Direct Desulfurization Research Articles

Visible-light-promoted direct desulfurization of glycosyl thiols to access C-glycosides

C-Glycosides are essential for the study of biological processes and the development of carbohydrate-based drugs. Despite the tremendous hurdles, glycochemists have often fantasized about the efficient, highly stereoselective synthesis of C-glycosides with the shortest steps under mild conditions. Herein, we report a desulfurative radical protocol to synthesize C-alkyl glycosides and coumarin C-glycosides under visible-light induced conditions without the need of an extra photocatalyst, in which stable and readily available glycosyl thiols that could be readily obtained from native sugars are activated in situ by pentafluoropyridine. The benefits of this procedure include high stereoselectivity, broad substrate scope, and easy handling. Mechanistic studies indicate that the in situ produced tetrafluoropyridyl S-glycosides form key electron donor–acceptor (EDA) complexes with Hantzsch ester (for C-alkyl glycosides) or Et3N (for coumarin C-glycosides), which, upon irradiation with visible light, trigger a cascade of glycosyl radical processes to access C-glycosides smoothly.

Preparation of Ni2P with a Surface Nickel Phosphosulfide Layer by Reduction of Mixtures of Na4P2S6 and NiCl2

AbstractA series of physical mixtures of Na4P2S6 and NiCl2 (P‐NiPS(x), where x represents the P/Ni molar ratio) were employed for the preparation of Ni2P. For comparison, a sulfur‐containing Ni2P catalyst (Ni2P‐S) and a sulfur‐free Ni2P catalyst (Ni2P‐TPR) were prepared by reduction of Ni2P2S6 and a nickel phosphate precursor, respectively. The reduction of the P‐NiPS(x) precursors with P/Ni ratios above 2/3 yielded Ni2P catalysts with a distinct nickel phosphosulfide layer (NiPS(x)), and the Ni2P phase started to form at ca. 200 °C. The reduction of Ni2P2S6 to Ni2P most likely follows a disproportionation mechanism. The P3+ species in Ni2P2S6 disproportionate to PH3 and P5+ during the reduction, and PH3 further reacts with nickel and sulfur species to form Ni2P and the surface nickel phosphosulfide layer. The sulfur atoms in the nickel phosphosulfide phase were in the form of S2−. The introduction of sulfur to Ni2P favored the hydrogenation pathway of the hydrodesulfurization (HDS) of dibenzothiophene (DBT), but hardly affected the direct desulfurization (DDS) pathway and inhibited the hydrogenation of biphenyl. The DDS pathway rate constants of DBT HDS over the Ni2P‐TPR and NiPS(x) catalysts were observed to increase linearly with the increase in their surface Ni atomic concentrations.

Regulating the microenvironments and the d-band center of hierarchical NiMoS/TS-1 catalyst by ZrO2 to enhance the hydrodesulfurization performance of dibenzothiophene

The microenvironments including the surface hydroxyls, the oxygen vacancies, and the d-band center of hierarchical TS-1 zeolite pickled by hydrochloric acid were regulated by ZrO2, the effect of ZrO2 on the physicochemical properties and the catalytic performances of the corresponding NiMoS supported catalysts were studied. The experimental and theoretical calculation results show that the d-band center, the surface hydroxyl groups, and the oxygen vacancies were regulated after incorporation of ZrO2. Resulting in the modulated acidity of the support and the metal support interaction of the catalysts, further promoting the formation of type-II NiMoS active phases. The catalytic performance evaluations show that catalyst NiMo/1-ZAT exhibits the superior HDS performance, kinetic study further demonstrated that the enhanced catalytic activity was mainly contributed by the improved direct desulfurization activity generated from the moderate support acidity, suitable MSI, highest sulfidation degrees, most type-II NiMoS active phase and highest activity of individual active sites.

Regulating the coordination environment of surface alumina on NiMo/Al2O3 to enhance ultra-deep hydrodesulfurization of diesel

Herein, a set of NiMo/Al2O3 catalysts with distinct coordination state of surface alumina were design and prepared by a facile calcination strategy. Various characterization methods were employed to analyze the structural properties of NiMo/Al2O3 catalysts, and the catalytic performances of corresponding catalysts were tested for hydrodesulfurization (HDS) of 4,6-dimethyldibenzothiophene (4,6-DMDBT). The results indicate that the synthesized samples show uniform specific surface area (130 m2·g−1) and pore size (3.5 nm), but varying penta-coordinated aluminum content, which significantly influences the NiMo/Al2O3 catalysts’ surface acidity. Therein, NiMo/Al2O3-600 prepared by calcination at 600 °C exhibits the highest ratio of penta-coordinated aluminum species, which endows more abundant Brønsted acid than that of tetra- and hexa-coordinated aluminum counterparts, thereby substantially promoting the isomerization and direct desulfurization pathways of 4,6-DMDBT HDS, and thereafter considerably boosting the HDS performance of NiMo/Al2O3-600 with 94.5 % 4,6-DMDBT conversion, which is notably higher than that of NiMo/Al2O3-500 (74.4 %) and NiMo/Al2O3-700 (62.7 %).

