Single-Atom Catalysts Supported by Crystalline Porous Materials: Views from the Inside
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Zhang, Tianjun↗
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Graphene Supported Single Atom Transition Metal Catalysts for Methane Activation
Not provided.
Chemistry↗
Single-atom automobile exhaust catalysts
Single-atom catalysts (SACs) with isolated metal centers are attracting great research interest because of their maximized metal utilization rates and unique structures. In the last decade, significant efforts have been made to design highly efficient and costeffective SACs with applications in automobile exhaust aftertreatment. SACs have not only demonstrated their high potential for improving the catalytic performance of current automobile exhaust catalysts but also provided an ideal platform for understanding the origins of catalyst reactivity. In this review, we summarize the general strategies for promoting the reactivity of metal SACs while maintaining their thermal stability during exhaust-abatement-related reactions. Highlights are provided on well-performed SACs for CO oxidation, unburnt hydrocarbon (HC) oxidation, and the selective catalytic reduction of NOx. The reaction mechanism and structure– performance relationship of SAC during these reactions are also discussed. Finally, perspectives are given on the trending research fields for designing more efficient single-atom automobile exhaust catalysts in the future.
Lu, Yubing↗
Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interactions with Uranyl Oxo Atoms: Isolating Equatorial and Oxo Based Influences on Uranyl Vibrational Spectroscopy in a Family of Hybrid Materials Featuring Halogen Bonding Interaction
Not provided.
Chemistry↗
A survey of nuclear quadrupole deformation in order to estimate the nuclear MQM and its relative contribution to the atomic EDM: Searching for the best candidate to focus on an atomic EDM measurement: A nuclear physics perspective
Abstract Measurement of a non-zero permanent electric dipole moment (EDM) in fundamental particles, such as in an electron or a neutron, or in nuclei or atoms, can help us gain a handle on the sources of Charge-Parity (CP) violation, both in the Standard Model (SM) and beyond. The nuclear magnetic quadrupole moment (MQM), the central topic of this work, is also CP, P, and T violating. Nucleons and nuclei have a non-zero MQM from sources within the SM, but the nuclear MQM is dramatically enhanced if the nuclei are structurally quadrupole deformed. Multiple sources contribute to an atomic EDM namely: (i) nuclear EDM through its Schiff moment, which is enhanced by nuclear octupole deformation, (ii) CP violating interactions between the electrons and the nuclei, and (iii) the nuclear MQM that contributes to the atomic EDM in atoms with an unpaired valence electron. Our survey of nuclear quadrupole deformation identified 48 isotopes as ideal systems in which to search for a CP violating EDM via their enhanced nuclear MQM. Of these candidates, $$^{223,225}$$ 223 , 225 Fr, $$^{223}$$ 223 Ra, $$^{223,225,227}$$ 223 , 225 , 227 Ac, $$^{229}$$ 229 Th, and $$^{229}$$ 229 Pa also have maximally enhanced nuclear Schiff moment contribution due to their octupole deformation. Laser cooling of the isotopes of Fr and Ra, among a few others, has already been demonstrated, making $$^{223,225}$$ 223 , 225 Fr and $$^{223}$$ 223 Ra some of the best systems in which to measure an EDM.
MohanMurthy, Prajwal↗
Atomic-level heterogeneity and defect dynamics in concentrated solid-solution alloys
Performance enhancement of structural materials in extreme radiation environments has been activelyinvestigated for many decades. Traditional alloys, such as steel, brass and aluminum alloys, normallycontain one or two principal element(s) with a low concentration of other elements. While these existin either a mixture of metallic phases (multiple phases) or in a solid solution (single phase), limited orlocalized chemical disorder is a common characteristic of the main matrix. Fundamentally different fromtraditional alloys, recently developed single-phase concentrated solid-solutio n alloys (CSAs) contain mul-tiple elemental species in equiatomic or high concentrations with different elements randomly arrangedon a crystalline lattice. Due to the lack of ordered elemental arrangement in these CSAs, they exhibit sig-nificant chemical disorder and unique site-to-site lattice distortion. While it is well recognized intraditional alloys that minor additions lead to enhanced radiation resistance, it remains unclear inCSAs how atomic-level heterogeneity affects defect formation, damage accumulation, and microstruc-tural evolution. These knowledge gaps have acted as roadblocks to the development of future-generation energy technology. CSAs with a simple crystal structure, but complex chemical disorder,are unique systems that allow us, through replacing principal alloying elements and modifying concen-trations, to study how compositional complexity influences defect dynamics, and to bridge the knowl-edge gaps through understanding intricate electronic- and atomic-level interactions, mass and energytransfer processes, and radiation resistance performance. Recent advances in defect dynamics and irradi-ation performance of CSAs are reviewed, intrinsic chemical effects on radiation performance arediscussed, and direction for future studies is suggested.
