氧化铈对F-T反应铁锆催化剂的助催化作用

应用ＸＲＤ、ＸＰＳ、Ｍｏｓｓｂａｕｅｒ谱、ＴＰＲ、ＣＯ－ＴＰＤ、ＣＯ＋Ｈ２反应性能测量试等手段研究了ＣｅＯ２对Ｆ－Ｔ合成制低碳烯烃Ｃｅ－Ｆｅ／ＺｒＯ２催化剂催化性能的影响。结果表明，与Ｆｅ／Ｚｒ催化剂相比，加铈助剂后的催化剂Ｆ－Ｔ反应催化活性明显上升。     

锰助剂对Fe／ZrO2催化剂F—T反应催化性能的影响

应用ＸＲＤ，ＸＰＳ，Ｍｏｓｓｂａｕｅｒ谱，ＴＰＲ，ＣＯ化学吸附ＣＯ－ＴＰＤ，ＣＯ＋Ｈ２反应性能测试等手段研究了锰助剂对Ｆ－Ｔ合成制低碳烯烃Ｍｎ－Ｆｅ／ＺｒＯ２催化剂结构及催化性能的影响。结果表明，与Ｆｅ／Ｚｒ催化相比，加锰助剂后的催化剂Ｆ－Ｔ反应催化活性上升，甲烷选择性降低，低碳烯烃选择性增加。     

含过渡金属HMS的合成和催化性能

利用中性伯胺（十二胺）作模板剂,合成了过渡金属Ｃｕ、Ｔｉ、Ｃｏ、Ｆｅ取代的ＨＭＳ中孔材料,ＸＲＤ和ＦＴ＝ＩＲ表征表明,Ｃｕ、Ｔｉ能有效地嵌入ＨＭＳ骨架壁中而不会造成其中孔有序度的下降;而Ｃｏ、Ｆｅ的嵌入会明显降低表面活性剂的模板组装作用,从而造成中孔结晶有序度的显著下降,催化实验结果表明：Ｃｕ－ＨＭＳ、Ｆｅ－Ｓｉｌｉｃａ是苯要不要羟基化的有效催化剂,而Ｔｉ－ＨＭＳ则是苯乙烯环氧化的有效催化剂。     

制备高碳醇用Cu－Fe系催化剂的活性相

用共沉淀法制备了Ｃｕ－Ｆｅ系催化剂，它是由脂肪酸甲酯加氢制备高碳醇的新催化体系．催化剂经焙烧后的物相为ＣｕＯ，γ－Ｆｅ２Ｏ３和ＭｇＯ，形成了活性相的结构前驱．在反应条件下，ＣｕＯ首先被还原为金属态的Ｃｕ０，然后γ－Ｆｅ２Ｏ３被还原为Ｆｅ３Ｏ４；Ｃｕ０和Ｆｅ３Ｏ４共同参与催化该反应．本文用ＸＲＤ，ＴＧ－ＤＴＡ和Ｍｏｓｓｂａｕｅｒ谱等手段，结合催化剂的活性测定，确定了催化剂的活性相为Ｃｕ０和Ｆｅ３Ｏ４；ＭｇＯ可改变催化剂的电子结构和几何构型，起到重要的助催化作用     

镧助剂对Fe/ZrO2催化剂结构及F-T反应性能的影响

用ＸＲＤ，Ｍｏｓｓｂａｕｅｒ谱，ＴＰＲ，ＣＯ－ＴＰＤ和ＣＯ加氢反应性能测试等手段研究了镧助剂对Ｆｅ／ＺｒＯ２催化剂结构及Ｆ－Ｔ合成催化剂性能的影响。结果表明，不同的制备方法明显影响催化剂的结构及反应的性能，镧助剂以Ｌａ２Ｏ３形式存在时，催化剂上甲烷选择降低，烯烃选择性提高；镧助剂以ＬａＦｅＯ３形式存在时，催化剂的催化活性大大提高，但同时甲烷选择性上升，烯烃选择性下降。     

用MES及XRD研究FT合成催化剂的活性结构

采用穆斯堡尔谱及Ｘ光衍射法研究了共沉淀法制备的不同Ｆｅ／Ｍｎ比催化剂在焙烧、合成气还原及ＦＴ反应后体系相结构的变化。结果表明：锰助剂的加入使催化本相由铁磁性逐渐转化为超顺磁性，相应使催化剂还原逐渐难，Ｍｎ助剂促进了ＦＴ合成反应进行。反应性能与Ｆｅ／Ｍｎ尖晶石（Ｆｅ１－ｙＭｎｙ）３Ｏ４组成含量及式中ｙ大小密切相关，与ＭｎＣｏ３及ＭｎＯ的存在也有一定关系。富铁催化剂中Ｍｎ主要起电子助剂作用，而富锰催化     

