多环芳烃在贵金属催化剂上竞争加氢反应的研究

采用水蒸汽脱铝获得了超稳Y载体, 并用离子交换法制备了金属含量约为0.8 wt%的双贵金属催化剂. 用NH₃程序升温脱附、X射线衍射、N₂吸附-脱附等方法表征了载体和催化剂. 以萘、蒽、芘加氢为模型反应, 在高压反应釜中研究了催化剂的加氢活性以及它们之间竞争加氢的反应. 结果表明, 催化剂具有深度加氢的能力. 萘与蒽竞争加氢的结果表明, 蒽的加氢活性高于萘加氢活性, 并且蒽抑制萘加氢, 萘抑制了八氢蒽向全氢蒽的转化. 说明对于分子动力学直径相当的混合体系中, 多环物质抑制少环物质的加氢. 分子动力学直径不同的萘与芘加氢结果表明, 萘的转化率始终高于芘的转化率, 并且单和混合体系中萘和芘的转化率变化程度不大, 说明分子能否扩散进入分子筛孔道内也是影响加氢活性的重要因素.     

分子筛在加氢脱硫催化剂深度脱硫方面的应用

本文综述了分子筛对加氢脱硫催化剂深度脱硫性能的影响,对分子筛基加氢脱硫催化剂上涉及含硫大分子4,6-二甲基二苯并噻吩(4,6-DMDBT)加氢脱硫反应的研究进展作了总结。主要介绍了微孔分子筛、介孔分子筛、微介孔复合分子筛和纳米分子筛在加氢脱硫催化剂针对4,6-DMDBT加氢脱硫反应方面的应用进展。简要介绍了分子筛基加氢脱硫催化剂上4,6-DMDBT加氢脱硫反应的反应途径、反应机理及抑制过度裂化反应的措施。最后展望了该研究领域的发展前景。     

贵金属固体催化剂的纳米结构及催化性能

 综述了贵金属催化剂纳米结构的形成和制备方法,以及催化活性与纳米粒子尺寸的关系. 还以负载型双金属催化剂为例,介绍了催化剂中的短程有序结构.     

低温燃料电池贵金属催化剂的老化

催化剂的老化是导致燃料电池性能衰减的重要因素之一.对于低温燃料电池,贵金属催化剂的老化主要体现在粒径的增长、金属氧化态的改变、组分的迁移和流失以及碳载体的腐蚀四个方面.本文综述了低温燃料电池贵金属催化剂老化方面的最新研究进展,探讨了导致催化剂老化的主要原因.     

贵金属催化剂上氢气选择性催化还原NOx

NO_x的控制对于改善大气环境质量具有重要意义,而氢气选择性催化还原(H₂-SCR)NO_x作为一种高效环保的脱硝技术而备受关注。本文总结概述了近年来贵金属催化剂在H₂-SCR脱硝反应中的研究进展,首先介绍了H₂-SCR反应机理,在此基础上分别论述了影响贵金属催化剂性能的因素(如活性组分、载体类型、助剂添加及组分存在形式等)及催化剂结构与性能的构效关系。最后,针对目前存在的问题展望了H₂-SCR脱硝未来的发展方向。     

Preparation, Characterization and Catalysis of Intrazeolite Molybdenum, Cobalt and Cobalt–Molybdenum Sulfide Clusters: A Molecular Approach to Hydrodesulfurization Catalysts

Better understandings of the nature of Co–Mo sulfide catalysts are of great importance to a rational design of highly active hydrodesulfurization catalysts on a molecular level. Synthesis of uniform binary sulfide clusters well-defined in structure and thermally stabilized on a support is desirable for such purposes. In the present study, successful preparations, using metal carbonyls as precursors, of Mo, Co and Co–Mo sulfide clusters encaged in zeolite are reported. The structure, location and catalytic properties of the clusters are described on the basis of XPS, XAFS, XRD, XRF, IR, HREM and adsorptions of benzene and NO. Implications for the generation of catalytic synergy between Co and Mo sulfides are presented in brief. It is suggested that the host–guest interactions between zeolite framework oxygens and precursor molecules and product clusters are crucial to the size and structure of the intrazeolite clusters.     

