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Interpretation of the difference of optimal Mo density in MoS2-Al2O3 and MoS2-TiO2 HDS catalysts

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The first part of this paper deals with the morphology of the MoS2 phase and its oxide precursor, the MoO3 phase, mainly from a geometrical point of view. After giving a brief review of the literature describing the structure of these compounds, Mo densities in both phases were calculated along various crystallographic planes. Further, using structural models recently proposed by others, Mo densities in MoS2 were also calculated in the case of an epitactic growth on γ-Al2O3 and TiO2 model surfaces. Then, the calculated Mo densities were compared with experimental results (Mo density when HDS activity is maximal) previously obtained for catalysts constituted of MoS2 supported on a low SSA TiO2, a high SSA TiO2 and a conventional γ-alumina. It was suggested that either on alumina or titania the MoS2 phase is growing as (100) MoS2 planes. However, while on the alumina the optimal MoS2 phase might be constituted of dispersed MoS2 slabs covering only a part of the alumina surface (2.9–3.9 Mo atoms/nm2), on titania the optimal MoS2 phase might be constituted of a uniform MoS2 monolayer (5.2 atoms/nm2 for the high SSA titania, which is equal to the Mo density of a perfect MoS2 (100) plane). This difference may originate in the creation of a 'TiMoS' phase enhancing the S atoms mobility over Mo/TiO2-sulfided catalysts. Indeed, while in the case of a γ-alumina carrier the active sites (labile S atoms) are located on the edge of MoS2 slabs making the ratio Moedge/Mototal a crucial parameter for the catalytic performances, in the case of a titania carrier the labile sulfur atoms might be statistically distributed all over the TiMoS active phase. Further, the higher Mo density observed over the high SSA titania (5.2 atoms/nm2) when compared to that over the low SSA titania (4.2 atoms/nm2) was supposedly due to the pH-swing method advantageously used to prepare the former carrier. Indeed, this method allows giving a solid with enhanced mechanical properties providing a good stability to the derived catalysts under experimental conditions. In addition, this TiO2 carrier exhibits a great homogeneity, with a surface structure substantially uniform, which might be adequate for a long-range growth of (100) MoS2 slabs.


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