CO_2在Fe-Zn-M/HY复合催化剂上加氢合成异丁烷的研究(英文)

对ＣＯ_２在Ｆｅ－Ｚｎ－Ｍ（Ｍ＝Ｚｒ,Ａｌ,Ｇａ和Ｃｒ）／ＨＹ复合催化剂上的加氢反应进行了研究。通过对复合催化剂的配比、反应温度以及气体空速的考察,确定了由ＣＯ_２加氢合成异丁烷的最佳反应条件。在对反应机理研究后发现,ＣＯ_２在复合催化剂上的加氢反应是一个混合了甲醇合成和甲醇制汽油（ＭＴＧ）的反应过程,而不是传统的ＦＴ反应过程。实验结果指出,反应中生成的烯烃是产生异丁烷的重要中间产物。在所有的催化剂上,异丁烷的组成在烃类中是最高的。在Ｈ２／ＣＯ２＝３,５ Ｍｐａ, ３０００ｈ~（－１）及３６０℃的反应条件下, ＣＯ_２在Ｆｅ－Ｚｎ－Ｚｒ／ＨＹ复合催化剂上进行加氢反应时,异丁烷在烃类中的选择性高达３８％,异丁烷的时空产率可达３．０ Ｃ－ｍｏｌ％,这是迄今为止我们所知由ＣＯ_２加氢合成异丁烷所得的最好结果。     

电镀及化学镀磁记录介质薄膜的最新进展

本文综述了近年来国外电镀及化学镀磁记录介质薄膜的最新研究进展、电镀及化学镀镀液组成、工艺条件及其对薄膜性能的影响、存在问题及发展方向等．磁记录介质薄膜的制备，过去一直采用溅射方法，近年来国外开展了电镀及化学镀方法制备的研究．电镀方法包括水溶液电镀（如：Ｎｉ－Ｆｅ、Ｆｅ－Ｃｏ合金等）和非水溶液电镀（如Ｔｂ－Ｆｅ、Ｎｄ－Ｆｅ、Ｔｂ－Ｆｅ－Ｃｏ合金等），化学镀则是在Ｎｉ－Ｐ、Ｃｏ－Ｐ合金的基础上，通过添加其它金属盐，得到磁记录介质薄膜，如：Ｃｏ－Ｎｉ－Ｐ、Ｃｏ－Ｗ－Ｐ、Ｃｏ－Ｍｎ－Ｐ、Ｃｏ－Ｎｉ－Ｒｅ－Ｐ合金等     

Fe_2O_3／ZrO_2催化剂上一氧化碳加氢反应制低碳烯烃 Ⅱ．预处理条件对催化剂结构及性能的影响

用ＴＰＲ，Ｍｏｓｓｂａｕｅｒ谱法，ＸＰＳ，ＸＲＤ及反应评价等手段研究了Ｆｅ２Ｏ３／ＺｒＯ２催化剂的还原行为、铁物种状态和ＣＯ加氢反应性能．结果表明，预处理条件明显影响Ｆｅ２Ｏ３／ＺｒＯ２催化剂表面铁原子的数量、铁锆间的相互作用、催化剂的物相变化以及ＣＯ加氢反应的催化性能．以Ｆｅ２Ｏ３／ＺｒＯ２经氢氟混合气程序升温至７５３Ｋ还原生成的Ｆｅ－Ｚｒ－Ｏ物种为前身，在合成气中进一步还原得到的铁锆催化剂，具有较好的Ｆ－Ｔ反应合成低碳烯烃的选择性．     

Fe—Mo／KZSM—5上甲醇氧化为甲醛的研究

采用浸渍法制备了Ｆｅ／Ｍｏ／ＨＺＳＭ－５和Ｆｅ－Ｍｏ／ＫＺＳＭ－５分子筛催化剂,利用ＮＨ３－ＴＰＤ和Ｏ２－ＴＰＤ对催化剂的表面酸性和吸附Ｏ２物种进行了表征,考察了温度、Ｍｏ／Ｆｅ摩尔比,空气／甲醇摩尔比及ＷＨＳＶ对催化性能的影响。实验结果表明,在Ｆｅ－Ｍｏ／ＫＺＳＭ－５催化剂上,适宜的反应条件下,甲醇转化率接近１００％,甲醛选择性达到９０．６％,同时还进行了９６ｈ的催化剂的稳定性实验。     

