Few-Unit-Cell MFI Zeolite Synthesized using a Simple Di-quaternary Ammonium Structure-Directing Agent.

Synthesis of a pentasil-type zeolite with ultra-small few-unit-cell crystalline domains, which we call FDP (few-unit-cell crystalline domain pentasil), is reported. FDP is made using bis-1,5(tributyl ammonium) pentamethylene cations as structure directing agent (SDA). This di-quaternary ammonium SDA combines butyl ammonium, in place of the one commonly used for MFI synthesis, propyl ammonium, and a five-carbon nitrogen-connecting chain, in place of the six-carbon connecting chain SDAs that are known to fit well within the MFI pores. X-ray diffraction analysis and electron microscopy imaging of FDP indicate ca. 10 nm crystalline domains organized in hierarchical micro-/meso-porous aggregates exhibiting mesoscopic order with an aggregate particle size up to ca. 5 µm. Al and Sn can be incorporated into the FDP zeolite framework to produce active and selective methanol-to-hydrocarbon and glucose isomerization catalysts, respectively.

Low-Temperature Thermopower in CoSbS.

We report on giant thermopower of S=2.5 mV/K in CoSbS single crystals: a material that shows strong high-temperature thermoelectric performance when doped with Ni or Se. Changes of low-temperature thermopower induced by a magnetic field point to the mechanism of electronic diffusion of carriers in the heavy valence band. Intrinsic magnetic susceptibility is consistent with the Kondo-insulatorlike accumulation of electronic states around the gap edges. This suggests that giant thermopower stems from temperature-dependent renormalization of the noninteracting bands and buildup of the electronic correlations on cooling.

Pb2MnTeO6 Double Perovskite: An Antipolar Anti-ferromagnet.

Pb2MnTeO6, a new double perovskite, was synthesized. Its crystal structure was determined by synchrotron X-ray and powder neutron diffraction. Pb2MnTeO6 is monoclinic (I2/m) at room temperature with a regular arrangement of all the cations in their polyhedra. However, when the temperature is lowered to ∼120 K it undergoes a phase transition from I2/m to C2/c structure. This transition is accompanied by a displacement of the Pb atoms from the center of their polyhedra due to the 6s(2) lone-pair electrons, together with a surprising off-centering of Mn(2+) (d(5)) magnetic cations. This strong first-order phase transition is also evidenced by specific heat, dielectric, Raman, and infrared spectroscopy measurements. The magnetic characterizations indicate an anti-ferromagnetic (AFM) order below TN ≈ 20 K; analysis of powder neutron diffraction data confirms the magnetic structure with propagation vector k = (0 1 0) and collinear AFM spins. The observed jump in dielectric permittivity near ∼150 K implies possible anti-ferroelectric behavior; however, the absence of switching suggests that Pb2MnTeO6 can only be antipolar. First-principle calculations confirmed that the crystal and magnetic structures determined are locally stable and that anti-ferroelectric switching is unlikely to be observed in Pb2MnTeO6.

New layered fluorosulfide SrFBiS2.

We have synthesized a new layered BiS2-based compound, SrFBiS2. This compound has a similar structure to LaOBiS2. It is built up by stacking up SrF layers and NaCl-type BiS2 layers alternatively along the c axis. Electric transport measurement indicates that SrFBiS2 is a semiconductor. Thermal transport measurement shows that SrFBiS2 has a small thermal conductivity and large Seebeck coefficient. First principle calculations are in agreement with experimental results and show that SrFBiS2 is very similar to LaOBiS2, which becomes a superconductor with F doping. Therefore, SrFBiS2 may be a parent compound of new superconductors.

Lattice instability and magnetic phase transitions in strongly correlated MnAs.

