Hydrodesulfurization Reaction Research Articles

Synthesis, characterization, and performance evaluation of unsupported tetrametallic CoMoMnAl and CoMoZnAl catalysts for selective hydrodesulfurization (HDS)

New formulations of unsupported tetrametallic catalysts derived from layered double hydroxides (LDH) compounds were synthesized by a constant pH coprecipitation method, characterized, and evaluated in the selective hydrodesulfurization (HDS) of thiophene in the presence of cyclohexene. The layered double hydroxides were prepared using terephthalate (C8H8O2)2- as the interlayer anion with nominal aluminum molar fraction of 0.5, and nominal cobalt to MII (M = Zn or Mn) ratios of 0.2, 0.4 and 0.6. Molybdenum introduction in the LDH precursor was accomplished by an ion exchange process using the heptamolybdate anion. The calcined Mn samples showed a higher surface area than those obtained from Zn. The sulfidation was carried out in situ with a heating ramp up to 673 K and the catalysts were evaluated in a tubular flow reactor. The catalytic evaluation of Zn and Mn-based materials for simultaneous thiophene HDS and cyclohexene hydrogenation (HYD) was conducted at 573 K and 20 bar. The results show that the Zn-based unsupported catalysts synthesized here exhibited higher selectivity for the HDS reaction than an industrial one.

Sulfured FeMo carbides and nitrides catalysts upgrade extra heavy crude oil quality

In the context of the energy transition scenario, effective sulfur management is crucial. Enhancing the quality of extra heavy crude oil (EHCO) through catalytic processes, specifically hydrotreatment, is essential for reducing pollutant emissions like SOx into the atmosphere. Traditional hydrotreatment, utilizing MoS2-based catalysts typically on Al2O3 support, faces challenges with EHCO due to its elevated S and N content, which hampers catalyst efficiency. Metal carbides and nitrides exhibit promising electronic structures that confer resistance to deactivation in the presence of heteroatoms. This study compares the catalytic performances of Fe-promoted Mo sulfides, carbides, and nitrides (FeMoS(C,N)) in the thiophene hydrodesulfurization (HDS) reaction, serving as a model molecule for sulfur removal. Subsequently, we investigate the upgrading of a Venezuelan EHCO in terms of pollutant reduction, API gravity, and feedstock aromaticity. Catalysts were prepared from oxide precursors, varying the (Fe/(Fe+Mo)) atomic ratios (x = 0.00, 0.10, 0.33, 0.50, and 1.00), employing a temperature-programmed reaction protocol. Catalytic upgrading of EHCO was conducted in a stirred batch reactor, and the results were compared with a commercial CoMo-based catalyst. FeMoC(N) outperformed the commercial catalyst in sulfur removal. The elemental composition and nitrogen content of the feed remained constant; however, the sulfur content of asphaltenes decreased. Furthermore, the API gravity of crude oil increased when employing FeMoS and FeMoN catalysts, except with FeMoC, possibly linked to dealkylation reactions and the enrichment of lighter fractions with alkanes. FeMoN increased asphaltene aromaticity, while FeMoC decreased it. These results highlight the promise of FeMoC(N) as catalysts for HDS and upgrading heavy feedstocks.

Enhancing simultaneous hydrodesulfurization and hydrodenitrogenation reactions: Kinetic modeling of stacked NiMoP and CoMoP catalysts beds

Stringent environmental regulations require reducing fuel sulfur content for adequate operation of vehicle emission control systems. Deep hydrodesulfurization (HDS) removes over 99 % of sulfur compounds, including the less reactive ones like 4,6-dimethyldibenzothiophene (4,6-DMDBT). However, HDS kinetics is inhibited by compounds like H2S, nitrogenous compounds, and aromatics. This article delves into kinetic modeling of concurrent hydrodesulfurization (HDS) of 4,6-DMDBT and hydrodenitrogenation (HDN) of quinoline (Q) reactions. It explored the use of stacked beds of CoMoP and NiMoP catalysts in two configurations. The effects of temperature and weight hourly space velocity (WHSV) on conversions and product yields were investigated. Higher reaction temperatures, in addition to the expected increase of 4,6-DMDBT and quinoline overall conversions, also led to an increased in hydrogenation selectivity. Kinetic models were developed for these reactions and catalysts, and kinetic parameters were estimated using a hybrid numerical procedure. The configuration where CoMoP was the first catalyst to encounter the reaction feedstock exhibited higher conversions for both reactions. The apparent activation energies for 4,6-DMDBT HDS were 99 and 41 kJ mol−1 for NiMoP and CoMoP, respectively while for HDN, values of 62 and 68 kJ mol−1 were estimated. For the adsorption enthalpy of nitrogenous compounds, values of −59 and −40 kJ mol−1 were observed for NiMoP and CoMoP, respectively.

