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キーワード:
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要旨:
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 aliovalent
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 freezedrying 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 codoping, 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.