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.

Tailoring the electronic structure of Ni2P/Al2O3 by Pt introduction to boost the ultradeep hydrodesulfurization performance

The catalytic performances of conventional Ni(Co)Mo(W)/Al2O3 catalysts for hydrodesulfurization (HDS) of fuel are far from meeting the near zero emission standards. Therefore, the development of more efficient ultradeep HDS catalyst is highly desirable. Herein, a novel Pt-Ni2P/Al2O3 catalyst with 0.5 wt% Pt loading was prepared, and its catalytic performance for HDS of 4,6-dimethyldibenzothiophene (4,6-DMDBT) was investigated. The introduction of Pt considerably promoted the reducibility and hydrogen atoms produced by the dissociated adsorbed hydrogen molecules on the Pt surface overflowing to the Ni2P because of the lower electronegativity of Pt than that of Ni, thereby increasing the number of stronger Lewis and Brønsted acid sites, and thereafter greatly boosting the direct desulfurization and isomerization pathways. As a result, Pt-Ni2P/Al2O3 catalyst achieved the ultradeep HDS of 4,6-DMDBT, with 100% conversion at 340 °C, remarkably higher than that of Ni2P/Al2O3 (49.8%) and NiMo/Al2O3 (62.0%) counterparts.

Antimony Extraction from Sulfide Concentrates by Direct Electrolytic Desulfurization in Molten Salt

Antimony Extraction from Sulfide Concentrates by Direct Electrolytic Desulfurization in Molten Salt

MOF-derived CoP/C catalyst for efficient dibenzothiophene hydrodesulfurization

The design of an active and sulfur-resistant catalyst for dibenzothiophene (DBT) hydrodesulfurization (HDS) in crude oil purification is highly desirable but remains a grand challenge. Here, two carbon-supported cobalt phosphide catalysts Co2P/C and CoP/C, and a reference sample Co/C are successfully synthesized using a metal–organic-frameworks (MOFs) precursor. A P/Co ratio dependence on crystal phases is found, leading to the formation of two pure-phase cobalt phosphide catalysts CoP/C and Co2P/C. Catalyst evaluation in HDS of DBT shows that the CoP/C catalyst exhibits a higher activity and stability than Co2P/C and Co/C, giving a 93.7 % DBT conversion with 100 h stability under 3 MPa and 380 ◦C. Moreover, a 67.4 % biphenyl yield characterizes the dominance of the direct desulfurization (DDS) pathway. The obtained catalytic performance over the CoP/C catalyst is also superior to the published cobalt phosphide catalysts. Multiple characterization techniques co-evidence that the copious specific surface area, efficient electron transport from Co to P, high thermal stability of Co nanoparticles (NPs), and strong sulfur resistance account for the enhanced catalytic performance of CoP/C. The findings of this report suggest that phosphorus-modified cobalt over the carbon support can act as a promising catalyst for the HDS of DBT.

Peptide and Protein Desulfurization with Diboron Reagents.

In this Letter, we report a direct and robust desulfurization method employing water-soluble phosphine, specifically tris(2-carboxyethyl)phosphine hydrochloride (TCEP), and tetrahydroxydiboron (B2(OH)4), which serves as a radical initiator. This innovative reaction exhibits compatibility with a diverse array of substrates, including cysteine residues in chemically synthesized oligopeptides and cyclic peptides, alkyl thiols in bioactive molecules, disulfides in commercial proteins, and selenocysteine. We optimized the reaction conditions to minimize the formation of undesired oxidized and borylated byproducts. Furthermore, the refined desulfurization process is executed after native chemical ligation (NCL) in a single pot, streamlining the existing synthetic approaches. This demonstrates its potential applications in the synthesis of complex peptides and proteins, showcasing a significant advancement in the field.