Flower-like hierarchical TS-1/Al2O3 composite supported NiMo catalysts for efficient hydrodesulfurization of dibenzothiophenes

Flower-like Al2O3 materials were successfully incorporated by TS-1 nanocrystals to synthesize Flower-like TS-1-Al2O3 (FTA) micro-mesoporous composite by a facile nano self-assembly method. FTA supported NiMo bimetallic catalysts (NiMo/FTA) were further constructed and applied to the hydrodesulfurization (HDS) reactions for dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT). FTA composites were constructed from flower-like pore structures stacked with nanosheets, which are conducive to the even load and dispersion of active species and the diffusion of macromolecular sulfur-containing compounds with relatively low resistance. The fabrication of TS-1 nanocrystals effectively enhanced the acidic sites, regulated the metal-support interaction, which could increase the stacking layer of MoS2 slabs, and producing more NiMoS-II type active phase. NiMo/FTA-10 presented the excellent HDS conversion of DBT (99.3 %) and 4,6-DMDBT (93.2 %) at 10 h−1, the highest reaction rate constant (2.6 × 10-7 mol g−1 s−1) and turnover frequency values (6.7 × 10-4 s−1) for 4,6-DMDBT HDS reaction. Compared to the direct desulfurization route (DDS), hydrogenation route (HYD) and isomerization route (ISO) can effectively eliminate the steric hindrance of 4,6-DMDBT, which is more conducive to the HDS reaction.

The regulatory role of cysteine in active phase construction of polyoxometalate-based hydrodesulfurization catalysts: Reduction, chelation, and dispersion

Polyoxometalate-based hydrodesulfurization (HDS) catalysts were modified using cysteine to construct efficient CoMoS active phase. Cysteine, characterized by chelating (–COOH, –NH2) and reducing (−SH) groups, assumed a triple role in catalyst synthesis, including reduction, chelation, and dispersion. Cysteine pre-reduced polyoxometalates to heteropoly blue, significantly increasing the catalyst sulfidation. The increased nucleophilicity of heteropoly blue enhanced their attraction to Co2+ ions, intensifying the Co-Mo bimetallic synergy. The formation of Co-chelate species delayed Co sulfidation, allowing for the concurrent sulfidation of both Co and Mo species and promoting the generation of the CoMoS active phase. Carbonaceous deposits from the high-temperature carbonization of cysteine weakened the metal-support interaction, facilitating the dispersion of the active phase. The S-CoPMo12-Cys/Al2O3 catalyst demonstrated high activity in the HDS reaction of dibenzothiophene, showcasing their potential for advanced HDS reaction.

Optimizing the Incorporation Modes of TiO2 in TiO2-Al2O3 Composites for Enhancing Hydrodesulfurization Performance of Corresponding NiMoP-Supported Catalysts

TiO2-Al2O3 supports with different incorporation methods of titania were synthesized via three methods: impregnation (TA-I), co-precipitation (TA-CP), and co-precipitation–hydrothermal treatment (TA-HT). And the NiMoP catalysts prepared on the corresponding supports were evaluated for hydrodesulfurization (HDS) reactions. The results demonstrated that the Ti atoms in TA-I are attached to alumina through hydroxyl groups, while the Ti atoms in TA-CP and TA-HT can be dispersed in the alumina skeleton. Variations in the incorporation modes of TiO2 affect the support properties, consequently influencing the nature of the active metal on the supports. The Ti atoms dispersed in the Al2O3 skeleton allow an increase in the basic hydroxyl groups. Meanwhile, TiO2 in TA-CP and TA-HT can absorb hydrogen molecules and be partially reduced. Furthermore, metal species supported on the TA-CP and TA-HT are more easily reduced and better dispersed. For the NiMoP catalysts prepared with TA-CP and TA-HT, the Ti element promotes the sulfidation degree of Mo, besides shortening the average (Ni)MoS2 slab. The catalysts prepared with TA-CP exhibited superior activity for 4,6-DMDBT hydrodesulfurization. This can be ascribed not only to the relatively high sulfidation degree of Mo and proportion of the NiMoS active phase but also to the well-dispersed (Ni)MoS2 slabs. Moreover, the Ti4+ ions dispersed in the Al2O3 skeleton can be partially reduced to act as electron donors, enhancing the metallic character of the S layers in MoS2, which facilitates the improvement of the hydrogenation desulfurization activity.

