The reactions between SO2 and C2H2 (and C2H4) at elevated temperatures. A single-pulse shock tube investigation

The high-temperature reaction between sulfur dioxide and acetylene in an excess of argon was studied in a 1?in. i.d. single-pulse shock tube. Mixtures ranging from 1.81% to 5.40% SO₂ and 1.60% to 4.90% C₂H₂ were heated to reflected shock temperatures of 1550°–2150°K, for dwell times of about 0.6 msec and gas dynamically quenched. Total reaction densities were 0.89 to 5.4 × 10^?2 moles/1. The reaction products were analyzed by gas chromatography. A technique was developed for separating Ar, C₂H₄, C₂H₂, SO₂, CO, CO₂, H₂S, COS, and CS₂. The major products of the reaction are CO, H₂, CS₂, and sulfur. The products observed were compared with those predicted on the assumption that equilibrium was attained. Several preliminary experiments were carried out with ethylene-sulfur dioxide mixtures, and the results indicated that for this combination the sulfur dioxide probably reacted with the acetylene generated from the decomposition of the ethylene, rather than directly with the ethylene. The rate of decline in the sulfur dioxide content in C₂H₂-SO₂ mixtures was found to be approximately second order (total) and can be empirically represented by A mechanism is proposed to account for the overall reaction kinetics.     

改性Y型分子筛对FCC汽油脱硫性能的研究

采用液相离子交换法制备了Cu(I)Y、NiY、CeY分子筛,利用XRD、ICP/MS、N₂吸附脱附等技术对其物化性质进行了表征,使用固定床技术和色谱-硫化学发光检测(SCD)偶联技术系统考查了改性Y分子筛对FCC汽油的选择性吸附脱硫性能,着重探讨了FCC汽油选择性吸附脱硫过程中硫化物的脱除规律。结果表明,不同金属阳离子改性的Y分子筛对FCC汽油中不同硫化物选择性有所不同,对CeY分子筛:2-甲基-5-乙基噻吩<噻吩3硫醇< C₂噻吩<2或3-甲基噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,而NiY与Cu(I)Y选择性相同:C₃硫醇<2-甲基-5-乙基噻吩2噻吩<2或3-甲基噻吩<噻吩<苯并噻吩<3,4-二甲基噻吩≈2,3,4-三甲基噻吩<四氢噻吩,改性Y分子筛对噻吩及小分子烷基取代噻吩类硫化物的选择性较差。     

硫粉为硫源,多元醇辅助合成硫化钼纳米片

MoS₂ nanosheets are prepared with sulfur powder and Na₂MoO₄ by a one-pot two-phase method at 170-200 ℃ for 8 h. In addition, a three-step growth mechanism based on the aggregation and coalescence model is proposed. The reassembly of sulfur powder ensures the transformation from sulfur powder to H₂S to reduce Na₂MoO₄ and plays a key role in the successful preparation of MoS₂ nanosheets. The as-prepared MoS₂ nanosheets are rich in unsaturated sulfur atoms, probably resulting from the dislocation cores of the MoS₂ nanosheets, which have been found to be beneficial for hydrogen evolution reaction catalysis. The method and growth mechanism adopted in this study may be applied to other transition metal dichalogenides for similar structures. The facile and green method provides an alternative for the preparation of MoS₂ nanosheets.     

Kinetics and Mechanism of low-Temperature Oxidation of H2S with Oxygen in the gas Phase

The possibility of the formation of polysulfides during oxidation of H₂ S with oxygen on oxide catalysts has been checked, and the sequence of the reaction stages at temperatures below the sulfur dew point determined. The amount of polysulfides formed during H₂ S oxidation has been found to exceed significantly that obtained in the reaction of sulfur with H₂ S. Polysulfides are concluded to be intermediates in H₂ S oxidation to sulfur. The rate of formation of SO₂ from sulfur vapor is shown to be negligibly low at 100-200°C. A reaction scheme involving the formation of sulfur from polysulfides and the formation of sulfur dioxide by direct oxidation of H₂ S is suggested.     

Synthesis and Characterization of Ag2S Nanocrystals in Hyperbranched Polyurethane at Room Temperature

Ag₂S nanoparticles in hyperbranched polyurethane matrix were prepared through the in situ reaction with thioacetamide as the sulfur source at room temperature. Transmission electron microscopic analysis revealed a uniform spherical shape for Ag₂S nanoparticles, with an average size of about 4-10 nm and a narrow size distribution. X-ray powder diffraction and UV-vis spectroscopy were also used to characterize the obtained nanoparticles     

Metal carbonyl-promoted reactions of ferrocenylacetylene with sulfur to form thiophene, dithiine, thioketone and vinylthioketone derivatives

Photolysis of a hexane solution of ferrocenylacetylene and sulfur powder in presence of Cr(CO)₆ resulted in the formation of 2,6-diferrocenyldithiine and 2,5-diferrocenylthiophene. Similar reactions with Mo(CO)₆ or W(CO)₆ gave only the thiophene derivative. Formation of ferrocenyl-substituted thioketone complexes was observed in the reaction of ferrocenylacetylene with water and sulfur, in presence of W(CO)₆. Use of D₂O confirmed water as source of protons for the conversion of acetylenic CH to CH₃.     

