Structure of molybdenum oxide clusters prepared in zeolite cages

Molybdenum hexacarbonyl entrapped in NaY zeolite was oxidized with molecular oxygen by UV-irradiation at room temperature or by thermal treatment at 343–373 K. Both oxidation procedures resulted in the identical molybdenum(VI) oxide; molybdenum dimer species (Mo-Mo distance: 0.321 nm). The Mo-Mo bonding of the oxide species was degraded on an evacuation at 673 K, while it was considerably stable in the presence of gaseous oxygen.     

新型含USL分子筛柴油加氢精制催化剂的研究

制备了NiW/Al₂O₃-USL系列催化剂,采用XRD、NH₃-TPD、UV-vis DRS(紫外-可见漫反射光谱)以及BET比表面积分析等多种技术对催化剂的基本物性进行表征,并以柴油为原料,在高压加氢微反装置中进行催化剂的加氢脱硫(HDS)活性评价。结果表明,在相同反应条件下具有适宜USL添加量的NiW/Al₂O₃-USL^-1催化剂的加氢脱硫效果优于参比的商业加氢催化剂,并且所得柴油产品硫含量<10 μg·g^-1,满足世界燃油规范IV类的标准。     

Redox chemistry of highly dispersed rhodium in zeolite NaY

NaY zeolite exchanged with [Rh(NH₃)₅Cl]²⁺ ions have been studied using temperature programmed oxidation (TPO), temperature programmed reduction (TPR), and Fourier transformed infrared spectroscopy. The TPO profiles show that ammine ligands in NaY encaged [Rh(NH₃)₅Cl]²⁺ are destroyed above 300 °C, whereas the Rh precursor ion remains intact after calcination at 200 °C. TPR profiles in conjunction with the CO_ads IR spectra show that the reducibility of Rh by H₂ is largely controlled by the concentration of the surface protons, i.e. Rh³⁺+H₂Rh⁺+2H⁺ Rh⁺ + 1/2H₂Rh⁰+H⁺ In the presence of ammonia, the protons are neutralized and Rh³⁺ is reduced to Rh⁰. However, reduction remains incomplete when the concentration of protons is high. The ammonia was provided either by NH₃ admission or by conservation of ammine ligands by controlled calcination. CO adsorption does not lead to reoxidation of Rh⁰ particles to Rh⁺ ions.     

ZSM-5-MCM-41复合分子筛负载NiMo双金属硫化物催化剂的制备及其加氢脱硫性能

以十六烷基三甲基溴化铵作为模板剂,将ZSM-5用不同浓度氢氧化钠处理脱硅,并利用重结晶法成功合成了具有较强酸性的ZSM-5-MCM-41复合分子筛〔记为ZMC-M(x), M=1.5,2.0,2.5 mol/L NaOH, x=n(SiO2)/n(Al2O3) 〕。然后,采用浸渍法制备了MoS2/ZMC和Ni-MoS2/ZMC催化剂。考察了不同NaOH处理浓度对复合分子筛ZMC结构和性质的影响。同时以噻吩/十四烷为模型化合物,考察了ZMC的硅铝比、NiMo双金属硫化物对噻吩加氢脱硫的影响。结果表明,随着NaOH浓度的增加,复合分子筛ZMC会生成更多的介孔相,但是过高的NaOH处理浓度会破坏ZSM-5的结构。因此确定了最佳NaOH处理浓度为2.0 mol/L。随着ZMC的硅铝比增加,催化剂加氢脱硫活性增加提高,并且复合分子筛负载NiMo双金属硫化物的加氢脱硫性能优于复合分子筛负载MoS2。在H2压力3 MPa、温度280 ºC、40 ml(1000 ug/L)噻吩/十四烷的条件下,20%MoS2/ZMC-2.0(70)和20%Ni-MoS2/ZMC-2.0(70)催化剂对噻吩的转化率脱硫率分别达到84.1 %和95.2 %。     

Catalytic activity of Co,Mo and CoMo supported on NaY zeolite: hydrodesulfurization of gas oil at high pressure

Three series of Co/NaY, Mo/NaY and CoMo/NaY zeolite catalysts with variable metal content, prepared by a conventional impregnation method, were characterized by XRD, IR spectroscopy (oxide state) and acidity measurements (sulfide state), and tested in hydrodesulfurization (HDS) of gas oil at high pressure in the temperature range 275–350°C. The combined results of surface area, XRD and IR showed that in the catalysts with high metal loading a small loss in crystallinity and a partial blockage of the zeolite supercages were produced by Mo oxide species. The number of acid sites, which was lower for the Co/NaY than for the Mo/NaY catalysts, increased with increasing Co or Mo loading, but the strength of the acid sites was stronger for the Co/NaY series. HDS specific activities of the Co/NaY and Mo/NaY monometallic catalysts reached a maximum at very low loadings of Co ( 0.10 at. nm^–2) or Mo ( 0.16 at. nm^–2) by the double action of the metal sulfide species and the strong acid sites generated on the zeolite by the Co or Mo incorporation. In the binary CoMo/NaY catalysts, the synergy between Co and Mo species was significant for high Mo contents only.     

