Search Results
The effect of supported MoOX structures on the reaction pathways of propene formation in the metathesis of ethylene and 2-butene
2014, Hahn, T., Kondratenko, E.V., Linke, D.
The kind of surface MoOX structures on Al2O3–SiO2 was found to determine propene selectivity in the metathesis of ethylene and 2-butene. Compared to isolated tetrahedral MoOX species, their polymerized octahedral counterparts show significantly lower activity for isomerisation of 2- to 1-butene thus hindering non-selective metathesis of these butenes. In addition, they reveal higher ability to engage ethylene in propene formation.
X-ray imaging of chemically active valence electrons during a pericyclic reaction
2014, Bredtmann, T., Ivanov, M., Dixit, G.
Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions.
Two types of magnetic shape-memory effects from twinned microstructure and magneto-structural coupling in Fe1 +yTe
2019, Rößler, S., Koz, C., Wang, Z., Skourski, Y., Doerr, M., Kasinathan, D., Rosner, H., Schmidt, M., Schwarz, U., Rößler, U.K., Wirth, S.
A detailed experimental investigation of Fe1+yTe (y = 0.11, 0.12) using pulsed magnetic fields up to 60 T confirms remarkable magnetic shape-memory (MSM) effects. These effects result from magnetoelastic transformation processes in the low-temperature antiferromagnetic state of these materials. The observation of modulated and finely twinned microstructure at the nanoscale through scanning tunneling microscopy establishes a behavior similar to that of thermoelastic martensite. We identified the observed, elegant hierarchical twinning pattern of monoclinic crystallographic domains as an ideal realization of crossing twin bands. The antiferromagnetism of the monoclinic ground state allows for a magnetic-field–induced reorientation of these twin variants by the motion of one type of twin boundaries. At sufficiently high magnetic fields, we observed a second isothermal transformation process with large hysteresis for different directions of applied field. This gives rise to a second MSM effect caused by a phase transition back to the field-polarized tetragonal lattice state.
Single molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene
2017, Liu, F., Krylov, D.S., Spree, L., Avdoshenko, S.M., Samoylova, N.A., Rosenkranz, M., Kostanyan, A., Greber, T., Wolter, A.U.B., Büchner, B., Popov, A.A.
Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y 2 @C 80 and Dy 2 @C 80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy 2 @C 80 (CH 2 Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy 2 @C 80 (CH 2 Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μ B with a dysprosium-electron exchange constant of 32 cm -1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.
Restoration of rhythmicity in diffusively coupled dynamical networks
2015, Zou, W., Senthilkumar, D.V., Nagao, R., Kiss, I.Z., Tang, Y., Koseska, A., Duan, J., Kurths, J.
Plasmon-driven sequential chemical reactions in an aqueous environment
2014, Zhang, X., Wang, P., Zhang, Z., Fang, Y., Sun, M.
Plasmon-driven sequential chemical reactions were successfully realized in an aqueous environment. In an electrochemical environment, sequential chemical reactions were driven by an applied potential and laser irradiation. Furthermore, the rate of the chemical reaction was controlled via pH, which provides indirect evidence that the hot electrons generated from plasmon decay play an important role in plasmon-driven chemical reactions. In acidic conditions, the hot electrons were captured by the abundant H + in the aqueous environment, which prevented the chemical reaction. The developed plasmon-driven chemical reactions in an aqueous environment will significantly expand the applications of plasmon chemistry and may provide a promising avenue for green chemistry using plasmon catalysis in aqueous environments under irradiation by sunlight.