One–pot solvothermal preparation of the porous NiS2//MoS2 composite catalyst with enhanced low-temperature hydrodesulfurization activity

The simple preparation of mesoporous NiS2//MoS2 composite catalyst through a one-pot solvothermal method is presented. The improvement of the specific surface area (220 m2/g) and the construction of the porous structure are realized by this method in the case of no support. The organics acts as a microscopic binder contribute to uniform stacking of MoS2 with NiS2 clusters. The composite structure including NiS2 and MoS2 was obtained (proved by XRD, XPS, TEM, IR, UV–vis and RAMAN) and changed the microelectronic environment of the active metal surface (DFT calculation). The mesoporous NiS2//MoS2 catalyst (Ni1Mo1-200) showed an excellent hydrodesulfurization performance of dibenzothiophene (DBT conversion: 78 % at 260 °C) and a high ratio of direct desulfurization pathway (SDDS/HYD = 16.6) at a low reaction temperature. By combining the characterization and theoretical calculation results, the advantages of this NiS2//MoS2 composite structure in synergistic catalysis was further confirmed.

In situ synthesis of mesoporous NiS2-MoS2 sphere-flower hybrid for hydrodesulfurization of thiophene and 4,6-dimethyl-dibenzothiophene

A series of new NiS2-MoS2-x (x = 0–0.5) sphere-flower hybrids with different Ni/Mo molar ratios, synthesized via a one-pot hydrothermal method, were used as catalysts for hydrodesulfurization (HDS) of thiophene (TP) and 4,6-dimethyl-dibenzothiophene (4,6-DMDBT). The characterizations show that the microstructure of MoS2, including the size of MoS2 nano-flowers, the length of MoS2 slabs, and the number of defects, was regulated by changing Ni/Mo ratios. Increasing the Ni/Mo ratio in the NiS2-MoS2-x catalysts significantly boosts their HDS activity, with the optimum ratio being 0.2. In addition, the NiS2-MoS2-0.2 catalyst exhibits the best direct desulfurization performance, which is associated with the minimum ratio of average slab length (Lav) to average stacking number (Nav) as well as the highest concentration of Ni-promoted Mo sites and sulfur vacancies. Moreover, Ni-containing NiS2-MoS2-x catalysts, characterized by a highly stable sphere-flower configuration, exhibit superior structural stability and catalytic durability than the Ni-free NiS2-MoS2-0 catalyst.

Highly Dispersed FeAg-MCM41 Catalyst for Medium-Temperature Hydrogen Sulfide Oxidation in Coke Oven Gas.

The traditional hydrolysis-cooling-adsorption process for coke oven gas (COG) desulfurization urgently needs to be improved because of its complex nature and high energy consumption. One promising alternative for replacing the last two steps is selective catalytic oxidation. However, most catalysts used in selective catalytic oxidation require a high temperature to achieve effective desulfurization. Herein, a robust 30Fe-MCM41 catalyst is developed for direct desulfurization at medium temperatures after hydrolysis. This catalyst exhibits excellent stability for over 300 h and a high breakthrough sulfur capacity (2327.6 mgS gcat-1). Introducing Ag into the 30Fe-MCM41 (30Fe5Ag-MCM41) catalyst further enhances the H2S removal efficiency and sulfur selectivity at 120 °C. Its outstanding performance can be attributed to the synergistic effect of Fe-Ag clusters. During H2S selective oxidation, Fe serves as the active site for H2S adsorption and dissociation, while Ag functions as the catalyst promoter, increasing Fe dispersion, reducing the oxidation capacity of the catalyst, improving the desorption capacity of sulfur, and facilitating the reaction between active oxygen species and [HS]. This process provides a potential route for enhancing COG desulfurization.

Controlling the growth of ZnNiMoSx on biomass-derived porous carbon materials for deep hydrodesulfurization

Controlling the growth of small-sized catalysts with more accessible active sites and low cost is of great significance to promote their hydrodesulfurization (HDS) performance. Herein, we have synthesized an efficient ZnNiMoSx/C composite catalyst by using biomass-derived porous carbon as the support. With ZnCl2 to regulate porous structure, the obtained carbon support presents an enhanced specific surface area (1581.1 m2/g), which promotes the dispersion of ZnNiMoSx catalysts. The ZnNiMoSx on ZnNiMoSx/C-3 shows fewer layers (2–4 layers) and shorter length (about 4–5 nm), indicating more corner and edge active sites. Besides, the addition of Zn species improves the sulfurization degree of ZnNiMoSx and provides more sulfur vacancies for the enhanced HDS performance. The synthesized ZnNiMoSx/C-3 catalyst shows the kHDS value of dibenzothiophene to be 39.42 × 10−7 mol/(g s) and the direct desulfurization selectivity up to 94.5 %. This study provides a new thought for the development of HDS catalysts with cheap biomass-derived materials.