贵金属助剂对费-托合成用钴基催化剂的促进作用

贵金属助剂促进的费-托合成用钴基催化剂具有高活性和长链烃(C₅⁺)选择性优越等特点,被广泛应用于由合成气制清洁燃料的合成反应中。 本文重点讨论了贵金属助剂对活性钴物种的结构（还原度、分散度、双金属颗粒或合金的构成）, 钴基催化剂稳定性以及其对费-托合成的反应速率和产物选择性的影响规律。     

贵金属纳米粒子/硅纳米线复合纳米材料的制备及其催化性能研究

以十二烷基硫酸钠(SDS)作为保护剂, 利用贵金属阳离子(Mⁿ⁺)与HF处理后的硅纳米线(SiNWs)之间的氧化还原反应, 在SiNWs表面负载了贵金属纳米粒子. 通过调控SDS/Mⁿ⁺物质的量比、反应物浓度、反应温度等实验参数, 制备出了金属纳米粒子粒径均一且负载密集的AuNPs/SiNWs, PtNPs/SiNWs复合材料. 将AuNPs/SiNWs复合材料应用在亚甲基蓝的还原反应, 实验结果显示, 60 min内AuNPs/SiNWs可以将55%的亚甲基蓝还原, 表明AuNPs/SiNWs具有良好的催化活性. 这种复合材料易于从反应溶液中分离出来, 可以实现纳米催化剂的循环使用.     

Pd/ZSM-5/MCM-41催化剂加氢脱硫性能研究

本工作将三种材料：全硅MCM-41 （Si-MCM-41）、通过机械混合Si-MCM-41和HZSM-5得到的Z-MCM-41-M、通过在HZSM-5外部包覆Si-MCM-41制备得到的Z-MCM-41,采用XRD、N₂吸附-脱附、NH₃-TPD、Py-IR手段进行了表征.分别以这些材料为载体,制备出负载型贵金属Pd催化剂,以二苯并噻吩（DBT）为模型化合物,在固定床反应器上进行加氢脱硫（HDS）性能考察.反应结果表明,载体的表面积或分散程度并不是影响负载型Pd催化剂HDS性能的关键性因素,催化剂的HDS性能受到载体的孔尺寸和载体的酸性双重影响.负载在酸性载体上表现出较好的HDS性能和加氢选择性,与溢流氢有关.其中,在三种催化剂中,Pd/Z-MCM-41催化剂表现出最高的HDS活性和优异的加氢活性,说明在载体的介孔孔道结构中引入微孔的酸中心对提高加氢脱硫活性有重要影响,仅靠机械混合方式制备的载体不能将介孔的孔道优势与微孔的酸性优势表现出来,不能产生较好的协同催化作用,具有介孔孔道结构和适中酸性的Z-MCM-41复合材料是潜在的贵金属加氢脱硫催化剂载体.     

Electrodynamics of Noble Metal Nanoparticles and Nanoparticle Clusters

In this paper we examine the electrodynamics of silver nanoparticles and of clusters of nanoparticles, with an emphasis on extinction spectra and of electric fields near the particle surfaces that are important in determining surface-enhanced Raman (SER) intensities. The particles and clusters are chosen to be representative of what has been studied in recent work on colloids and with lithographically prepared particles. These include spheres, spheroids, truncated tetrahedrons, and clusters of two or three of these particles, with sizes that are too large to be described with simple electrostatic approximations but small compared to the wavelength of light. The electrodynamics calculations are mostly based on the discrete dipole approximation (DDA), which is a coupled-finite element approach which produces exact or nearly exact results for particles of arbitrary size and shape if fully converged. Mie theory results are used to study the validity of the DDA for spherical particles, and we also study the validity of the modified long wavelength approximation (MLWA), which is based on perturbative corrections to the electrostatic limit, and of the single dipole per particle approximation (SDA). The results show how the dipole plasmon resonance properties and the electric field contours around the particle vary with particle shape and size for isolated particles. For clusters of particles, we study the effect of interparticle spacing on plasmon resonance characteristics. We also show that the quadrupole resonance is much less sensitive to particle shape and interparticle interactions than the dipole plasmon resonance. These results provide benchmarks that will be used in future comparisons with experiment.     

