Browsing by Author "Roddatis, Vladimir"

Real time in-situ microscopy imaging of surface structure and atom dynamics of heterogeneous catalysts is an important step for understanding reaction mechanisms. Here, using in-situ environmental transmission electron microscopy (ETEM), we directly visualize surface atom dynamics at manganite perovskite catalyst surfaces for oxygen evolution reaction (OER), which are ≥20 times faster in water than in other ambients. Comparing (001) surfaces of La0.6Sr0.4MnO3 and Pr0.67Ca0.33MnO3 with similar initial manganese valence state and OER activity, but very different OER stability, allows us to distinguish between reversible surface adatom dynamics and irreversible surface defect chemical reactions. We observe enhanced reversible manganese adatom dynamics due to partial solvation in adsorbed water for the highly active and stable La0.6Sr0.4MnO3 system, suggesting that aspects of homogeneous catalysis must be included for understanding the OER mechanism in heterogeneous catalysis.

Superlattices (SLs) comprising layers of a soft ferromagnetic metal La2/3Sr1/3MnO3 (LSMO) with in-plane (IP) magnetic easy axis and a hard ferromagnetic insulator La2MnCoO6 (LMCO, out-of-plane anisotropy) were grown on SrTiO3 (100)(STO) substrates by a metalorganic aerosol deposition technique. Exchange spring magnetic (ESM) behavior between LSMO and LMCO, manifested by a spin reorientation transition of the LSMO layers towards perpendicular magnetic anisotropy below TSR = 260 K, was observed. Further, 3ω measurements of the [(LMCO)9/(LSMO)9]11/STO(100) superlattices revealed extremely low values of the cross-plane thermal conductivity κ(300 K) = 0.32 Wm−1K−1. Additionally, the thermal conductivity shows a peculiar dependence on the applied IP magnetic field, either decreasing or increasing in accordance with the magnetic disorder induced by ESM. Furthermore, both positive and negative magnetoresistance were observed in the SL in the respective temperature regions due to the formation of 90°-Néel domain walls within the ESM, when applying IP magnetic fields. The results are discussed in the framework of electronic contribution to thermal conductivity originating from the LSMO layers.

Abstract Normally, volatiles in silicate melts are ephemeral components that escape as gases when the melt reaches fluid saturation. When fluid saturation occurs at elevated pressure, magmatic fluids may have large amounts of oxide solute dissolved, are less volatile, and may resemble viscous gels. In Cyprus we have the rare case that solutes of a magmatic fluid coexist with H 2 O saturated basaltic to boninitic glasses. Quenching of the melts and fluid solutes was induced by fluid segregation. When the fluids exsolved, the liquidus temperature was raised and the melts were left supercooled, while the system temperature remained ± constant. Quenching rates deduced from the morphologies and compositions of quench crystals were high. We analyzed coexisting glasses and fluid solutes for major and trace elements. The fluid mobile trace elements (Rb, K, Pb, Sr) are enriched in both the glasses and fluid solutes. Both endmembers (melt and fluid) have a common parentage and originated within a hydrous mantle source. The glasses have 2.5 ± 0.25 wt.% H 2 O and record residual H 2 O contents left after fluid exsolution was completed. Water contents in glasses correspond to an H 2 O partial pressure (pH 2 O) of 65 ± 10 MPa and an emplacement depth on the seafloor of 6500 ± 1000 m, provided equilibrium was reached between the pH 2 O imposed by the melts and the seawater column. Following fluid exsolution, the degree of supercooling ∆T of the melts relative to the dry MgO-in-melt liquidus temperature was  – 65 ± 10 °C. The cooling rate ∆T/t at the time of crystallization of dendritic clinopyroxene crystals can be semi-quantified from the distribution of Al 2 O 3 between metastable clinopyroxene dendrites and melt, to at least  – 50 °C h −1 . Toward the end of the article we speculate if other cases exist where quenching was triggered by fluid exsolution. A possible example are spinifex textures deep inside komatiite flows where quenching rates by conductive cooling did not exceed 0.3 to 1 °C h −1 . Our proposition assumes that many spinifex-textured komatiites were hydrous, that they contained H 2 O in quantities sufficient to reach fluid saturation at emplacement pressure, and that spinifex textures formed as a result of supersaturation by fluid loss.