Zhang, Yanwen↗
Coupled electronic and atomic effects on defect evolution in silicon carbide under ion irradiation
Not Available
Zhang, Yanwen↗
Friction consolidation of gas-atomized Fe−Si powders for soft magnetic applications
Soft magnetic materials are often limited in scalability due to conventional processes that do not retain beneficial microstructures, and their associated physical properties, during densification. In this work, friction consolidation (FC) has been studied to fabricate Fe−Si soft magnetic materials from gas-atomized powder precursors. Fe−Si powder is consolidated using variable pressure and tool rotation speed in an effort to evaluate this unique densification approach for potential improvements in magnetic properties. FC, due to the high shear deformation involved, is shown to result in uniform gradual grain structure refinement across the consolidated workpiece from the center nearest the tool to the edge. Magnetic properties along different orientations indicate little, if any, textural orientation in the refined grain structure. The effect of annealing on the magnetic properties is evaluated and shown to decrease coercivity. FC processing was able to retain the magnetization of the original gas-atomized powders but further process optimization is needed to reach the optimal coercivity for the soft magnetic materials applications. - Highlights: •Friction stir processing was utilized to consolidate Fe−Si soft magnetic powders. •The resultant microstructure and magnetic properties were correlated to the processing conditions. •Friction consolidation refined the grain size of the materials by ~ 40%. •Annealing successfully reduced the coercivity induced by the stress during processing. •The results shine light on the possible scaling up of nanostructured materials.
36 MATERIALS SCIENCE↗
Atomic and molecular adsorption on Au(111)
Periodic self-consistent density functional theory (DFT-GGA) calculations were used to study the adsorption of several atomic species, molecular species and molecular fragments on the Au(111) surface with a coverage of 1/4 monolayer (ML). Binding geometries, binding energies, and diffusion barriers were calculated for 27 species. Furthermore, we calculated the surface deformation energy associated with the binding events. The binding strength for all the analyzed species can be ordered as follows: NH 3 < NO < CO < CH 3 < HCO < NH 2 < COOH < OH < HCOO < CNH 2 < H < N < NH < NOH < COH < Cl,< HCO 3 < CH 2 < CN b HNO < O < F < S < C < CH. Although the atomic species preferred to bind at the three-fold fcc site, no tendency was observed in site preference for the molecular species and fragments. The intramolecular and adsorbate-surface vibrational frequencies were calculated for all the adsorbates on their most energetically stable adsorption site. Most of the theoretical binding energies and frequencies agreed with experimental values reported in the literature. In general, the values obtained with the PW91 functional are more accurate than RPBE in reproducing these experimental binding energies. The energies of the adsorbed species were used to calculate the thermochemical potential energy surfaces for decomposition of CO, NO, N 2 , NH 3 and CH 4 , oxidation of CO, and hydrogenation of CO, CO 2 and NO, giving insight into the thermochemistry of these reactions on gold nanoparticles. These potential energy surfaces demonstrated that: the decomposition of species is not energetically favorable on Au(111); the desorption of NH 3 , NO and CO are more favorable than their decomposition; the oxidation of CO and hydrogenation of CO and NO on Au(111) to form HCO and HNO, respectively, are also thermodynamically favorable.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Atomic Scale Studies of La/Sr Ordering in Colossal Magnetoresistant La 2-2x Sr 1+2x Mn 2 O 7 Single Crystals
To date, it is unclear whether chemical order (or disorder) is in any way connected to double exchange, electronic phase separation, or charge ordering (CO) in manganites. In this work, we carry out an atomic resolution study of the colossal magnetoresistant manganite La 2-2x Sr 1+2x Mn 2 O 7 (LSMO). We combine aberration-corrected electron microscopy and spectroscopy with spectroscopic image simulations, to analyze cation ordering at the atomic scale in real space in a number of LSMO single crystals. We compare three different compositions within the phase diagram: a ferromagnetic metallic material (x=0.36), an insulating, antiferromagnetic charge ordered (AF-CO) compound (x=0.5), which also exhibits orbital ordering, and an additional AF sample (x=0.56). Detailed image simulations are essential to accurately quantify the degree of chemical ordering of these samples. We find a significant degree of long-range chemical ordering in all cases, which increases in the AF-CO range. However, the degree of ordering is never complete nor can it explain the strongly correlated underlying ordering phenomena. Our results show that chemical ordering over distinct crystallographic sites is not needed for electronic ordering phenomena to appear in manganites, and cannot by itself explain the complex electronic behavior of LSMO.