An X-ray absorption study on the local structures of highly dispersed supported titanium oxides prepared by a CVD method

Titanium oxides supported on SiO₂ and Al₂O₃ prepared by a CVD method have been characterized by XANES/EXAFS technique. Titanium species on SiO₂ are highly dispersed in a tetrahedral coordination. Titanium species on Al₂O₃ are also highly dispersed in fivefold coordination. High dispersion was substantiated by their photoluminescence emitted by excitation at 300–350 nm.     

Synergism between Brønsted acid sites and metal sulfide particles in the hydrodesulfurization of thiophene on ultrastable Y zeolite catalysts W/USY and Ni/USY

The influence of the acidity of ultrastable Y (USY) zeolite-supported tungsten or nickel sulfide catalysts, prepared at different pH values, on thiophene hydrodesulfurization activity has been studied. The acidity affects the catalysts' deactivation. The results of the initial activity clearly show a synergic effect between the metal sulfide centers and the Brønsted acid sites present in the zeolites. © 1998 SCI     

Comparison of (non)-sulfided NiNaY zeolite catalysts prepared by ion-exchange and impregnation by xenon adsorption and129Xe NMR

Ni²⁺ exchanged and NiCl₂ impregnated non-sulfided and sulfided NaY zeolites were characterized by xenon adsorption isotherms,¹²⁹ Xe NMR and thiophene hydrodesulfurization. The nickel species are located mainly inside the micropores of the zeolites in all samples. Ion-exchange results in a more homogeneous distribution of these species than impregnation. This explains their lower hydrodesulfurization activity compared to the ion-exchanged samples.On leave of absence from the Institute of Isotopes, Budapest, Hungary.     

The catalytic activity of Ni/W bimetallic sulfide nanostructured catalysts in the hydrodesulfurization of dibenzothiophene

Two types of catalysts containing NiW bimetallic sulfide nanostructures were prepared by a chemical method employing ammonium thiotungstate and nickel nitrate as metal-sulfide precursors followed by sulfidation in H₂S/H₂ at 400 °C. The nanostructures were grown with excess of Ni, at atomic ratio R = 0.75, 0.85 (R = Ni/Ni + W). High resolution electron microscopy (HRTEM) micrographs revealed the formation of two types of nanostructures, nickel sulfide nanoparticles and long nanorods of tungsten suboxide, both coated by WS₂ layers. The Ni/W catalyst containing mostly nanorods presented twice the catalytic activity (pseudo-zero order constant rate k = 12 × 10⁻⁷ mol/s.g) of the Ni/W catalyst containing nanoparticles (k = 6.3 × 10⁻⁷ mol/s.g) with a low selectivity for tetrahydrodibenzothiophene (THDBT) and high selectivity to cyclohexylbenzene (CHB, 50 mol%). In turn the Ni/W catalyst containing nanoparticles presented a catalytic activity comparable to a Ni/Mo catalyst without inorganic fullerene (IF) nanostructures (k = 7.2 × 10⁻⁷ mol/s.g) but with higher selectivity for hydrogenation to THDBT, (14 mol%) than the sample with nanorods.     

Characteristics of intermetallic NdNi5 as an unsupported catalyst in thiophene hydrodesulfurization

A systematic research is carried out on intermetallic NdNi₅ for the hydrodesulfurization (HDS) of thiophene. The effect of calcination and presulfidation of intermetallic NdNi₅ on thiophene HDS was examined and property changes of the catalyst during calcination, presulfidation, and reaction were observed by XRD, SEM, and surface area techniques. The intermetallic compound of NdNi₅ is disintegrated to fine powder and recrystallized to Nd/Ni oxide and sulfide by calcination, presulfidation, and reaction. A model for the surface area increase of the catalyst during calcination, presulfidation, and reaction was proposed and the role of neodymium was explained.     