Using variable temperature x-ray total scattering in magnetic field, we study the interaction between lattice and magnetic degrees of freedom in MnAs, which loses its ferromagnetic order and hexagonal ('H') lattice symmetry at 318 K to recover the latter and become a true paramagnet when the temperature is increased to 400 K. Our results show that the 318 K transition is accompanied by highly anisotropic displacements of Mn atoms that appear as a lattice degree of freedom bridging the 'H' and orthorhombic phases of MnAs. This is a rare example of a lowering of an average crystal symmetry due to an increased displacive disorder emerging on heating. Our results also show that magnetic and lattice degrees of freedom appear coupled but not necessarily equivalent control variables for triggering phase transitions in strongly correlated systems in general and in particular in MnAs.

Iron chalcogenide superconductors at high magnetic fields.

Iron chalcogenide superconductors have become one of the most investigated superconducting materials in recent years due to high upper critical fields, competing interactions and complex electronic and magnetic phase diagrams. The structural complexity, defects and atomic site occupancies significantly affect the normal and superconducting states in these compounds. In this work we review the vortex behavior, critical current density and high magnetic field pair-breaking mechanism in iron chalcogenide superconductors. We also point to relevant structural features and normal-state properties.

Tailoring defects and nanocrystal transformation for optimal heating power in bimagnetic CoyFe1-yO@CoxFe3-xO4 particles.

The effects of cobalt incorporation in spherical heterostructured iron oxide nanocrystals (NCs) of sub-critical size have been explored by colloidal chemistry methods. Synchrotron X-ray total scattering methods suggest that cobalt (Co) substitution in rock salt iron oxide NCs tends to remedy their vacant iron sites, offering a higher degree of resistance to oxidative conversion. Self-passivation still creates a spinel-like shell, but with a higher volume fraction of the rock salt Co-containing phase in the core. The higher divalent metal stoichiometry in the rock salt phase, with increasing Co content, results in a population of unoccupied tetrahedral metal sites in the spinel part, likely through oxidative shell creation, involving an ordered defect-clustering mechanism, directly correlated to core stabilization. To shed light on the effects of Co-substitution and atomic-scale defects (vacant sites), Monte Carlo simulations suggest that the designed NCs, with desirable, enhanced magnetic properties (cf. exchange bias and coercivity), are developed with magnetocrystalline anisotropy which increases due to a relatively low content of Co ions in the lattice. The growth of optimally performing candidates combines also a strongly exchange-coupled system, secured through a high volumetric ratio rock salt phase, interfaced by a not so defective spinel shell. In view of these requirements, specific absorption rate (SAR) calculations demonstrate that the rock salt core sufficiently protected from oxidation and the heterostructure preserved over time, play a key role in magnetically mediated heating efficacies, for potential use of such NCs in magnetic hyperthermia applications.

Hidden Local Symmetry Breaking in Silver Diamondoid Compounds is Root Cause of Ultralow Thermal Conductivity.

Typically, conventional structure transitions occur from a low symmetry state to a higher symmetry state upon warming. In this work, an unexpected local symmetry breaking in the tetragonal diamondoid compound AgGaTe2 is reported, which, upon warming, evolves continuously from an undistorted ground state to a locally distorted state while retaining average crystallographic symmetry. This is a rare phenomenon previously referred to as emphanisis. This distorted state, caused by the weak sd3 orbital hybridization of tetrahedral Ag atoms, causes their displacement off the tetrahedron center and promotes a global distortion of the crystal structure resulting in strong acoustic-optical phonon scattering and an ultralow lattice thermal conductivity of 0.26 W m-1 K-1 at 850 K in AgGaTe2 . The findings explain the underlying reason for the unexpectedly low thermal conductivities of silver-based compounds compared to copper-based analogs and provide a guideline to suppressing heat transport in diamondoid and other materials.

Phase diagram of K(x)Fe(2-y)Se(2-z)S(z) and the suppression of its superconducting state by an Fe2-Se/S tetrahedron distortion.