沸石催化的2,4,4-三甲基-1-戊烯的酰化反应

通过HY沸石与某些传统催化剂的比较，发现HY在2，4，4-三甲基-1-戊烯与乙酸酐的酰化反应中比那些传统催化剂更有效．用HY沸石作催化剂，室温下通过2，4，4-三甲基-1-戊烯与乙酸酐的酰化反应，合成了三种异构体，即4-（2，2-二甲基丙基）-4-戊烯-2-酮、（E）-4，6，6-三甲基-4-庚烯-2-酮和（Z）-4，6，6-三甲基-4-庚烯-2-酮．考察了HY沸石的用量对该酰化反应的影响．当2，4，4-三甲基-1-戊烯／乙酸酐／HY沸石=1mmol／10mmol／0．250g，反应温度25℃、反应时间2h时，生成的三种异构体产率之和为72％，HY沸石对于该反应具有极好的选择性和优良的活性稳定性，不同阳离子交换的Y沸石也用于催化2，4，4-三甲基-1-戊烯的酰化反应。     

甲苯-甲醇侧链烷基化合成苯乙烯的研究进展

甲苯-甲醇侧链烷基化合成苯乙烯具有极高的工业应用前景和学术研究意义.我们介绍了甲苯与甲醇侧链烷基化反应制苯乙烯的课题背景,总结了改性X型分子筛、复合型分子筛、多孔碳和金属氧化物以及其它类型催化剂在甲苯-甲醇侧链烷基化反应中的应用状况,分析了其反应机理及甲醛深度分解的原因以及目前催化剂的不足,并提出了可能的改进方案.最后对该领域的今后研究重点进行了展望,为提升甲苯与甲醇侧链烷基化催化剂的活性、选择性及使用寿命等相关研究提供参考.     

Synthesis and Applications of SAPO-34 Molecular Sieves

Silicoaluminophosphate zeolite (SAPO-34) has been attracting increasing attention due to its excellent form selection and controllability in the chemical industry, as well as being one of the best industrial catalysts for methanol-to-olefin (MTO) reaction conversion. However, as a microporous molecular sieve, SAPO-34 easily generates carbon deposition and rapidly becomes inactivated. Therefore, it is necessary to reduce the crystal size of the zeolite or to introduce secondary macropores into the zeolite crystal to form a hierarchical structure in order to improve the catalytic effect. In this review, the synthesis methods of conventional SAPO-34 molecular sieves, hierarchical SAPO-34 molecular sieves and nanosized SAPO-34 molecular sieves are introduced, and the properties of the synthesized SAPO-34 molecular sieves are described, including the phase, morphology, pore structure, acid source, and catalytic performance, in particular with respect to the synthesis of hierarchical SAPO-34 molecular sieves. We hope that the review can provide guidance to the preparation of the SAPO-34 catalysts, and stimulate the future development of high-performance hierarchical SAPO-34 catalysts to meet the growing demands of the material and chemical industries.     

Oxidative Transformations of Organic Compounds Mediated by Redox Molecular Sieves

Zeolites are viewed by some as the “philosopher's stone” of modern chemistry.^[1] They are more or less indispensable in oil refining and petrochemicals manufacture where they are widely applied as solid acid catalysts. More recently attention has been focused on their use in the manufacture of fine chemicals. The synthetic utility of zeolites and related molecular sieves (zeotypes) has been considerably extended by the incorporation of redox metals into their frameworks. The resulting redox molecular sieves catalyze a variety of selective oxidations under mild conditions in the liquid phase. Their structural diversity–including variation of the redox metal, incorporation of metal complexes, and the size and polarity of the micropores–provides the possibility of designing tailor-made solid catalysts (“mineral enzymes”) for liquid-phase oxidations with clean oxidants such as O₂, H₂O₂, and RO₂H. Hence, they have enormous potential in industrial organic synthesis as environmentally friendly alternatives to traditional oxidations employing inorganic oxidants in stoichiometric amounts. A primary aim of this review is to familiarize organic chemists with the synthetic potential of redox molecular sieves. An outline of their synthesis, structures, and chemical properties, highlighting their unique advantages, is followed by a discussion of general (mechanistic) features that influence the choice of a suitable catalyst for a particular type of oxidation. The main part of the review deals with the oxidation of various substrates of synthetic interest–such as alkanes, alkenes, (alkyl)arenes, alcohols, and amines–and emphasizes the advantages of redox molecular sieves (including selectivity and stability) over their homogeneous counterparts. New directions towards truly biomimetic solid catalysts, for example zeolite-encapsulated chiral metal complexes as heterogeneous catalysts for asymmetric oxidations, are high-lighted.     