A copper-catalyzed three-component reaction of alkenes,cycloketone oximes and DABCO·（SO2）2: Direct C（sp2）-H cyanoalkylsulfonylation

A copper-catalyzed three-component reaction of alkenes, cycloketone oximes and DABCO·（SO₂）₂ is developed, which provides a convenient route for the synthesis of diverse（E）-cyanoalkylsulfonyl alkenes in moderate to good yields with excellent regio-and stereoselectivity. A broad substrate scope with excellent functional group tolerance is observed. A plausible radical pathway is proposed, which involves copper-catalyzed ring-opening C–C bond cleavage of O-acyl oxime and inser...     

Preparation of magnetically supported chromium and sulfur co-doped TiO2 and use for photocatalysis under visible light

Novel magnetic chromium and sulfur co-doped TiO₂ photocatalysts (M-Cr/S/TiO₂) have been prepared by a sol?Cgel process, using magnetic hollow fly ash microspheres as support material. The crystal phase of M-Cr/S/TiO₂ was characterized by X-ray diffraction, UV?Cvisible absorption spectroscopy, and transmission electron microscopy. The photocatalytic activity of the photocatalysts was examined by photodegradation of methyl orange in aqueous solution under visible light irradiation. The results showed that chromium and sulfur co-doped catalysts (Cr/S/TiO₂) containing 0.60?% (atomic ratio) chromium and 1.2?% (atomic ratio) sulfur calcined at 450?°C for 2?h had high catalytic efficiency under visible irradiation. It is worth mentioning that the floating M-Cr/S/TiO₂ catalyst had greater photocatalytic activity than Cr/S/TiO₂ powder. Therefore, M-Cr/S/TiO₂ is a promising, high-performing, visible-light-driven photocatalyst.     

WS2纳米颗粒的合成及摩擦学性能研究

将自制的WO₃纳米颗粒前驱体与S粉混合,在自制的反应装置氢气氛中,于550～750 ℃下煅烧得到二硫化钨纳米颗粒,反应中用H₂代替H₂S以减少对周围环境的污染。该合成路线简单且产物纯度高。用XRD、SEM、TEM和HRTEM对二硫化钨纳米结构进行了表征和分析,并将WS₂纳米颗粒作为添加剂添加到N40基础油中,在MS-T3000摩擦磨损仪测试其摩擦学性能。结果显示:制备的二硫化钨颗粒平均粒径在50 nm以内,其形状为球形或类球形。WS₂纳米颗粒作为普通润滑油的纳米级固体添加剂表现出了较优异的摩擦学性能。     

杂原子Y分子筛的二次合成及其吸附脱硫性能

采用液-固相同晶取代反应制备了骨架含Ga的Y型分子筛, 并对其吸附脱硫性能进行了研究. 在室温, 空速为7 h−1的条件下, 镓化Y型分子筛([Ga]AlY)处理噻吩、四氢噻吩、4,6-二甲基二苯并噻吩(4,6-DMDBT)正壬烷溶液(硫含量500 μg•g−1), 每克吸附剂吸附硫的量分别为7.7、17.4、14.5 mg. 采用密度泛函理论(DFT)中的广义梯度近似方法(GGA)计算各分子中硫原子上的电荷数, 噻吩中硫原子的电荷数为−0.159, 而4,6-DMDBT和四氢噻吩分别为−0.214、0.298. 四氢噻吩和4, 6-DMDBT中硫原子上的电子密度大于噻吩中硫原子上的电子密度, 这就使得四氢噻吩和4,6-DMDBT中的硫原子与吸附位间的作用会远大于噻吩中的硫原子与吸附位间的作用, 吸附容量必然会大很多. 采用[Ga]AlY处理抚顺石油二厂的催化裂化汽油(硫含量：299 μg•g−1), 每克吸附剂处理2.1 mL汽油时, 处理后汽油的硫含量为54.8 μg•g−1, 说明[Ga]AlY对汽油脱硫有一定的效果.     

