Tunable reactivity of supported single metal atoms by impurity engineering of the MgO(001) support

Development of novel materials may often require a rational use of high price components, like noble metals, in combination with the possibility to tune their properties in a desirable way. Here we present a theoretical DFT study of Au and Pd single atoms supported by doped MgO(001). By introducing B, C and N impurities into the MgO(001) surface, the interaction between the surface and the supported metal adatoms can be adjusted. Impurity atoms act as strong binding sites for Au and Pd adatoms and can help to produce highly dispersed metal particles. The reactivity of metal atoms supported by doped MgO(001), as probed by CO, is altered compared to their counterparts on pristine MgO(001). We find that Pd atoms on doped MgO(001) are less reactive than on perfect MgO(001). In contrast, Au adatoms bind CO much stronger when placed on doped MgO(001). In the case of Au on N-doped MgO(001) we find that charge redistribution between the metal atom and impurity takes place even when not in direct contact, which enhances the interaction of Au with CO. The presented results suggest possible ways for optimizing the reactivity of oxide supported metal catalysts through impurity engineering.Comment: 26 pages, 8 figures, 4 tables, 65 references, submitted to Physical Chemistry Chemical Physic

The oxidative coupling of methane and the oxidative dehydrogenation of ethane over a niobium promoted lithium doped magnesium oxide catalyst

The promoting effect of niobium in a Li/MgO catalyst for the oxidative coupling of methane (OCM) and for the oxidative dehydrogenation of ethane (ODHE) has been studied in some detail. It has been found that a Li/Nb/MgO catalyst with 16 wt % niobium showed the highest activity for the C2 production in the OCM reaction; the activity at 600 °C was ten times that of the Li/MgO catalyst at the same temperature. The Li/Nb/MgO catalyst was also slightly more active for the ODHE reaction than was the Li/MgO catalyst. However, the Li/Nb/MgO catalyst produced considerably more carbon dioxide in the both reactions. Structural investigation of the catalyst showed that the addition of niobium to the Li/MgO catalyst increased the surface area and gave an increase in the lithium content of the calcined catalysts. Two niobium phases, LiNbO3 and Li3NbO4, were formed; it is shown that the first of these probably causes the increased activity. Ageing experiments showed that the activity of the catalyst was lost if the catalyst was used above 720 °C, the melting point of the lithium carbonate phase. The catalyst showed a decrease of surface area after ageing and a sharp decrease of the amount of the two niobium phases. The addition of carbon dioxide to the feed could not prevent the deactivation of the Li/Nb/MgO catalyst

Electrical spin injection in p-type Si using Fe/MgO contacts

We report the successful electrical creation of spin polarization in p-type Si at room temperature by using an epitaxial MgO(001) tunnel barrier and Fe(001) electrode. Reflection high-energy electron diffraction observations revealed that epitaxial Fe/MgO(001) tunnel contacts can be grown on a (2 x 1) reconstructed Si surface whereas tunnel contacts grown on the (1 x 1) Si surface were polycrystalline. Transmission electron microscopy images showed a more flat interface for the epitaxial Fe/MgO/Si compared to that of the polycrystalline structure. For the Fe/MgO/p-Si devices, the Hanle and inverted Hanle effects were clearly observed at 300 K by using a three-terminal configuration, proving that spin polarization can be induced in the Si at room temperature. Effective spin lifetimes deduced from the width of the Hanle curve were 95 +/- 6 ps and 143 +/- 10 ps for the samples with polycrystalline and epitaxial MgO tunnel contacts, respectively. The observed difference can be qualitatively explained by the local magnetic field induced by the larger roughness of the interface of the polycrystalline sample. The sample with epitaxial Fe/MgO tunnel contact showed higher magnitude of the spin accumulation with a nearly symmetric behavior with respect to the bias polarity whereas that of the polycrystalline MgO sample exhibited a quite asymmetric evolution. This might be attributed to the higher degree of spin polarization of the epitaxial Fe/MgO(001) tunnel contact, which acts as a spin filter. Our experimental results suggest that an epitaxial MgO barrier is beneficial for creating spins in Si.Comment: Paper presented at SPIE Nanoscience + Engineering, Spintronics V session in San Diego, US on August 13th, 201

The effect of Nb2O5 and ZrO2 additions on the behaviour of Li/MgO and Li/Na/MgO catalysts for the oxidative coupling of methane