富氧条件Co/H-ZSM-5催化剂上CH4选择催化还原NO的研究

采用离子交换法制备了一系列具有不同硅铝比和不同Co负载量的Co/H-ZSM-5催化剂样品。富氧条件下考察了硅铝比、Co负载量、空速、O₂浓度及酸位对催化剂选择催化还原活性的影响。并对其进行了XRD、BET、H₂-TPR和DRS-UV-vis等表征。催化结果表明，催化剂的催化活性随Co负载量的增加而增加，随硅铝比的增加而减少；NO转化率随着空速的增加而降低。O₂体积分数为2%时，NO达最大转化率。表征结果表明，Co²⁺为活性中心，酸中心的存在对催化活性有一定的促进作用。     

Effect of synthetic reducing agents on morphology and ORR activity of carbon-supported nano-Pd–Co alloy electrocatalysts

Three different reducing agents, ethylene glycol (EG), formaldehyde (HCHO), and sodium borohydrate (NaBH₄), were used in the synthesis of carbon-supported Pd–Co catalysts (Pd–Co/C–EG, Pd–Co/C–HCHO, and Pd–Co/C–NaBH₄, respectively). The differences among these three catalysts in morphology and electrocatalytic activity for oxygen reduction reaction (ORR) were observed and characterized using X-ray diffraction, energy dispersive X-ray analysis, transmission electron microscope, Fourier transform infrared spectra, surface cyclic voltametry, and rotating disk electrode technique. It was observed that by using a mild reducing agent such as EG, well-controlled and homogenous nucleation and growth could be achieved during the catalyst synthesis. With respect to the morphology and ORR activity of synthesized catalysts, the order of preferred reducing agents was found to be EG > NaBH₄ > HCHO. In order to improve activity and stability, the catalysts were heat-treated at temperatures ranging from 300 °C to 700 °C. It was found that for all three Pd–Co/C catalysts, a temperature of 300 °C gave the best catalyst morphology and ORR activity. The investigation in ORR kinetics catalyzed by these three catalysts revealed that all three could catalyze a four-electron reduction of oxygen to produce water. The average Tafel slope of the catalyzed ORR was found to be 70 mV/dec, suggesting that the determining step in the mechanism is a one-electron transfer process. In an effort to validate the theoretical explanation, the ORR activity as a function of particle size, Pd lattice constant, and Pd–Pd bond distance of the three Pd–Co/C catalysts was also investigated. In addition, in the case of EG as reducing agent the impregnation–reduction method employed in this work was simplified, because the need for a stabilizing agent usage was removed and water was used as the solvent.     

Realizing the enhancement of interfacial interaction in semicrystalline polymer/filler composites via interfacial crystallization

Polymer/filler composites have been widely used in various areas. One of the keys to achieve the high performance of these composites is good interfacial interaction between polymer matrix and filler. As a relatively new approach, the possibility to enhance polymer/filler interfacial interaction via crystallization of polymer on the surface of fillers, i.e., interfacial crystallization, is summarized and discussed in this paper. Interfacial crystallization has attracted tremendous interest in the past several decades, and some unique hybrid crystalline structures have been observed, including hybrid shish-kebab and hybrid shish-calabash structures in which the filler served as the shish and crystalline polymer as the kebab/calabash. Thus, the manipulation of the interfacial crystallization architecture offers a potential highly effective route to achieve strong polymer/filler interaction. This review is based on the latest development of interfacial crystallization in polymer/filler composites and will be organized as follows. The structural/morphological features of various interfacial crystallization fashions are described first. Subsequently, various influences on the final structure/morphology of hybrid crystallization and the nucleation and/or growth mechanisms of crystallization behaviors at polymer/filler interface are reviewed. Then recent studies on interfacial crystallization induced interfacial enhancement ascertained by different research methodologies are addressed, including a comparative analysis to highlight the positive role of interfacial crystallization on the resultant mechanical reinforcement. Finally, a conclusion, including future perspectives, is presented.     

Functionalization of carbon nanomaterials for advanced polymer nanocomposites: A comparison study between CNT and graphene

The allotropes of carbon nanomaterials (carbon nanotubes, graphene) are the most unique and promising substances of the last decade. Due to their nanoscale diameter and high aspect ratio, a small amount of these nanomaterials can produce a dramatic improvement in the properties of their composite materials. Although carbon nanotubes (CNTs) and graphene exhibit numerous extraordinary properties, their reported commercialization is still limited due to their bundle and layer forming behavior. Functionalization of CNTs and graphene is essential for achieving their outstanding mechanical, electrical and biological functions and enhancing their dispersion in polymer matrices. A considerable portion of the recent publications on CNTs and graphene have focused on enhancing their dispersion and solubilization using covalent and non-covalent functionalization methods. This review article collectively introduces a variety of reactions (e.g. click chemistry, radical polymerization, electrochemical polymerization, dendritic polymers, block copolymers, etc.) for functionalization of CNTs and graphene and fabrication of their polymer nanocomposites. A critical comparison between CNTs and graphene has focused on the significance of different functionalization approaches on their composite properties. In particular, the mechanical, electrical, and thermal behaviors of functionalized nanomaterials as well as their importance in the preparation of advanced hybrid materials for structures, solar cells, fuel cells, supercapacitors, drug delivery, etc. have been discussed thoroughly.