Klaus-Peter Dinse

Temperature‐Dependent Morphology, Magnetic and Optical Properties of Li‐Doped MgO

Li‐doped MgO is a potential catalyst for the oxidative coupling of methane, whereby surface Li+u2009O− 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 700u2005K, Li starts segregating towards the surface and forms irregular Li‐rich oxide patches. Above 1050u2005K, 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.

Characterization and Quantification of Reduced Sites on Supported Vanadium Oxide Catalysts by Using High‐Frequency Electron Paramagnetic Resonance

VOx (1.4–1.7u2005Vu2009nm−2) supported on SBA‐15, Al2O3, or TiO2 was studied before and after exposure to oxidative dehydrogenation of propane (ODP), and pure hydrogen or propane. After treatment, samples were quenched and frozen in quartz vials and characterized by using high‐frequency electron paramagnetic resonance (HF‐EPR). For SBA‐15‐ and Al2O3‐supported vanadia, V4+ sites were the most abundant paramagnetic species, whereas Ti3+ was dominant in TiO2‐supported V2O5. For the quantification of paramagnetic reduced sites, Mn2+ was used as reference. The maximum relative numbers of reduced V4+ or Ti3+ sites were found to increase in the sequence SBA‐15 (11u2009% V4+/V)

Pulsed EPR and ENDOR investigation of hydrogen atoms in silsesquioxane cages

High sensitivity and spectral resolution provided by pulsed electron paramagnetic resonance and electron nuclear double resonance techniques at high Larmor frequencies open the way for a study of atoms in chemical traps. As an example we studied deuteron atoms encased in silsesquioxane cages to probe the cage symmetry as function of temperature. An analysis of the temperature dependence showed that the system undergoes a structural phase transition near 100 K. At this temperature the character of distortion of the ideal cubic symmetry changes from oblate to prolate (or vice versa). With quantum chemical methods, a model for cage escape of the encased atom could be derived. The calculated escape barrier of 0.9 eV is close to the experimental value derived by thermal release experiments. Although the encased deuterium atom exhibits an isotropic hyperfine coupling constant nearly identical with the free atom value, a spin population analysis revealed that approximately 10% of the spin density is transferred to the cage. We therefore conclude that confinement of the hydrogen atom leads to a compression of its wave function compensating the decrease of spin density. In this respect the system falls somewhat short of the properties of an ideal cage, being defined by well decoupled atomic and molecular wave functions.

Li/MgO Catalysts Doped with Alio-valent Ions. Part II. Local Topology Unraveled by EPR/NMR and DFT Modeling

The role of Li in Li/MgO as a catalyst for oxidative coupling of methane (OCM) is to promote MgO surface morphology change rather than serve as a constituent of catalytically active sites. While Li/MgO is unstable at realistic conditions with respect to loss of Li, the resulting samples show enhanced selectivity towards C2 hydrocarbons versus CO2, although activity is low and close to pristine MgO. The way (co‐)doping with alio‐valent metal ions affects the catalytic performance of Li/MgO has now been explored. To analyze the structure and the stability of the samples, catalysts with well‐defined stoichiometry were prepared using a co‐precipitation method with freeze‐drying and subsequent annealing. Gd and Fe were used as dopants. Apart from their potential direct role in catalysis, these dopants are anticipated to stabilize Li in the catalyst under the reaction conditions, allowing further clarification of the role of Li. In the case of Gd/Li co‐doping, changes observed in EPR and 7Li‐NMR spectra indicate the formation of correlated, next‐neighbor Li−Mg⋅⋅⋅Gd+Mg pairs co‐existing with “isolated” Gd3+ ions at octahedral Mg lattice sites. For Li/Fe co‐doping, no significant change in the EPR pattern is observed in the presence of Li+ ions, indicating a larger distance between the Li+ and Fe3+ cations in the MgO lattice. Hybrid DFT calculations explain the difference between Fe and Gd co‐doping by a less efficient screening of the Coulomb repulsion between Gd3+ and neighboring cations in Gd doped samples, leading to the stabilization of LiMg near GdMg.

Li/MgO Catalysts Doped with Alio-valent Ions. Part I: Structure, Composition, and Catalytic Properties

Doping of Li/MgO with additional metal ions is suggested leading to an improved system with respect to the catalytic performance and stability when used for oxidative coupling of methane. We used Gd and Fe as dopants and characterized the resulting materials, showing that Fe seems to be completely and Gd partly incorporated into the MgO lattice. The catalytic performance is improved in most cases, but all materials still suffer from severe deactivation. A loss of Li is observed when being used under reaction conditions, but this Li loss is retarded for Fe‐Li/MgO as compared to undoped Li/MgO.