Agostic bonds in cyclometalation

Cyclometalation reactions proceed very easily with one step reaction between metal compounds and substrates having a heteroatom such as O, S, N, P and As. However, under mild reaction conditions, many agostic compounds which are intermediates in these cyclometalation reactions, can be isolated. The metal compounds used for the formation of these agostic intermediates are both transition metal and main group metal compounds. The substrates are nitrogen-containing compounds, phosphorus-containing compounds, oxygen-containing compounds and sulfur-containing compounds. These agostic intermediates are mainly δ-C-H agostic compounds, some are γ-C-H agostic compounds and very few are ?-C-H-agostic compounds. The agostic intermediates are prepared, usually, under mild reaction conditions in the cyclometalation reaction. These agostic compounds are also prepared from cyclometalation reaction products, e.g., by the protonation, irradiation, and elimination of ligand molecules by vacuum, inert gas current, dehydration with a molecular sieves 4A, etc. Some agostic compounds are utilized for preparation of stable catalysts, e.g., hydrogenation catalysts.     

烯烃裂解中分子筛催化剂的稳定性研究进展

低碳烯烃催化裂解增产丙烯是一项新技术,高水热稳定催化剂的研究和开发是关键技术之一,硅酸铝分子筛催化剂因具有相对较好的稳定性而得到了广泛研究. 本文总结了HY, HZSM-5和 MCM-22等微孔、介孔以及具有微-介孔复合结构的新型分子筛在烯烃催化裂解反应中的稳定性,特别是水热稳定性方面的研究进展,归纳了提高酸性分子筛催化剂水热稳定性的方法,比较了不同方法制得分子筛的催化裂解性能,对高稳定性催化剂在实际应用中的问题和前景进行了探讨,为研发新一代低碳烯烃裂解催化剂提供参考.     

一氧化碳参与不饱和烃类化合物羰基化反应的研究进展

不饱和烃类化合物的羰基化反应是指在过渡金属催化剂存在条件下, 将一氧化碳(CO)分子以羰基的形式插入到烯烃(或者炔烃)与不同的亲核试剂中, 合成更高附加值化学品的转化过程. 本文综合评述了羰基化反应合成高附加值化学品的重要性, 介绍了几种不同类型的羰基化反应(氢甲酰化反应、 氢酯化反应、 氢酰胺化反应和氢羧基化反应)在发展新型催化剂体系及高效合成目标产物方面的研究进展, 并对羰基化反应存在的问题及未来发展方向和趋势进行了展望.     

Palladium-triazine aminoalcohol nanocomposite, its reactivity on Heck reaction

Several studies on dendrimer synthesis and reactivity have been carried out in order to control the size and functionality of compounds. From such studies, it has been suggested that these molecules may be used as ligands to synthesize potential homogeneous catalysts, firstly, in order to get the benefits of both homo- and heterogeneous catalysis (i.e. high activity and/or selectivity, good reproducibility, accessibility of the metal site, intermediaries detection, etc.); secondly, because, unlike other polymeric species, they can be readily recoverable after reaction. In this paper, following our interest in homogeneous catalysts, we would like to present our findings from studies on the synthesis and characterization of a prime molecule, triazine aminoalcohol, as starting or zero generation dendrimer and its interaction-reaction with palladium nanoparticles as well as our results on the reactivity on Heck type catalysis.     

离子热法合成分子筛的研究进展

离子热法是以离子液体或低共熔混合物为介质的一种新型的分子筛合成方法, 它提供了一种离子态的独特合成环境, 为合成新型分子筛及研究分子筛的生成机理提供了机会. 本文综述了离子热法在分子筛合成方面取得的一些进展, 包括合成方法的创新、合成机理的研究、新材料的合成以及新型催化剂的制备等, 并展望了其发展前景.