Thiophene Hydrogenation to Tetrahydrothiophene over Tungsten Sulfide Catalysts

Independent reactions of thiophene reduction to tetrahydrothiophene and thiophene hydrogenolysis to form hydrogen sulfide and C₄ hydrocarbons are shown to occur over supported tungsten sulfide catalysts and unsupported tungsten sulfide at an elevated temperature and a high pressure. The highest rate of tetrahydrothiophene formation over the supported catalysts is observed when alumina was used as a support, and the lowest reaction rate is found when silica gel was used as a support. Both catalysts are less active than unsupported tungsten disulfide. The rate of thiophene hydrogenation over tungsten disulfide increases with increasing thiophene concentration and hydrogen pressure and is inhibited by tetrahydrothiophene. The selectivity to tetrahydrothiophene is constant (70–90%) in the whole range up to high thiophene conversions. The high selectivity over tungsten sulfide catalysts is suggested to be due to the reaction pathway through thiophene protonation mediated with the surface SH groups and to the inhibition of hydrogenolysis.     

Solvent-free coupling of aldehyde,alkyne, and amine over a versatile catalyst: Ag-functionalized mesoporous S,P-doped g-C3N4

In the present study, we introduce mesoporous g-C₃N₄/Ag co-doped with P and S which was designed and acquired by using mesoporous silica (SBA-15) as a hard templating agent and thiourea and chitosan phosphate as the dopants. The prepared catalyst was completely identified by FT-IR (Fourier-transform infrared spectroscopy), XRD (X-ray powder diffraction), FE-SEM (field-emission scanning electron microscopy), EDX (energy-dispersive spectroscopy), TEM (transmission electron microscopy), and Raman spectroscopy. The efficiency of the synthesized catalyst was evaluated toward the three-component coupling reaction, frequently named as A3 coupling. The higher activity of the prepared catalyst is because of the synergistic effects of phosphorus and sulfur co-doped together with Ag deposition. The desired products were achieved by an environmentally safe catalyst under the optimized conditions in high yields and short reaction time ranges.

     

Quantum chemical study of MoS2 hydro desulfurization catalysts

The electronic and bonding properties of MoS₂, thiophene, tetrahydrothiophene and their related adsorption systems are studied by DV-X_α calculations on model clusters. The calculated results indicate that for MoS₂ the Mo-S bonding is not very strong. The Mo atoms are held together through bonding with S and the S atoms are held together through bonding with Mo. Three types of S atoms may be distinguished by their location, coordination and bond type. The d band of MoS₂ is different from that of Group VIII transition metals and markedly influence its adsorptive properties. The adsorption of a thiophene molecule on MoS₂ is weak, the interaction is complicated, and little activation is indicated. It may be inferred that thiophene is first hydrogenated to tetrahydrothiophene and then desulfurized.     

Zur Kinetik der Bildung von Na2PdC2

On the Kinetics of the Formation of Na₂PdC₂ The kinetics of the formation of Na₂PdC₂ from Na₂C₂ and palladium were investigated by means of time‐resolved synchrotron powder diffraction (powder diffractometer at beamline B2, HASYLAB/Hamburg) at different temperatures in the range 513 to 533 K. By Rietveld analysis of the resulting diffraction patterns the molar ratio of Na₂PdC₂ was determined in dependence of the reaction time. The calculated crystallization curves were analysed by using the Avrami‐Erofe'ev model for the kinetics of solid‐state reactions. A diffusion mechanism was found and an activation energy of 480(120) KJ/mol was determined. Reasons for the low accuracy of this value are discussed.     

CO2 laser-induced interaction between sulfur hexafluoride and carbon disulfide

Interaction between carbon disulfide and sulfur hexafluoride is excited by cw CO₂ laser radiation and has been investigated for different ratios over a pressure range from 3.1 to 34.6 kPa. The reaction yields sulfur tetrafluoride, sulfur, carbon, thiocarbonyl fluoride, tetrafluoromethane and hexafluoroethane, the ratio of these latter products is dependent on the partial pressure of sulfur hexafluoride in the initial CS₂-SF₆ mixture. Interaction is considered to include both the SF₆-sensitized decomposition of carbon disulfide and reaction between sulfur hexafluoride and carbon disulfide.     

