumina and can account for the high activity observed for the direct oxidation of propylene on the Ag aggregates. The barriers for oxygen dissociation on these model systems both at the interface and on the surfaces are small compared to crystalline surfaces, indicating that availability of oxygen will not be a rate limiting step for the aggregates, as in the case of the crystalline surfaces. Experimentally, we investigate Ultrananocrystalline Diamond (UNCD)-supported silver aggregates under reactive conditions of propylene partial oxidation. The UNCD-supported Ag clusters are found to be not measurably active toward propylene oxidation, in contrast to the alumina supported Ag clusters. This suggests that the lack of metal-oxide interfacial sites of the Ag-UNCD catalyst, limits the epoxidation catalytic activity. This combined computational and experimental study shows the importance of the metal-oxide interface as well as the non-crystalline nature of the alumina-supported sub-nanometer Ag aggregate catalysts for propylene epoxidation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
CoP as an Acid-Stable Active Electrocatalyst for the Hydrogen-Evolution Reaction: Electrochemical Synthesis, Interfacial Characterization and Performance Evaluation
Films of CoP have been electrochemically synthesized, characterized, and evaluated for performance as a catalyst for the hydrogen-evolution reaction (HER). The film was synthesized by cathodic deposition from a boric acid solution of Co 2+ and H 2 PO 2 – on copper substrates followed by operando remediation of exogenous contaminants. The films were characterized structurally and compositionally by scanning-electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectrophotometry. The catalytic activity was evaluated by cyclic voltammetry and chronopotentiometry. Surface characterization prior to electrocatalysis indicated that the film consisted of micrometer-sized spherical clusters located randomly and loosely on a slightly roughened surface. The composition of both the clusters and surface consisted of cobalt in the metallic, phosphide, and amorphous-oxide forms (CoO·Co 2 O 3 ) and of phosphorus as phosphide and orthophosphate. The orthophosphate species, produced by air-oxidation, were eliminated upon HER electrocatalysis in sulfuric acid. The operando film purification yielded a functional electrocatalyst with a Co:P stoichiometric ratio of 1:1. After the HER, the surface was densely packed with micrometer-sized, mesa-like particles whose tops were flat and smooth. The CoP eletrodeposit exhibited an 85 mV overvoltage (η) for the HER at a current density of 10 mA cm –2 and was stable under operation in highly acidic solution, with an increase in η of 18 mV after 24 h of continuous operation. In conclusion, the comparative HER catalytic performance of CoP, film or nanoparticles, is as follows: ηPt < ηCoP film = ηCoP NP, ηNi 2 P < ηCoSe 2 < ηMoS 2 < ηMoSe 2 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ligand-Mediated Ring → Cube Transformation in a Catalytic Subnanocluster: Co 4 O 4 (MeCN) n with n = 1–6
We studied the Co 4 O 4 subnanocluster and its MeCN-coated species using density functional theory, and we found that the Co 4 O 4 core presents distinctive structures in bare and ligand-coated species. We propose a possible ligand-mediated ring→cube transformation mechanism during the ligand-coating process of the Co 4 O 4 core due to the stronger binding energies of the MeCN ligands to the 3D distorted cube structure than to the 2D ring and ladder structures; theory indicates that three ligands are sufficient to stabilize the cube structure. Both ring and cube structures are ferromagnetic. Furthermore, our finding is potentially useful for understanding the catalysis mechanism of Co 4 O 4 species, which have important applications in solar energy conversion and water splitting; these catalysis reactions usually involve frequent addition and subtraction of various ligands, and thus possibly involve core rearrangement processes similar to our findings.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dual-site catalysts featuring platinum-group-metal atoms on copper shapes boost hydrocarbon formations in electrocatalytic CO2 reduction
Abstract Copper-based catalyst is uniquely positioned to catalyze the hydrocarbon formations through electrochemical CO 2 reduction. The catalyst design freedom is limited for alloying copper with H-affinitive elements represented by platinum group metals because the latter would easily drive the hydrogen evolution reaction to override CO 2 reduction. We report an adept design of anchoring atomically dispersed platinum group metal species on both polycrystalline and shape-controlled Cu catalysts, which now promote targeted CO 2 reduction reaction while frustrating the undesired hydrogen evolution reaction. Notably, alloys with similar metal formulations but comprising small platinum or palladium clusters would fail this objective. With an appreciable amount of CO-Pd 1 moieties on copper surfaces, facile CO * hydrogenation to CHO * or CO-CHO * coupling is now viable as one of the main pathways on Cu(111) or Cu(100) to selectively produce CH 4 or C 2 H 4 through Pd-Cu dual-site pathways. The work broadens copper alloying choices for CO 2 reduction in aqueous phases.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
