Possible unconventional order parameter in single crystals of SrPt3P superconductor.

Anisotropic properties of single crystals of SrPt3P were studied using London penetration depth and electrical resistivity measurements. The upper critical field,Hc2(T), was determined from four-probe electrical resistivity measurements for three orthogonal directions of a magnetic field with respect to the crystal. The London penetration depth,λ(T), was determined from the magnetic susceptibility of the Meissner-London state measured using a tunnel-diode resonator technique. WhereasHc2(T)and the normal-stateρ(T)are practically identical for all three magnetic field orientations, the London penetration depth shows significant unidirectional anisotropy. The low-temperatureλ(T)is exponentially attenuated when a small excitation radiofrequency magnetic field,Hrf, is applied along thec''-direction, in which case screening currents flow in thea''b''-plane, while for the other two orientations,Hrf∥a''andHrf∥b'', the London penetration depth shows a much stronger,λ(T)∼T2, variation. Such unusual and contrasting behavior of the two anisotropies,γHT=Hc2,ab/Hc2,c=ξab/ξcandγλT=λc/λab, imposes significant constraints on the possible order parameter. Although our measurements are insufficient to derive conclusively the superconducting gap anisotropy, the order parameter with two point nodes and a modulation in the perpendicular direction is qualitatively consistent with the experimental observations.

Two-dimensional metal NaCu6.3Sb3 and solid-state transformations of sodium copper antimonides.

A novel layered compound, NaCu6.3Sb3, has been successfully synthesized from elements. This unique structure crystallizes in the hexagonal space group P63/mmc and has lattice constants of a = 4.2166(2) Å and c = 24.041(1) Å. The structure consists of complex Cu/Sb 2D blocks separated by Na ions. These blocks contain graphene-like hexagonal layers of either Cu or CuSb. The solid-state transformations in the Na-Cu-Sb system between Cu2Sb-NaCu6.3Sb3-NaCu4Sb2 were explored using annealing at different partial vapor pressures of Na, differential scanning calorimetry, and in situ synchrotron powder X-ray diffraction. Full reversibility of the transformation was observed, indicating that the bulk 3D Cu2Sb phase is capable of reversible intercalation of Na ions, forming layered intercalated phases similar to intercalated graphite. The characterization of the transport properties shows that the metallic nature of the electrical conductivity is preserved, even for the Na-rich phase of NaCu4Sb2. Electronic structure calculations support metallic properties in the Cu-Sb layers and predict that no bands cross the Fermi level across the layers, supporting NaCu6.3Sb3 as a two-dimensional metal.

Controlling superstructural ordering in the clathrate-I Ba8M16P30 (M = Cu, Zn) through the formation of metal-metal bonds.

Order-disorder-order phase transitions in the clathrate-I Ba8Cu16P30 were induced and controlled by aliovalent substitutions of Zn into the framework. Unaltered Ba8Cu16P30 crystallizes in an ordered orthorhombic (Pbcn) clathrate-I superstructure that maintains complete segregation of metal and phosphorus atoms over 23 different crystallographic positions in the clathrate framework. The driving force for the formation of this Pbcn superstructure is the avoidance of Cu-Cu bonds. This superstructure is preserved upon aliovalent substitution of Zn for Cu in Ba8Cu16-x Zn x P30 with 0 < x < 1.6 (10% Zn/Mtotal), but vanishes at greater substitution concentrations. Higher Zn concentrations (up to 35% Zn/Mtotal) resulted in the additional substitution of Zn for P in Ba8M16+y P30-y (M = Cu, Zn) with 0 ≤ y ≤ 1. This causes the formation of Cu-Zn bonds in the framework, leading to a collapse of the orthorhombic superstructure into the more common cubic subcell of clathrate-I (Pm3n). In the resulting cubic phases, each clathrate framework position is jointly occupied by three different elements: Cu, Zn, and P. Detailed structural characterization of the Ba-Cu-Zn-P clathrates-I via single crystal X-ray diffraction, joint synchrotron X-ray and neutron powder diffractions, pair distribution function analysis, electron diffraction and high-resolution electron microscopy, along with elemental analysis, indicates that local ordering is present in the cubic clathrate framework, suggesting the evolution of Cu-Zn bonds. For the compounds with the highest Zn content, a disorder-order transformation is detected due to the formation of another superstructure with trigonal symmetry and Cu-Zn bonds in the clathrate-I framework. It is shown that small changes in the composition, synthesis, and crystal structure have significant impacts on the structural and transport properties of Zn-substituted Ba8Cu16P30.

Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation.

Replacing noble metals in heterogeneous catalysts by low-cost substitutes has driven scientific and industrial research for more than 100 years. Cheap and ubiquitous iron is especially desirable, because it does not bear potential health risks like, for example, nickel. To purify the ethylene feed for the production of polyethylene, the semi-hydrogenation of acetylene is applied (80 × 10(6) tons per annum; refs 1-3). The presence of small and separated transition-metal atom ensembles (so-called site-isolation), and the suppression of hydride formation are beneficial for the catalytic performance. Iron catalysts necessitate at least 50 bar and 100 °C for the hydrogenation of unsaturated C-C bonds, showing only limited selectivity towards semi-hydrogenation. Recent innovation in catalytic semi-hydrogenation is based on computational screening of substitutional alloys to identify promising metal combinations using scaling functions and the experimental realization of the site-isolation concept employing structurally well-ordered and in situ stable intermetallic compounds of Ga with Pd (refs 15-19). The stability enables a knowledge-based development by assigning the observed catalytic properties to the crystal and electronic structures of the intermetallic compounds. Following this approach, we identified the low-cost and environmentally benign intermetallic compound Al(13)Fe(4) as an active and selective semi-hydrogenation catalyst. This knowledge-based development might prove applicable to a wide range of heterogeneously catalysed reactions.

Cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y): crystal structure, homogeneity range, and physical properties.

A new cationic clathrate I Si(46-x)P(x)Te(y) (6.6(1) < or = y < or = 7.5(1), x < or = 2y at 1375 K) was synthesized from the elements and characterized by X-ray powder diffraction, thermal analysis, scanning electron microscopy, wavelength dispersive X-ray spectroscopy (WDXS), neutron powder diffraction, and (31)P NMR spectroscopy. The thermal behaviors of the magnetic susceptibility and resistivity were investigated as well. Si(46-x)P(x)Te(y) reveals a wide homogeneity range due to the presence of vacancies in the tellurium guest positions inside the smaller cage of the clathrate I structure. The vacancy ordering in the structure of Si(46-x)P(x)Te(y) causes the change of space group from Pm3n (ideal clathrate I) to Pm3 accompanied by the redistribution of P and Si atoms over different framework positions. Neutron powder diffraction confirmed that P atoms preferably form a cage around the vacancy-containing tellurium guest position. Additionally, (31)P NMR spin-spin relaxation experiments revealed the presence of sites with different coordination of phosphorus atoms. Precise determination of the composition of Si(46-x)P(x)Te(y) by WDXS showed slight but noticeable deviation (x < or = 2y) of phosphorus content from the Zintl counting scheme (x = 2y). The compound is diamagnetic while resistivity measurements show activated behavior or that of heavily doped semiconductors. Thermal analysis revealed high stability of the investigated clathrate: Si(46-x)P(x)Te(y) melts incongruently at approximately 1460 K in vacuum and is stable in air against oxidation up to 1295 K.