We report structurally tuned superconductivity in a K(x)Fe(2-y)Se(2-z)S(z) (0 ≤ z ≤ 2) phase diagram. Superconducting T(c) is suppressed as S is incorporated into the lattice, eventually vanishing at 80% of S. The magnetic and conductivity properties can be related to stoichiometry on a poorly occupied Fe1 site and the local environment of a nearly fully occupied Fe2 site. The decreasing T(c) coincides with the increasing Fe1 occupancy and the overall increase in Fe stoichiometry from z = 0 to z = 2. Our results indicate that the irregularity of the Fe2-Se/S tetrahedron is an important controlling parameter that can be used to tune the ground state in the new superconductor family.

High-Capacity Aqueous Storage in Vanadate Cathodes Promoted by the Zn-Ion and Proton Intercalation and Conversion-Intercalation of Vanadyl Ions.

Aqueous Zn-ion batteries (AZIBs) are promising alternatives to lithium-ion batteries in stationary storage. However, limited storage capacity and cyclic life impede their large-scale implementation. We report reversible electrochemical insertion of multi-ions into sodium vanadate (NaV3O8) cathode materials for AZIBs, achieving a maximum storage capacity of 450 mAh g-1 at 0.05 A g-1 and a capacity retention of 82% after 500 cycles at 0.4 A g-1. In addition to Zn2+ and H+ insertion, in situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) collectively provide explicit evidence on vanadyl ions (VO2+) conversion-intercalation at the NaV3O8 cathode, showing the deintercalation of VO2+ from NaV3O8 and the consequent conversion of VO2+ into V2O5 on charging, and vice versa on discharging. Our study is the first to report on the cation conversion-intercalation mechanism in AZIBs. This reversible multi-ion storage mechanism provides a design principle for developing high-capacity aqueous electrode materials by engaging both the intercalation and conversion of charge carriers.

X-ray scattering reveals ion clustering of dilute chromium species in molten chloride medium.

Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments, ab initio molecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr3+ metal ions in a molten KCl-MgCl2 salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr-Cr dimers in the high-temperature low Cr3+ concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr3+ exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.

Elucidating Ionic Correlations Beyond Simple Charge Alternation in Molten MgCl2-KCl Mixtures.

The development of technologies for nuclear reactors based on molten salts has seen a big resurgence. The success of thermodynamic models for these hinges in part on our ability to predict at the atomistic level the behavior of pure salts and their mixtures under a range of conditions. In this letter, we present high-energy X-ray scattering experiments and molecular dynamics simulations that describe the molten structure of mixtures of MgCl2 and KCl. As one would expect, KCl is a prototypical salt in which structure is governed by simple charge alternation. In contrast, MgCl2 and its mixtures with KCl display more complex correlations including intermediate-range order and the formation of Cl--decorated Mg2+ chains. A thorough computational analysis suggests that intermediate-range order beyond charge alternation may be traced to correlations between these chains. An analysis of the coordination structure for Mg2+ ions paints a more complex picture than previously understood, with multiple accessible states of distinct geometries.

Multiband electronic transport in α-Yb1-x Sr x AlB4 [x = 0, 0.19(3)] single crystals.

We report on the evidence for the multiband electronic transport in α-YbAlB4 and α-Yb0.81(2)Sr0.19(3)AlB4. Multiband transport reveals itself below 10 K in both compounds via Hall effect measurements, whereas anisotropic magnetic ground state sets in below 3 K in α-Yb0.81(2)Sr0.19(3)AlB4. Our results show that Sr(2+) substitution enhances conductivity, but does not change the quasiparticle mass of bands induced by heavy fermion hybridization.

Physical properties of K(x)Ni(2-y)Se2 single crystals.

We have synthesized K0.95(1)Ni1.86(2)Se2 single crystals. The single crystals contain K and Ni deficiencies not observed in KNi2Se2 polycrystals. Unlike KNi2Se2 polycrystals, the superconductivity is absent in single crystals. The detailed physical property study indicates that the K0.95Ni1.86Se2 single crystals exhibit heavy-fermion-like characteristics. The transition to a heavy fermion state below T ~ 30 K results in an enhancement of the electron-like carrier density whereas the magnetic susceptibility shows little anisotropy and suggests the presence of both itinerant and localized Ni orbitals.