The LAMP instrument at the Linac Coherent Light Source free-electron laser
The Laser Applications in Materials Processing (LAMP) instrument is a new end-station for soft X-ray imaging, high-field physics, and ultrafast X-ray science experiments that is available to users at the Linac Coherent Light Source (LCLS) free-electron laser. While the instrument resides in the Atomic, Molecular and Optical science hutch, its components can be used at any LCLS beamline. The end-station has a modular design that provides high flexibility in order to meet user-defined experimental requirements and specifications. The ultra-high-vacuum environment supports different sample delivery systems, including pulsed and continuous atomic, molecular, and cluster jets; liquid and aerosols jets; and effusive metal vapor beams. It also houses movable, large-format, high-speed pnCCD X-ray detectors for detecting scattered and fluorescent photons. Multiple charged-particle spectrometer options are compatible with the LAMP chamber, including a double-sided spectrometer for simultaneous and even coincident measurements of electrons, ions, and photons produced by the interaction of the high-intensity X-ray beam with the various samples. Here in this paper we describe the design and capabilities of the spectrometers along with some general aspects of the LAMP chamber and show some results from the initial instrument commissioning.
47 OTHER INSTRUMENTATION↗
The massive star population in M101. II. Spatial variations in the recent star formation history
We investigate star formation history (SFH) as a function of radius in M101 using archival Hubble Space Telescope Advanced Camera for Surveys photometry. We derive the SFH from the resolved stellar populations in five 2' wide annuli. Binning the SFH into time frames corresponding to stellar populations traced by Hα, far-ultraviolet, and near-ultraviolet emission, we find that the fraction of stellar populations young enough to contribute in Hα is 15%-35% in the inner regions, compared to less than 5% in the outer regions. This provides a sufficient explanation for the lack of Hα emission at large radii. We also model the blue to red supergiant ratio in our five annuli, examine the effects that a metallicity gradient and variable SFH have on the predicted ratios, and compare to the observed values. We find that the radial behavior of our modeled blue to red supergiant ratios is highly sensitive to both spatial variations in the SFH and metallicity. Incorporating the derived SFH into modeled ratios, we find that we are able to reproduce the observed values at large radii (low metallicity), but at small radii (high metallicity) the modeled and observed ratios are discrepant.
79 ASTRONOMY AND ASTROPHYSICS↗
THE CASE FOR THE DUAL HALO OF THE MILKY WAY
Carollo et al. have recently resolved the stellar population of the Milky Way halo into at least two distinct components, an inner halo and an outer halo. This result has been criticized by Schoenrich et al., who claim that the retrograde signature associated with the outer halo is due to the adoption of faulty distances. We refute this claim, and demonstrate that the Schoenrich et al. photometric distances are themselves flawed because they adopted an incorrect main-sequence absolute magnitude relationship from the work of Ivezic et al. When compared to the recommended relation from Ivezic et al., which is tied to a Milky Way globular cluster distance scale and accounts for age and metallicity effects, the relation adopted by Schoenrich et al. yields up to 18% shorter distances for stars near the main-sequence turnoff (TO). Use of the correct relationship yields agreement between the distances assigned by Carollo et al. and Ivezic et al. for low-metallicity dwarfs to within 6%-10%. Schoenrich et al. also point out that intermediate-gravity stars (3.5 {<=}log g < 4.0) with colors redder than the TO region are likely misclassified, with which we concur. We implement a new procedure to reassign luminosity classifications for the TO stars that require it. New derivations of the rotational behavior demonstrate that the retrograde signature and high velocity dispersion of the outer-halo population remain. We summarize additional lines of evidence for a dual halo, including a test of the retrograde signature based on proper motions alone, and conclude that the preponderance of evidence strongly rejects the single-halo interpretation.