Thermal Behaviour of a TiO2—ZrO2 Microcomposite Prepared by Chemical Coating

A microcomposite powder in the system TiO₂—ZrO₂ as a precursor of zirconium titanate (ZT) materials has been studied by thermal methods (DTA-TG) and X-ray diffraction (XRD). The microcomposite powder has been prepared by chemical processing of crystalline TiO₂ (rutile, 10 mass% anatase),as inner core, coated with in situ precipitated amorphous hydrated zirconia gel, asouter core. The morphology and chemical composition of the resultant powders has been examined by SEM-EDX (Scanning electron microscopy-energy dispersive X-ray spectroscopy). Thermal behaviour of the microcomposite powder was reported, showing the dehydration and dehydroxylation of the zirconia gel, the crystallization into metastable cubic/tetragonal zirconia at temperatures 400—470°C, and the feasibility of preparing ZT powder materials by progressive reaction of TiO₂ and ZrO₂ at higher temperatures (1400°C).This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of H<Subscript>2</Subscript> in the synthesis of COS using liquid sulfur and CO or CO<Subscript>2</Subscript> as reactants

The synthesis of COS from CO, CO₂ and liquid sulfur in the presence and absence of hydrogen was explored. The reaction of H₂ with liquid sulfur produced H₂S and polysulfanes, which increase the reactivity of liquid sulfur and provide alternative complementary reaction routes for the formation of COS. The reaction from CO₂ proceeds by forming CO as intermediate. Elevated pressure favors formation of COS from both carbon oxides due to the increasing residence time and the saturation of gases in the liquid. Above 350 °C, the solubility of H₂S in sulfur and the hydrogenation of COS limit the conversion of CO. The approach provides a highly efficient method for the preparation of COS under mild reaction conditions, without using a catalyst or water adsorbents.     

Interaction of petroleum-relevant organosulfur compounds with TiO2(110)

The interaction of two sets of structurally related molecules, thiophenol/thioanisole, and thiophene/tetrahydrothiophene, with vacuum-annealed and ion-bombarded TiO(2)(110) surfaces has been studied using a combination of temperature-programmed reaction spectroscopy (TPRS) and X-ray photoelectron spectroscopy (XPS). All thioethers studied were observed to adsorb and desorb from both surfaces without producing reaction products, while thiophenol, the only species studied containing a S-H bond, reacted with both surfaces. Approximately 25% of surface bound thiophenol decomposed over the vacuum-annealed surface. On the bombarded surface, thiophenol both decomposed into surface-bound C(x)H(y)/S fragments, and reacted to form benzene, which desorbed from the surface at 400 K. We propose that phenylthiolate formation on the bombarded surface leads to the observed production of benzene. These results highlight the importance of defects in the reactivity of titania, and lay the foundation for the study of larger, refractory sulfur compounds present in fuel.     

Comparative Studies on the Deactivation and Regeneration of TiO2 Nanoparticles in Three Photocatalytic Oxidation Systems: C7H16, SO2, and C7H16-SO2

Three photocatalytic oxidation (PCO) systems: C₇H₁₆-O₂, SO₂-O₂ and C₇H₁₆-SO₂-O₂ were carried out with the aid of UV-illuminated TiO₂ nanoparticles at room temperature in a batch reactor. In C₇H₁₆-O₂-TiO₂ system, no catalyst deactivation was observed, while for SO₂-O₂-TiO₂ and C₇H₁₆-SO₂-O₂-TiO₂ systems, the photocatalytic activity of used TiO₂ powder showed decreasing and eventually no activity after used consecutively. The reaction products such as sulfur trioxide or sulfuric acid adsorbed onto the surface of TiO₂ catalyst were poisoning species. Photocatalytic activity of the deactivated TiO₂ powder could be regenerated by sonicating treatment with water and methanol for the two systems, respectively.     

Coaxial Carbon/MnO2 Hollow Nanofibers as Sulfur Hosts for High‐Performance Lithium‐Sulfur Batteries

Lithium‐sulfur (Li‐S) batteries have recently attracted a large amount of attention as promising candidates for next‐generation high‐power energy storage devices because of their high theoretical capacity and energy density. However, the shuttle effect of polysulfides and poor conductivity of sulfur are still vital issues that constrain their specific capacity and cyclic stability. Here, we design coaxial MnO₂‐graphitic carbon hollow nanofibers as sulfur hosts for high‐performance lithium‐sulfur batteries. The hollow C/MnO₂ coaxial nanofibers are synthesized via electrospinning and carbonization of the carbon nanofibers (CNFs), followed by an in situ redox reaction to grow MnO₂ nanosheets on the surface of CNFs. The inner graphitic carbon layer not only maintains intimate contact with sulfur and outer MnO₂ shell to significantly increase the overall electrical conductivity but also acts as a protective layer to prevent dissolution of polysulfides. The outer MnO₂ nanosheets restrain the shuttle effect greatly through chemisorption and redox reaction. Therefore, the robust S@C/MnO₂ nanofiber cathode delivers an extraordinary rate capability and excellent cycling stability with a capacity decay rate of 0.044 and 0.051 % per cycle after 1000 cycles at 1.0 C and 2.0 C, respectively. Our present work brings forward a new facile and efficient strategy for the functionalization of inorganic metal oxide on graphitic carbons as sulfur hosts for high performance Li‐S batteries.