DBT derivatives adsorption over molybdenum sulfide catalysts: a theoretical study

Cristol, Sylvain; Paul, Jean‐François; Payen, Edmond; Bougeard, D.; Hutschka, F.; Clémendot, S.

doi:10.1016/j.jcat.2004.02.008

Cited by 110 publications

(62 citation statements)

References 45 publications

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“…The higher HYD activity compared to the Co-MoS 2 /SBA-15 catalysts prepared applying the same method (HYD/ DDS = ca. 0.2 [9]) suggests that the active site for HYD is distinct from that for DDS, which is in good agreement with the previous studies [47,48]. Moreover, the Ni-MoS 2 / SBA-15 catalysts prepared from ATM exhibit larger HYD/ DDS ratios (0.79-1.01) compared to the ratio for the above-mentioned commercial NiMo/c-Al 2 O 3 catalyst (0.53).…”

Section: Catalytic Activity and Selectivitysupporting

confidence: 90%

SBA-15 as Support for Ni–MoS2 HDS Catalysts Derived from Sulfur-containing Molybdenum and Nickel Complexes in the Reaction of HDS of DBT: An All Sulfide Route

et al. 2008

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MoS 2 HDS catalysts promoted with Ni supported on SBA-15 were synthesized from sulfur containing Mo (ammonium thiomolybdate, ATM, and tetramethylammonium thiomolybdate, TMATM) and a Ni complex (Nickel diethylthiocarbamate, NiDETC). The catalysts have been characterized by X-ray diffraction (XRD), N 2 -physisorption and High-resolution transmission electron microscopy (HRTEM). The catalytic performance in the hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT) was examined at T = 623 K and P H2 = 3.4 Mpa. In comparison with the impregnation mode, the nature of the employed thiomolybdate complex shows a stronger influence on the MoS 2 morphology and consequently on the HDS activity of DBT. A similar high HDS activity to a commercial NiMo/c-Al 2 O 3 catalyst despite the pronounced stacking number is shown for a NiMoS 2 /SBA-15 catalyst derived from ATM. The catalysts derived from TMATM showed lower HDS activities compared to the catalysts obtained from ATM precursors due to probably the presence of closed shell structures (nano-onions) of MoS 2 which offer significantly smaller amount of HDS active sites (edge sites). Moreover, the HYD/DDS ratios are interestingly higher with respect to the HYD/DDS ratio of the commercial NiMo/c-Al 2 O 3 catalyst which could be ascribed to the generation of multilayered MoS 2 active phase.

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Section: Catalytic Activity and Selectivitysupporting

confidence: 90%

SBA-15 as Support for Ni–MoS2 HDS Catalysts Derived from Sulfur-containing Molybdenum and Nickel Complexes in the Reaction of HDS of DBT: An All Sulfide Route

et al. 2008

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“…This is of significant importance, since molecules such as thiophene and dibenzoethiophene have been found to make weak chemical bonds with the equilibrium edge structures and single vacancies on the equilibrium edges. 2,5,10,14,15 The linear correlation found in Fig. 4 could be used to estimate the vdW contribution for larger molecules such as dibenzothiophene and could therefore prove to be useful in the development of reaction path diagrams including vdW forces.…”

Section: Cyclic and Heterocyclic Moleculesmentioning

confidence: 99%

“…[2][3][4][5][7][8][9][10][11][12][13][14][15] In calculating accurate chemisorption energies of molecules on surfaces, the DFT has a well-proven record. 16 The calculation of physisorption energies has been much more of a challenge, however, due to the absence of the ubiquitous van der Waals ͑vdW͒ forces in the most widely used implementations of DFT.…”

Section: Introductionmentioning

confidence: 99%

Density functional study of the adsorption and van der Waals binding of aromatic and conjugated compounds on the basal plane of MoS2