79 ASTRONOMY AND ASTROPHYSICS↗
TOWARD A REMOVAL OF TEMPERATURE DEPENDENCIES FROM ABUNDANCE DETERMINATIONS: NGC 628
The metal content of a galaxy, a key property for distinguishing between viable galaxy evolutionary scenarios, strongly influences many of the physical processes in the interstellar medium. An absolute and robust determination of extragalactic metallicities is essential in constraining models of chemical enrichment and chemical evolution. Current gas-phase abundance determinations, however, from optical fine-structure lines are uncertain to 0.8 dex as conversion of these optical line fluxes to abundances is strongly dependent on the electron temperature of the ionized gas. In contrast, the far-infrared (far-IR) emission lines can be used to derive an O{sup ++} abundance that is relatively insensitive to temperature, while the ratio of the optical to far-IR lines provides a consistent temperature to be used in the derivation of an O{sup +} abundance. We present observations of the [O III] 88 μm fine-structure line in NGC 628 that were obtained as part of the Key Insights on Nearby Galaxies: a Far Infared Survey with Herschel program. These data are combined with optical integrated field unit data to derive oxygen abundances for seven H II regions. We find the abundance of these regions to all lie between the high and low values of strong-line calibrations and to be in agreement with estimates that assume temperature fluctuations are present in the H II regions.
79 ASTRONOMY AND ASTROPHYSICS↗
THE DENSEST GALAXY
We report the discovery of a remarkable ultra-compact dwarf galaxy around the massive Virgo elliptical galaxy NGC 4649 (M60), which we call M60-UCD1. With a dynamical mass of 2.0 × 10{sup 8} M {sub ☉} but a half-light radius of only ∼24 pc, M60-UCD1 is more massive than any ultra-compact dwarfs of comparable size, and is arguably the densest galaxy known in the local universe. It has a two-component structure well fit by a sum of Sérsic functions, with an elliptical, compact (r{sub h} = 14 pc; n ∼ 3.3) inner component and a round, exponential, extended (r{sub h} = 49 pc) outer component. Chandra data reveal a variable central X-ray source with L{sub X} ∼ 10{sup 38} erg s{sup –1} that could be an active galactic nucleus associated with a massive black hole or a low-mass X-ray binary. Analysis of optical spectroscopy shows the object to be old (∼> 10 Gyr) and of solar metallicity, with elevated [Mg/Fe] and strongly enhanced [N/Fe] that indicates light-element self-enrichment; such self-enrichment may be generically present in dense stellar systems. The velocity dispersion (σ ∼ 70 km s{sup –1}) and resulting dynamical mass-to-light ratio (M/L{sub V} = 4.9 ± 0.7) are consistent with—but slightly higher than—expectations for an old, metal-rich stellar population with a Kroupa initial mass function. The presence of a massive black hole or a mild increase in low-mass stars or stellar remnants is therefore also consistent with this M/L{sub V} . The stellar density of the galaxy is so high that no dynamical signature of dark matter is expected. However, the properties of M60-UCD1 suggest an origin in the tidal stripping of a nucleated galaxy with M{sub B} ∼ –18 to –19.
