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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. [ABSTRACT FROM AUTHOR]

The first part of this paper is a short review of the [sup 35]S radioactive tracer methods developed in recent years. Then, the experimental results obtained so far on Mo/Al[sub 2]O[sub 3] catalysts are compared with computer simulation results recently claimed in order to elucidate the coordinatively unsaturated site (CUS) creation/replenishment/ regeneration mechanism over MoS[sub 2] crystallites. The computer simulations allowed us to pre-select thermodynamically acceptable mechanisms among a set of suggested ones. Then, by comparison of the calculated activation energies with the [sup 35]S experiments results we could further validate the most probable mechanism. This mechanism involved the dissociative adsorption of an H[sub 2] molecule on the metallic edge of a MoS[sub 2] crystallite surface with further creation of a CUS by release of one H[sub 2]S molecule in the gas phase. Both laboratory and computer simulated experiments permitted to calculate the activation energy for the H2S liberation reaction. In both cases, this energy was about 10- 12 kcal/mol, confirming the accuracy of the proposed mechanism. Moreover, the calculated activation energy of the rate-limiting step for the creation of one CUS by the proposed mechanism was about 23 kcal/mol, which was also in good agreement with the experimental activation energy of the dibenzothiophene (DBT) hydrodesulphurisation (HDS) reaction (typically about 20- 22 kcal/mol). This correlation indicated that the DBT HDS reaction rate might be intrinsically governed by the CUS formation/replenishment process, i.e. that the vacancy formation process is a crucial parameter in the global HDS reaction mechanism. Nevertheless, in the case of the 4,6-dimethyl DBT (4,6-DMDBT) HDS reaction, the experimental activation energy is higher (approx. 30 kcal/mol), confirming that external parameters induced by the 4,6-DMDBT-specific properties themselves are likely to play an important role in the reaction process, in addition to the ones intrinsic to the catalytic phase. [ABSTRACT FROM AUTHOR]