Suppression of inactive sites in NiMo@amorphous alumina catalysts for hydrodesulfurization reaction: Effect of Ga doping

Hydrodesulfurization (HDS) reaction activity depends on the formation of active NiMoS (completely sulfided multilayer type 2 sites) and inactive NiAl2O4/NixSy phases on the catalyst surface. These inactive phases not only itself inactive for the reaction but also hinder the formation of active NiMoS phases. In addition, the formation of strong Mo-O-Al bonds also lowers the reducibility of the catalyst, suggesting lesser catalytic activity (type 1 sites, partially sulfided single-layer sites). To this end, we report the formation of NiMo/Ga doped amorphous alumina (A-Al2O3) catalysts prepared by the colloidal synthesis method. A-Al2O3 was chosen as a support because it has lower surface energy, better physicochemical properties, and enhanced acidic sites than the crystalline alumina phase, which favours the formation of type 2 sites or weak metal-support interaction (completely sulfided multilayer NiMoS sites). Further, the Ga doping in A-Al2O3 support substitute the tetrahedral Al sites and form GaAl2O4 phases by reducing NiAl2O4 inactive sites, and the free Ni decorate the edges of MoS2 to form HDS active NiMoS sites. Therefore, NiMo/Ga doped A-Al2O3 catalyst (at 1 wt% Ga loading) reported enhanced HDS catalytic activity (25%), HDS reaction rate constant (kHDS-2.15 times) and turn over frequency (TOF-1.3 times) than the conventional NiMo/γ-Al2O3 catalysts.

N-octyltrimethylammonium bromide-assisted self-assembly of CoMo precursors to prepare CoMoS/Al2O3 catalysts for highly selective hydrodesulfurization of thiophene

A novel (C11H26N)2Co(MoS4)2 complex was prepared via the n-octyltrimethylammonium bromide-assisted self-assembly of CoMo precursors for the selective hydrodesulfurization (HDS) of thiophene. The complex was generated by the interaction between the negatively charged CoMo compound and the positively charged n-octyltrimethylammonium ions. Then positively charged bimolecular layers were formed owing to van der Waals forces between the C11H26N+ and the complex, and they were anchored on the negatively charged γ-Al2O3. Compared with CoMoS/γ-Al2O3 catalysts prepared by impregnation, the optimal CoMoN-0.3/γ-Al2O3 catalyst exhibited better performance for selective HDS due to the enhanced Mo dispersion, the close contact between Co and Mo, and the increased amount of CoMoS phases on γ-Al2O3. Among these catalysts, the optimal CoMoN-0.3/γ-Al2O3 catalyst with the highest concentration of CoMoS phases exhibited the highest HDS reaction rate constant of 6.95 × 10-6 mol·g−1·s−1 and the best selective factor of 26.1 for the selective HDS of thiophene with 1-hexene.

Insights into the hydrodesulfurization reaction mechanisms catalyzed by different K-promoted MoS2 edge sites

The K-promoted MoS2 active phase structure and its catalytic mechanism in the hydrodesulfurization reaction were investigated through the density functional theory calculations. On the basis of the calculations, the sulfur vacancy formation mechanism and the direct desulfurization of thiophene were systematically explored, and the structure–activity relationship was also discussed in detail. In the sulfur vacancy generation process, it could be found that the formation of sulfur vacancies was more favorable over the sulfur-rich edges, such as K-promoted S-edge with 100 % S coverage. In addition, the K-promoted S-edge was more preferable for the C-S bond scissions compared with the K-promoted M−edge. Furthermore, potassium atoms could prevent the adsorptions of toluene and 2-butene adsorptions, in order to reduce the excessive hydrogenation saturation of olefins and monocyclic aromatics, which would be beneficial for the octane rating maintenance during the production process of gasoline.