Noble Metal Nanoparticles Stabilized by Hyper-Cross-Linked Polystyrene as Effective Catalysts in Hydrogenation of Arenes

This work is addressing the arenes’ hydrogenation—the processes of high importance for petrochemical, chemical and pharmaceutical industries. Noble metal (Pd, Pt, Ru) nanoparticles (NPs) stabilized in hyper-cross-linked polystyrene (HPS) were shown to be active and selective catalysts in hydrogenation of a wide range of arenes (monocyclic, condensed, substituted, etc.) in a batch mode. HPS effectively stabilized metal NPs during hydrogenation in different medium (water, organic solvents) and allowed multiple catalyst reuses.     

聚合物负载贵金属催化剂的合成及其在氢化反应中的应用进展

聚合物负载贵金属催化剂大多具有良好的光学催化活性,并且反应后容易从反应物中分离,重复实用性高,成为近年来人们研究的热点。常见的聚合物载体主要为有机聚合物及多种无机-有机杂化材料。本文主要按聚合物载体种类的不同,综述了聚合物负载Pt、Pd、Rh等贵金属催化剂的制备方法及其在烯烃、二烯烃、炔烃和硝基芳香化合物等物质的催化氢化中的应用情况。同时,对以树形分子为载体的催化剂、负载多元金属催化剂以及负载金型催化剂的研究及应用情况也进行了总结和评述。     

不同方法制备的CoMo/Al2O3加氢脱硫催化剂的表征

 采用干混法、湿混法和浸渍法制备了CoMo/Al2O3加氢脱硫催化剂. 物理性质分析、X射线光电子能谱、X射线能量色散谱和程序升温硫化表征结果表明,干混法和湿混法催化剂的孔容和比表面积相当,均大于浸渍法催化剂. 浸渍法催化剂的表面粒子明显大于两种混捏法. 两种混捏法催化剂可以在低温区硫化,浸渍法催化剂的硫化可分别在低温区和高温区进行. 干混法催化剂中Co和Mo在微区内分布不均匀,浸渍法催化剂中Co和Mo在催化剂表面的分散量明显高于催化剂内部,湿混法催化剂中Co和Mo在微区内呈均匀分布. 湿混法催化剂的Co和Mo在催化剂表面的分散状态好于干混法和浸渍法,制备方法对催化剂中Co和Mo的存在环境及价态没有影响. 石脑油加氢脱硫反应评价结果表明,湿混法催化剂的加氢脱硫活性高于浸渍法和干混法催化剂.     

过渡金属改性的ZSM-5催化剂应用于甲硫醚转化制甲硫醇

负载过渡金属的ZSM-5 催化剂用于催化甲硫醚（DMS）转化成甲硫醇（MT）的反应. 实验结果表明,催化剂的甲硫醚转化率提高和甲硫醇选择性降低的趋势一样,都是以下顺序：Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. 表征结果表明,由于过渡金属阳离子（W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺）比Al³⁺活泼,而改性过程中W⁶⁺、Ni²⁺、Co³⁺、Mo⁶⁺分别代替了部分Al³⁺,使得改性催化剂对DMS和MT的化学吸附作用更强. 过渡金属的引入使得ZSM-5总酸度增强,提高了C―S键的裂解能力,从而改进了催化转化DMS的能力. 研究结果发现,在转化DMS的过程中,金属活性位和酸性位之间通过强的协同效应起作用.     

