RÉSUMÉ
Connections between crystal chemistry and critical temperature Tc have been in the focus of superconductivity, one of the most widely studied phenomena in physics, chemistry, and materials science alike. In most Fe-based superconductors, materials chemistry and physics conspire so that Tc correlates with the average anion height above the Fe plane, i.e., with the geometry of the FeAs4 or FeCh4 (Ch = Te, Se, or S) tetrahedron. By synthesizing Fe1-ySe1-xSx (0 ≤ x ≤ 1; y ≤ 0.1), we find that in alloyed crystals Tc is not correlated with the anion height like it is for most other Fe superconductors. Instead, changes in Tc(x) and tetragonal-to-orthorhombic (nematic) transition Ts(x) upon cooling are correlated with disorder in Fe vibrations in the direction orthogonal to Fe planes, along the crystallographic c-axis. The disorder stems from the random nature of S substitution, causing deformed Fe(Se,S)4 tetrahedra with different Fe-Se and Fe-S bond distances. Our results provide evidence of Tc and Ts suppression by disorder in anion height. The connection to local crystal chemistry may be exploited in computational prediction of new superconducting materials with FeSe/S building blocks.
RÉSUMÉ
We report the synthesis and characterization of Fe0.36(4)Pd0.64(4)Se2 with a pyrite-type structure. Fe0.36(4)Pd0.64(4)Se2 was synthesized using ambient pressure flux crystal growth methods even though the space group Pa3 is high-pressure polymorph for both FeSe2 and PdSe2. Combined experimental and theoretical analysis reveal magnetic spin glass state below 23 K in 1000 Oe that stems from random Fe/Pd occupancies on the same atomic site. The frozen-in magnetic randomness contributes significantly to electronic transport. Electronic structure calculations confirm dominant d-electron character of hybridized bands and large density of states near the Fermi level. Flux-grown single crystal alloys in Pd-Fe-Se atomic system therefore open new pathway for exploring different polymorphs in crystal structures and their novel properties.
RÉSUMÉ
The modification of the fly ash (FA) by magnetite (M) was performed to obtain FAM adsorbent with improved adsorption efficiency for arsenate removal from water. The novel low cost adsorbents are characterized by liquid nitrogen porosimetry (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), Mössbauer spectroscopy (MB) and Fourier transform infrared (FTIR) spectroscopy. The optimal conditions and key factors influencing the adsorbent synthesis are assessed using the response surface method (RSM). The adsorption experiment was carried out in a batch system by varying the contact time, temperature, pH, and mass of the adsorbent. The adsorption capacity of the FAM adsorbent for As(V), calculated by Langmuir model, was 19.14â¯mgâ¯g-1. The thermodynamic parameters showed spontaneity of adsorption with low endothermic character. The kinetic data followed the pseudo-second-order kinetic model (PSO), and Weber-Morris model indicated intra-particle diffusion as rate limiting step. Alternative to low desorption capability of the FAM was found by five consecutive adsorption/magnetite precipitation processes which gave exhausted layered adsorbent with 65.78â¯mgâ¯g-1 capacity. This research also has shed light on the mechanism of As(V)-ion adsorption, presenting a promising solution for the valorization of a widely abundant industrial waste.
