Li-doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+ O- centers are suggested to be the chemically active species. To elucidate the role of Li in the MgO matrix, two model systems are prepared and their morphological, optical and magnetic properties as a function of Li doping are investigated. The first is an MgO film deposited on Mo(001) and doped with various amounts of Li, whereas the second is a powder sample fabricated by calcination of Li and Mg precursors in an oxygen atmosphere. Scanning tunneling and transmission electron microscopy are performed to characterize the morphology of both samples. At temperatures above 700 K, Li starts segregating towards the surface and forms irregular Li-rich oxide patches. Above 1050 K, Li desorbs from the MgO surface, leaving behind a characteristic defect pattern. Traces of Li also dissolve into the MgO, as concluded from a distinct optical signature that is absent in the pristine oxide. No electron paramagnetic resonance signal that would be compatible with Li+O- centers is detected in the two Li/MgO samples. Density-functional theory calculations are used to determine the thermodynamic stability of various Li-induced defects in the MgO. The calculations clarify the driving forces for Li segregation towards the MgO surface, but also rationalize the absence of Li+O- centers. From the combination of experimental and theoretical results, a detailed picture arises on the role of Li for the MgO properties, which can be used as a starting point to analyze the chemical behavior of the doped oxide in future
Distortion is the key: In situ EPR spectroscopy provides the first experimental confirmation that the adsorption of O2 molecules on a stoichiometric ultrathin MgO(001) film on Mo(001) leads to the spontaneous formation of O2.− radicals. The results show that polaronic distortion of the MgO lattice (see picture; Mg yellow, O blue) stabilizes the radical, and this distortion is only possible in very thin films.
Misfit dislocations in a thin MgO/Mo͑001͒ film have been investigated by conductance and light-emission spectroscopy using scanning tunneling microscopy and electron-paramagnetic resonance ͑EPR͒ spectroscopy. The line defects exhibit a higher work function than the pristine MgO, being explained by their ability to trap electrons. The electron traps are associated with a nonstoichiometric defect composition in thin oxide films and attractive pockets in the Madelung potential in thicker ones. The latter traps can be reproducibly filled by the adsorption of atomic hydrogen, which gives rise to a free-electronlike signal in EPR spectroscopy.
Despite the growing geological evidence that fluid boiling and vapour-liquid separation affect the distribution of metals in magmatic-hydrothermal systems significantly, there are few experimental data on the chemical status and partitioning of metals in the vapour and liquid phases. Here we report on an in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of antimony speciation and partitioning in the system Sb2O3-H2O-NaCl-HCl at 400°C and pressures 270—300 bar corresponding to the vapour-liquid equilibrium. Experiments were performed using a spectroscopic cell which allows simultaneous determination of the total concentration and atomic environment of the absorbing element (Sb) in each phase. Results show that quantitative vapour-brine separation of a supercritical aqueous salt fluid can be achieved by a controlled decompression and monitoring the X-ray absorbance of the fluid phase. Antimony concentrations in equilibrium with Sb2O3 (cubic, senarmontite) in the coexisting vapour and liquid phases and corresponding SbIII vapour-liquid partitioning coefficients are in agreement with recent data obtained using batch-reactor solubility techniques. The XAFS spectra analysis shows that hydroxy-chloride complexes, probably Sb(OH)2Cl0, are dominant both in the vapour and liquid phase in a salt-water system at acidic conditions. This first in situ XAFS study of element fractionation between coexisting volatile and dense phases opens new possibilities for systematic investigations of vapour-brine and fluid-melt immiscibility phenomena, avoiding many experimental artifacts common in less direct techniques.
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