The modification of titanium in mesoporous silica for Co-based Fischer–Tropsch catalysts

Ordered SBA-15 mesoporous silica with incorporated titanium was successfully synthesized via a one-pot hydrothermal crystallization method. The characterization including powder X-ray diffraction, Brunauer–Emmett–Teller, transmission electron microscope, temperature-programmed reduction, temperature-programmed desorption, Fourier transform infrared and ultraviolet-visible-near infrared spectrometer was performed to explore the physical and chemical structures of both the supports and the catalysts. The results showed that titanium was successfully incorporated into the mesoporous silica framework with a limited amount of titanium (Si/Ti > 20), and the mesoporous structure was retained. However, the increased titanium content inevitably resulted in the formation of anatase TiO ₂ particles on the support surface. The increased incorporated titanium strengthened the interactions between cobalt species and supports, which was favorable for the cobalt species dispersion, despite the limited cobalt oxide reducibility. The enhanced metal-support interactions were beneficial for the CO/H₂ ratio at the active cobalt sites, which facilitated the formation of more C₅₊ hydrocarbons. This study provides a promising method for support modification with incorporated-heteroatoms for the rational development of Fischer–Tropsch catalysts.     

纳米粒度金属氧化物催化剂制备方法的研究进展

金属氧化物是一类重要的催化剂,在催化领域中已得到广泛的应用,将金属氧化物纳米化后,其催化性能更加优良,可以预见,纳米金属氧化物将是催化剂发展的重要方向。综述了近年来国内外金属氧化物催化剂的研究进展,讨论了纳米金属氧化物催化剂的各种制备方法,如溶胶 凝胶法、水解法、水热合成法、 微乳法、沉淀法、固相反应法、超临界干燥法、微波固相法、热分解法、燃烧合成法和撞击流反应 沉淀法等,并对各种方法的特点作了总结和归纳。     

A ternary mechanism for the facilitated transfer of metal ions onto metal–organic frameworks: implications for the ‘‘versatility’’ of these materials as solid sorbents

Although metal–organic frameworks offer a new platform for developing versatile sorption materials, yet coordinating the functionality, structure and component of these materials remains a great challenge. It depends on a comprehensive knowledge of a “real sorption mechanism”. Herein, a ternary mechanism for U(VI) uptake in metal–organic frameworks was reported. Analogous MIL-100s (Al, Fe, Cr) were prepared and studied for their ability to sequestrate U(VI) from aqueous solutions. As a result, MIL-100(Al) performed the best among the tested materials, and MIL-100(Cr) performed the worst. The nuclear magnetic resonance technique combined with energy-dispersive X-ray spectroscopy and zeta potential measurement reveal that U(VI) uptake in the three metal–organic frameworks involves different mechanisms. Specifically, hydrated uranyl ions form outer-sphere complexes in the surface of MIL-100s (Al, Fe) by exchanging with hydrogen ions of terminal hydroxyl groups (Al-OH₂, Fe-OH₂), and/or, hydrated uranyl ions are bound directly to Al(III) center in MIL-100(Al) through a strong inner-sphere coordination. For MIL-100(Cr), however, the U(VI) uptake is attributed to electrostatic attraction. Besides, the sorption mechanism is also pH and ionic strength dependent. The present study suggests that changing metal center of metal–organic frameworks and sorption conditions alters sorption mechanism, which helps to construct effective metal–organic frameworks-based sorbents for water purification.     

Denitrification performance and sulfur resistance mechanism of Sm–Mn catalyst for low temperature NH3-SCR

MnO_x and Sm–Mn catalysts were prepared with the coprecipitation method, and they showed excellent activities and sulfur resistances for the selective catalytic reduction of NO_x by NH₃ between 50 and 300 °C in the presence of excess oxygen. 0.10Sm–Mn catalyst indicated better catalytic activity and sulfur resistance. Additionally, the Sm doping led to multi-aspect impacts on the phases, morphology structures, gas adsorption, reactions process, and specific surface areas. Therefore, it significantly enhances the NO conversion, N₂ selectivity, and sulfur resistance. Based on various experimental characterization results, the reaction mechanism of catalysts and the effect of SO₂ on the reaction process about the catalysts were extensively explored. For 0.10Sm–Mn catalyst, manganese sulfate and sulfur ammonium cannot be generated broadly under the influence of SO₂ and the amount of surface adsorbed oxygen. The Bronsted acid sites strengthen significantly due to the addition of SO₂, enhancing the sulfur resistance of the 0.10Sm–Mn catalyst.     