Incorporation of Nb2O5 or ZrO2 into both Li/MgO and Li/Na/MgO systems produced ternary and quaternary catalysts, respectively, capable of attaining optimal C2 yields and selectivities at lower temperatures relative to the unpromoted materials. The degree of enhancement effected by these metal oxide additives was compared to that produced by Li/MgO and Li/Na/MgO catalysts promoted with SnO2 or Co3O4. At reaction temperatures < 700°C, the Li/Co/MgO ternary system showed marked differences in behaviour compared to the other ternary catalysts tested. This was particularly evident in the variation in C2 selectivity with time on stream during ageing studies of (i) untreated materials, (ii) materials pretreated in CO2, and (iii) materials dosed periodically with CHCI3

Biaxially textured cobalt-doped BaFe2As2 films with high critical current density over 1 MA/cm2 on MgO-buffered metal-tape flexible substrates

High critical current densities (Jc) > 1 MA/cm2 were realized in cobalt-doped BaFe2As2 (BaFe2As2:Co) films on flexible metal substrates with biaxially-textured MgO base-layers fabricated by an ion-beam assisted deposition technique. The BaFe2As2:Co films showed small in-plane crystalline misorientations (delta fai BaFe2As2:Co) of ~3o regardless of doubly larger misorientaions of the MgO base-layers (delta fai MgO = 7.3o), and exhibited high self-field Jc up to 3.5 MA/cm2 at 2 K. These values are comparable to that on MgO single crystals and the highest Jc among iron pnictide superconducting tapes and wires ever reported. High in-field Jc suggests the existence of c-axis correlated vortex pinning centers.Comment: Published in Appl. Phys. Let

Hard X-ray standing-wave photoemission insights into the structure of an epitaxial Fe/MgO multilayer magnetic tunnel junction

The Fe/MgO magnetic tunnel junction is a classic spintronic system, with current importance technologically and interest for future innovation. The key magnetic properties are linked directly to the structure of hard-to-access buried interfaces, and the Fe and MgO components near the surface are unstable when exposed to air, making a deeper probing, nondestructive, in-situ measurement ideal for this system. We have thus applied hard X-ray photoemission spectroscopy (HXPS) and standing-wave (SW) HXPS in the few kilo-electron-volt energy range to probe the structure of an epitaxially grown MgO/Fe superlattice. The superlattice consists of 9 repeats of MgO grown on Fe by magnetron sputtering on an MgO(001) substrate, with a protective Al2O3 capping layer. We determine through SW-HXPS that 8 of the 9 repeats are similar and ordered, with a period of 33 ± 4 Å, with the minor presence of FeO at the interfaces and a significantly distorted top bilayer with ca. 3 times the oxidation of the lower layers at the top MgO/Fe interface. There is evidence of asymmetrical oxidation on the top and bottom of the Fe layers. We find agreement with dark-field scanning transmission electron microscope (STEM) and X-ray reflectivity measurements. Through the STEM measurements, we confirm an overall epitaxial stack with dislocations and warping at the interfaces of ca. 5 Å. We also note a distinct difference in the top bilayer, especially MgO, with possible Fe inclusions. We thus demonstrate that SW-HXPS can be used to probe deep buried interfaces of novel magnetic devices with few-angstrom precision

Large Tunneling Anisotropic Magneto-Seebeck Effect in a CoPt|MgO|Pt Tunnel Junction

We theoretically investigate the Tunneling Anisotropic Magneto-Seebeck effect in a realistically-modeled CoPt|MgO|Pt tunnel junction using coherent transport calculations. For comparison we study the tunneling magneto-Seebeck effect in CoPt|MgO|CoPt as well. We find that the magneto-Seebeck ratio of CoPt|MgO|Pt exceeds that of CoPt|MgO|CoPt for small barrier thicknesses, reaching 175% at room temperature. This result provides a sharp contrast to the magnetoresistance, which behaves oppositely for all barrier thicknesses and differs by one order of magnitude between devices. Here the magnetoresistance results from differences in transmission brought upon by changing the tunnel junction's magnetization configuration. The magneto-Seebeck effect results from variations in asymmetry of the energy-dependent transmission instead. We report that this difference in origin allows for CoPt|MgO|Pt to possess strong thermal magnetic-transport anisotropy.Comment: 6 pages, 6 figure