Single Atom Alloy Preparation and Applications in Heterogeneous Catalysis

There have been remarkable progresses in manipulating heterogeneous catalysts' nanostructures in the past decade. The concept of single atom alloy (SAA) was firstly proposed in 2012 when researchers successfully stabilized single Pd atoms on the Cu(111) surface. However, earlier work in 2009, which focused on replacing one Au atom with a Pd atom in thiolate protected Au₂₅ nanoclusters, could also be considered as the pioneer work of single atom alloy. Both kinds of single atom alloys exhibited the potential of maximum utilization of scarce elements and attractive catalytic performances. The well‐defined structures of SAA catalysts make accurate modeling possible, which further realizes the rational design of single atom alloy catalysts. In this review, we summarize the research trajectory of single atom alloys as well as recent achievements in this field. We also introduce several commonly adopted characterization methods for SAA catalysts such as scanning tunneling microscopy (STM), temperature programmed reaction (TPR), extended X‐ray absorption fine structure (EXAFS) spectra, matrix assisted laser desorption/ionization mass spectrum (MALDI‐MS) and differential pulse voltammetry (DPV). Through discussing recent progresses in SAA catalysts, we propose that future researches in this filed should be focused on exploring new kinds of metal nanocrystals and controlling the nanostructure of SAA even more precisely.     

Morphological effect on spectral property of poly(9,9-dihexylfluorene-alt-2,5-dihexyloxybenzene) films

In this study the optical property and film morphology of a conjugated polymer, poly(9,9-dihexylfluorene-alt-2,5-dihexyloxybenzene) (PF6OC6), are investigated. It is found that the intensity of the 0-1 emission relative to the 0-0 emission in the PL spectra and the full width at the half-maximum (fwhm) of PL spectra of the PF6OC6 films decrease firstly and then increase with increasing the annealing temperature. The polymer films also exhibit different morphological features after annealing at different temperatures. The optical and morphological results suggest that the vibronic structure of PF6OC6 is closely related to the film morphology, and its formation is enhanced in the amorphous (or less ordered) films and inhibited in the ordered films.     

Density functional study of the l-proline-catalyzed α-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity

The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H₂O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper.     

Some inequalities for partial orders

We establish some inequalities connecting natural parameters of a partial order P. For example, if every interval [a,b] contains at most maximal chains, if some antichain has cardinality v, and if there are ₁ chains whose union is cofinal and coinitial in P, then the chain decomposition number for P is ₁v (Theorem 2.2), and the inequality is sharp in a certain sense (Section 3).This paper was written while the authors were visitors at the Laboratoire d'algèbre ordinale, Département de Mathématiques, Université Claude Bernard, Lyon 1, France.Research supported by NSERC grant # A5198.     

Effects of surface nonlinear interactions on the local critical behavior

The energy spectrum and the wave functions of quantum wells in strong magnetic fields parallel to the potential walls are calculated analytically by means of a new, graph supported method. This Arrow Train Method allows to solve the recurrence relations which originate in the evaluation of eigenvalue determinants of infinite order. The energy eigenvalues for infinite barrier height are computed as a power series in the magnetic fieldB and the center of orbit coordinatez ₀. The power series is evaluated up to the 18th order inB ² for the first four levels and for cyclotron radii comparable to or considerable less than the well width. The corresponding wave functions and the field dependent center of mass shifts are obtained.Work supported in part by the Deutsche Forschungsgemeinschaft     

Cluster model study of lightp-shell Λ-hypernuclei with OBE-based effective ΛN interaction

The structures of the lightp-shell hypernuclei \({}_\Lambda ^6 He,{}_\Lambda ^7 Li,{}_\Lambda ^9 Liand{}_\Lambda ^9 Be\) are studied by using a realistic effectiveΛN interaction (YNG), and compared to those with the use of the simple one-range Gaussian (ORG) interaction. The YNG interaction, which simulates theΛNG-matrix for the Nijmegen OBE modelD, is characterized by the inner repulsive core and the density-dependence along with the space-exchange and spin-spin components. The framework we adopt is the microscopic α +x + Λ (x=n, d, t or α) three-cluster model, where nucleon antisymmetrization is exactly treated. The characteristic behaviors ofΛ?x andΛ?(αx) interactions derived from the YNG are displayed and discussed. In spite of the remarkable characteristic of YNG, the calculated energy levels of the four hypernuclei are very similar to those previous obtained by using the simple ORG interaction. The stabilization and contraction of the hypernuclear system due to the glue-like role ofΛ-particle persists in the present calculation, though the repulsive core of theΛN interaction tends to prevent from too much contraction.     

The global topological meaning of cocycles in a Gauge group

This Letter shows explicitly that the descent sequence of cocycles in a gauge group realizes the ech-de Rham double complex. Meanwhile the ech complex corresponds to finite gauge transformations. This Letter also shows how the indices of each order of cocycles characterizes the obstructions on overlapping spheres in different dimensions and how these indices are equal to a common one.