Controlled construction of Co3S4@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect

A yolk-shell structured Co3S4@CoMoS catalyst was prepared through Oswald ripening method and subsequently used for hydrodesulfurization (HDS) reaction. The shells, constructed from Co-promoted MoS2 nanosheets, possess abundant active sites and facilitate the adsorption of reactants through the development of pore channels. The MoS2 sheets are arranged in a staggered and convoluted manner, creating numerous defect sites. The shorter MoS2 slabs provide a wide distribution of reactive sites, ensuring efficient reactions. The Co3S4 species within the inner core acts as an auxiliary active phase, inducing the hydrogen spillover effect in the HDS system. This facilitates the transfer of active hydrogen species to the CoMoS shell, where both CoMoS and Co3S4 phases synergistically enhance the HDS reaction. The Co3S4@CoMoS catalyst achieved up to 99.2% dibenzothiophene (DBT) conversion and 94.9% 4,6-dimethyldibenzothiophene conversion at the lower dosage (30 mg). The structure-activity relationships between active phase and HDS activity were investigated via in-situ infrared spectroscopy and other characterizations as well as density functional theory calculations.

Non-equilibrium electronic structure of Fe-based bulk catalysts: Dual-channel electron transfer behavior among Fe, Zn, and P species and its impact on hydrodesulfurization reaction pathway

Regulation of electronic structure of metal active phase for catalysts has been known as efficient in promoting its catalytic activity; however, manipulating the activity of catalysts via controllable metal active phase electronic structure is still challenging. A non-equilibrium electronic structure Fe-based bulk catalyst has been developed via controllably adding P species, where the non-equilibrium electronic structure of Fe species is formed through the electron transfer from the Zn species through the P electronic channel. As a result, the catalytic activity of the modified Fe-based bulk catalysts has increased by 24.4–50.4%. Meanwhile, the sulfurization degree (SD) of the modified Fe-based bulk catalysts has increased by 5.6–25.9%. In addition, the HDS reaction rate constant (kHDS) has increased by about 2.0 times, and the DDS reaction rate constant (kDDS) has increased by about 2.4 times. The P modifying can regulate the directional transfer of unpaired free electrons between Fe and Zn species to form a more non-equilibrium electronic structure of Fe species, which can reduce the energy barrier of the C–S bond adsorbed on the P-modified Fe-based bulk catalysts. Importantly, the P species can be used as an active site to adsorb S-containing compounds in the modified Fe-based bulk catalysts, which is conducive to generating more coordinatively unsaturated sites (CUSs). The former can promote the formation of the more non-equilibrium electronic structure of Fe species, and the latter can adjust the adsorption active site of S-containing on the catalyst surface. Therefore, an electron transfer channel is formed among Fe, Zn, and P species, and another one is formed among Fe, P, and S-containing compounds, which form a dual-channel electron transfer behavior. Furthermore, the specific surface area, total pore volume, and reducibility of the modified Fe-based bulk catalysts have also shown varying degrees of improvement via the controllable addition of P species.

Boosting ultra-deep hydrodesulfurization of diesel by tuning sulfidation degree of metals on NiMo/AlOOH catalyst

By using a room-temperature discharge-based sulphurization (RT-DS) process, we efficiently tune sulfidation degree of metal on γ-AlOOH-supported NiMo catalyst via simply changing feedstock amount for preparing catalysts, thus preparing a NiMoS/AOH-4 catalyst for hydrodesulfurization (HDS) of diesel. NiMoS/AOH-4 shows an excellent HDS performance, with S content of diesel being reduced from 18000 μg g−1 to 3 μg g−1 and without catalytic efficiency decrease after 1000 h reaction. Moreover, NiMoS/AOH-4 shows higher rate constant, higher turnover frequency but lower activation energy in HDS reaction, as compared with those on widely reported catalysts. The excellent HDS performance of NiMoS/AOH-4 is resulted from the appropriate sulfidation degree of Mo, which creates more abundant catalytic active Ni-Mo-S phases. RT-DS process for preparing NiMoS/AOH-4 proceeds in Ar at room temperature and atmospheric pressure, without using H2S and heating. This makes RT-DS process suitable for large-scale industrial applications to fabricate more efficient HDS catalysts.

