Project description:Recent results have evidenced that carbon plays an important role in stabilizing the structure of the active phase in catalysts. In this work, carbon-coated alumina was prepared by applying polydopamine (PDA) as a sacrificial carbon source to modify the surface properties of γ-alumina, which then was used as a support to prepare supported NiMo catalysts for hydrodesulfurization (HDS) of dibenzothiophene (DBT). NiMo/Al2O3 catalysts exhibited limited hydrodesulfurization performances due to their strong metal-support interaction. Herein, we report an unexpected phenomenon that sacrificial carbon layers can be constructed on the surface of the Al2O3 support from the carbonization of polydopamine (PDA) and mediated the interaction between the active site and support. Through the removal of carbon layers and sulfidation, the resulting NiMo catalysts exhibit excellent performance for HDS reaction of dibenzothiophene (DBT), which is associated with adequate loading of residual carbon species, leading to an enhanced amount of active species under sulfidation conditions. Moreover, the facile synthetic strategy can be extended to the stabilization of the active phase on a broad range of supports, providing a general approach for improving the metal-support interaction supported nanocatalysts.
Project description:The hydrodesulfurization process is one of the cornerstones of the chemical industry, removing harmful sulfur from oil to produce clean hydrocarbons. The reaction is catalyzed by the edges of MoS2 nanoislands and is operated in hydrogen-oil mixtures at 5-160 bar and 260-380 °C. Until now, it has remained unclear how these harsh conditions affect the structure of the catalyst. Using a special-purpose high-pressure scanning tunneling microscope, we provide direct observations of an active MoS2 model catalyst under reaction conditions. We show that the active edge sites adapt their sulfur, hydrogen, and hydrocarbon coverages depending on the gas environment. By comparing these observations to density functional theory calculations, we propose that the dominant edge structure during the desulfurization of CH3SH contains a mixture of adsorbed sulfur and CH3SH.
Project description:Alkali metal promoters have been widely employed for preparation of heterogeneous catalysts used in many industrially important reactions. However, the fundamentals of their effects are usually difficult to access. Herein, we unravel mechanistic and kinetic aspects of the role of alkali metals in CO2 hydrogenation over Fe-based catalysts through state-of-the-art characterization techniques, spatially resolved steady-state and transient kinetic analyses. The promoters affect electronic properties of iron in iron carbides. These carbide characteristics determine catalyst ability to activate H2 , CO and CO2 . The Allen scale electronegativity of alkali metal promoter was successfully correlated with the rates of CO2 hydrogenation to higher hydrocarbons and CH4 as well as with the rate constants of individual steps of CO or CO2 activation. The derived knowledge can be valuable for designing and preparing catalysts applied in other reactions where such promoters are also used.
Project description:In this study, a novel, simple, high yield, and scalable method is proposed to synthesize highly porous MoS2/graphene oxide (M-GO) nanocomposites by reacting the GO and co-exfoliation of bulky MoS2 in the presence of polyvinyl pyrrolidone (PVP) under different condition of ultrasonication. Also, the effect of ultrasonic output power on the particle size distribution of metal cluster on the surface of nanocatalysts is studied. It is found that the use of the ultrasonication method can reduce the particle size and increase the specific surface area of M-GO nanocomposite catalysts which leads to HDS activity is increased. These nanocomposite catalysts are characterized by XRD, Raman spectroscopy, SEM, STEM, HR-TEM, AFM, XPS, ICP, BET surface, TPR and TPD techniques. The effects of physicochemical properties of the M-GO nanocomposites on the hydrodesulfurization (HDS) reactions of vacuum gas oil (VGO) has been also studied. Catalytic activities of MoS2-GO nanocomposite are investigated by different operating conditions. M9-GO nanocatalyst with high surface area (324 m2/g) and large pore size (110.3 Å), have the best catalytic performance (99.95%) compared with Co-Mo/γAl2O3 (97.91%). Density functional theory (DFT) calculations were also used to elucidate the HDS mechanism over the M-GO catalyst. It is found that the GO substrate can stabilize MoS2 layers through weak van der Waals interactions between carbon atoms of the GO and S atoms of MoS2. At both Mo- and S-edges, the direct desulfurization (DDS) is found as the main reaction pathway for the hydrodesulfurization of DBT molecules.
Project description:Hydrodesulfurization catalysis ensures upgrading and purification of fossil fuels to comply with increasingly strict regulations on S emissions. The future shift toward more diverse and lower-quality crude oil supplies, high in S content, requires attention to improvements of the complex sulfided CoMo catalyst based on a fundamental understanding of its working principles. In this study, we use scanning tunneling microscopy to directly visualize and quantify how reducing conditions transforms both cluster shapes and edge terminations in MoS2 and promoted CoMoS-type hydrodesulfurization catalysts. The reduced catalyst clusters are shown to be terminated with a fractional coverage of sulfur, representative of the catalyst in its active state. By adsorption of a proton-accepting molecular marker, we can furthermore directly evidence the presence of catalytically relevant S-H groups on the Co-promoted edge. The experimentally observed cluster structure is predicted by theory to be identical to the structure present under catalytic working conditions.