In-situ desulfurization using porous Ca-based materials for the oxy-CFB process: A computational study

Within circulating fluidized bed (CFB) processes, gas and solid behaviors are mutually affected by operating conditions. Therefore, understanding the behaviors of gas and solid materials inside CFB processes is required for designing and operating those processes. In addition, in order to minimize the environmental impact, modeling to reduce pollutants such as SOx emitted from those processes is essential, and simulation reproduction is necessary for optimization, but little is known. In this study, the gas and solid behaviors in a pilot-scale circulating fluidized bed combustor were investigated by using computational particle fluid dynamics (CPFD) numerical simulation based on the multiphase particle-in-cell (MP-PIC) method under oxy-fuel combustion conditions. In particular, the combustion and in-situ desulfurization reactions simultaneously were considered in this CPFD model. Effect of fluidization number (ULS/Umf) was investigated through the comparison of particle circulation rates with regards to the loop seal flux plane and bed height in the standpipe. In addition, the effects of parameters (temperature, Ca/S molar ratio, and particle size distribution), sensitive indicators for the desulfurization efficiency of limestone, were confirmed. Based on the cycle of the thermodynamic equilibrium curve of limestone, it is suggested that direct and indirect desulfurization occur simultaneously under different operating conditions in CFB, creating an environment in which various reactions other than desulfurization can occur. Addition of the reaction equations (i.e., porosity, diffusion) to the established simple model minimizes uncertainty in the results. Furthermore, the model can be utilized to optimize in-situ desulfurization under oxy-CFB operating conditions.

Chiral and Catalytic Effects of Site-Specific Molecular Adsorption.

The changes of properties and preferential interactions based on subtle energetic differences are important characteristics of organic molecules, particularly for their functionalities in biological systems. Only slightly energetically favored interactions are important for the molecular adsorption and bonding to surfaces, which define their properties for further technological applications. Here, prochiral tetracenothiophene molecules are adsorbed on the Cu(111) surface. The chiral adsorption configurations are determined by Scanning Tunneling Microscopy studies and confirmed by first-principles calculations. Remarkably, the selection of the adsorption sites by chemically different moieties of the molecules is dictated by the arrangement of the atoms in the first and second surface layers. Furthermore, we have investigated the thermal effects on the direct desulfurization reaction that occurs under the catalytic activity of the Cu substrate. This reaction leads to a product that is covalently bound to the surface in chiral configurations.

Reactivity of Sulfur and Nitrogen Compounds of FCC Light Cycle Oil in Hydrotreating over CoMoS and NiMoS Catalysts

NiMoS and CoMoS catalysts were synthesized and applied to hydrotreating (HDT) of FCC light cycle oils (FCC-LCO) in an autoclave batch reactor at 613 K and 8.6 MPa H2. The S and N compounds in LCO were classified into four and three groups, respectively, in terms of the HDT reactivity. The individual and the competitive reactivities of the S and N compounds in the HDS and the HDN were investigated over the conventional CoMoS and NiMoS catalysts using S and N model compounds (dibenzothiophene, DBT, and carbazole, CBZ). In the HDS of DBT, both the direct desulfurization (DDS) and pre-hydrogenation pathway (HYD) were found to proceed, whereas the HYD pathway was favored for the HDN of CBZ. As a result, the NiMoS catalyst that facilitates the HYD pathway showed better activity in the HDN of LCO than the CoMoS (k = 10.20 × 10−2 vs. 1.80 × 10−2 h−1). Indeed, the HDS of LCO over the NiMoS was more favorable than that over the CoMoS catalyst (k = 4.3 × 10−1 vs. 3.6 × 10−1 h−1).