Monodisperse dendritic micro-mesoporous composite self-assembled with tiny TS-1 seeds as efficient catalysts for hydrodesulfurization of dibenzothiophenes

Novel TS-1/dendritic mesoporous silica nanoparticles (TS-1/DMSNs, TD) micro-mesoporous composites with different morphology were prepared for NiMo catalysts (NiMo/TD-TEA). Series catalysts were tested in dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) hydrodesulfurization (HDS) reactions in a fix-bed reactor. TS-1 were uniformly compounded with mesoporous materials in the form of Si-O-Ti bonds, which did not affect the typical dendritic morphology. The introduction of TEA could inhibit the growth of support particles, and modulate the acidity and the metal-support interaction (MSI) of catalysts. Optimized NiMo/TD-TEA catalyst showed the optimal DBT (98.0 %) and 4,6-DMDBT (92.3 %) desulfurization rate as well as the excellent hydrogenation (HYD) selectivity for DBT and 4,6-DMDBT HDS with the optimal reaction rate constant (12.2 mol·g−1·h−1, 6.7 mol·g−1·h−1) and turnover frequency (2.3 h−1, 1.4 h−1). By correlating to the catalyst acidity–activity and active phase–activity, the activity and selectivity were not only depended on the presence of Brønsted (B) acid and the total acid content but also associated with the dispersion and morphology of MoS2 slabs.

Liquid-phase adsorption of nitrogen compounds from model diesel fuel on activated carbons

One of the great challenges in deep hydrodesulfurization (HDS) to produce ultra-low-sulfur diesel (ULSD) is the coexisting heterocyclic nitrogen-containing compounds in middle distillates, which significantly inhibit the HDS reactions. This study investigates various activated carbon (AC) samples for selectively removing nitrogen compounds from a model diesel fuel through adsorption. The physical and chemical properties of the AC samples were characterized using low-temperature N2 adsorption–desorption, SEM–EDS, and FT-IR to explore their impact on the adsorption performance. The results indicate that the adsorption performance is influenced not only by the surface area and by the number of oxygen-containing functional groups on the surface but also by the pore diameter distribution. Among all AC samples tested, AC-W exhibited the highest adsorption capacity, achieving a nitrogen removal rate of 97.8% with the addition of 10 wt.% of AC-W. The adsorption capacity was approximately 24.0 mg-N/g-A at a nitrogen equilibrium concentration of 200 ppmw. The adsorption isotherms for total nitrogen and individual nitrogen compounds in the fuel over AC can be described well by the Freundlich isotherm model. An approach for improving the ADN performance of AC is discussed based on the findings in this study.

The organic–inorganic dual anchoring strategy based on organic chelators and lacunary polyoxometalates for the preparation of efficient CoWS hydrodesulfurization catalysts

Designing catalysts with bimetallic intimate synergistic effects to enhance catalytic activity has always been a focused problem for hydrodesulfurization (HDS) systems. Efficient HDS catalysts with abundant CoWS active phases were prepared through novel organic–inorganic ligand dual anchoring strategy based on the organic chelating agents and lacunary polyoxometalates (POMs). Citric acid (CA) chelating agent and Co2+ promoter are pre-coordinated in the impregnating solution, the trivacant Keggin [SiW9O34]10- (SiW9) POMs attract the promoter through the nucleophilic oxygen groups at the vacant sites to form the CA-Co@SiW9 “sandwich-like” structure, which allows the organic chelator-promoter-active center to be intimate interaction in a single molecule, thus achieving atomic-scale Co-W proximity on the precursor. In the subsequent sulfidation process, CA delayed the reduction temperature of cobalt species, enabling more Co promoter to be anchored at the edge sites of WS2 clusters to form abundant CoWS active phases, which fully exerted the bimetallic intimate synergism in the HDS reaction. Furthermore, the carbon deposits generated from CA carbonation acted as secondary support weakening the interaction of active metals with Al2O3 support and increasing the sulfidation degree as well as the dispersion of active metals. As a result, the S-Co(CA)W/Al2O3 catalyst achieves a remarkable turnover frequencies (TOF) value of 1.24 × 10-3 s−1 in HDS reaction of dibenzothiophene (DBT). This dual anchoring method based on POMs inorganic ligand and organic chelator ligand provides a new idea for designing novel HDS catalysts.