Project description:Sulfur compounds in fuel oils are a major source of atmospheric pollution. This study is focused on the hydrodesulfurization (HDS) of dibenzothiophene (DBT) via the coupled application of 0.5 wt% Pd-loaded Co-Mo/Al2O3 and Ni-Mo/Al2O3 catalysts with ionic liquids (ILs) at ambient temperature (120 °C) and pressure (1 MPa H2). The enhanced HDS activity of the solid catalysts coupled with [BMIM]BF4, [(CH3)4N]Cl, [EMIM]AlCl4, and [(n-C8H17)(C4H9)3P]Br was credited to the synergism between hydrogenation by the former and extractive desulfurization and better H2 transport by the latter, which was confirmed by DFT simulation. The Pd-loaded catalysts ranked highest by activity i.e. Pd-Ni-Mo/Al2O3 > Pd-Co-Mo/Al2O3 > Ni-Mo/Al2O3 > Co-Mo/Al2O3. With mild experimental conditions of 1 MPa H2 pressure and 120 °C temperature and an oil : IL ratio of 10 : 3.3, DBT conversion was enhanced from 21% (by blank Ni-Mo/Al2O3) to 70% by Pd-Ni-Mo/Al2O3 coupled with [(n-C8H17)(C4H9)3P]Br. The interaction of polarizable delocalized bonds (in DBT) and van der Waals forces influenced the higher solubility in ILs and hence led to higher DBT conversion. The IL was recycled four times with minimal loss of activity. Fresh and spent catalysts were characterized by FESEM, ICP-MS, EDX, XRD, XPS and BET surface area techniques. GC-MS analysis revealed biphenyl as the major HDS product. This study presents a considerable advance to the classical HDS processes in terms of mild operating conditions, cost-effectiveness, and simplified mechanization, and hence can be envisaged as an alternative approach for fuel oil processing.
Project description:The catalytically active site for the removal of S from organosulfur compounds in catalytic hydrodesulfurization has been attributed to a generic site at an S-vacancy on the edge of MoS2 particles. However, steric constraints in adsorption and variations in S-coordination means that not all S-vacancy sites should be considered equally active. Here, we use a combination of atom-resolved scanning probe microscopy and density functional theory to reveal how the generation of S-vacancies within MoS2 nanoparticles and the subsequent adsorption of thiophene (C4H4S) depends strongly on the location on the edge of MoS2. Thiophene adsorbs directly at open corner vacancy sites, however, we find that its adsorption at S-vacancy sites away from the MoS2 particle corners leads to an activated and concerted displacement of neighboring edge S. This mechanism allows the reactant to self-generate a double CUS site that reduces steric effects in more constrained sites along the edge.
Project description:Ni/La2O3/ZrO2 catalysts were prepared by a step-by-step impregnation method through regulation of the contents of the active component and alkali. The introduction of an alkaline promoter not only enhanced the alkalinity of the catalyst but also improved the dispersion of Ni on the catalyst owing to the strong interaction between Ni2+ and alkali promoter. The synergistic effect between Ni and La2O3 was beneficial to selective hydrogenolysis of sorbitol. Under the optimal reaction conditions, sorbitol conversion reached nearly 100% and target products (ethylene glycol, 1,2-propanediol, and glycerol) selectivity reached 74.8%. Metal-alkali coordination mechanism and possible pathways for target products formation were proposed.
Project description:The evolution in local structure and electronic properties of cobalt was investigated during in situ sulfurization. Using a combination of 1s X-ray absorption (XAS) and 1s3p resonant inelastic X-ray scattering (RIXS), the valence, coordination and symmetry of cobalt ions were tracked in two cobalt-promoted molybdenum oxide precursors of the hydrodesulfurization catalyst system, namely Co-Mo/Al2O3 and Co-Ni-Mo/Al2O3. Extended X-ray absorption fine structure shows that the Co-O bonds were replaced with Co-S bonds as a function of reaction temperature. The cobalt K pre-edge intensity shows that the symmetry of cobalt was modified from Co3+ Oh and Co2+ Oh to a Co2+ ion where the inversion symmetry is broken, in agreement with a square-pyramidal site. The 1s3p RIXS data revealed the presence of an intermediate cobalt oxy-sulfide species. This species was not detected from XAS and was determined from the increased information obtained from the 1s3p RIXS data. The cobalt XAS and RIXS data show that nickel has a significant influence on the formation of the cobalt oxy-sulfide intermediate species prior to achieving the fully sulfided state at T > 400°C.
Project description:The development of efficient catalysts for the direct synthesis of higher alcohols (HA) via CO hydrogenation has remained a prominent research challenge. While modified Fischer-Tropsch synthesis (m-FTS) systems hold great potential, they often retain limited active site density under operating conditions for industrially relevant performance. Aimed at improving existing catalyst architectures, this study investigates the impact of highly dispersed metal oxides of Co-Cu, Cu-Fe, and Co-Fe m-FTS systems and demonstrates the viability of ZrO2 as a general promoter in the direct synthesis of HA from syngas. A volcano-like composition-performance relationship, in which 5-10 mol % ZrO2 resulted in maximal HA productivity, governs all catalyst families. The promotional effect resulted in a 2.5-fold increase in HA productivity for the optimized Cu1Co4@ZrO2-5 catalyst (Cu:Co = 1:4, 5 mol % ZrO2) compared to its ZrO2-free counterpart and placed Co1Fe4@ZrO2-10 among the most productive systems (345 mgHA h-1 gcat-1) reported in this category under comparable operating conditions, with stable performance for at least 300 h. ZrO2 assumes an amorphous and defective nature on the catalysts, leading to enhanced H2 and CO activation, facilitated formation of metallic and carbide phases, and structural stabilization.