三元金属硫化物-石墨相氮化碳异质结催化剂的制备及光催化性能

以双氰胺、醋酸锌、钼酸铵、醋酸镉和硫化钠为原料,采用水热法合成了一系列Zn-Mo共掺杂CdS(Zn-Mo-CdS),并与g-C₃N₄组成异质结催化剂(Zn-Mo-CdS/g-C₃N₄)。采用X射线衍射光谱(XRD)、紫外-可见(UV-Vis)光谱、电感耦合等离子体-原子发射光谱(ICP-AES)、电化学阻抗谱(EIS)、X光电子能谱(XPS)等分析手段对制备的催化剂进行了表征。结果表明, Zn-Mo-CdS与g-C₃N₄之间紧密结合并形成异质结,促进界面电荷迁移,抑制光生电子-空穴对的复合。以可见光下降解染料罗丹明B (RhB)为探针反应考察了催化剂性能。结果表明, Zn-Mo-CdS/g-C₃N₄异质结催化剂的光催化性能与单纯g-C₃N₄、Zn-Mo-CdS及双金属硫化物/g-C₃N₄异质结催化剂相比均有大幅度提高,质量比m(Zn-Mo-CdS)/m(g-C₃N₄) = 4 : 1时制备的异质结催化剂表现出最大的降解速率常数,是单纯g-C₃N₄和Zn-Mo-CdS的30倍和10倍。不仅Zn-Mo-CdS,其他三元金属复合硫化物如Mo-Ni-CdS和Ni-Sn-CdS与g-C₃N₄之间也能有效构筑异质结,促进电子-空穴对的分离和催化性能提升。     

Ni含量及预硫化对NiW/γ-Al2O3催化剂上噻吩加氢脱硫反应活性的影响

 采用连续流动微反装置考察了活性组分Ni／（Ni＋W）原子比及\r\n预硫化条件对NiW／γ－Al2O3催化剂噻吩加氢脱硫（HDS）反应活性的\r\n影响．用X射线光电子能谱和电镜微区元素分析方法对硫化态催化剂进\r\n行了表征．结果表明，催化剂的组成、硫化方法、硫化度和反应条件等\r\n都能影响NiW／γ－Al2O3催化剂的HDS反应活性．对于在较低温度（30\r\n0℃）下硫化的催化剂，当反应温度较低（260～290℃）时，最佳Ni／\r\n（Ni＋W）原子比为0．50，而当反应温度较高（330～360℃）时，最佳\r\nNi／（Ni＋W）原子比为0．23．当催化剂在300～450℃下硫化时，其噻\r\n吩HDS反应活性随硫化温度升高而增大，表明硫化度较高的催化剂具有\r\n较高的HDS反应活性．     

Comparison of HDS of Dibenzothiophene and HDN of Quinoline Over Supported MO and CoMo Nitrided and Sulfided Catalysts

Catalytic activities of sulfided and nitrided forms of alumina supported molybdenum as well as cobalt-molybdenum catalysts were compared in the reactions of hydrodesulfurization of dibenzothiophene and hydrodenitrogenation of quinoline. Effect of catalyst composition as well as of the method of its activation on the reaction pathways and catalyst selectivity is discussed.     

Immobilization of Polymer-Stabilized Noble Metal Colloids and Their Catalytic Properties for Hydrogenation of Olefins

Polymer-stabilized noble metal colloids were efficiently immobilized on silica by the addition of organic acids under mild conditions. The function of organic acids in the immobilization was studied by infrared spectroscopy. Transmission electron micrographs indicate that the immobilized colloids have a controlled particle size and size distribution. They serve as catalysts in the hydrogenation of cyclohexene and cyclopentadiene, the results of which show that this new type of immobilized colloid has high selectivity and good stability.     

Preparation,Functionality, and Application of Metal Oxide‐coated Noble Metal Nanoparticles

With their remarkable properties and wide‐ranging applications, nanostructures of noble metals and metal oxides have been receiving significantly increased attention in recent years. The desire to combine the properties of these two functional materials for specific applications has naturally prompted research in the design and synthesis of novel nanocomposites, consisting of both noble metal and metal‐oxide components. In this review, particular attention is given to core–shell type metal oxide‐coated noble metal nanostructures (i.e., metal@oxide), which display potential utility in applications, including photothermal therapy, catalytic conversions, photocatalysis, molecular sensing, and photovoltaics. Emerging research directions and areas are envisioned at the end to solicit more attention and work in this regard.