负载型金属配合物催化硅氢加成反应研究进展

硅氢加成反应是有机硅化学中制备含Si-C化合物的一类重要反应。综述了硅氢加成反应中负载型金属配合物催化剂的种类、催化性能及催化机理,并展望了此类反应的研究前景,表明探索价廉高效的硅氢加成催化体系将是这一领域的主要研究方向。     

后过渡金属烯烃聚合催化剂的研究进展

综述了以后过渡金属 (Ni,Pd ,Fe和Co)络合物为主催化剂的烯烃聚合催化剂的发现、沿革及研究进展 ,包括催化剂的合成、结构、性能、催化烯烃聚合机理等。     

硫化铂族金属加氢催化剂的研究进展

硫化铂族金属催化剂为可提高有机液相加氢反应选择性的高效催化剂,能提高含羰基、羟基和卤素等官能团化合物催化加氢反应的选择性,应用广泛。综述了国内外负载型Pt和Pd等硫化贵金属催化剂的制备方法,包括采用H_2S和Na_2S无机硫化以及Ph_2S和DMSO(二甲基亚砜)等有机硫化剂进行硫化;综述了Pt和Pd硫化贵金属催化剂在有机液相催化加氢体系中的应用;并对硫化Pt族金属催化剂的硫化机理和催化机理进行探讨,展望了硫化贵金属催化剂的应用前景。     

烯烃聚合后过渡金属催化剂负载化研究进展

综述了后过渡金属催化剂负载化方式和载体的种类及其催化特性,该催化剂载体包括无机载体、聚合物载体、自固载和介孔分子筛等。通过与均相催化剂性能的比较,进一步阐述了负载的目的和必要性。随着这一领域研究深入,将对后过渡金属催化剂工业化发展具有重要的意义。     

双金属氰化物催化剂在外循环反应器中的应用研究

介绍了双金属氰化物催化剂在1.5m3外循环生产装置上的工业应用试验情况。结果表明,该催化剂活性高,诱导期短,缩短了生产周期,提高了产品质量。     

基于超临界流体密度的烷基化内扩散影响动力学

利用烷基化反应实验数据和超临界流体密度计算数据,开展了考虑内扩散影响的烷基化反应动力学研究,采用优化计算方法进行模型参数估值,确定了烷基化反应速率常数、有效扩散系数、催化剂失活速率常数.研究结果表明,基于PengRobinsn(PR)方程计算流体密度的动力学模型在显著性水平α=0.01下有较高的实验数据拟合精度和模型可信度,说明该方法是计算超临界流体密度的较好方法.从有效因子大小可以看出,烷基化反应总体上处于中孔扩散阻力区.     

Sonogashira偶联反应的过渡金属催化剂研究进展

Sonogashira偶联反应是形成新的C—C键及炔基化的最有效方法之一,金属催化剂在其中起着重要的催化作用。综述了近年来Sonogashira偶联反应中新发展起来的过渡金属催化剂,重点介绍了新型钯类催化剂在绿色化中的应用,以及其它过渡金属催化剂在Sonogashira偶联反应中的应用。指出Pd/C催化剂有望成为Sonogashira反应工业化应用的生力军,并且,水的存在、合适的催化体系以及碱体系等反应条件的选择对改善反应的环境亲和性具有重要意义。     

Design and fabrication of non‐noble metal catalyst‐based air‐cathodes for metal‐air battery