79 ASTRONOMY AND ASTROPHYSICS↗
Formation of dysprosium carbide on the graphite (0001) surface
When using scanning tunneling microscopy, we characterize a surface carbide that forms such that Dy is deposited on the basal plane of graphite. In order to form carbide islands on terraces, Dy is first deposited at 650–800 K, which forms large metallic islands. Upon annealing at 1000 K, these clusters convert to carbide. Deposition directly at 1000 K is ineffective because nucleation on terraces is inhibited. Reaction is signaled by the fact that each carbide cluster is partially or totally surrounded by an etch pit. The etch pit is one carbon layer deep for most carbide clusters. Carbide clusters are also identifiable by striations on their surfaces. Based on mass balance, and assuming that only the surface layer of carbon is involved in the reaction, the carbide has stoichiometry D y 2 C . This is Dy-rich compared with the most common bulk carbide Dy C 2 , which may reflect limited surface carbon transport to the carbide.
36 MATERIALS SCIENCE↗
Imaging atomic-scale effects of high-energy ion irradiation on superconductivity and vortex pinning in Fe(Se,Te)
Maximizing the sustainable supercurrent density, J C , is crucial to high-current applications of superconductivity, and to achieve this, preventing dissipative motion of quantized vortices is key. Irradiation of superconductors with highenergy heavy ions can be used to create nanoscale defects that act as deep pinning potentials for vortices. This approach holds unique promise for high-current applications of iron-based superconductors because JC amplification persists to much higher radiation doses than in cuprate superconductors without significantly altering the superconducting critical temperature. However, for these compounds, virtually nothing is known about the atomic-scale interplay of the crystal damage from the high-energy ions, the superconducting order parameter, and the vortex pinning processes. We visualize the atomic-scale effects of irradiating FeSe x Te 1$-$x with 249-MeV Au ions and find two distinct effects: compact nanometer-sized regions of crystal disruption or “columnar defects,” plus a higher density of single atomic site “point” defects probably from secondary scattering. We directly show that the superconducting order is virtually annihilated within the former but suppressed by the latter. Simultaneous atomically resolved images of the columnar crystal defects, the superconductivity, and the vortex configurations then reveal how amixed pinning landscape is created, with the strongest pinning occurring at metallic core columnar defects and secondary pinning at clusters of point-like defects, followed by collective pinning at higher fields.
Critical Current by Design↗
Materials Data on LiB13C2 by Materials Project
Li(B)6B7C2 crystallizes in the triclinic P1 space group. The structure is zero-dimensional and consists of twelve boron, metallic molecules; two litio molecules; and two B7C2 clusters. In each B7C2 cluster, there are seven inequivalent B+0.23+ sites. In the first B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.62 Å. In the second B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.62 Å. In the third B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.62 Å. In the fourth B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.63 Å. In the fifth B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.62 Å. In the sixth B+0.23+ site, B+0.23+ is bonded in a single-bond geometry to one C2- atom. The B–C bond length is 1.63 Å. In the seventh B+0.23+ site, B+0.23+ is bonded in a linear geometry to two C2- atoms. Both B–C bond lengths are 1.42 Å. There are two inequivalent C2- sites. In the first C2- site, C2- is bonded to four B+0.23+ atoms to form corner-sharing CB4 tetrahedra. In the second C2- site, C2- is bonded to four B+0.23+ atoms to form corner-sharing CB4 tetrahedra.
36 MATERIALS SCIENCE↗
Metal-poor stars. II - Initial horizontal- branch models
Initial horizontal branch metal poor star models, examining opacities, luminosity and cluster ages of RR Lyrae stars
Rood, R. T.↗
Improvements in Ionized Cluster-Beam Deposition
Lower temperatures result in higher purity and fewer equipment problems. In cluster-beam deposition, clusters of atoms formed by adiabatic expansion nozzle and with proper nozzle design, expanding vapor cools sufficiently to become supersaturated and form clusters of material deposited. Clusters are ionized and accelerated in electric field and then impacted on substrate where films form. Improved cluster-beam technique useful for deposition of refractory metals.
Fitzgerald, D. J.↗