Moses

Mortensen

Lundqvist

et al. 2009

The Journal of Chemical Physics

110

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Accurate calculations of adsorption energies of cyclic molecules are of key importance in investigations of, e.g., hydrodesulfurization ͑HDS͒ catalysis. The present density functional theory ͑DFT͒ study of a set of important reactants, products, and inhibitors in HDS catalysis demonstrates that van der Waals interactions are essential for binding energies on MoS 2 surfaces and that DFT with a recently developed exchange-correlation functional ͑vdW-DF͒ accurately calculates the van der Waals energy. Values are calculated for the adsorption energies of butadiene, thiophene, benzothiophene, pyridine, quinoline, benzene, and naphthalene on the basal plane of MoS 2 , showing good agreement with available experimental data, and the equilibrium geometry is found as flat at a separation of about 3.5 Å for all studied molecules. This adsorption is found to be due to mainly van der Waals interactions. Furthermore, the manifold of adsorption-energy values allows trend analyses to be made, and they are found to have a linear correlation with the number of main atoms.

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“…The majority of sulfur-containing hydrocarbons in liquid fuels are converted to sulfur-free compounds and H 2 S by catalytic hydrodesulphurization (HDS) reactions during the fuel processing. Although the HDS process is the best known technology for desulfurization of liquid fuels, it cannot efficiently remove thiophenic compounds (TC) including dibenzothiophene (DBT), 4,6-dimethyldibenzothiophene (4,6-DMDBT), and benzothiophene (BT) to meet the new environmental regulations of 15-30 ppm sulfur in the processed fuels [1][2][3][4][5]. Reactivity studies of BT, DBT and their alkylated homologues in HDS reactions over Co, Mo/Al 2 O 3 , Ni, Mo/Al 2 O 3 and sulfide Co, Mo/γ-Al 2 O 3 catalysts indicate that the alkyl group substituents, especially in positions subject to steric hindrance effects (e.g., 4 and 6 in the 4,6-DMDBT molecule) significantly reduce the reactivity of TC in HDS reactions [2][3][4].…”

Section: Introductionmentioning

confidence: 99%

Adsorption of Thiophenic Compounds from Model Diesel Fuel Using Copper and Nickel Impregnated Activated Carbons

2012

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Adsorption of sulfur compoundsby porous materials is an effective way to produce cleaner diesel fuel.In this study, adsorption of refractory thiophenic sulfur compounds, i.e., benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in single-solute systems from n-hexane solutions onto metal-impregnated activated carbons was investigated. A hydrogen-treated activated carbon fiber was selectively loaded with Ni, NiO, Cu, Cu 2 O, and CuO species to systematically assess the impact of each metal species on the adsorption of thiophenic compounds (TC). Metal-loaded adsorbents had the same total metal contents and similar microporosities, but contained different types of copper or nickel species. All metal-loaded adsorbents showed enhanced adsorption of tested TC. Cu 2 O-or NiO-loaded adsorbents exhibited the highest uptakes, due to more specific interactions between Cu + or Ni 2+ species and TC molecules. The theoretical monolyer coverage of TC on the exposed Cu + sites was estimated and compared with that calculated from the experimental data. Results suggested catalytic conversion of TC molecules to other compounds on the Cu + sites, followed by adsorption of reaction products onto the carbon surface or multilayer accumulation of TC molecules on the Cu + sites. TC adsorption uptake of the majority of adsorbents followed the order of: 4,6-DMDBT > DBT > BT due to higher intensity of specific and non-specific interactions of larger TC molecules with adsorbents.

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DBT derivatives adsorption over molybdenum sulfide catalysts: a theoretical study

Cited by 110 publications

References 45 publications

SBA-15 as Support for Ni–MoS2 HDS Catalysts Derived from Sulfur-containing Molybdenum and Nickel Complexes in the Reaction of HDS of DBT: An All Sulfide Route

SBA-15 as Support for Ni–MoS2 HDS Catalysts Derived from Sulfur-containing Molybdenum and Nickel Complexes in the Reaction of HDS of DBT: An All Sulfide Route

Density functional study of the adsorption and van der Waals binding of aromatic and conjugated compounds on the basal plane of MoS2

Adsorption of Thiophenic Compounds from Model Diesel Fuel Using Copper and Nickel Impregnated Activated Carbons

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