Design of active phase structure with high activity and stability in residue hydrotreating reactions

The catalyst with well-dispersed (Ni)MoS2 active phase characteristic of short slab length and low stacking numbers was designed by strengthening metal-support interaction (MSI) and metal dispersion, which displayed high activity and long-term stability in real-life residue hydrodesulfurization (HDS) reactions. Furthermore, the impacts of pseudo-boehmite and catalyst calcination temperature on surface properties were thoroughly investigated. Mo equilibrium adsorption method, Al27 NMR, XRD, Raman, UV–Vis DRS, and H2-TPR characterization showed that the hydroxyl groups concentration and tetrahedral cation vacancies increased upon reducing the pseudo-boehmite extrudates calcination temperature. Increasing calcination temperature of the catalysts further strengthened MSI, resulted in well-dispersed Mo species with enhanced MSI. Therefore, well-dispersed (Ni)MoS2 active phase was acquired on novel designed catalyst. XPS coupled with HRTEM indicated that the more potential active sites, less propensity for active phase evolution and gradual increase in sulfidation degree with processing time contributed to the high HDS performance of the designed active phase. This work can deepen our understanding toward evolution pattern of active phase during residue HDS catalysts, and give guidance for developing high performance catalyst by strengthening MSI and enhancing metal dispersion.

Targeted fabrication of 1T-MoS2 enriched nanosheets vertically oriented on spiny-shaped nanospheres with sufficient sulfur vacancies and “rim” sites for co-enhancing the hydrodesulfurization activity and hydrogenation selectivity

The 1T-enriched spiny-shaped nanospheres with vertically oriented MoS2 nanosheets over the surface was successfully prepared with the novel solvent induced micelle-limited Mo-CTA+ composites self-assembly (SIMMS) strategy under the dual effects of mixed sulfur sources (thiourea and thioacetamide) and cetyltrimethylammonium bromide (CTAB). In the proposed strategy, the molybdenum source and CTAB are firstly assembled to Mo-CTA+ by strong electrostatic attraction to avoid the molybdenum source from polymerization and forming large polymolybdate anions. Meanwhile, the CTAB moleculars self-assemble to spherical micelles, which can adsorb Mo-CTA+ through van der Waals force and obtain spherical precursors with a controllable number of nucleation sites. Under the sulfurization from mixed sulfur source, appropriate reducibility can control the formation of crystal seeds and crystal growth during the crystallization process of MoS2, whereas CTAB can regulate and control the growth behavior and micro-morphology of MoS2, which is ultimately also retained between the MoS2 nanolayersto expand their interlayer spacing and stabilize the 1T phase. Therefore, the 1T-enriched spiny-shaped nanospheres with vertically oriented MoS2 nanosheets can be controllably prepared. In the hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT) over these catalysts, the MoS2-75%/0.25 catalyst with the highest concentration of sulfur vacancies as well as “rim” and “rim-like” sites can reach the highest HDS activity (99.1%) and HYD/DDS ratio (4.76), which are much higher than those of the MoS2-H catalyst prepared by conventional hydrothermal method (HDSDBT%=46.0%, HYD/DDS ratio=0.90).

Insights into Correlations among the Hydrodesulfurization, Hydrodenitrogenation, and Hydrogen Evolution Reactions over Molybdenum Phosphide Catalysts Modified by Cerium Oxide

Insights into Correlations among the Hydrodesulfurization, Hydrodenitrogenation, and Hydrogen Evolution Reactions over Molybdenum Phosphide Catalysts Modified by Cerium Oxide

Few-Layered Defect-Rich MoS2 Nanosheets with Ni Doping as Catalysts for Efficient Hydrodesulfurization Reaction

Few-Layered Defect-Rich MoS₂ Nanosheets with Ni Doping as Catalysts for Efficient Hydrodesulfurization Reaction

NiMoS nanocubes for the selective removal of sulfur from 3-methyl-thiophene

In this study, NiMoS nanocubes were prepared by simple hydrothermal synthesis using low-cost precursors. The HRTEM micrographs exhibited variation in the size and definition of the particle shape with the Mo/Ni molar ratio. The crystallographic composition of the nanocubes also varies with the molar ratio passing from Ni3S4 polydymite, NiSO4·6 H2O, and NiS phases in the Mo/Ni low values to NiS2 in the Mo/Ni= 1.0 as revealed by the X-ray diffraction study. Meanwhile, the surface of the nanocubes resulted enriched with Mo as the Mo/Ni ratio increases, as XPS analysis demonstrated. These materials exhibited outstanding catalytic activity in the hydrodesulfurization reaction of a naphtha model compound under atmospheric pressure conditions. The selectivity displayed indicated low saturation of the C5 olefins obtained as products in all ranges of temperature tested. The high activity observed was explained in terms of the Ni inverse promotion effect on MoS2 slabs present at the nanocubes outer surface.