36 MATERIALS SCIENCE↗
Measurement Error in Atomic-Scale Scanning Transmission Electron Microscopy—Energy-Dispersive X-Ray Spectroscopy (STEM-EDS) Mapping of a Model Oxide Interface
Abstract With the development of affordable aberration correctors, analytical scanning transmission electron microscopy (STEM) studies of complex interfaces can now be conducted at high spatial resolution at laboratories worldwide. Energy-dispersive X-ray spectroscopy (EDS) in particular has grown in popularity, as it enables elemental mapping over a wide range of ionization energies. However, the interpretation of atomically resolved data is greatly complicated by beam–sample interactions that are often overlooked by novice users. Here we describe the practical factors—namely, sample thickness and the choice of ionization edge—that affect the quantification of a model perovskite oxide interface. Our measurements of the same sample, in regions of different thickness, indicate that interface profiles can vary by as much as 2–5 unit cells, depending on the spectral feature. This finding is supported by multislice simulations, which reveal that on-axis maps of even perfectly abrupt interfaces exhibit significant delocalization. Quantification of thicker samples is further complicated by channeling to heavier sites across the interface, as well as an increased signal background. We show that extreme care must be taken to prepare samples to minimize channeling effects and argue that it may not be possible to extract atomically resolved information from many chemical maps.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber
The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Atomic Origins of Water-Vapour-Promoted Alloy Oxidation
The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of both vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.
Luo, Langli (ORCID:000000026311051X)↗
Atomic-scale identification of Pd leaching in nanoparticle catalyzed C–C coupling: Effects of particle surface disorder
C–C coupling reactions are of great importance in the synthesis of numerous organic compounds, where Pd nanoparticle catalyzed systems represent new materials to efficiently drive these reactions. Despite their pervasive utility, the catalytic mechanism of these particle-based reactions remains highly contested. Herein we present evidence of an atom leaching mechanism for Stille coupling under aqueous conditions using peptide-capped Pd nanoparticles. EXAFS analysis revealed Pd coordination changes in the nanoparticle consistent with Pd atom abstraction, where sizing analysis by SAXS confirmed particle size changes associated with a leaching process. It is likely that recently discovered highly disordered surface Pd atoms are the favored catalytic active sites and are leached during oxidative addition, resulting in smaller particles. Thus, probing the mechanism of nanoparticle-driven C–C coupling reactions through structural analyses provides fundamental information concerning these active sites and their reactivity at the atomic-scale, which can be used to improve catalytic performance to meet important sustainability goals.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Electron-stimulated reactions in layered CO/H{sub 2}O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol
Low-energy (100 eV) electron-stimulated reactions in layered H{sub 2}O/CO/H{sub 2}O ices are investigated. For CO layers buried in amorphous solid water (ASW) films at depths of 50 monolayers (ML) or less from the vacuum interface, both oxidation and reduction reactions are observed. However, for CO buried more deeply in ASW films, only the reduction of CO to methanol is observed. Experiments with layered films of H{sub 2}O and D{sub 2}O show that the hydrogen atoms participating in the reduction of the buried CO originate in the region that is 10–50 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried CO layers, the CO reduction reactions quickly increase with temperature above ∼60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol to account for the observations.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ
This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO 2 measurements. As a result, the new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO 2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H 2 and natural gas uptake/storage.
36 MATERIALS SCIENCE↗
Inhomogeneous distribution of manganese atoms in ferromagnetic ZnSnAs{sub 2}:Mn thin films on InP revealed by three-dimensional atom probe investigation
Atomic-scale Mn distributions in ferromagnetic ZnSnAs{sub 2}:Mn thin films grown on InP substrates have been studied by applying three-dimensional atom probe (3DAP) microscopy. It is found that Mn atoms in cross-sectional 3DAP maps show the presence of inhomogeneities in Mn distribution, which is characteristic patterns of a spinoidal decomposition phase with slightly high and low concentration regions. The high Mn concentration regions are expected to be coherently clustered MnAs in the zinc-blende structure, resulting in the formation of Mn-As random connecting patterns. The origin of room-temperature ferromagnetism in ZnSnAs{sub 2}:Mn on InP can be well explained by the formation of atomic-scale magnetic clustering by spinoidal decomposition without breaking the continuity of the zinc-blende structure, which has been suggested by previous theoretical works. The lattice-matching between magnetic epi-layers and substrates should be one of the most important factors to avoid the formation of secondary hexagonal MnAs phase precipitates in preparing ferromagnetic semiconductor thin films.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