Controllable synthesis of nanostructured nickel phosphosulfide by reduction of mixtures of Na4P2S6 and NiCl2 with low P/Ni ratios in hydrogen plasma

Transition-metal phosphides and phosphosulfides constitute a class of versatile and promising catalysts in the field of enery production. The preparation of nanostructured phosphides and phosphosulfides is chanllenging because the thermal reduction of phosphate precursors requires high temperatures. In the present work, nanostructured nickel phosphosulfide catalysts composed of Ni2P particles surrounded by a distinct sulfur-containing layer were prepared by reduction of mixtures of Na4P2S6 and NiCl2 in H2 plasma. The minimum P/Ni ratio needed for the formation of nickel phosphosulfide was between 4/7 and 2/3, and the input voltage of the plasma generator (Vin) should be higher than 40 V. The control of the particle sizes of the nickel phosphosulfide catalysts was realized by simply regulating Vin. Another minor factor affecting the particle size was H2 flow rate. The actual precursor for the formation of nickel phosphosulfide can be Ni2P2S6, which underwent fast reduction in H2 plasma to yield NiS. In the hydrodesulfurization of dibenzothiophene, the nanostructured nickel phosphosulfide catalyst exhibited higher activity and hydrogenation pathway (HYD) selectivity than the one with large particle size. The optimal P/Ni ratio of the nickel phosphosulfide catalysts was found to be 4/5, and the HYD pathway was more favored by the increase in the P/Ni ratio than the direct desulfurization pathway.

Recent progress in photoinduced direct desulfurization of thiols.

The reduction of mercaptans plays an important role in diverse areas such as protein synthesis, polymer science, environmental study, and pharmaceutical chemistry. Despite significant advancements in this area, particularly in light-induced transformations, review articles have rarely been reported on this topic. Thus, this review article emphasizes the direct photoinduced desulfurization and functionalization of thiols to alkanes or coupling products, with a focus on significant advancements made in the last decade. The progress is discussed according to the types of bonds formed from the cleavage of Csp3-SH bonds.

Theoretical investigation on the inert pair effect of Ga on both the Ga-Ni-Mo-S nanocluster and the direct desulfurization of 4,6-dimethyldibenzothiophene

Non-periodic computational model for Ga-Ni-Mo-S nanocluster was established and the inert pair effect of Ga species on both the electron structures of the Ga-Ni-Mo-S nanocluster and the direct desulfurization (DDS) reaction of 4,6-dimethyldibenzothiophene(4,6-DMDBT) were systematically investigated. The stability of the established Ga-Ni-Mo-S nanocluster was enhanced due to the inert pair effect of Ga species. Moreover, the inert pair effect of Ga species makes both the electron and bonding properties of the edge active site of the Ga-Ni-Mo-S nanocluster inclined to be similar with the corner active sites. The adsorption behaviors of the reactant and the intermediates over the edge active sites changed profoundly due to the enhanced electron acceptor characteristics. The inert pair effect of Ga made it possible for the 4,6-DMDBT undergo DDS reaction because the activation energy drastically decreased from about 201.50 kJ·mol−1 over Ni-Mo-S cluster to about 154.56 kJ·mol−1 over Ga-Ni-Mo-S nanocluster at the Mo-edge active site, which would be further effectively compensated by the higher adsorption energy (about −50 kJ·mol−1) of the generated C14H13S over the edge active site than the corner active site of the established Ga-Ni-Mo-S nanocluster.

Simultaneous hydrodesulfurization of thiophene and benzothiophene over NiMoS catalysts supported on γ-Al2O3 composites containing ZSM-5

Alumina composites containing microporous ZSM-5 (Z-5) and mesoporous ZSM-5 (MZ-5), corresponding to xZA and xMZA, were developed by incorporating Z-5 and MZ-5 into γ - Al2O3, respectively. The two series of NiMoS/xMZA and NiMoS/xZA catalysts were prepared with these two composites as supports, respectively, and were used for the simultaneous hydrodesulfurization (HDS) of thiophene (T) and benzothiophene (BT). The results show that NiMoS/xMZA series catalysts exhibit higher HDS activity than that of NiMoS/xZA and NiMoS/γ-Al2O3, and the HDS activity of NiMoS/xMZA catalysts increases with the increase of MZ-5. The high HDS activity can be mainly attributed to the synergistic effects of the efficient diffusing pore channels, high dispersion of type II NiMoS phases, suitable acidity, and moderate Mo-support interaction. Moreover, the product distribution of HDS shows that the NiMoS/xMZA catalysts possess the dominant direct desulfurization (DDS) selectivity and the selectivity increases with the increase of MZ-5 content due to more corner sites and suitable Brønsted (B) acid sites, whereas the NiMoS/xZA catalysts perform more excellent hydrogenation (HYD) selectivity, and the selectivity increases with the increase of Z-5 content because of the existence of more edge sites. Based on this, the possible reaction network for T and BT hydrodesulfurization over the catalysts are proposed.