In this paper, cost‐effective non‐noble metal catalyst‐based air‐cathodes are designed, developed, and fabricated for a metal‐air battery, particularly in a non‐toxic neutral solution environment (sodium chloride). The air‐cathode and its fabrication method comprise two gas diffusion layers (GDLs) bonded on to each side of the current collector (nickel mesh) by a rolling method, and a catalyst layer bonded on one GDL by a spraying method. The GDL paste consists of carbon powder and hydrophobic chemicals, and the catalyst layer contains non‐noble metal catalyst, carbon powder, and hydrophilic chemicals. Several characterization techniques such as DTA/TG thermal analysis, electrochemical impedance spectroscopy, linear sweep voltammetry, and their associated theories are used to understand the properties and performance of the developed air‐cathodes. The advantages of the current method of forming the air‐cathode can decrease the internal electronic resistance and gas flow restriction of the system, and therefore increase air permeability as well as water transportation to the reaction sites. By using such an integrated structure of an air diffusion cathode, the cost‐effectiveness in terms of materials and manufacturing compared to the commercial air‐cathode, and the overall fabrication procedure is achieved, and the method can be easily transferred into a continuous industrial manufacturing process.     

负载复合后过渡金属烯烃聚合催化剂研究进展

综述了负载和复合型后过渡金属烯烃聚合催化剂的研究进展。把后过渡金属催化剂负载化,可以适合现有工业生产的工艺要求,改善聚合物产品的形态结构、抑制粘釜现象等。用后过渡金属催化剂与其他过渡金属催化剂(如Ziegler-Natta催化剂、茂金属催化剂等)进行复合的目的主要是制备具有某些特定性能聚烯烃产物及使单一乙烯单体聚合制备支化聚乙烯。后过渡金属催化剂进行负载和复合后在改善聚烯烃产物性能、降低生产成本等方面有突出的优势．具有十分广阔的工业应用前景。     

甲醇合成气中羰基金属化合物对催化剂的影响及对策

羰基铁、羰基镍是导致铜基合成甲醇催化剂中毒的物质。详细论述了羰基铁、羰基镍的形成机理及对甲醇催化剂的影响,指出使用脱羰基铁、羰基镍吸附剂是延长催化剂使用寿命,提高甲醇产品质量的有效措施。     

新型后过渡金属烯烃催化剂的研究进展

综述了近年来－系列新型α－二亚胺型后过渡金属（Ni、Pd、Fe、Co）催化剂在烯烃聚合、极性单体共聚、烯烃齐聚、环烯烃加成聚合、烯烃活性聚合和聚烯烃纳米复合物等方面的最新进展。系统地阐述了不同的中心过渡金属离子、α－二亚胺骨架、骨架上的取代基和不同的聚合条件（温度、压力）分别对催化剂的聚合活性、聚烯烃支化率、聚合物分子量和分子量分布以及聚合产物的性质等影响，并且简要说明了这一类催化剂的制备方法和新特点。     

烯烃/极性单体共聚催化剂的研究进展

综述了烯烃和含极性基团的烯类单体共聚催化剂的研究进展。后过渡金属催化剂和稀土金属催化剂对共聚合有较好的催化活性,只要对配体结构进行优化或适当组合螯合配体与过渡金属共享电子,就可得到性能更好且适合工业生产的催化剂。     

甲醇合成气中羰基金属化合物对催化剂的影响及对策

羰基铁和羰基镍是铜基合成甲醇催化剂的毒物。论述了羰基铁和羰基镍的形成机理及对甲醇催化剂的影响,指出使用脱羰基铁、羰基镍吸附剂是延长催化剂使用寿命、增加甲醇产量和提高甲醇产品质量的有效措施。     

介孔碳材料及其负载金属催化剂的制备及应用研究进展

介孔碳材料具有较高比表面积、均一可控纳米孔分布和可调节的表面化学性能,在催化领域具有重要应用前景.综述了介孔碳材料及其负载金属催化剂的制备方法及催化应用进展.     

贵金属催化剂催化氧化处理氨氮废水的研究进展

概述了氨氮废水处理的必要性及传统处理技术存在的缺陷,重点综述了贵金属催化剂在氨氮废水催化氧化处理中的应用研究进展,并针对贵金属催化剂在研究应用过程中存在的不足之处,对贵金属催化剂材料的开发及其在工艺应用上的改进等提出了展望。